Search Documents

By C. S. Roberts

The creep mechanism and kinetics of fine-grained magnesium have been studied over the temperature range 200&apos; to 600°F. As a result of a photographic study of microstructural changes, transient and steady-state creep components have been correlated with slip, subgrain formation, and cyclic deformation at the grain boundaries. THE approach of this research has been the blend of a quantitative study of the creep strain of polycrystalline magnesium as a function of time, stress, and temperature with direct microstructural observations of the operative deformation processes. The validity of the conclusions is dependent on the condition that the microstructural changes seen on the polished surface qualitatively represent those occurring in the bulk of the metal. The work was intended as much to lay a background to a study of highly creep-resistant magnesium alloys as to provide a description of the behavior of the base metal itself. The spectroscopic analysis of the electrolytic magnesium used in this study is as follows: Al, 0.009 pct; Ca, <0.01; Cu, 0.0011; Fe, 0.021; Mn, 0.012; Ni, 0.0004; Pb, 0.0012; Si, <0.001; Sn, <0.001; and Zn, <0.01. The impurity level is approximately that of commercial magnesium alloys. The original ingot was melted under Dow type 310 flux and cast as a 3 in. diam billet. It was extruded into 1 in. flat stock under the conditions: billet preheat 800°F (1 hr), container and die temperature 800°F, speed 3 ft per min, and area reduction ratio 45:1. The extrusion process was chosen in preference to rolling and recrystallization because it allowed easier grain size control from specimen to specimen. The grains of the extruded metal were fairly equi-axial and uniform in the size range of 4 to 6 thousandths of an inch. The preferred orientation of basal planes about the transverse direction was determined by an X-ray diffraction surface reflection method. A beam of filtered copper radiation was directed at an angle of 17" to both the transverse direction and the surface yet perpendicular to the extrusion axis. Analysis of the (002) diffraction arcs in the resulting photographic patterns gave an approximate intensity distribution along the great circle which extends through the center of the basal plane pole figure and to the extrusion axis poles. Successive layers of metal were removed by macro-etching between exposures. The extruded texture is relatively sharp, but the most significant point is the position of the maximum basal plane pole density and its variation with depth below the surface. Fig. 1 shows that this maximum is rotated 15" from the normal at the surface toward the extrusion direction. Such an inclination has been reported for extruded 1 pct Mn and 8 pct A1-0.5 pct Zn alloys.&apos; The inclination decreases until the maximum splits at about 0.025 in. depth into two elements of equal and opposite rotations from the ideal. The double texture persists to as great a depth as was experimentally convenient to examine. It probably continues to the very center of the extrusion. There is no great change in the sharpness of the individual elements of the texture with depth. A plate of metal about 0.015 in. thick at the surface of the extruded stock was produced by etching. A transmission diffraction pattern was made for the purpose of determining any preferred orientation of a direction in the basal planes. Relatively uniform {loo) and {101) rings were produced. There is little tendency for parallelism of a given direction in the plane with the projection of the extrusion axis on it. The creep specimens were machined from 6¼ in. lengths of the extruded stock. Creep was measured on the reduced section, ½x1/8X2¼ in. long. This section was electropolished on one side for the studies of microstructural changes during creep. An orthophosphoric acid-ethyl alcohol electrolyte was used under the conditions recommended by Jacquet.² Hand polishing was used for previous mechanical preparation. Electropolishing was continued until all mechanical twins had been removed. The electro-polished surface was protected from oxidation during creep testing by a thin layer of silicone oil. All micrographs were taken at room temperature on conventional metallographic equipment and after removal of the oil film. The creep tests were performed with machines which have been described in detail by Moore and McDonald." Five testing temperatures, 200°, 300°, 400°, 500°, and 600° ±3°F were used. Difference in temperature between the two ends of the specimen reduced section was 2°F or less. The testing was done at constant load. Strain readings were taken as frequently as necessary to develop usable creep curves. Tensile Creep vs Time, Stress, and Temperature A definition of terms is necessary. Whenever successive sections of a creep strain-time curve show decreasing, constant, and increasing slope with time they will be termed primary, secondary, and tertiary

Jan 1, 1954

By W. B. Dancy, A. Adams

Laboratory test work on heavy liquid separation of sylvite from halite is reported. Numerous tests were run on sylvite ore sized in the ranges of 4x20 mesh, 10x65 mesh, 8x100 mesh, -8 mesh and -10 mesh with heavy liquids in the range of 2.05 to 2.15 sp gr. From the test results, it was concluded that, with the type of ore under study and a size in the range of -8 mesh, a recovery as high as 90% could be achieved with a product grade of 70% KCl. However, a final product at an acceptable recovery cannot be made with one pass, and the float must either be further processed with heavy liquids or dried and sent to a conventional froth flotation circuit. Potash ores occurring in this country consist essentially of sylvite and halite plus minor amounts of magnesium sulfate salts and montmoril-lonite-type clays. Recovery of potash minerals from evaporite ores in the North American potash fields is accomplished almost exclusively by use of amine flotation. European practice involves froth flotation as well as solution-crystallization processes. Laboratory and pilot plant test work has been reported in Europe and the U. S. on the application of heavy media separation to potash ore beneficiation. Work was probably discontinued because of lack of ore with the required very coarse liberation characteristics (1/8 to 1/2 in. liberation size). Sylvite, with a gravity of 1.99, and halite, with a gravity of 2.17, appear to be ideal for separation by heavy liquids, which are now available in gravities from 1.59 to 2.95. This paper reviews preliminary results obtained from laboratory test work on heavy liquid separation of sylvite from halite. TEST WORK The heavy liquids used in the tests under discussion were chlorobromethane, with a specific gravity of 1.923, and dibromethane, with a gravity of 2.490. These liquids, completely miscible, were combined in the proportions needed to give a mixture having the desired specific gravity. Feed for the laboratory tests was mine-run ore screened to the desired mesh sizes. In conducting the tests, the sample was fed at a constant rate into a stream of heavy liquid and the mixture directed into a small separatory vessel. The float overflowed into a collecting pan while the sink collected in the bottom of the separatory vessel and was removed at the end of the test. Approximately 500 g of feed constituted a charge. Pulp density of the feed was kept low to prevent particle to particle interference in separation. With feed in the range of 8x100 mesh, a pulp density of under 10% solids by weight was found advisable. With coarser feed the pulp density could be carried as high as 15% solids. Time of separation was very rapid. In the case of 4x20-mesh material, separation was effected in 15 to 30 sec; with -10-mesh feed, separation required about 1 to 2 min. SPECIAL EQUIPMENT Since heavy liquids are toxic to varying degrees, all separatory work was carried out in a standard laboratory fume hood. It was noted that complete removal of fumes was not being effected; therefore the hood construction was modified, resulting in a completely satisfactory arrangement for heavy liquid test work. In the interest of safety, details of this fume hood are reported here. Unlike most fumes, heavy liquid fumes tend to settle and flow like water, rather than to rise like a gas. Working on this assumption, a standard water drain was installed in the hood. Across the front of the hood a 1-in. barrier was constructed. In the rear of the hood a false back was installed, with an adjustable sliding door on both the bottom and top of this panel. As shown in Fig. 1, the exhaust fan pulled a vacuum behind the barrier, sucking the heavy fumes from the bottom of the hood. Another addition was the drying box, shown to the right of the hood. This is simply a box covered on top with hardware cloth and connected by a 6-in. inlet to the hood. Sample trays made of fine mesh wire filter screens were found ideal for drying samples. With this arrangement, air flowed completely through the sample and all fumes were drawn into the hood. In use, it was found effective to cover with a

Jan 1, 1963

By A. E. Blakeslee

Morphological and electrical properties of GaAs epitaxial layers are influenced not only by changes in the nominal substrate orientation but also by small amounts of misorientation from the exact crystal planes. Deviations up to 5 deg from {11IA}, {11IB}, and (100) planes were investigated. Growth rates increase progressively with angle, approximately I u per hr per deg. Size and density of growth pyramids fall off with increasing angle, but other effects that are deleterious to the surface may occur which are heightened by increased misorientation. Carrier concentration decreases and electron mobility consequently increases as the angular offset increases, except in the case of strong compensation, where the mobility trend is reversed. It has long been known that changes in the crystallo-graphic orientation of the substrate may cause pronounced effects on the morphological properties of vapor grown semiconductor films. Reports of orienta-tion-dependent growth rates and surface characteristics are as old as the literature on epitaxy itself. shawl has recently published a comprehensive study of the dependence of growth rate on substrate temperature and orientation in epitaxial GaAs. It is also well-known that misorienting the substrate surface a few degrees away from the nominal low-index crystal-lographic plane often produces a much smoother epitaxial surface. This was reported by Tung2 for silicon, Reisman and Berkenblit3 for germanium, and by Kontrimas and Blakeslee4 for GaAs, and use is commonly made of this fact in the semiconductor industry to help guarantee smooth vapor deposits. The effects of substrate orientation on the carrier concentration and mobility of vapor grown GaAs were first documented by williams5 in 1964 and have been observed by several other authors since then,6,7 but no one has yet reported a careful study of how small changes influence these properties. We have made such a study and have found that sizable differences in growth rate, morphology, carrier concentration, and mobility can indeed be observed for epitaxial films grown on substrates that are oriented by progressive small increments away from the exact crystal plane. EXPERIMENTAL Early in the investigation an arsine synthesis system of conventional design8 was employed to produce growths on {111A}-oriented GaAs substrate crystals. In that early work, pronounced effects on carrier concentration and electron mobility were observed as a function of slight misorientation from this low index plane. That observation led to the more careful study that is reported here. An AsC13 system, differing in major aspect from those commonly in use today9 only in that the reactor is vertical rather than horizontal, was used for the detailed study. The gallium source was at 900°C and the substrates were at 750°C. The flow rate of pal-ladium-diffused H2 through the AsCl3 bubbler was 200 cu cm per min, and the flow rate of bypass H2 was also 200 cu cm per min. The substrates consisted of chro-mium-doped semiinsulating GaAs to facilitate elec-trical evaluation of the overgrowth by means of Hall and conductivity measurements on conventional eight-legged Hall bridges. They were misoriented by 0 to 5 deg from the {111A}, {111B}, and (100) planes, toward the (100) from the {111A} and {111B} and randomly toward the <111A> or <111B> from the {loo). The crystals were oriented for sawing by the Laue back-re-flection technique, which is good only to about ±1/2 deg; but after polishing or sometimes after epitaxial growth the wafers were checked by a diffractometer technique which is accurate to about * 0.1 deg. After lapping, the wafers were polished with NaOCl after the technique of Reisman and Rohr,10 and just before use they were cleaned in NaOC1, thoroughly rinsed with de-ionized water, and blown dry with nitrogen. Each run employed four wafers, each misoriented by differing amounts from one of the three major faces, and at least two runs were made for each orientation. The runs were continued long enough to provide at least a 15-µ or thicker layer. SURFACE MORPHOLOGY The appearance of all the films that were grown in a given run always changed from wafer to wafer as a function of increasing misorientation, but not always in the same regular fashion. At least three different trends were observed. These are more easily seen than described, and reference to the series of photo-

Jan 1, 1970

By J. D. Mote, J. E. Dorn

This investigation was undertaken to study the effects of piledup arrays of dislocations on inducing slip, twinning, and fracturing in magnesium bicrystals. A series of variously oriented bicrystals of magnesium having a vertical grain boundary were prepared and tested in tension. It was found that piled-up arrays of dislocations at the grain boundary could, under appropriate conditions, induce slip, twinning- and cracking. The results that were obtained substantiate, at least qualitatively, the general dislocation mechanism for transmission of strain across grain boundaries and the Petch-Stroh concept of fracturing. WHEREAS single crystals of magnesium generally exhibit extensive deformation, coarse-grained poly-crystalline magnesium at subatmospheric temperatures fractures after a few percent elongation.&apos; Although a small amount of ductility is obtained, several features of this fracturing are characteristic of typical brittle behavior. Over a rather broad temperature range the fracture stress is insensitive to the test temperature and the fracture stress increases linearly with the reciprocal of the square root of the mean grain diameter. The course of fracturing is predominantly intergranular, but small fragments of adjacent grains frequently adhere to the fractured surface.2 The brittle behavior of polycrystalline magnesium is attributable to the limited number of facile deformation mechanisms it exhibits at low temperatures. For a general deformation of a randomly oriented polycrystalline aggregate, each grain must exhibit at least five independent mechanisms of deformation to permit accommodation of the imposed deformation from grain to grain.= Although minor amounts of prismatic slip occur in corners of grains where stress concentrations are known to be high, glide in polycrystalline magnesium at low temperatures takes place almost exclusively by basal slip.&apos; The common type of twinning, which takes place on the (1012) pyramidal planes, can under the most favorable orientations, lead to a. strain of only 6.9 pet; the contribution of twinning to the tensile strain would indeed be much less than this in a randomly oriented polycrystalline aggregate of magnesium. Since the three mechanisms of basal slip are coplanar, they are equivalent to only two independent mechanisms, a number insufficient for a general deformation. Consequently, once the permissible twinning has taken place in conjunction with basal slip, no further plastic deformation is possible because of interference to slip at the boundaries of dissimilarly oriented grains. At this stage brittle fracturing takes place due to high stress concentrations at the juncture of slip bands with the grain boundaries; the predominance of intergranular fracturing in magnesium, in preference to transcrystalline fracturing which is prevalent in zinc, has not yet been rationalized. A more atomistic description of the plastic behavior and fracture characteristics of magnesium follows from the analyses made by stroh4 on the stresses induced by piledup arrays of dislocations. Slip first takes place by dislocation motion in the most favorably oriented grains. As the dislocations approach the boundary of a dissimilarly oriented adjacent grain they begin to form an array of dislocations with its attendant stress field. Piledup arrays of screw and edge dislocations introduce high localized shear stresses at the spur of the array; piledup arrays of edge dislocations also induce high tensile stresses localized in the vicinity of the grain boundary. Whereas the shear stresses can induce slip to take place, the tensile stresses, if sufficiently high, can cause fracturing. The localized shear stress will be relieved if sufficient numbers of mechanisms of deformation become operative in the original and the adjacent grain to permit accommodation of the dislocations in the grain boundary. In this event a ductile behavior will be obtained. But if the number of deformation mechanisms is insufficient for complete migration of dislocation arrays into the grain boundary, the tensile stresses due to the edge components of piledup dislocation arrays will continue to increase with increasing applied stress until fracturing takes place. Whereas face-centered-cubic metals have a sufficient number of mechanisms of slip for accommodation of dislocations in their grain boundaries to exhibit ductile behavior, hexagonal-close-packed metals, in general, do not. Consequently, hexagonal-close-packed metals are usually brittle except when conditions such as alloying or temperature permit facile slip by a number of mechanisms. The arguments presented above suggest that the mechanical behavior of magnesium depends on whether or not dislocation arrays in adjacent grains can enter the grain boundary. When such accommodation is possible, ductile behavior is expected; but when such accommodation is impossible, fracturing will ensue. To further test the validity of these arguments it was considered advisable to study the

Jan 1, 1961

By J. Alfred Berger, O. M. Katz

The Zv-Hf-H ternary system was studied between 500° and 900°C at pressures less than 1 atm of hydrogen gas between 1 and 60 at. pct H. A new and unique microgravimentric apparatus was used. Cizanges of slope on pressure-hydrogen composition isothernis delineated phase boundaries. These boundaries separatecl the three regions, a, 0, and y—so designated to correspond to the regions of the Zr-H binary system—from the multiphased areas between them. A eutectoidal decomposition was found with the ß region phase or phases decornposing into a lamellar product on quenching to rool ter,zperatuve. Reproducible decomposition-pressure hysteresis occilrved lnainly at lower hydrogen cornpositions and at lower temperatures across multiplzase vegions between a and 0 and a and y. Tire effects of hqfniur7z on the hydriding charactevistics of zirconiurrz weYe as follows: 1) stabilization of the a and y vegions while destabilizing the 0 region; 2) a/?preciable elevation of the decomposition pressrkres in the multiphase region between the a and /3 field; 3) ~nouenzent of the eutectoid reaction to high te~nperatures; 4) reduction in the total qiiantity of hydrogen absorbed under one atmospheve of Hz p7-essure; and 5) introduction of a split deconzposilion at the eiitectoiclal poinl in pa?? of the ternavy. Assuru~ptions based on an ir-2terstitial vandonl-solulion rtioclel 0.f hydrogen in metals slzowed that the bindit~g energy between solute sites prednnzinatecl at low /i?!dvogen concentrations. However, at high hydrogen contents the entropy was the predorninatlt factor in determining the stability of the Zr-Hf-H al1o.s. This was interpreted to mean a scarcity of filrtlzer itltevslilinl solute sites caused by hydrogen-hydvogen intet-actions in the metal lattice. INTEREST in the reaction of hydrogen with metals has increased in the past few years for the following reasons: 1) the formation or use of high hydrogen potential environments in nuclear reactors; 2) the reaction of hydrogen with alloys in nuclear reactors with the accompanying deleterious effects on the mechanical and corrosion properties; 3) the theoretical implications of thermodynamic data on the theory and rules of alloy formation in the metal-hydrogen systems; 4) the use of hydrogen-containing fuels in rocket engines; 5) the need for a process of making fine metal powders of high-melting reactive metals; and 6) the beneficial impregnation of superconducting alloys with hydrogen. In nuclear pressurized-water reactors, the problem exists of limiting the hydrogen pickup of zirconium alloys which are utilized as fuel cladding, heat shields, and support members. In general, zirconium alloys have good mechanical and corrosion-resistant properties in high-temperature water. However, hydrogen is absorbed from the corrosion reaction between metal and water, greatly accelerating the formation of the corrosion product ZrOz as well as mechanically embrittling the underlying metal. In addition, recent observations1 at zirconium to hafnium welds showed that secondary elements in zirconium can have an appreciable, and somewhat unexpected, effect on hydrogen absorption. This paper lists the thermochemical data in the range 500" to 900°C for the equilibrium reaction of four high-purity Zr-Hf alloys with hydrogen. Phase boundaries and thermodynamic functions are determined while the structural data will be presented in a future paper. In general, the Zr-Hf-H system approximates the well-known, eutectoidal, Zr-H diagram2,3 with modifications introduced through the behavior of hafnium.4,5 The Hf-H system,&apos; published while this work was in progress, provided a consistent trend with the Zr-Hf-H data. PREPARATION OF Zr-Hf ALLOYS Table I presents a complete flow chart of the preparation procedure. The zirconium and hafnium crystal bars were completely immersed in high-purity kerosene and slowly cut into thin wafers. Wafers were then cold-sheared into approximately 1-g pieces, thoroughly cleaned, weighed, and inserted into the furnace. The alloys, B-2, B-4, B-6, and B-8, were then nonconsumable arc-melted under 500 mm of purified argon. Additional purification of the argon was accomplished by melting a large titanium button each time an alloy was re-melted or a different alloy melted. Each alloy button, which weighed 25 g, was remelted four times in an approach to complete homogeneity. Material losses were less than 0.02 wt pct. Alloy buttons were alternately cold-rolled and vacuum-annealed into 10- and 20-mil sheets. Table I1 gives the composition of the four alloys used. Very little elemental segregation existed be-

Jan 1, 1965

By Craig R. Barrett

The influence of the stress dependence of the dislocation density on the overall stress dependence of The steady-state creep rate is discussed. Experimental measurements of dislocation densities and creep rates jor an Fe-3.1 pct Si alloy tested over a wide range of stress are presented which indicate a close correlation between the two quantities. EXPRESSING the stress dependence of high-temperature steady-state creep rates has been the subject of numerous investigations over the past decade. From these investigations have emerged a few general equations which fit most of the available data reasonably well. Garofalo 1 has proposed that for a wide range of stress and temperature the creep rate, i, can be expressed by a relationship of the form: where A, ß, and n are temperature-dependent and is the applied stress. Eq. [I] gives a stress dependence of a at low stresses and exp(nßo) at high stresses, both consistent with experimental observation where n = 5. A number of other investigatorshave proposed a similar expression where: where m and w are in general functions of temperature. Theoretical justification for Eqs. 111 and [2J comes from two different approaches, theories based on dislocation glide3-5 and theories based on the balance between work-hardening and recovery.&apos; Dislocation glide theories predict where p is the mobile dislocation density and V is the activation volume. In order for Eq. [3] to predict a on stress dependence at low stresses with n = 5, it is necessary for p to be a strong function of stress, about proportional to u3 or u4.436 Recovery models of creep start with the general expression:&apos; where r is the recovery rate and h is the work-hardening rate, and then employ a detailed model to determine the stress dependencies of r and h. As example, weertman2 has described a model based on pile-up hardening which results in an expression similar to Eq. [2] with m = 2 and p = 2.5. A recent, seemingly more general approach suggested by McLean is to use Friedels dislocation network growth expression to calculate the stress dependence of r. This model predicts r = p 3,2 and, as h is taken to be a relatively weak function of stress, the stress dependence of i should be about proportional to p3, 2. Once again, it is required that p be a strong function of stress to yield i This recovery model is by no means complete as the stress dependence of network growth is calculated in the absence of an applied stress meaning that r should probably be a stronger function of stress than given by p3, 2 and also some recent work by Mitra and McLean8 suggests that the stress dependence of h may be as large as Because of the importance of the stress dependence of p in determining the overall stress dependence of the strain rate it seems reasonable to examine this relationship in some detail. Measurements made on dislocation densities present during high-temperature steady-state creep generally obey the following relationship a =o0 + aGVWp [5] where uo is usually called a friction stress, a is a numerical constant about equal to unity, G is the shear modulus, and b is the Burgers vector. Depending on the magnitude of uo, data obeying Eq. [5] can give rise to a range of stress dependencies of p. For example, if we assume that the expression where 6 is some constant, adequately represents the stress dependence of p over a range of o, then from Although Eq. [6] obviously breaks down when u 5uo for uo 6 can vary over a wide range of values. In particular, if u > a, > 0 then 6 will be greater than 2. As an example the data of Ishida and McLean are plotted in Fig. 1 showing excellent agreement with dynes per sq cm) and also showing good agreement with a p cc u3 dependence when plotted on a log-log basis. As oo increases 6 tends to increase and correspondingly the stress dependence of the predicted creep rate should also increase,* as-

Jan 1, 1968

By F. H. Callaway, W. O. Keller

The various theories as to the well spacing-recovery relationship are reviewed in considerable detail and these theories analyzed in terms of their consistency with modern reservoir engineering concepts. It is concluded that the well spacing problem must be analyzed in terms of recovery efficiency and that a positive answer to the relation between well density and recovery efficiency is not available from direct comparisons of the production histories of wells and fields. The results of an engineering analysis designed to permit approximate calculation of recovery efficiencies as a function of well spacing in a depletion type reservoir from basic reservoir data is presented. Results of this type analysis indicate that the effect of well spacing on recovery efficiency in depletion type reservoirs can be expected to be very small. Limitations of this approach are pointed out, particularly with respect to its application in lenticular reservoirs. Testing techniques are outlined which should indicate whether or not a reservoir is continuous between wells and whether or not satisfactory drainage is being obtained with present spacings. A mass of data of this type indicates continuity to exist in most fields. INTRODUCTION The purpose of this paper is to review critically the engineering aspects of the well spacing problem, both from the standpoint of certain concepts and from the standpoint of reservoir mechanics. The well spacing problem is primarily an economic problem in which the optimum well density for a particular field is that density which will yield the greatest oil recovery consistent with justifiable development costs. The well spacing answer in terms of economic conditions, however, is extremely sensitive to the variation in recovery efficiency with well density. The variation in recovery efficiency with &apos;References given at end of paper. Manuscript received at the office of the Petroleum Branch October 2, 1949. Paper presented at the Petroleum Branch Meeting in San Antonio. Texas, October 5-7. 1949. well density is properly an engineering problem. Different opinions as to the correct answer to this engineering problem is the basis for most of the wide difference in opinion among various members of the industry as to optimum well spacing. This paper will be confined to the engineering problem of the relation between well density and ultimate oil recovery; economic considerations necessary for the evaluation of optimum well density for any particular field will not be discussed. The paper can be logically divided into two parts. The first part deals with a critical examination of the background and logic of the Cutler Rule and of similar studies by other authors and of related well spacing concepts. It is indicated that the variations in recoveries with well density* observed by Cutler and. others can be logically attributed to regional migration. Theoretical justification of the Cutler type relation wherein observed variations in recovery with well density in the same field is attributed to variations in recovery effiiency, in terms of energy relations, is refuted. The second part consists of a review of concepts of reservoir mechanics with regard to the well density-recovery relation. It is indicated that little variation of recovery efficiency with well density can be expected in a depletion type reservoir, unless lenticular conditions prevent communication between wells. The significance of field test data with regard to the existence or non-existence of lenticular conditions is pointed out. THE CUTLER RULE The first published article concerning the engineering aspects of the well spacing problem to receive wide attention was the work of W. W. Cutler&apos; of the U. S. Bureau of Mines, published in 1924. In a study of decline curves from a large *The expression "well density" as utilized herein refers to the number of acres attributed to each well in a uniform well pattern, and is expressed in acres per well. The term "well spacing" Is utilized to denote the average distance between adjacent wells in a uniform well pattern. †Although the Cutler rule is treated critically in this discussion the authors intend no personal criticism of W. W. Cutler or of his hark The currently accepted concepts of reservoir mechanics were no": existent at the time of Cutler&apos;s work, as were even the moat basic tools (such as the bottom hole pressure bomb) for observing reservoir behavior.

Jan 1, 1950

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The effects of grain size and shape on alloys of titanium with nitrogen and aluminum have been determined. Increasing a grain size decreases strength and hardness and increases impact resistance. Quenching from the ß field produces subgrain markings delineating a plates in Ti-N alloys but not in Ti-AI alloys. This suggests a precipitation from the high nitrogen alloys. ALPHA titanium alloys are single-phase alloys with the hexagonal-close-packed structure of a titanium. If these alloys are worked and annealed within the a field, equiaxed structures result in which strength is derived from the solid solution of the alloying elements present. Strain hardening can be used to increase further the strength of a titanium alloys. This is the only other mode of strengthening the a type of alloy. Quenching from the ß field has been noted by many investigators to have little effect on the strength of iodide titanium and on commercial titanium. Ti-A1 alloys were found to be little different in hardness, whether annealed in the a field or quenched from the ß field.&apos; These facts illustrate a characteristic of a titanium alloys: they are insensitive to heat treatments from the ß field. Underlying this heat-treatment insensitivity are the facts that the a-ß field is generally narrow in a titanium alloys, the transformation-temperature range increases with a-stabilizing content, and the a solubilities of the alloying elements are greater than the ß solubilities. When quenching is done from the ß field, there is no supersaturation of the alloying elements in the acicular transformation structure produced. Welds in a titanium alloys generally are ductile, because no transformation hardening occurs during cooling.1,2 Other desirable features of a alloys are: no thermal-stability problem, excellent toughness, and retention of strength at elevated temperatures better than a-ß or ß alloys of comparable room-temperature strength. The prime factors governing the properties of a titanium alloys are the amount and kind of solute present. This can change the a phase from a soft, tough material into a hard, brittle material with no apparent change in microstructure. Moreover, brit-tleness can exist over a wider alloy-content range, without change of phase, than in most other metals. The solutes for a titanium may be divided into interstitial and substitutional types. Oxygen and nitrogen dissolve interstitially in rather large amounts, extending well through the brittle range, and the transformation-temverature ranges are raised in the process.:&apos; , carbon has a maximum interstitial solubility of about 0.5 pct at the peritectoid temperature, while at lower temperatures the solubility decreases to about 0.2 pct.3,5 Substitutional a solutes include aluminum and tin. Aluminum has a high a solubility of 25 pct Al, and increases the transformation-temperature range markedly.6,7 Tin has a high a solubility of about 20 pct, but has a relatively innocuous effect on the transformation-temperature range.&apos; The choice between interstitial and substitutional solutes generally has been conceded to the substitutional solutes because of a belief that they do not have as adverse an effect on ductility and notch toughness. However, a recent investigation8 on the effect of hydrogen on titanium has shown that this element, which is not under compositional control, has a powerful detrimental effect on notch toughness. Hydrogen was shown to form a hydride which is practically insoluble (about 0.002 pct) in a titanium at room temperature, although the solubility at the eutectoid temperature of about 300°C is relatively high, about 0.16 pct. Limited data were presented on the effect of hydrogen on a alloys, where the same impairment of toughness as in unalloyed titanium is found. The work reported here describes the effects of interstitial and substitutional solutes on 1—the mechanical properties of high purity titanium free of titanium hydride and 2—the influence of structural variables on these properties. Nitrogen was selected as an example of an interstitial solute with high solubility and aluminum as a substitutional solute with high solubility. All compositions were well within the ductile range, since it was not intended to study the brittleness problem here, but to study only the factors influencing optimum mechanical properties. Procedures The alloys were prepared from iodide titanium as 1/2 Ib ingots double melted to insure homogeneity.

Jan 1, 1955

By C. S. Smith, E. W. Palmer

IN 1934, when Gregg and Daniloffl wrote their excellent monograph on the alloys of iron and copper, the most recent literature on the constitution of the alloys indicated a narrow single-liquid area for 20" above the liquidus with a closed liquid mis-cibility gap above this. Since that time, however, a number of investigators have confirmed the much earlier studies of Mushet2 and Stead3 who, among others in the nineteenth century, had described the true state of affairs. Liquid copper and iron are completely miscible in the absence of carbon, but small amounts of carbon cause liquid segregation. In 1934, one of the writers&apos; mentioned evidence for the absence of liquid separation in carbon-free alloys at temperatures up to 1700°C. Two years later, Mad-docks and Claussen5 unequivocally established the absence of liquid segregation and published a revised diagram, reproduced in fig. 1. They also studied the limits of the two-liquid area in ternary alloys of iron, copper, and carbon as a function of carbon and iron content. In the same year Simpson and Bannister" and Schumacher and Souden7 described in some detail the properties of alloys containing 50 to 75 pct Cu. More recently Hodges et al.16 have developed the copper-rich alloys for use as high-strength conductors. In 1937, Iwase, Okamoto, and Ameniya8 published data on the miscibility gap in ternary alloys of iron, copper, and carbon that supported the conclusions of Maddocks and Claussen, and definitely located the two-liquid area at temperatures of 1450" and 1540°C. They also reported that additions of 1 pct Al, Ni, Pb, Sn, or Zn caused no segregation in 50 pct Cu alloys at 1540°C. The use of copper in amounts approximating 1 pct has found industrial employment to an increasing degree in both wrought and cast steels, for such steels are capable of being precipitation-hardened following normalizing, and have high yield strengths. This is summarized by Gregg and Daniloff,1 Sallitt,9 and Lorig and Adams,10 while Alexander" gives additional information on the heat treatment of copper-steel castings. Lippert12 has described Digby&apos;s two-phase steels containing copper and chromium. The work described in the present paper was done in the years 1932 to 1934, at which time much of the information was new. The excellent work subsequently done in other laboratories but more promptly published makes the present paper in part only a confirmation of what is now well known. There has not, however, been published any unified study of

Jan 1, 1951

By T. D. Mueller

Many investigators have used the response of the "dimensionless aquifer" to a unit pressure drop or a unit fluid-withdrawal volume to calculate the performance of an aquifer in supplying water influx to an oil reservoir. In the past, these response functions have been calculated with the aid of the Laplace transform. With the advent of ultra highspeed digital computers, it becomes practical to solve for the response functions with finite-difference techniques. The computer method also permits extension of the dimensionless-aquifer concept to include the nonhomogeneous aquifer wherein the permeability and other properties vary as a function of the space co-ordinates. This paper gives results of calculating the response functions for a series of nonhomogeneous aquifers. Response functions are presented for both linear and radial aquifers whose thickness, permeability-viscosity ratio and porosity-compressibility vary. These functions are new and should prove useful to the petroleum engineer in analyzing the behavior of nonbomogeneous aquifers. Results are presented in the form of charts that can be easily used by the field engineer. INTRODUCTION Aquifers which surround many oil and gas reservoirs have the ability to supply water influx to such reservoirs as oil and gas are withdrawn. This water influx, called natural water drive, provides one of the most effective driving mechanisms for the production of oil and gas. In producing a reservoir, therefore, it behooves one to make the maximum use of natural water drive. To achieve the maximum use, the reservoir engineer must be able to predict the performance of an aquifer under a variety of production schemes that may be proposed for the reservoir. Unfortunately, the physical properties which dictate aquifer behavior often are known only within limits. Seldom do wells penetrate the porous strata of the aquifer. Even when they do, quantitative information regarding porosity, permeability and water compressibility is seldom available. It is known, however, that the water efflux from most aquifer systems is governed by a single, relatively simple, linear, partial differential equation. Also, the general physical location of the aquifer boundaries often are known. A technique originall proposed by Hurst1 and van Everdingen and Hurst2 has been found useful in analyzing reservoirs in this situation. The idea was later expanded by van Everdingen, Timmerman and McMahan3 to include the mathematical technique of least-squares fitting. This latter method will be referred to as the VTM method. The basic assumptions of the VTM method include the following. 1. The location of the physical boundaries of the aquifer are known. 2. The flow conditions at these physical bound-daries are also known. 3. The aquifer is homogeneous; e.g., thickness, permeability, water compressibility and porosity are constant throughout. In the VTM method, a material balance is made on the fluids entering and leaving the reservoir. In the balance equations, the water-influx term is represented as the product of the water influx from an arbitrarily-selected, dimensionless aquifer system times an unknown conversion number. This balance can be formed as many times as there are data points in the history of the reservoir. Each time, the conversion number can be evaluated. If the reservoir engineer has picked the correct dimensionless aquifer to represent the real aquifer, the conversion number remains constant for all balances that have been made over the history period. If such a situation occurs, the reservoir engineer can then predict the performance of the reservoir for any type of production scheme by using the function associated with that particular dimensionless system and the derived conversion number. These functions will be referred to as the response function of the aquifer. If the aquifer is nonhomogeneous (e.g., if the porosity, permeability, thickness, porosity, or

By D. L. Albright, R. W. Kraft

Solidification experiments were conducted with the objective of testing the theory of eutectic colony formation. Appropriate control of variables in tests on a series of high-purity aluminum-copper specimens of eutectic composition resulted in the observation of three types of eutectic microstructures, these being a unique structure consisting of lamellae essentially parallel to one another, a banded structure, and the colony structure. Lamellar faults, which are morphologically similar in many respects to edge dislocation models in crystals, produced a complex substructure in these specimens. SOLUTE rejection at the advancing solid-liquid interface of a unidirectionally solidified single-phase metal can cause the liquid immediately in front of the interface to become constitutionally super-cooled below the equilibrium liquidus temperature. Constitutional super-cooling occurs if the solidification rate, R, is too rapid, or if the thermal gradient in the liquid at the interface, G, is too low. 1 This constitutionally supercooled layer in turn stabilizes a cellular rather than a planar interface.&apos; A similar cellular interface has been observed when lamellar and other types of eutectics were unidirectionally solidified, and it has been shown that the cellular interface led to the formation of eutectic colonies.&apos; The lamellar structure is fan-shaped at the edges of colonies (which correspond to valleys or grooves in the cellular interface) because the lamellae grow normal to the local interface. One of the possible mechanisms which might cause the formation of the cellular interface, in the case of solidifying eutectic alloys, is constitutional supercooling of the liquid with respect to a third component rejected by both phases of the eutectic.3,4 On the basis of the analogy between the solidification of single-phase metals and binary eutectics, a eutectic alloy should solidify with a planar interface if the ratio of G/R is sufficiently high to compensate for any impurity which might be present and causing constitutional supercooling. The fan-like microstruc-ture of eutectic colonies should not occur under these conditions and the lamellae should be parallel to one another and to the solidification direction for extended distances. The experiments conducted in this investigation were designed to test these ideas. Following a resume of the experimental procedure, the various microstructures observed during the study are described, and their relationship to the growth conditions which produced them is discussed. EXPERIMENTAL PROCEDURE The eutectic between an aluminum solid solution and 0 phase (approximate composition CuA12) was chosen for this work for the following reasons: it was known that a lamellar structure forms, the eutectic temperature is low enough to facilitate experimental work, and the components can be procured commercially in a very pure form. High-purity copper (est. 99.999 pct Cu, obtained from National Research Corp.) and spectrographic aluminum rods, having impurities other than copper estimated to be Zn-15 ppm, Mg-10 ppm, Fe-3 ppm, Na-2 ppm, Cd-1 ppm, and Mn < 1 ppm, were melted in a stabilized zirconia crucible in a vacuum induction furnace at a pressure of 10 pof Hg. The melt was superheated to about 1000°C to assure mixing, cooled to 780°C and cast into an investment mold which yielded sixteen cylindrical specimen blanks 1/2 in. in diam and 5 1/2 in. long. The casting was allowed to solidify under vacuum. This master heat had an analysis of 32.6 wt pct Cu and 67.4 wt pct A1 by difference. The cylindrical specimen blanks were remelted and solidified unidirectionally in an apparatus illustrated schematically in Fig. 1. An RF induction coil heated

Jan 1, 1962

By Haydn H. Murray

The term clay is somewhat ambiguous unless specifically defined because it is used both as a rock term and as a particle size term. Actually most persons using the term clay realize that it has a double meaning and in most instances define it. As a rock term, clay is difficult to define because of the wide variety of materials that compose it so that the definition has to be general. Clay is a natural, earthy, fine-grained material composed largely of a limited group of crystalline minerals known as the clay minerals. Many definitions state that a clay has the property of plasticity when wet, but some clays are not plastic, i.e., halloysite and flint clay; however, most clay materials are plastic when wet. As a particle size term, clay is used for the category that includes the smallest particles. The maximum size particles in the clay size grade are defined differently on some grade scales. Soil investigators and mineralogists generally use 2 microns as the maximum size. The Wentworth scale&apos; defines clay as material finer than approximately 4 microns. Grim&apos; has found it convenient to use the term clay material for any fine-grained, natural, earthy, argillaceous material and in this way can include clays, shales, or argillites, and some soils if they are argillaceous. Even though no standard definition of the term clay is accepted by geologists, agronomists, engineers, and others, still the term is generally understood by all who use it. Clay is an abundant natural raw material and has an amazing variety of uses and properties which will be discussed in this chapter. In order to understand better the relationships between the clays and their uses, a brief discussion of the structure, chemical composition, and identification of the clay minerals is given. Mineralogical Composition of Clays Clays are composed of certain groups of hydrous aluminum, magnesium, and iron silicates that may contain calcium, potassium, and other ions, which are called the clay minerals, and other minerals of variable composition, which are nonclay minerals. Both clay minerals and nonclay minerals influence the properties of a clay material. In order to understand the relationship between clay minerals and the properties of a clay material, a short summary of the structure and composition of clay minerals is necessary. Any scheme of classification tends to impose a certain rigidity and as new and additional data become available it is necessary to revise classifications. Brindley3 has discussed the classification and structural mineralogy of clays in very lucid fashion and chose a classification based on structural features and chemical composition. Grim2 proposed a tentative classification which is based on the structural attributes of the various clay minerals. This classification is relatively simple and workable, and is shown as follows: I. Amorphous Allophane group II. Crystalline A. Two-layer types (sheet structures composed of units of one layer of silica tetrahedrons and one layer of alumina octahedrons). 1. Equidimensional Kaolin group kaolinite, dickite, nacrite 2. Elongate Halloysite group

Jan 1, 1960

By J. M. Flaitz, A. S. Parks

OF the various methods of sampling gas-condensate wells, a method that secures a continuous representative sample of the well stream is desirable. Such a method, consisting of a sampling tube introduced into the well tubing, has proved satisfactory. The method is sufficiently accurate for operating and engineering problems A portable testing apparatus can be used with the sampling tube to obtain data useful in studying the economic and technical aspects of the development and operation of gas-condensate properties. Introduction The recent discovery and development of gas reserves that contain hydrocarbons that condense with reduction of temperature or Pressure, or both, to form a product known as condensate, has brought many new problems to the oil and gas industries. With further discovery of deep, high-pressure fields it is presumable that many more gas fields of this type will be added to the steadily increasing number. Such gas reserves are found either associated with oil as a gas cap or in separate formations. There seems to be no positive correlation between the physical or geological nature of the reservoir, and the chemical composition or phase characteristics of its contents. Knowledge of the chemical make-up and phase behavior of gas-condensate reserves is needed to cope with many problems. A knowledge of the chemical composition and phase characteristics of the reservoir material is necessary to properly design a gasoline or recycling plant, to estimate natural gas and condensate reserves, to enable the operator to study the economic and technical aspects of various methods of operation and development, and to carry Out the plan of operating subsurface and surface lease equipment. This information is often useful in questions of mineral ownership, proration, legal position, and taxation. It is the purpose of this paper to discuss methods used by the writers to determine the chemica1 composition and phase characteristics of the fluids produced from a condensate well. The scope of the paper includes a discussion and description of the method of sampling, the results of tests on the accuracy of the sampling method, a description of a portable testing apparatus used to examine the phase characteristics, typical results of tests on wells from several condensate fields, and some of the applications of these data to production problems. References to previous work on this subject are cited at the end of the paper. The Problem At reservoir conditions of temperature and pressure, the fluids produced from a condensate well exist in a homogeneous vaporous condition. The consequent reduction of temperature and pressure that occurs as this gas enters and flows up the well tube results in condensation of some of the hydrocarbon material to form a liquid. The relative amount of liquid condensed at any point in the flowing system

Jan 1, 1942

By W. R. Purcell

An apparatus is described whereby capillary pressure curves for porous media may be determined by a technique that involves forcing mercury under pressure into the evacuated pores of solids. The data so obtained are compared with capillary pressure curves determined by the porous diaphragm method, and the advantages of the mercury injection method are stated. Based upon a simplified working hypothesis, an equation is derived to show the relationship of the permeability of a porous medium to its porosity and capillary pressure curve, and experimental data are presented to support its validity. A procedure is outlined whereby an estimate of the permeability of drill cuttings may be made with sufficient acuracy to meet most engineering requirements. INTRODUCTION The nature of capillary pressures and the role they play in reservoir behavior have been lucidly discussed by Lev-rett&apos;, Hassler, Brunner, and Deah12, and others. As a result of these publications the value of determining capillary pressure curves for cores has come to be generally recognized within the oil industry. While considerable attention has been directed toward the subject in an effort to provide a reliable method of estimating percentages of connate water, it has been recognized that capillary pressure data may prove of value in other equally important applications. This paper describes a method and procedure for determining capillary pressure curves for porous media wherein mercury is forced under pressure into the evacuated pores of the solids. The pressure-volume relationships ob- tained are reasonably similar to capillary pressure curves determined by the generally accepted porous diaphragm method. The advantages of the method lie in the rapidity with which the experimental data can be obtained and in the fact that small, irregularly shaped samples, e.g., drill cuttings, can be handled in the same manner as larger pieces of regular shape such as cores or permeability plugs. Based upon a simplified working hypothesis, a theoretical equation will be derived which relates the capillary pressure curve to the porosity and permeability of a porous solid, and experimental data will be presented to support its validity. This relationship aplied to capillary pressure data obtained for drill cuttings by the procedure described provides a means for predicting the permeability of drill cuttings. METHODS FOR DETERMINING CAPILLARY PRESSURES Several techniques have so far been employed in determining capillary pressure curves and these fall into two principal categories: (1) Liquid is removed from, or imbibed by, the core through the medium of a high displacement pressure porous diaphragm (2) Liquid is removed from the core which is subjected to high centrifugal forces in a centrifuge4,&apos;. There are? however, certain limitations inherent in both methods. The greatest capillary pressure which can be observed by method (I), above, is determined by the maximum displacement pressure procurable in a permeable diaphragm which at the present time appears to be less than 100 psi. An even more serious limitation of the diaphragm method is imposed hy the fact that several days may be required to reach saturation equilibrium at a given pressure; hence, the time re- quired to obtain a well-defined curve may be measured in terms of weeks. Furthermore, to date, no suitable technique for handling relatively small, irregularly shaped pieces of rock, such as drill cuttings, has been reported and, therefore, measurements must be made, in general, on cores, or portions thereof. The centrifuge method offers the distinct advantage over the porous diaphragm method of arriving at saturation equilibrium in a relatively short time by virtue of the elimination of the transfer medium for the liquid. The calculation of capillary pressures from centrifuge speeds is somewhat tediousa, however, and the equipment required is fairly elaborate. While there exists the possibility that this method might be adaptable to the determination of the capillary pressures of cuttings, this particular ramification has not been investigated, as far as is known. In view of the limitations of the two principal methods for determining capillary pressures, the apparatus described in the following sections has been devised in order that difficulties previously encountered might be circumvented. MERCURY INJECTION METHOD FOR DETERMINING CAPILLARY PRESSURES Theory The methods described above for determining capillary pressures are characterized by the fact that one of the fluids present within the pore spaces of the solid is a liquid which "wets" the solid, i.e., the contact angle which the liquid forms against the solid is less than 90" as measured through that phase. For these "wetting" liquids the action of surface forces is such that the fluid spontaneously fills the voids within the solid. These forces likewise oppose the withdrawal of the fluid from the pores of the solid.

Jan 1, 1949

By T. L. MacKay

Oxidation rates of single-crystal and poly crystalline zirconium in oxygen at temperatures from 307° to 815°C obey the parabolic rate law for short ex-posure time, 4 to 6 hr. The activation energy for the oxidation of single-crystal zirconium between 420° and 790°C is 42.6 ± 0.7 kcal per mole, and in the temperature range 307" to 600°C the activation energy for oxidation of poly crystalline zirconium is approximately the same. The high-activation energy is indicative that diffusion through the bulk oxide film is the primary mode of mass transport for both types of metal. The higher oxidation rates for poly -crystalline zirconium in this temperature range were attributed to differences in the orientation of the grains in the metal with respect to the oxidizing surfaces. Above 600°C, vain growth was observed in polycrystalline zirconium, and the oxidation rates approached those of single-crystal zirconium. ThE kinetic data of previous oxidation studies1-&apos; of zirconium in oxygen have been interpreted by both parabolic and cubic rate laws. There is some evidence that there is a transition from the parabolic to the cubic rate law at prolonged exposures, but the question is still controversial. For the parabolic rate law activation energies are reported in the range 18.6 to 35 kcal per mole, and for the cubic rate law in the range 38 to 47 kcal per mole. So far as the mechanism of zirconium oxidation is concerned, inert marker studies10,11 have indicated that the oxidation proceeds by oxygen (anion) diffusion through the oxide film toward the metal-metal oxide interface. Pemslerl2 observed that the orientation of the grains in the zirconium metal substrate affected the rate of formation of the oxide film on the surfaces of the grains and that the orientation dependence of the corrosion rate persisted beyond the initial stages of reaction. The rate of oxidation was a minimum when the c axis of the grain was parallel to the surface of the sample, and rose to a maximum when the c axis was inclined at about 20 deg to the plane of sample surface, and decreased again at higher inclinations. cox13 observed that in 300°C steam a thin oxide film was formed initially on zirconium and that this oxide film, which exhibited interference colors, became dark first along the grain boundaries and then over the whole surface in an inhomogeneous manner as the film thickened. Cox proposed a mechanism in which oxygen diffused along preferred paths created by grain boundaries in the metal and formed a much thicker film at or near the grain boundary than on the central zone of the grain. In the present study, the oxidation rates of single crystals of zirconium were measured in oxygen and compared with the oxidation rates of polycrystalline zirconium of the same bar stock. It was felt that such a comparison would elucidate the role of grain boundaries in the metal substrate. SAMPLE PREPARATION Single crystals of zirconium were prepared by following the procedure of I3apperport,14 starting with 1/4-in. rod purchased as crystal-bar zirconium. Zirconium rods 2 in. long were wrapped in tungsten foil and sealed in quartz tubes at pressures of less than 10-6 mm of mercury. Large single crystals were grown by thermal cycling above and below the a-/3 transformation temperature, 862°C. Several specimens were simultaneously subjected to the same cycling procedure, heating to 1200°C, holding for 4 hr, then cooling in the furnace and holding at a temperature of 840°C for 5 to 10 days. This cycle was repeated five or six times for each set of specimens. The grain size of the crystal-bar zirconium before thermal cycling was between 10 and 30 p. Fig. 1 shows the microstructure of an end section of as-received crystal-bar zirconium. A longitudinal section of each zirconium rod after thermal cycling was polished and examined under polarized light, see Fig. 2, and the largest single crystals were selected for this study. Zirconium rods 1/8 in. in diameter and 1/2 in. long with spherical ends were machined from the single crystals and from the as-received bar stock. An X-ray examination showed that the c axis of the single crystals made either a 34-deg or an 89-deg angle with the rod axis. The specimens were chemically etched for 2 min in solution consisting of 15 parts hydrofluoric acid (48 pct), 80 parts nitric acid, and 80 parts water. The chemical polish removed 1 to 2 mils from the surface. EXPERIMENTAL The Sartorius vacuum microbalance used in this study has a sensitivity of 0.5 pg and a capacity of

Jan 1, 1963

By W. R. Purcell

An apparatus is described whereby capillary pressure curves for porous media may be determined by a technique that involves forcing mercury under pressure into the evacuated pores of solids. The data so obtained are compared with capillary pressure curves determined by the porous diaphragm method, and the advantages of the mercury injection method are stated. Based upon a simplified working hypothesis, an equation is derived to show the relationship of the permeability of a porous medium to its porosity and capillary pressure curve, and experimental data are presented to support its validity. A procedure is outlined whereby an estimate of the permeability of drill cuttings may be made with sufficient acuracy to meet most engineering requirements. INTRODUCTION The nature of capillary pressures and the role they play in reservoir behavior have been lucidly discussed by Lev-rett&apos;, Hassler, Brunner, and Deah12, and others. As a result of these publications the value of determining capillary pressure curves for cores has come to be generally recognized within the oil industry. While considerable attention has been directed toward the subject in an effort to provide a reliable method of estimating percentages of connate water, it has been recognized that capillary pressure data may prove of value in other equally important applications. This paper describes a method and procedure for determining capillary pressure curves for porous media wherein mercury is forced under pressure into the evacuated pores of the solids. The pressure-volume relationships ob- tained are reasonably similar to capillary pressure curves determined by the generally accepted porous diaphragm method. The advantages of the method lie in the rapidity with which the experimental data can be obtained and in the fact that small, irregularly shaped samples, e.g., drill cuttings, can be handled in the same manner as larger pieces of regular shape such as cores or permeability plugs. Based upon a simplified working hypothesis, a theoretical equation will be derived which relates the capillary pressure curve to the porosity and permeability of a porous solid, and experimental data will be presented to support its validity. This relationship aplied to capillary pressure data obtained for drill cuttings by the procedure described provides a means for predicting the permeability of drill cuttings. METHODS FOR DETERMINING CAPILLARY PRESSURES Several techniques have so far been employed in determining capillary pressure curves and these fall into two principal categories: (1) Liquid is removed from, or imbibed by, the core through the medium of a high displacement pressure porous diaphragm (2) Liquid is removed from the core which is subjected to high centrifugal forces in a centrifuge4,&apos;. There are? however, certain limitations inherent in both methods. The greatest capillary pressure which can be observed by method (I), above, is determined by the maximum displacement pressure procurable in a permeable diaphragm which at the present time appears to be less than 100 psi. An even more serious limitation of the diaphragm method is imposed hy the fact that several days may be required to reach saturation equilibrium at a given pressure; hence, the time re- quired to obtain a well-defined curve may be measured in terms of weeks. Furthermore, to date, no suitable technique for handling relatively small, irregularly shaped pieces of rock, such as drill cuttings, has been reported and, therefore, measurements must be made, in general, on cores, or portions thereof. The centrifuge method offers the distinct advantage over the porous diaphragm method of arriving at saturation equilibrium in a relatively short time by virtue of the elimination of the transfer medium for the liquid. The calculation of capillary pressures from centrifuge speeds is somewhat tediousa, however, and the equipment required is fairly elaborate. While there exists the possibility that this method might be adaptable to the determination of the capillary pressures of cuttings, this particular ramification has not been investigated, as far as is known. In view of the limitations of the two principal methods for determining capillary pressures, the apparatus described in the following sections has been devised in order that difficulties previously encountered might be circumvented. MERCURY INJECTION METHOD FOR DETERMINING CAPILLARY PRESSURES Theory The methods described above for determining capillary pressures are characterized by the fact that one of the fluids present within the pore spaces of the solid is a liquid which "wets" the solid, i.e., the contact angle which the liquid forms against the solid is less than 90" as measured through that phase. For these "wetting" liquids the action of surface forces is such that the fluid spontaneously fills the voids within the solid. These forces likewise oppose the withdrawal of the fluid from the pores of the solid.

Jan 1, 1949

By John S. Johnson

The maintenance cost, or renewal cost, in any preparation plant is a large item of expense and reflects in the total cost of producing and preparing the ton of coal. It is given constant study to the end that ways and means of controlling and reducing this proportion of the total cost may be developed. Study of this item of cost has proceeded along usual lines, which are: proper functioning of the maintenance organization; systematic and thorough inspection to prevent breakdonns; the making of repairs before renewals are needed; maintenance work done thoroughly the first time, instead of patching, study of parts needing frequent renewal or repairs or conditions resulting in delays, thorough knowledge of cost by the mall responsible for maintenance; and the use of special equipment and materials. This paper is to deal with special equipment and materials to reduce the maintenance cost hut before going into that I want to express an opinion on the general subject. Maintenance Organization Usually maintenance is taken care of by a group of men who perform their work on the off shift. The work is arranged by the operating official who should be thoroughly familiar with maintenance, so that materials needed may be made up for the particular job and waste of time in looking up materials be prevented. To perfect the maintenance organization, all operating attendants should be thoroughly trained to be familiar with all working parts of their equipment, to make a thorough inspection and to write out the slip for the work required. This requires job analysis, but it is worth the effort, because the attendant usually is better informed than anyone else about his particular equipment. The operating official can judge the scope of the work to direct the repair and to have material ready. Lubrication is an important item in maintenance, and a subject by itself. Usually the breaker oiler is designated to perform this task. This man should be picked for his ability and put in line for promotion to machinist. He should be trained as an inspector, as he is constantly visiting most parts of the breaker and has an opportunity to observe needed maintenance. The first thing is to lay out maintenance work and arrange to have it done; the next is to check the work and see that it has been properly done. This check should be made by the operating official, and through the attendant. The cost statement showing the various items of maintenance cost is not often understood by the man in direct charge. Cost sheets should be simplified and worked up by breaker sections; e.g., the cost of

Jan 1, 1947

By N. Van Wingen, Norris Johnston

Laboratory flood pot testing of California sands has progressed to a considerable extent in the past 18 months. Flood evaluations have been carried out on over 200 large core samples. Many of these were heavy oil sands of high permeability and completely unconsolidated in nature. The oil frequently formed a bank, though some of the oil was recovered in the subordinate phase of the flood, by viscous drag. Flood pot recoveries as high as 1400 bbl/acre ft have been recorded. Reservoir analysis suggests a conformance factor of 0.4 to reduce laboratory recovery to probable field practice. Oils with viscosities up to 1800 cp have been successfully handled in flood pot evaluations. The shallow, loose sands are not well adapted to the application of- high pressures to offset the high viscosities. INTRODUCTION Secondary recovery may be said to have started 60 years ago when accidental floods occurred in the Bradford sand in Pennsylvania. About 1921 artificially conducted water drives came into extensive use and since that time the great Bradford field has been almost completely subjected to water flooding. During the last 30 years, most of the known medium and deeper production in California has been discovered and is being exploited by primary recovery methods supplemented in some instances by high pressure gas injection. The California area is just beginning to feel the need for secondary recovery in view of an unprecedented market demand and the rapidly rising cost of new pool discoveries. With the presently recognized desirability of secondary recovery in California, there must also be appreciated a number of serious differences between the water flooding problems here as compared to the territory east of the Rockies. California sands are generally thicker, and are frequently soft and argillaceous. The oils are often heavier and asphaltic. Much of the oil is below 15°API, occurs at shallow depth, is cool and free from appreciable dissolved gas, which results in relatively high reservoir oil viscosity. Secondary recovery is particularly beneficial where primary recovery has been poor and where no natural water drive exists. These conditions apply particularly to the heavy, shallow, clean production from soft, often argillaceous California sands so abundantly found at depths less than 1500 feet. Often, too, there is a totally insufficient supply of water of satisfactory quality to inject at a reasonable cost. Also, the crude oils are priced far below the premium Bradford crude. Although these and a number of minor problems beset the operator desirous of starting secondary recovery, great progress has been made in the past few years in finding how to adapt previous Mid-Continent and Eastern experience to water flooding in California. There are about nine projects for subsurface injection of water which can be said to classify as secondary recovery operations. Subsurface water disposal would so classify when the sand receiving the water is a nearby oil producer, as is often the case. When water is injected subsurface into a barren sand, the operation does not classify as secondary recovery. Several of the most active operators avail themselves extensively of preliminary engineering and laboratory work to guide their decisions, while others enter small scale flooding operations directly in the field. It is the laboratory work pertinent to several of the California secondary recovery projects that this paper discusses. PURPOSES OF LABORATORY FLOODING TESTS Experience in areas where water flood operations have been carried out has indicated that careful engineering planning is an important requisite for subsequent economically successful field operation. Floods that fail are more frequently those where operations were instigated without a prior engineering investigation to determine the effectiveness of the injection fluid as an oil displacing medium. Laboratory data are essential in the evaluation of an oil property for secondary recovery possibilities. Success or failure of secondary operations can under certain special circumstances be determined directly by cores and their subsequent routine analysis. This is particularly the case where flushing of the cores in the course of coring is negligible and where the results of the analysis can be compared with existing secondary recovery operations. Where these conditions cannot be&apos; fulfilled, the application of core analysis is more limited. In such event, the results obtained by water flooding core samples in the laboratory have been found to be of prime importance. Cores may be flooded "raw" as taken from the well or in the event flushing and depletion of the cores in the process of drilling are major factors the fluid content may be artificially restored prior to the flooding. Laboratory studies should also be made to determine the suitability of the water selected for injection. Thus interaction between injected and formation water may cause precipitates to be formed which may plug the sand. Even more important, especially to California operations, is the possibility of the hydration of formation clays by the injection water. The aims of flood pot and associated tests are basically to determine the residual oil saturation after flood, the water-oil throughput ratio and to establish whether an oil bank is formed. Additional information which can be obtained from flood pot tests pertains to the pressure differential required to effect displacement, the relative permeability to oil in the oil bank and the relative permeability to water in the watered out region behind the bank.

Jan 1, 1953

By A. Muan

Liquidus data are presented for mixtures in the ternary system FeO-Fe2O3-SiO2 in equilibrium with a gas phase with O2 pressures ranging from 10-10.9 to 1 atm. Data obtained are combined with previously published data to construct lines of equal 02 pressures and lines of equal CO2/H2 mixing ratios along the liquidus surface. Courses of crystallization of selected mixtures under conditions of constant total composition, constant O2 pressures, and constant CO2/H2 mixing ratios are discussed. PHASE equilibrium studies of silicate systems where iron is one component are complicated by the fact that iron readily occurs in three different states of oxidation: Fe3+, Fe2+, and Fe0. Success or failure in work with iron silicate systems is to a large extent dependent on control of the oxidation state of iron and all investigations therefore must be carried out under carefully controlled atmospheric conditions. Silicate systems containing only strongly electropositive metals (like Na+, Ca2+, Mg", etc.) can, for simplicity, be treated as condensed systems, that is, the gas phase can be neglected and the phase relationships discussed in terms of the phase rule written in the well known simplified form P + F = C + 1. In the case of iron silicate systems, however, the composition of the condensed phases varies with the gas composition, and a complete picture of phase relationships can be obtained only by varying the gas composition over a wide range. In order to understand the phase relationships in the more complicated multicomponent silicate systems with iron oxide as one of the constituents, a knowledge of the ternary system FeO-Fe2O3-SiO2 is essential, since it constitutes a bounding portion of all such systems. It was with this in mind that the present study was undertaken. Previous Work A considerable amount of work has been done on various aspects of the chemistry and metallurgy of systems containing silica and iron oxides. The two bounding binary systems FeO-Fe2O3 and FeO-SiO2" The first attempt to obtain information on phase relationships of iron oxide-SiO, mixtures at different 0, pressures was made by Greig.&apos; Darken" determined the melting points of iron oxide on solid silica under various atmospheric conditions. Darken did not determine experimentally the composition of the melts at liquidus temperatures but discussed very ably the principles involved in applying the phase rule to the system. In a recent study Schuhmann, Powell, and Michal8 determined experimentally the liquidus surface of a portion of the ternary system and combined the new information with data in the literature to construct a phase diagram. Their method was briefly as follows: Homogeneous mixtures with various contents of SiO2, FeO, and Fe2O3 were made up by melting together stock mixtures in various proportions. Samples of the homogeneous mixtures, the compositions of which were determined by chemical analysis, were then heated in platinum crucibles in an inert atmosphere until equilibrium among the condensed phases was achieved. The samples were quenched to room temperature and the phases present determined by microscopic examination. Assuming that no change in composition takes place during the equilibration run in inert atmosphere, the liquidus surface can be determined, but no information is obtained regarding the partial pressures of 0, of the gas phase in equilibrium with the condensed phases. The author&apos;s method, to be described in the next section, permitted the location of points at the liquidus surface as well as a calculation of the corresponding partial pressures of O2. Experimental Method General Procedure: The standard quenching technique was adapted for a study under controlled variable atmospheric conditions. Premelted mixtures of silica and iron oxides in platinum envelopes were held at constant temperature under chosen atmospheric conditions until equilibrium was reached among solid, liquid, and gas phases. The sample was then quenched to room temperature, the phases present identified, and, for the most significant runs, the composition was determined by chemical analysis. The corresponding partial pressure of 0, was calculated from known equilibrium constants of the gas reactions occuring in the furnace atmosphere. Materials: Starting materials were oxides of commercially highest available purity; cp silicic acid was dehydrated by heating to 1350°C for 6 hr and cp Fe2O3 was dried at 400° C for the same length of time. Samples of 10 g were made up by mixing

Jan 1, 1956

By L. L. Handy

Solvent floods using slugs of solvent have been found to show continuity in behavior from the vapor pressure of the solvent to the critical pressure for the two-component driving gas-solvent system. In the pressure region between the solvent vapor pressure and the critical pressure for the gas-solvent system, the gar and solvent are only partially miscible. Although complete miscibility cannot be obtained at these pressures, complete oil recovery is possible in principle. In two-phase solvent floods the solvent is propagated tllrough the reservoir, primarily, in the vapor phase. The carrier gas requirements constitute a significant factor in the economics of the process. A qualitative theory is proposed for estimating the amount of dry gas required to move the solvent through the reservoir. The theory shows that for two-phase solvent floods the total gas needed is a minimum at the vapor pressure of the solvent and at the critical pressure for the gas-solvent system, and is a maximum at some intermediate pressure. The predictions of the theory are supported by experimental studies using methane, butane and decane or methane, propane and decane in a natural sandstone core. INTRODUCTION Previously, solvent slug processes have been found effective for oil recovery in two pressure ranges. First, conventional miscible displacements are possible at pressures greater than the critical pressure for the gas-solvent system. Second, Jenks, et al,&apos; have shown that, at pressures slightly in excess of the vapor pressure of the solvent, a solvent slug can be propagated through a reservoir by a gas essentially insoluble in the liquid solvent. The solvent bank displaces the oil ahead of it. Both of these processes, at least ideally, are capable of recovering all of the oil in the swept regions. Slug processes for which the gas and solvent are partially miscible have not been considered; that is, those systems for which the solvent and driving gas form two equilibrium phases in which the vapor phase contains a significant amount of solvent and the liquid phase an appreciable amount of the driving gas. Welge and Johnson&apos; have shown that the gas needed to movc a solvent slug through the reservoir increases with increasing pressure above the vapor pressure of the solvent. It will be shown that solvent slug processes can, theoretically, recover all of the oil at any pressure greater than the vapor pressure of the solvent. But the amount of gas required to move the solvent through the reservoir depends very much on the pressure and temperature. In the present study a maximum in the gas requirements was both predicted theoretically and observed experimentally. This result has not been reported previously, and would not have been predicted from the Welge and Johnson model. The gas requirements are a minimum at the pressures corresponding to the vapor pressure of the solvent and again at the critical pressure for the gas-solvent system, and are a maximum at some intermediate pressure. AN APPROXIMATE THEORY FOR TWO-PHASE SOLVENT FLOODING The differences and similarities between conventional solvent floods and two-phase solvent floods are best understood by referring to concepts developed for miscible displacement in which miscibility is generated in the reservoir. In Fig. 1(A), a ternary diagram is shown for a hypothetical gas-solvent-oil system. To be rigorous the three components should each consist of a single molecular species. The pressure for Fig. 1(A) is greater than the critical pressure for the binary gas-solvent system at the specified temperature. Diagrams of this type are the ones most frequently referred to in discussions of enriched-gas drive and miscible displacement. A limiting tie line is shown tangent to the two-phase envelope and intersecting the gas-solvent line at Point A. To obtain generated miscibility with this type system, others have shown that, for an oil of Composition D, a mixture of gas and solvent must be injected which is richer in solvent than that composition indicated by A. An oil repeatedly contacted with a gas phase richer than A changes toward a composition which would be at equilibrium with the injected mixture, that is, a composition lying on a tie line which passes through the injected-gas composition. Since no such tie line exists, the oil is enriched to the point at which it becomes directly miscible with the injected mixture. At pressures lower than the critical pressure for the gas-solvent system, other types of phase diagrams are observed. The ones of interest in this paper are for pressures greater than the vapor pressure of the solvent, but less than the critical pressure of the gas-solvent system. Such a ternary diagram is shown on Fig. 1(B). In this case, two-phase behavior is observed not only for gas-oil mixtures, but also for certain compositions in the gas-solvent system. If a gas of Composition A (a dew-point vapor) is injected, once again the original oil is enriched by successive