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By F. V. Lenel

Resistance sintering under pressure is a method of hot pressing in which a powder compact is subjected to pressure and simultaneously heated by passing a low voltage high amperage current through it. Equipment for this process is described. Its basic characteristics such as resistance requirements for powders and compacts, temperature distribution in compacts, and gas reactions during resistance sintering are discussed. Examples of the sintering process in compacts made of a single metal or an alloy powder and in compacts made of mixtures of powders are presented. Potential commercial applications of the process are evaluated. THE usual sequence of operations in commercial powder metallurgy is to compact metal powders in a die at room temperature and sinter the compact subsequently without applying pressure while the compact is in the sintering furnaces. In hot pressing, on the other hand, the compacting and the sintering are combined. The loose powder, or in many cases a cold formed compact, is inserted into the die which is held at the hot pressing temperature, the compact is left in the die until it attains its temperature, and then pressure is applied and maintained for a given length of time. The die may be heated by surrounding it with a suitable furnace, by high frequency induction heating, or by passing current through the die. In hot pressing, compacts of high density and good mechanical properties can be produced in a relatively short time. One of the principal difficulties in hot pressing is the lack of suitable die materials which will have adequate strength at the hot pressing temperature. This difficulty can be overcome at least partially by heating only the material to be hot pressed without heating the die directly. This can be done by passing a low voltage high amperage current through the material and simultaneously subjecting it to pressure. Either loose powders or compacts can be hot pressed by this method in which the desired temperature is produced by the power dissipated in the metal powder. This method of hot pressing has been termed "electrical resistance sintering under pressure." The most significant differences between this operation and conventional hot pressing are: 1—The sintering times are very short, usually a fraction of a second and at most a few seconds. 2—The powder and die are initially cold. 3—Heat is generated within the powder itself and not conducted in from the die. 4— The pressure used is high. 5—Cooling following sintering is rapid, amounting to a quench. Resistance sintering of metal powders under pressure has been suggested repeatedly. In 1933, G. F. Taylor' proposed an apparatus which consisted of an insulating tube made of glass, or a ceramic filled with the powder to be pressed, and plungers above and below the powder. The powder was to be heated by passing an electric current through it and pressure was then applied. The apparatus was intended principally for hot pressing cemented carbides. Although the principle of resistance sintering under pressure is clearly shown in this patent, few details are given. A sintering period of a second or a fraction of a second, which is terminated by the operation of an inertia switch, is mentioned but no values for current density are mentioned. Low pressures, such as atmospheric pressure or a somewhat higher pressure exerted through a lever, are suggested. W. D. Jones' discussed electrical resistance sintering under pressure and proposed using resistance welding apparatus for this purpose. In a patent issued in 1944, G. D. Cremera described a method of electrical resistance sintering under pressure using resistance welding apparatus which was to be applied mostly to nonferrous metals such as copper, brass, bronze, and aluminum. Current densities of 400,000 amp per sq in., sintering times of 1 and 2 cycles of 60 cycle current, and pressures of 5 to 10 tsi are proposed. Cremer suggested using an

Jan 1, 1956

By T. O. Anderson, E. J. Stahl

Tests to increase knowledge concerning the process of hydraulic fracturing have been performed on three wells in the Allegheny field in western New York. The fracture orientation and its physical appearance at the well-bore was determined by impression packers run at appropriate times throughout the program. Fract~tre azi171uth and its dimensions thus determined were compared to the rock properties and treatment conditions. Logs to provide data concerning rock properties and to improve identification of vertical fractures were run before each step of the fracture treatment. Pressure osc~illu~iot~s were studied after each phase of tile treatments surface pressures during treatment. These measurements show that subsurface pressures exhibit many of the same characteristics as surface pressures during treatment of a well; however, transient pressures are dampened and deelayed in time at the bottom of the well when COmpared with surface pressures. Data obtained from this study provides a means to help locale and determine orientation of vertical fractures made in the open wellbore. Although these rests were performed in only one area, much of the information gained may be applied to fracturing programs in orher areas. INTRODUCTION In this study, various tests were made to provide data to better understand formation fracturing in situ. The reservoir studied is the Richburg oil sand which is a part of a series of predominantly grey sandstones and shales with occasional brown sandstone layers, known as the Caneadea unit of the Canadaway group of Upper Devonian age. Average physical characteristics of 12 cored wells in this area are 13-ft thick gross sand formation, 12-ft thick net sand. 1.7 md permeability, 11 percent porosity, 44 percent oil saturation (before secondary recovery) and 16 percent water saturation (before secondary recovery). This particular area of the Allegheny oil field was originally drilled prior to 1890. The first waterflood secondary recovery attempt was made in 1929. The present sustained waterflood development began in 1951 and is being carried out on a 4.5 to 5-acre spacing. Objectives of these tests were to (I) study fracture azimuth and dimension in relation to rock properties and treating conditions, (2) improve fracture identification techniques, (3) compare surface and subsurface pressure during all phases of treatment and (4) compare the periods of the fluid column oscillations occurring after each phase of treatment. Although the areas of investigation listed appear divergent in purpose, the program was designed primarily to increase knowledge of down-hole conditions leading to rock failure and extension of the fracture thus created. TEST PROCEDURES Wells upon which tests were conducted are designated as Wells 1 through 3. Well 2 was located 440 ft north of Well 1, and Well 3 was located approximately 880 ft west of Well 1. Wells 1 and 2 were completed with cable tools, while the producing interval of Well 3 was rotary cored using fresh water as the drilling fluid to obtain oriented cores. Tests were divided into separate phases on each well as the fracturing program progressed and consisted of measurements performed prior to treatment, during and after the formation breakdown operation. during fracture treatment and after treatment. To verify location and azimuth of the fracture created, and to obtain an impression of wellbore irregularities, a packer was used (Fig. 1). This packer was lowered on tubing into the wellbore opposite the interval under study and inflated in stages to allow the impression material to conform to the wall of the wellbore. A magnetic compass was attached to the tool for orientation reference. Impressions made prior to treatment showed no existing fractures in the wells under study. Impressions made after both formation breakdown and treatment pro-

By N. A. Warner

Dense cylindrical specimens of artificial hematite were reduced in hydrogen over a range 0-f total pressures between 0.1 and 1.0 atm and temperatures between 650" and 950°C. Hydrogen reduction at a total pressure of 1.0 atm in the presence of a chemically inert diluent and reduction in hydrogen/water mixtures were also studied Znter.face movement during reduction was followed using metallographic techniques. Substantiu1 partial-pressure gradients are shown to exist in both the gas film and the reduced iron layer. The results are consistent with a mixed-control mechanism involving an interaction of gaseous-difusion effects with a first-order reversible chemical reaction at the iron/wüstite interface. Over the hydrogen-pressure range of 0.1 to 1.0 atm, the rate is not directly proportional to the hydrogen pressure in the bulk gas stream. Nitrogen dilution of the reducing gas masks the true effect of hydrogen partial pressure by influencing the effective molecular dif-fusivity and gives an apparent first-order relationship. The transport of hydrogen and water vapor across the iron layer is consistent with molecular gaseous diffusion rather than a Knudsen diffusion mechanism. ALTHOUGH the literature on the reduction of iron oxides is very extensive, it is only comparatively recently that a definite quantitative model for the reduction of hematite has been proposed. This development has been largely due to the work of McKewan. An extensive literature review of previous work has recently been compiled by Themelis and Gauvin. Exclusive control by gaseous diffusion in the reduction of hematite has been recently advocated by Kawasaki and coworkers.' Although the results of the latter workers are of considerable practical significance, the extreme porosity (approximately 30 pct) of their specimens precludes their application to a kinetic evaluation of the reduction of dense polycrystalline hematite. The salient features of the kinetic model used by McKewan for the gaseous reduction of dense hematite at temperatures in excess of 560°C (when FeO is stable) are: 1) The reduction is a topochemical reaction taking place through 'the series FeO/FesO4/FeO/ Fe; 2) The gas-solid type of reaction takes place only at the FeO/Fe interface and the internal reduction: FeO proceeds by solid state diffusion; 3) The iron layer formed is quite porous and offers negligible impedance to gaseous diffusion; 4) The rate-controlling step in the reduction is a chemical process occurring at the Fe/FeO interface. In view of the relatively fast reaction rates involved when hematite is reduced in a stream of hydrogen, it seemed possible that the simplifying assumptions of negligible diffusional resistance in both the bulk gas phase and the reduced iron layer could introduce serious errors in the interpretation of experimental reduction data. The present work was initiated to elucidate the effect of gaseous diffusion on the reduction rate and to determine its possible influence in the formulation of the reaction mechanism at the metal/oxide interface. EXPERIMENTAL Procedure and Apparatus. Dense cylindrical compacts of artificial hematite were prepared by sintering pressed compacts of reagent-grade ferric oxide, containing 99.6 pct FezO, in air at 1200°C for 80 hr. The resulting compacts had a final porosity of less than 2 pct and a height and diameter of approximately 1 cm. Variations in sintering atmosphere from air to pure oxygen, in sintering time from 20 to 80 hr, and temperature from 1150" to 1250°C had no effect on the subsequent reduction behavior. The reduction of the samples took place in a vertical tube furnace in which was placed a 1-in. transparent silica tube. The 24-in. heated length

Jan 1, 1964

By K. H. Ribe

Water often enters an oil reservoir during completion or workover operations on a well and forms a partial "water block" to oil production. A mathematical study of radial two-phase flow, neglecting capillary effects, has been employed to study the formation of such a water block and subsequent re-moval by production from the well. The effects of reduced oil permeability about the well on the well productivity were studied. The fluid saturation distributions about the well during formation and removal of the water block have also been computed. Several relative permeability relations and viscosity ratios were employed. If water has invaded the formation, its influence through relative permeability effects alone can cause the following. 1. Oil productivity will be depressed for extended periods after production is resumed and will build up only gradually as the water is removed. 2. Oil injected for treatment of water blocking will delay rather than promote restoration of full well productivity by enlarging the region invaded by water. Thus, unless the specific action of chemicals contained in the oil is needed, oil injection appears undesirable. INTRODUCTION During oilwell workover operations, water may enter the oil-bearing formation from the wellbore. When production is resumed, oil must flow through the region invaded by this water. The presence of this region can cause both well productivity and oil production rate to be low and oil to be produced with high water-oil ratio for some time after production is initiated. This situation is sometimes described as a water block. The introduction of water into the formation may result in other actions which also lead to reduction in well productivity and which are also usually included in the connotation of the broad term, water block. Often considered, for example, are the possibilities of clay swelling by contact with fresh water and the formation of emulsions with the formation oil. If it is suspected that such specific actions have taken place, remedial treatments are undertaken which usually involve the injection of chemicals in oil. Since the introduction of water, even in the absence of specific interactions with the formation or oil, will cause a temporary water block (which might be misinterpreted as evidence of a more severe situation), it is of importance to evaluate the magnitude and duration of this blocking which results purely from the reduction in relative permeability to oil in the vicinity of the wellbore. It is also of interest to evaluate the effect of oil injection on the productivity of a well blocked by water in this manner. Inasmuch as this unfavorable condition may persist for some time, it may lead to premature condemnation of a workover or premature abandonment of a potentially productive pay zone. A quantitative evaluation of the influence of water entry on the oil productivity through changes in relative permeability was made by solving a radial form of the Buckley-Leverett equation. The distribution of water saturation around the wellbore during the entry of water was calculated and was followed by a similar calculation of the saturation distribution during the period of resuming production. At any stage in the removal of the invading water, knowledge of the distribution of its saturation permitted calculating the attendant loss in oil productivity. The influence of the shape of the relative permeability relationships was also evaluated by carrying out the calculations for two hypothetical cases. Further, the effect of the oil-water viscosity ratio was examined by repeating the calculations, for several ratios of unity and greater, with the same relative permeabilities. Fi-nally, results are presented to show how the length of time a well must be swabbed to resume production depends on the length of time it has been subjected to invasion by water. STATEMENT OF THEORY Differential Equations Water is assumed to enter a producing formation which is initially at the connate-water saturation and contains no gas. The water and oil are treated as in-

By A. B. T. Werner, J. J. Schanz

A survey of the world's sources and markets for natural graphite and some predictions of future trends are presented here. The authors feel that there is no indication of major changes in sources of graphite over the next few years, but it is possible that the importance of domestic graphites as opposed to foreign carbons may increase in the more distant future. U.S. consumption of natural graphite, which has been in general decline for the past six years, and will probably continue downhill with the virtual disappearance of some markets. However, other markets such as bearings, brake linings and crucibles will probably grow. Natural graphite is the name given to all the naturally occurring mineral forms of carbon that crystallize in the hexagonal system. Natural graphite~ are generally divided into three broad classifications that are based on physical rather than chemical differences — crystalline flake, Ceylon amorphous and other amorphous. Crystalline flake graphites occur as thousands of small individual flakes disseminated throughout the ore and closely resemble shiny black fish scales. Ceylon amorphous graphite is mined from narrow veins of almost pure mineral. It is produced in lump form and often has a coarse platy or needlelike structure. Other amorphous graphites include all those that are extremely fine-grained and have a crystalline structure that is not visible under normal circumstances. In the primary raw material markets, the graphite's country of origin is also important. Crystalline flake graphites may, for example, be of the Alabaman, Bavarian or Madagascan types; Ceylon amorphous graphite may have originated in Montana or Ceylon; and other amorphous graphites may come from Mexico, Hong Kong or Korea. The distinctions between the graphites from each particular locality are small yet important, for the country of origin will signify certain inherent physical characteristics and will often give an idea of the amount of graphitic carbon contained in the shipment in question. .In certain instances, however, even this is not enough, since the actual mine at which the graphite is produced may have to be known before its true commercial value can be ascertained. Thus, the Madagascar flake graphite shipped from the Sahalambo mines of the Societe des Graphites de la Sahanavo is a thick flake which is known to be especially suited for use in crucibles, while the dull black earthy amorphous material formerly mined at Cranston, R.I., was ideal for stove polish. Synthetic, artificial, electric furnace and manufactured are terms used to describe graphites made from coke. These graphites will be considered in this paper only to the extent that they enter competition with natural graphite. DOMESTIC SOURCES OF NATURAL GRAPHITES Natural graphites have been produced from mines in Alabama, Alaska, California, Georgia, Montana, New Jersey, New York, North Carolina, Pennsylvania, Rhode Island, Texas and other states. The exception is the crystalline minerals resembling Ceylon graphite that have come from Montana and the amorphous meta-anthracites from Rhode Island. All the products mined have been flake graphite. In 1960, production was reported only in Texas and Pennsylvania. The Alabama graphite deposits of flake in quartz-mica schists are found southeast of Birmingham in a narrow belt that extends for about 60 miles southwest from Delta in Randolph County to Verbena in Chilton County. Since the long-run prospects for Alabama graphites appear to be fairly bright, especially if regular production of high quality output becomes possible, regional ore reserves of all kinds, including indicated and inferred, are estimated to be of the order of 25 million tons. Of this amount, 14 million tons are of the weathered variety. Alabama graphites are favored by their relative ease of mining, and by the fact that special methods of milling have been developed at the larger properties. In addition, the steady rise in ocean freight rates for Madagascar graphites, the tendency among crucible manufacturers to use flakes of a smaller size, and the possibility of producing other salable byproducts in addition to the graphite are favorable to Alabama producers. Against

Jan 1, 1962

By I. R. Dunlap, R. F. Burdyn, F. D. Patchen

The composition and properties of a new type of cementing mixture are discussed. In these compositions, API Class A or C cements are added to n stable water-in-oil emulsion instead of the crsual water. The cement disperses in the oil phase and remains out of contact with the water under normal conditions of mixing and storage. At higher temperatcrres, such as those encountered down-hole during placement, the emulsion breaks and cement hydration can then proceed. An extremely low filtration rate is obtained; the major part of the filtrate is oil. Thickening times of the mixture may be increased to meet the 18,000-ft casing cementing schedule by varying the amount of emzilsifier. As in conventional Portland cement mixtures, high-temperature strength retrogression can be overcome by addition of silica flour. Results of several field app1ication.r show that mixing presents no diffculty if emulsion blenders are used and the emulsion is prepared beforehand. INTRODUCTION Water-in-oil emulsions., in which oil is the continuous or external phase and in which water exists as discrete droplets, have for some time been used successfully in drilling muds to reduce filtration loss.1,2 Applied to cement slurries, the same results are obtained; i. e., the fluid-loss is greatly reduced. In addition, thickening times may be extended, lower densities and strengths obtained, and water-base borehole fluids more easily displaced without contamination of the cement. A low filtration rate is often a desirable property in oil well cements since loss of fluid increases placement difficulties and may also cause damage to water-sensitive producing formations.' In the casing cementing operation where the cement slurry is pumped into the narrow annulus between open hole and casing, rapid loss of fluid to a porous formation can cause the slurry to thicken and plug the annulus before the desired fill is obtained. Where a casing or a liner is cemented against a productive formation and the well completed through perforations, the fluid lost between the time the cement first contacts the formation and the time a set is obtained may invade the zone past the depth of the perforations. If the sand contains a material which will swell upon contact with cement filtrate, permanent damage may result. Previous methods for reducing the fluid-loss of cements have employed bentonite4 as an additive, usually with a lignosulfonate as a dispersant, or a derivative of some naturally occurring polymeric material such as cellulose ether." Oil emulsion cements have also been proposedv or fluid-loss reduction, but these have been of the oil-in-water type. Bentonite cements have been used most widely and have been successful in reducing incidence of premature setting of cement attributable to loss of water by filtration. It is the purpose of this paper to describe preparation and properties of a water-in-oil emulsion cement and to relate procedures followed and results obtained in several field applications. DESCRIPTION OF SYSTEM AND MECHANISMS A water-in-oil emulsion cement is prepared by adding an API Class A or C cement to a stable water-in-oil emulsion. Fig. 1 is a photomicrograph of this emulsion before addition of cement. Here the droplets are water and the surrounding medium is diesel oil. High emulsion stability is indicated by the small droplet size [1-5 microns], and by their uniformity.' To form a stable water-in-oil emulsion as illustrated, several conditions must be met. A predominantly hydrophobic emulsifier must be present in sufficient concentration to produce a strong interfacial film; initially, the phase volume ratio (the water-to-oil ratio) must be low;

By G. R. Purdy, J. A. Malcolm

The isothermal dendritic precipitation of y in p CuZnSn is compared with the isothermal formation of Widmanstatten a plates in p CuZn. Although both precipitates are evidently bounded by semicoherent interfaces, the dendritic shape of y evolves through smooth "sinuoidal" shape perturbations, while a-p interfaces tend to be strictly planar, or rnicroscopically faceted. An estimate of the average inter-facial free energy of cube-oriented y in p through the Mullins-Sekerka analysis indicates that it is low (of the order of 50 ergs per sq cm). Interface mication is apparently controlled by volunle dij'usion, and the observed anisotropy in growth probably results from anisotropy of inter facial free energy. Studies of the grain boundary precipitation of y in p indicate that the precipitate can grow in both $ grains, but becomes unstable with respect to the grain with which it shares a mobile semicoherent interface. Facets observed at the tips of Kurdjumov-Sacks-oriented Wid-manstatten a plates correspond to variants of an irrational hahit, near (231)0. Comparison with Hu and Smith's determination of relative interfacial free energies of a-(3 boundaries suggests that this system possesses an extremely deep o cup, which results in an ej'ective low-o zone. The possible effects of such a cup on the stability of a-p interfaces are discussed, a needles, grown during rapid continuous cooling, possess microscopically smooth interfaces, and are characterized by a high degree of' damage in the region of the boundaries. These boundaries, induced to move on tempering at 200"C, become faceted as equilibrium is approached, which seems to indicate that boundary structure and mobility in this system are dependent on the local degvee of departure from equilibrium MULLINS and sekerkal have elucidated the phase boundary stabilizing effect of surface tension. a factor not taken into account in previous treatments of morphological development. Their analysis applies to the isothermal growth of a pure spherical precipitate (planar in the limit of infinite radius) in a slightly supersaturated solution, under conditions of inter-facial local equilibrium and isotropy of interfacial free energy. More recently, several other factors which might tend to stabilize planar interfaces have received attention. These are: i) interface diffusion;4"8 and ii) slow interfacial reaction. cahn7 included a slight anisotropy in interfacial free energy, and showed that it has no stabilizing effect, but forces shape perturbations to reflect the anisotropy. shewmon4 noted that dendritic morphologies are rarely observed in solid-solid systems, and, in particular, postulated that slow interfacial reaction occurs at all boundaries between proeutectoid ferrite and austenite, except those which propagate parallel to {11 l)y planes (for Kurdjumov-Sachs [K-S] related phases). Previously, Aaronson~ had proposed interfacial reaction at the broad faces of Widmanstatten plates, and expected that the lateral motion of high-mobility incoherent ledge edges would produce planar precipitates bounded by law-mobility semi-coherent interfaces. The problem of interfacial reaction during the dif-fusional formation of precipitates has often been ignored, although it is apparent that a small component of chemical reaction must exist at any moving interface." Further, all solutions of the diffusion equations for boundary conditions corresponding to isothermal growth predict infinite growth rate at time zero, so that elements of interfacial reaction would be most easily detected at early times. However, reported deviations from diffusion control are comparatively rare," and the local-equilibrium diffusion-control model appears adequate for the description of many isothermal growth systems.'2"9 Cahn14 has treated the problem of migration of an interface which is able to reach positional energy minima, and concluded that such an interface, if subjected to a high local ther-modynamic "driving force", may migrate normal to itself without the benefit of ledges. As local equi-

Jan 1, 1968

By J. Chipman, J. C. Fulton

Reduction of Si from slag to carbon-saturated iron is a very slow reaction. The rate is nearly independent of stirring but is accelerated markedly by increased temperature. In a slag containing 45 pct SiO2, 38 pct CaO, 17 pct Al2O3, the energy of activation is approximately 130 kcal. AT temperatures of 1450" to 1600°C occurring in the hearth of the iron blast furnace, chemical reactions are normally expected to proceed with great rapidity. Many of the reactions of iron making are indeed quite rapid and attain a condition corresponding roughly to a state of equilibrium before metal and slag are tapped from the furnace. The one conspicuous exception is the reaction by which carbon in the coke or metal reacts with silica in the slag to deliver silicon to the metal. From the practical viewpoint the slowness of this reaction is indeed fortunate, for if it were fast enough to reach equilibrium during the time of contact, it would be difficult to produce pig iron of the desired low silicon content. The one other reaction which under certain circumstances can also be very slow is the transfer of sulfur from blast-furnace metal to slag. In their laboratory exeriments on this reaction, Hatch and Chipman found that at least 5 hr were required for the attainment of equilibrium in a small crucible and that the reaction was not accelerated by increasing the rate of stirring. Subsequently it was shown2 that the presence of a reducible oxide MnO greatly inhibited sulfur removal, and finally that SiO2 itself3 under some conditions has sufficient oxidizing Dower to interfere with sulfur transfer. The kinetics of sulfur removal are now rather well understood,4 and it has been shown3,5 that when the silicon content of the metal is high enough to prevent reduction of SiO,, the desulfurizing process is rapid. Thus the observations of slow removal of sulfur are associated with the coincident slow reduction of SiO2, a process which transfers both silicon and oxygen to the metal phase. It is, of course, the oxygen which interferes with sulfur removal. An explanation of the slowness of the silica reduction reaction has not been obtained. The sulfur transfer process has been shown by the authors5 to be at least partially transport-controlled in the absence of interference by silica. Under the experimental conditions. 99 pct of the total transfer at 1600" was accomplished within an hour. Under similar conditions the reduction of silica may not proceed half-way to equilibrium6 in 8 hr. It is scarcely imaginable that silica reduction could be transport-controlled when the slag contains 44 pct SiO2 and the metal about 1.4 pct C. The experiments reported here show definitely that it is controlled by a slow step or steps in the chemical reaction. One might expect to find such a slow step in the breaking of SiO bonds or in the slow removal of oxygen by carbon at the slag-metal or metal-crucible interface or by bubble formation. EXPERIMENTAL PROCEDURE The experimental procedure used in this investigation was similar to that used in the study of the kinetics of desulfurization.5 A sketch of the graphite crucible and stirrer used in the current work is shown in Fig. 1. The quantity of metal and slag used was adjusted so that the slag-metal interface was located between the top and bottom blades on the stirrer; the top of the slag layer was above the top blade. The stirrer shaft was hollow down to the metal level and served as thermocouple well or optical pyrometer target. Stirring speeds of 0 to 500 rpm were used. A carbon monoxide atmosphere was maintained in the furnace by flushing the gas over the slag surface, except in run No. 220 when it was bubbled

Jan 1, 1960

By F. A. Schaufelberger

METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on page 545. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.' The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited3 to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SO2,4 which may lead to contamination with sulfur, or C0,5 which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents,7 which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere.' It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution composition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farben10 claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic, antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373ºC), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred, probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

By C. N. J. Wagner, E. N. Aqua

Dilute Fe-Si alloys (0 to 5 wt pet Si) were cold-worked by making filings at room temperatuve. The analysis of the broadening of the X-vay powdev pattern peaks yields anisotropic particle sizes normal to the (110), (100), and (112) planes which are a consequence of deformation faults (probability a) and twin faults (probability p). The combined fault probability (1.5a +ß) increases from 0.01 in pure iron to 0.02 in Fe-5 pct Si. The root mean square stvains vary with crystallographic ovientation due to elastic anisotropy of the alloys, and increase from about 0.0035 in pure iron to 0.005 in Fe-5 pct Si measured in the [100] direction. Assuming that deformation and twin faults occur with equal probability, the X-ray data would imply that the stacking-fault energy does not change upon alloying. THE crystallographic aspects of the plastic deformation of dilute Fe-Si alloys has been studied many times since the observation of glide band structures by Barrett et a1.l These glide bands were much straighter than the wavy bands observed by Gough2 in unalloyed iron nearly 40 years ago. This difference in the morphology of the slip band structure has been verified many times, most recently by replication electron microscopy3 and dislocation etch-pitting methods.4,5 These observed differences in deformation behavior have been considered to result from the degree of cross slip that occurs in pure iron and in the Si-Fe alloys. The lowered tendency for cross slip would result from a lowering of the stacking-fault energy of iron by the silicon alloying addition. Experimental evidence for this lowered stacking-fault energy in the Si-Fe alloys, obtained with transmission electron microscopy, is the observation of dissociated dislocations in Fe-6 pct si6 and Fe-3 pct Si alloys,7 and the observation of sharply defined cellular substructures in Fe-3 pct si6,7 compared to the more diffuse substructure in zone-refined iron.' The activation energy for recovery of cold work is greater in the Si-Fe alloys than it is in pure iron, indicating that cross slip has become a more difficult process.9 The purpose of this investigation is to determine the change in stacking-fault probability from the broadening of powder pattern peaks in dilute silicon-in-iron solid solutions, when cold-worked at room temperature. The knowledge of the stacking-fault probability and the dislocation density, both of which can be deduced from line-broadening analysis of two orders of reflections from (110), (200), and (112) planes, will permit us to calculate the change in stacking-fault energy upon alloying silicon into iron. Previous X-ray investigation of cold-rolled Fe-5 wt pct Si (100)[001 ] single crystals did not reveal any line broadening, whereas cold-rolled Fe-3.1 wt pct Si (001) [110] and (001)[100] single crystals10 showed line bro2dening as a consequence of small particle sizes (-200A) and root mean square strains (-0.25 pct), which are comparable to those found in cold-worked iron filings.11 EXPERIMENTAL PROCEDURE A series of five Fe-Si alloys containing nominally 1 to 5 wt pct Si and pure iron were cold-worked by making filings at room temperature. The actual silicon content deviated at the most by +0.1 pct which is of no significance in the present study. The carbon contents of these materials were less than 0.02 pct. The X-ray diffraction patterns were measured with molybdenum, cobalt, and iron radiation using a GE and a Philips diffractometer. The (110)-(220), (200)-(400), and (112)-(224) pairs of reflections were

Jan 1, 1968

By K. D. Sheffler, R. W. Hertzberg, R. W. Kraft

The Ni-Ni,Ti lamellar eutectic alloy responds to unidirectional solidification by alig-nment of the platelets of the two phases roilghly perpendicular to the moving solid-liquid interface. X-ray diffraction and zetallographic experimenls show that the following cryslallographic relationships exist in the directionally solidified ingots: lamellar interface w [0001] Ni3Ti 11 (111 }Ni local growth direction (1120) Ni3Ti n (110) Ni These relationships are rationalized on the basis of the crystallography of the constituent phases. In recent years researchers in several laboratories have shown that an aligned or "controlled" micro-structure can be produced in many binary eutectic alloys by forcing the alloy to solidify unidirectionally in an elongated crucible.'-3 It also has been found that a unique crystallographic relationship often develops between the two phases in such a structure.4, 5 Since a parallel arrangement of phase particles in an alloy should, and, in many cases, does, produce unique and highly anisotropic properties, the alloys so produced are of potential interest in a variety of applications. Studies of these alloys are also of interest at the academic level because they help to improve our basic understanding of the way in which metals solidify. This paper reports the metallographic and crystallographic structure of another of these alloys—that between nickel and Ni3Ti. In a separate paper, hot tensile and stress rupture properties as well as deformation and fracture behavior of the same alloy are discussed.19 EXPERIMENTAL DETAILS AND RESULTS General Characteristics of the Eutectic Reaction. Several small exploratory Ni-Ti melts were made to resolve a conflict in Hansen6 over the eutectic composition. The alloy containing 16.4 at. pct Ti, Fig. 1, appeared metallographically to be closest to the eutectic composition, although small dendritic patches of proeutectic nickel are present. The eutectic morphology is lamellar and appears quite sharp and angular, indicating a strong influence of crystallographic factors upon the microstructure. Some of the eutectic nickel platelets are continuous with the primary phase, whereas in hyper eutectic melts a "halo" of nickel generally surrounded the proeutectic inter-metallic platelets, indicating that nickel is the nucleating phase in this eutectic reaction. Extensive precipitation of Ni3Ti has occurred in the primary nickel phase in a Widmanstatten pattern which makes the dendrites difficult to differentiate from the eutectic mixture. This phenomenon may account for discrepancies among the eutectic compositions reported in the literature. The sloping solvus line bounding the nickel primary solid solution explains the presence of the intermetallic precipitate. Poole and Hume-Rothery7 report that the solubility of titanium in nickel drops from 13.8 at. pct at the eutectic temperature (1304°C) to approximately 9 at. pct at 700°C (Ni3Ti, on the other hand, melts con-gruently and exhibits essentially no solubility for nickel or titanium). Lever rule calculations based upon Poole and Hume-Rothery's phase diagram indicate an increase from 21 vol pct Ni3Ti in the eutectic mixture at the eutectic temperature to 61 pct at room temperature. Selective point count measurements of the volume fraction of eutectic Ni3Ti platelets in the eutectic microstructure yielded a value of 46 i 2 vol pct, which required extensive precipitation of Ni3Ti from the nickel solid solution onto the eutectic intermetallic platelets during cooling from the solidification temperature. Influence of Directional Solidification. Nickel bar and titanium sponge of 99.9 pct purity were induction-melted in zirconia crucibles under argon in the proportion of 13.8 wt pct (16.4 at. pct) Ti to produce 14-lb master heats which were cast into investment molds yielding 5/8-in.-diam pins approximately 10 in. long. These pins were remelted under argon in horizontal zirconia boats and unidirectionally solidified to produce 1/2-in.-sq ingots approximately 44 in. long. Details of the experimental techniques and apparatus are described elsewhere.'

Jan 1, 1970

By R. E. Collins

The existence of fluid migration across fixed boundaries in oil and gas reservoirs has been known for many years. Several techniques have been developed in the past for estimating The rate of migration across fixed boundaries as an aid in planninng field development and in the valuation of oilfied properties. The principal de/errc7nt to the use of these techniques lies in the rather extensive reservoir and field data required for ca1cula1ion.s of fluid migration. For this reason, a new, simplified procedure has been developed which makes possible the calculation of fluid migration with a minimum of field and resrvoir data. This new technique is based on certain. solutions of the differential equations describing flour in the reservoir which assume, for the portion of the reservoir of interest, that the formation can be approximated by a homogeneous rock of uniforrn thickness, that only a Single mobile fluid phase exists, and {hut fluid production at the well is solely a result of expun.rioti of rile resersoir fluds. The results of the, present work are compiled in a set of curves. These curves can he used to calculate both rule and cummulative fluid migration when the abovc assumptions ore ju.r/ifiril. The only data required for such calcu1ations are the production hisrories of all wells in the field, the permeability and porosity of the reservoir., the, compressibility and viscosity of the fluid. and the shape of the reservoir, INTRODUCTION The migration of fluids across fixed boundaries in oil and gas reservoirs has long been recognized as an engineering and economic problem, but no methods for estimating the extent of migration during the development stage of a reservoir have been published. The investigation reported here has been directed toward providing a simple technique for estimating the extent of such migration and has therefore been restricted to the simple case of a homogeneous reservoir of uniform thickncss containing compressible liquids. It is assumed that only a single mobile fluid phase exists and that fluid production at the wells is solely by expansion of the reservoir fluids. Obviously, few, if any. reservoirs conform to these assumptions during their entire productive life. On the other hand, most reservoirs approximate fluid expansion reservoirs during their initial stages of primary production. Consequently, the present work should be applicable during the field development of most reservoirs, regardless of whether or not they ultimately are gas cap, dissolved-gas, or water-drive reservoirs. The mathematical analysis of this problem has been outlined in the Appendix, while the results of the investigation are presented in the following discussion. DISCUSSION OF CALCULATION PROCEDURE SLNGLE Well, Ini-iimite Reservoir The procedure for calculating fluid migrations is based on solutions of the partial differentia1 equations describing the flow of a homogeneous compressible liquid in a homogeneous reservoir of uniform thickness. This differential equation has the form of the well-known diffusion equation. The equation, as applicable to our problem, is where p is fluid density, is porosity, EL is viscosity, c is compressibility,* and k is permeability; .r, y and t are the space coordinates and time. Derivation of this equation is given in the Appendix. The analytical solution of this equation for a single well of negligible radius producing at a constant rate. q, from a reservoir of infinite areal extent for a time, 1. can he readily obtained. From this solution the rate of flow and also the cumulative flow across a straight line segment of length, 1, at a perpendicular distance. 6. from the well can be computed. One end of the line must be on the perpendicular joining the well to the

By P. L. Raffo, T. E. Mitchell

Single crystals of Ta-Re alloys have been deformed in tension and compression as a function of solute concentration and temperature. The temperature dependence of the yield stress is decreased by alloying. At low temperatures there is a minimum in the yield stress (at about 2 at. pct) as a function of concentration. Three-stage hardening was not observed in the alloys. Linear hardening rates, where observed, were characteristic of stage II in pure tantalum. At low temperatures and high concentrations, work softening was often prominent at high strains. Electron microscopy revealed that dislocations are mostly of screw orientation, although heavily jogged and cusped, and often occurring in dipole pairs. The alloys become more prone to cleavage with increasing rhenium content, due mostly to an increasing yield stress rather than a change in cleavage strength. Alloying apparently decreases the Peierls stress of bcc metals at low temperatures by facilitating kink nucleation at solule atoms on screw dislocations. Higher solute concentrations further increase the yield stress. Quantitative calculations and comparisons with other bcc alloy systems are made to show that the predominant hardening mechanism is due to the interaction of dislocations with misfitting solute atoms close to their slip planes. The interaction is so localized that the core dilatation of dislocations could be important. CONSIDERABLE interest has arisen in recent years concerning the mechanical properties of unalloyed bcc metal single crystals.'-7 These and similar studies on polycrystalline materials have resulted in a considerable understanding of the macroscopic yielding characteristics8, 9 and the process of work hardening.'' This latter advance is due in a large part to the increased use of transmission electron microscopy in P I RAFFO junior Membar AlMF is Metallyureist Iewis such studies and the general observance of three stages of work hardening in the shear stress-shear strain curves. The properties of substitutional alloy single crystals of bcc metals have not been determined in as much detail as in the pure metals. Insufficient systematic studies have been made on the effect of alloying on the magnitude and temperature dependence of the yield stress or the stress-strain curves. The alloy systems which have been studied to some extent have been Ta-W,11, 12 Ta-Mo," Ta-Nb,12'14 Mo-Re,15 W-Re,16 and alloys of iron with nickel,17 platinum,17 vanadium,18 and aluminum.18 A large body of data exists on Fe-Si alloys, but these have mainly been a result of the experimental convenience of using this material in place of unalloyed iron, rather than a comprehensive study of the mechanical properties of the alloy system per se. The present authors have previously reported additional data on the properties of Ta-Re, Ta-W, and Ta-Mo alloy single crystals.1g Some of the data on Ta-Re alloys will be described later in this paper. Briefly, single crystals of Ta-Re (1.2 to 10.6 pct), Ta-W (6.2 and 10.2 pct), and Ta-Mo (2.9 and 9.0 pct) were grown by the floating zone method in vacuum. Compression tests were performed in the temperature range 77" to 623°K. Slip was found to occur in Ta-Re alloys at 77' and 298°K on the (~ll)[lil] system and slip lines were coarser and straighter than in unalloyed tantalum. No three-stage hardening was observed in any of the alloy systems and the curves were nearly parabolic. At temperatures above 175°K the yield stress* increased monotonically with in- creasing composition while at 77" and 175°K the yield stress initially passed through a minimum after which it began to increase again for concentrations greater than about 2 pct Re. Similar minima were observed in Ta-Mo alloys and to a lesser extent in Ta-W alloys. The minimum was interpreted as being a result of a

Jan 1, 1969

By R. Kerby, T. R. lngraham

The rates of cadmiuln cementation from buffered solutions were studied on both the cylindrical and circular faces of a rotating zinc disk. The activation energies are equivalent on both surfaces, but the rate is more rapid on the cylindrical face. At higher temperatures and at pH values above 6.4, the rate of deposition increases because of an increase in the cathodic area of the deposit. The rate may also be increased by decreasing the thickness of the diffusion layer by rapid stirring. The presence of small amounts of copper, cadmium, lead, iron, or aluminum in the zinc does not affect the cementation rate, but when srnall amounts of copper, cobalt, and arsenic were present in the solution cadmium deposition ceased shortly after it started. Small amounts of copper in solution become cemented with the cadmium to form a coarse deposit of Cd3Cu. When zinc ores containing cadmium are processed for electrolysis, the cadmium appears with the zinc in the leach liquors. Because of the discharge potential of the cadmium ion and the hydrogen overvoltage on metallic cadmium, the cadmium ion must be removed prior to zinc electrolysis to prevent its codeposition. Cadmium is usually removed from acidic zinc sulfate solutions by cementation on zinc. When zinc sheets are used with the appropriate conditions of pH and temperature, a finely divided, high-purity cadmium powder is obtained; it floats to the surface with attached hydrogen bubbles and, after careful washing, may be processed directly to a marketable product.' The reaction on zinc sheets is relatively slow because of the limited amount of exposed cathodic area on the sheets. A much more rapid reaction is obtained when zinc powders are stirred into the solution, but this procedure does have a potential disadvantage: some unreacted zinc may be trapped in the cemented cadmium and thus lower its grade.1 The equilibrium constant at 25°C for the displacement of cadmium by zinc is of the order of lo", which indicates that at equilibrium the displacement would be essentially quantitative and no back reaction need be considered. This indication is not entirely true, however, because in the presence of oxygen any loose cadmium which is out of contact with metallic zinc tends to redissolve after cementation.' The overall effect is much the same as that to be expected if the equilibrium constant were much smaller. Previous experimental work on cementation reac- tions3 is in general agreement that the rates of cementation usually follow first-order kinetics. The metal on which cementation occurs is considered to consist of anodic areas from which metal dissolves and cathodic areas onto which the reactive metal is cemented. For the reaction to continue, the cemented deposit must remain open and porous for the removal of ions. Usually, the deposited metal influences the rate of cementation; when it blocks the pores in the deposit, the rate of cementation will be decreased. Alternatively, when the cemented metal grows as den-drites or as coarse powder the cathodic area is correspondingly increased and the rate of cementation increases,3 Thus, it is only during the initial stages of cementation, prior to the development of deposit effects, that the kinetic behavior of the reaction may be studied without ambiguity. In this paper, experiments will be described for cementation of cadmium from dilute solutions onto the surface of a rapidly spinning zinc cylinder. The effects of ionic concentration, disk rotation speed, temperature, and impurities will be described. APPARATUS AND PROCEDURE The apparatus used for the experiments was described in a previous paper.4 It consisted of a 2-liter vessel in which the contents were protected, against oxidation, by a stream of prepurified nitrogen. The vessel was immersed in a water bath which controlled

Jan 1, 1970

By A. N. Crownover, H. T. Kennedy, E. P. Miesch, C. H. Bowman

The paper presents correlations of (l) molar volume of gaseous hydrocarbon mixtures with pressure, temperature, composition and properties of the C,-plus fraction; (2) shrinkage of oils during flash and differential liberation of gas, including the calculation of formation volume factor under various conditions; and (3) bubble-point pressure with temperature, composition and characteristics of C, plus. The data on which the correlations are based comprise 1,615 measurements on 900 hydrocarbon systems, including numerous systems containing nitrogen, hydrogen sul-fide and carbon dioxide. In each correlation, the number of data points covered and the accuracy is substantially greater than in previously available work. Thus, the equation yielding molar volumes of gases has an average deviation of 2.04 per cent, applied to mixtures having temperatures up to 313F and pressures up to 9,800 psis, compared to 2.37 per cent for the Benedict-Webb-Rubin equation applied to the same data, and 4.53 per cent for the method based on the law of corresponding states. he equations resented are all explicit in the dependent variable, and require no iteration on the digital cow puter. INTRODUCTION The ease and accuracy of determining the composition of hydrocarbon mixtures, compared to the difficulty of measuring their properties under reservoir conditions, makes it desirable to utilize composition as the key to physical behavior to the greatest possible extent. As a result, there are available correlations between composition, or easily measured characteristics dependent on composition, and practically every important engineering property of reservoir fluids. The task confronting us is one of finding more exact relationships between important variables rather than extending correlations to new properties. This paper describes new correlations of molar volumes of gases, formation volume factors, and bubble-point pressures with composition, temperature and where possible, pressure. Each correlation is obtained by employing a sufficiently large amount of data so the calculated properties are probably as least as accurate as the measurement on which they are based. MOLAR VOLUME OF GASES Although many equations of state have been proposed for pure gases, only a few methods are applicable to hydrocarbons at conditions comparable to those in petroleum reservoirs. Still fewer arc useful in describing the behavior of mixtures, with which the petroleum engineer is largely concerned. The correlation presented here involves procedures similar to those of Alani and Kennedy The van der Waals equation is modified to make a and b functions of temperature instead of being constants for each material.This is a cubic equation, which may have either one or three real roots. The lowest root corresponds to liquid volume, while the highest applies to gas. When the procedure was applied to 703 pressure-temperature points of 164 gases of known composition and volume, the average deviation was 12.08 per cent, and the standard deviation 8.15. The above calculations were made using the constants derived for liquids by Alani and Kennedy and the mixture equation developed by them. A closer approximation to measured molar volumes is obtained by employing different sets of constants for different areas on the pressure-temperature chart, and by changing the relationship between a,,, and b,,, for mixtures and the a, and b, for individual hydrocarbons. The various sets are shown in Table 1, and the areas for which they are recommended are plotted in Figs. 1 through 7. In these figures, the area designated by zero is in the critical region for pure materials, and the values obtained for them may be unreliable. For normal mixtures, however, the area may be added to any of the bounding areas without substantial error. The new relationships employed are

Jan 1, 1966

By J. A. Elias, A. J. Heckler

A simplified method is described for the prepauatior~ of comnposite samples for determination of one quadrant of an X-ray pole figure of a sheet material by the Schulz reflection method. Other special conzposite sampling methods were used to investigate specific areas of the pole figures. Plotting nets for these sampling plans were drawn by a computer. Step-scanning techniques were used to obtain detailed information about specific regions of a pole figure. Satisfactory pole figures were obtained for large-grained (0.5 to 1 in. diam) sheet materials. COMPOSITE sampling techniques for preparing one quadrant of an X-ray pole figure have been reported by a number of authors.'-5 All of these methods are similar in that they use a composite sample prepared by stacking and holding together coupons cut from a sheet material. The schulze reflection technique is applicable to the composite sample so that only minor corrections are needed for defocusing and absorption effects. Also, a relatively large area of a sheet is sampled through the use of multiple cross sectional pieces. In general, sampling methods necessary to obtain a composite-type specimen have been formidable enough to discourage their use in routine pole figure determinations. This paper presents a versatile sampling technique which is simpler than those previously described along with an accurate method for obtaining stereographic plotting nets for any orientation of a composite specimen surface. A step-scanning technique is used to obtain more quantitative determinations of specific regions in pole figures, and the composite technique is satisfactorily applied to determine pole figures of very large grained sheet materials. REVIEW OF PREVIOUS TECHNIQUES Mueller and ~nott' first proposed a technique for obtaining one complete quadrant of an X-ray pole figure by using a sheet sample and six different composite samples in which the individual coupons were aligned and held together by two types of jigs. Data from the seven different samples were overlapped to obtain a single quadrant. ~eieran~ and Lopata and ~ula~ obtained a complete quadrant of a pole figure from a single sample prepared by forming a cube from coupons cut from a sheet. These coupons were bonded together using an epoxy cement, and a cut was made at 54.7 deg to the normal, transverse, and rolling directions of the sheet, Fig. I. The normal direction of the cut face projects into one quadrant of a stereographic projection at equal angles to the three principal orthogonal reference directions mentioned above. X-ray reflection data obtained along a spiral path in physical space could then be plotted on a stereographic net offset 54.7 deg from the normal, as shown in Fig. 2. A rotation about an axis representing the surface normal is designated as a, and a rotation about an axis lying in the plane of the surface is 4. From Fig. 2 it is apparent that a tilting angle of no more than 55 deg @ is necessary to obtain the complete quadrant. ~eber~ devised an improved sampling technique by cutting coupons 45 deg to the rolling direction of a sheet, stacking and bonding these with an epoxy cement at an angle of 54.7 deg to a reference plane, and finally grinding and lapping a flat specimen surface parallel to this plane. An important consideration of this technique and that of Lopata and ~ula~ is variation in the diffracting power of the specimen surface due to the bonding medium. While any composite-type sample will have some such variation due to boundaries between coupons, the problem can be minimized by elimination of the bonding medium and by avoiding prolonged etching times which could lead to significant inter lame llar attack of the coupon faces. EXPERIMENTAL TECHNIQUE We were working concurrently though independently on a technique similar to ~eber's,' but which does not

Jan 1, 1968

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

The mechanical properties of Ti-C and Ti-C-0 alloys can be altered by heat treatments to dissolve or reject carbon from solid solutions. The maximum strength is obtained by annealing just below the peritectoid temperature. Quenching from the ß-carbide field results in softening. Impact behavior is influenced by the extent of solution of interstitials CARBON is not as important in titanium alloys as it was in earlier years when graphite induction melting was more prevalent. With induction melting, carbon pickup is about 0.5 to 0.8 pct. Cold-mold arc melting with graphite electrodes, which is among the more current methods, results in carbon pickup of 0.1 to 0.2 pct. The titanium-sponge melting stock itself contains about 0.02 to 0.07 pct C, picked up from the magnesium used in the reduction process. Thus, carbon is still one of the more important contaminants in titanium and needs careful study and evaluation in order to understand titanium and titanium alloys. Moreover, it is equally proper to consider carbon as an alloying addition because, in controlled amounts in titanium alloys, it may serve a most useful function. This is particularly the case where the ultimate in toughness is not required. The addition of carbon to titanium results in a peritectoid-type system as illustrated in Fig. 1. The solubility of carbon is seen to be higher in the a phase than in the ß phase in the temperature range of interest. Below the peritectoid temperature, the solubility of carbon in a titanium decreases with decreasing temperature. This type of system permits many microstructural and heat-treatment variations which may influence the properties of the alloys. The study of how the microstructure variations affect mechanical properties is described in this paper. Experimental Procedures The experimental techniques and testing methods used in this work were the same as those described in detail in a previous paper.' No further descriptions will be given except where changes have been made. High purity iodide titanium, produced by the New Jersey Zinc Co., was used in all of the alloys. Carbon additions were made using high purity spectro-graphic carbon electrodes in order to obtain the highest purity carbon available. The alloys were prepared by double arc melting to reduce the possibility of segregation. The alloys were forged at 875°C to ¾ in. round, descaled, vacuum annealed for 5 hr at 900°C to remove the residual hydrogen, and swaged to ¼ in. round at 750°C. All heat treatments were made on material in this initial condition. Two of the early Ti-C ingots were found to have been contaminated in melting. Vacuum-fusion analyses showed that the two contaminated alloys had picked up oxygen, so the test results on these two alloys permitted an evaluation of ternary Ti-C-0 alloys. A list of the alloys and their compositions are given in Table I. Properties of Ti-C Alloys In a peritectoid-type system, such as the Ti-C system, the chief microstructural variable which influences the properties is solid-solution strengthening. For a given composition, it is possible to control the disposition of carbon, either in solid solution or as the compound Tic, by suitable heat treatments. When in solid solution, the carbon present in the alloy makes a definite contribution to the strength of the alloy. However, when present as Tic, it has very little effect on the strength. Other microstructural variables considered in this investigation were transformation structures and grain size. As discussed in subsequent sections, these variables have only a minor effect on properties as compared to the solid-solution effect. Solid-Solution Strengthening: The principal strengthening mechanism for Ti-C alloys has been found to be solid-solution strengthening. Carbon in interstitial solid solution strengthens titanium, but has very little strengthening effect if present as the compound. Since carbon has a higher solubility in

Jan 1, 1956

By G. R. St. Pierre, M. J. Pool, R. Speiser

The activities of chromium in solid Cr-Ti solulions contaitning from 10 to 90 at, pct Cr were measured over the temperatutre range 1250" to 1380°C. The Knzudsen effusion technique with direct weighing of the Knudsen cell was used. This was possible because the vapor pressure 0f chromium is about 600 times greater than the capor pressure of titanium so that the amount 0f titanium effusing could be neg-Lected. the activities of titanium were determined by g-raphical integration of the Gibbs-Duhertz equatiotz. The solutio~ls sllcdied exhibited positive deviations from Raoult's law, but they approached ideality as the temperature was raised from 125 to 138t C. The integral free energy of mixing was calclated from the activity values. AF has a maximum value of - 1.66 kcal a1 1390°C and a composition oj 55 at. pcl Cv. The free energy of formation of 'TiCr, is —0.76' lzcal a1 1250°C. The heats and entropies of mixing usere determined using the second law and thus tile mlues could be in error by a considerable amount. The Cv-Ti system is not a regular solution. ThE increasing emphasis on application of various models to alloy formation and solution behavior has led to an intensified interest in the thermochemistry of alloys. In a majority of the cases where different models have been applied the alloy system used was a simple one. However, the amount of data available on more complicated systems is small and in order to fully understand the behavior of metallic solutions more experimental work has to be carried out on these systems. The Cr-Ti system is reasonably complex and even though this system was being investigated as early as 1937 by Kroll,' no previous work has been done on the thermodynamic properties of either the liquid or solid state. This research was undertaken to determine the thermodynamic properties of solid Cr-Ti alloys. EXPERIMENTAL PROCEDURE The experiments on the Cr-Ti system were carried out in a water-cooled metal vacuum system. This system is composed of a brass vaporization chamber wound with copper tubing for cooling purposes, a brass liquid-nitrogen trap, an oil diffusion pump, and a Duo-Seal forepump. The pressure in the system is measured with an ionization gage. The interior of the vaporization chamber is shown schematically in Fig. 1. The Knudsen cell is supported by the molybdenum tripod, and a magnetically operated shutter is provided to protect the Pyrex sighting glass against deposition of metallic vapors in the intervals between temperature measurements. Heating is accomplished by means of a 20-kw 450-kc Westinghouse oscillator. The susceptor in this case is 10-mil tantalum seamless tubing which also forms the outside of the sample container. The remainder of the sample container consists Of an im~ervims re-crystallized alumina crucible and a 10-mil-thick tantalum lid. Two holes are drilled in the lid. The diameters of these holes were measured with the calibrated stage of a "Tukon" microhardness tester. The thicknesses were measured with a micrometer. A Leeds and Northrup disappear ing-filament optical pyrometer was used to measure the temperature. This is sighted through the smaller of the two holes in the lid and corrections for the emissivity of the sample were not necessary since the ratio bf cell length to hole diameter was large enough to insure a hohlraum. The pyrometer was calibrated at the ~~t~~~l Bureau of Standards, and the correction for the Pyrex sighting window was determined in the laboratory. The titanium used in this investigation was obtained from Mallory-Sharon and the chromium from The Union Carbide Metals Co. The reported purities were

Jan 1, 1968

By L. Luini, E. Lee

An exploratory survey of the heat treatment response of commercial titanium alloys (Ti-150A, RC-130B, and MST 3AI-5Cr al-loys) shows a wide range of possible hardness and microstructural characteristics. The hardening is primarily dependent on the solid state transformation of the phase. An age hardening reaction which apparently is associated with ß decomposition and precipitation has been shown. Brittleness and notch sensitivity appear to be characteristic of age hardening to high hardness. Ductility, tensile strengths, and elongations are given. A NUMBER of commercially produced titanium-base alloys have been made available by the titanium metals industry. These alloys were developed to combine the light weight of titanium with increased strength through alloy additions. Usually the properties of these alloys are reported for material in the hot rolled and annealed condition. Since the production of commercial titanium has preceded the investigation of titanium-base alloy systems, the potential of these alloys is not well known. Although heat treatability has been indicated for these alloys, data on the response to heat treatment are quite limited. The heat treatability of titanium is based on the allotropic transformation of the high temperature, body-centered cubic ß structure to the low temperature, hexagonal close-packed a structure at approximately 1625 °F. This transformation in the pure metal is of little practical significance in heat treatment since the high temperature phase is not amenable to controlled transformation. Alloy additions serve to alter the transformation kinetics and permit control of the transformation by heat treatment variables. The effects of different alloys on the allotropic transformation in titanium classify them in two general categories,1 a stabilizing and ß stabilizing elements. The a stabilizers, represented by aluminum and oxygen, raise the temperature limits of the low temperature phase and introduce a two-phase a + ß temperature range. The ß stabilizers, represented by molybdenum and columbium, lower the equilibrium temperature of ß and give rise to an extended temperature range where both a and ß phases are stable. Another type of ß stabilizer, represented by iron, chromium, and manganese, introduces a eutectoid reaction. Some commercial titanium alloys belong to complex multiple element systems. Based upon the phase diagrams of the binary systems, the general effect of commercial compositions is to vary the stability of the high temperature phase and significantly alter its transformation characteristics. Therefore it is expected that the characteristics of alloyed titanium can be altered by heat treatment. The present investigation was undertaken to survey the variations in hardness, microstructure, and mechanical properties as affected by heat treatment variables. Commercial Alloys lnvestigated The commercially available titanium-base alloys selected for this investigation and obtained as 3/4 in. diameter hot rolled and annealed bars are listed in Table I. The producer did not determine the chemical composition of the Ti-150A heats X1052 and L685. The early heats of Ti-150A, prefixed with the letter X, were melted with tungsten-tipped electrodes and cast in approximately 500 lb ingots 12 in. in diameter. The heats prefixed with the letter L were melted under a revised melting practice yielding approximately 1300 lb ingots 16 in. in diameter. The final annealing treatment was at 1200" to 1250°F for 1 hr. The MST-3A1-5Cr alloy was melted in an induction furnace and cast in 7 in. diameter ingots. This practice produces high carbon material and some variation in the amount of carbides was found in different sections of the same bar. The RC-130B alloy was melted with a carbon arc. This alloy showed approximately 2 pct carbides. No large segregation effects were observed.

Jan 1, 1955

By K. H. Coats

This paper describes an approximate technique for handling the problem of percolation of evolved gas upwards through the oil column in computer simulation of natural depletion. This technique has been incorporated into a general model for simulating three-phase flow in one, two or three dimensions. The mathematical model for perfonning these calculations is described in detail in a separate article. 1 While vertical gas percolation occurs during natural depletion in a reservoir of any configuration, it is especially pronounced in the pinnacle reel or bioherm. The reel may have an areal extent less than one section with a thickness of up to 800 It. The upward percolation of evolved gas often limits the time step in calculations as little as one day. Using this small time step, computer expense for a single 30- to 40-year simulation on even a one-dimensional basis has exceeded 92,000. The method described here for handling the percolation allows time steps of 60 days or more (depending on reservoir size and production rate), resulting in a considerable reduction in computing expense. The method also allows calculations in which secondary gas caps build up in tight zones of the oil column below the main gas cap. The validity of the method is indicated in connection with an example pinnacle reef field. Calculated results using a 2-day time step (where the method in question is not needed and not invoked) are compared with results using the method and a 60-day time step. The comparison shows good agreement. Results from one- and two-dimensional simulations of the reef are presented along with the corresponding computing times on the CDC 6600 computer. A three-dimensional simulation was also performed and the required computing time is given. INTRODUCTION A general analysis for simulating three-dimensional, three-phase flow in reservoirs has been developed. 1 In applying this model to reservoirs undergoing natural depletion, a time-step restriction was encountered due to the flow of evolved gas upwards through the oil column and toward the gas cap. A remedy for this problem has been incorporated in the analysis and is described here. The time-step restriction is encountered only in calculations which include flow in the vertical or near vertical direction. The restriction occurs to some extent in reservoirs of any geometrical configuration, but it is especially pronounced in the pinnacle reef or bioherm where the ratio of thickness to areal extent is unusually large. This paper describes the problem, a method of handling it, incorporation of the method in the three-dimensional, three-phase model, and, finally, a test of the method's validity in an application to an example pinnacle reef reservoir. THE PROBLEM During the early stages of reservoir depletion, pressure falls below bubble point in progressively lower regions of the oil column. Continuing production results in evolution of dissoived gas throughout the oil column. This gas then percolates upwards toward the top of the reservoir. If the gas encounters a sufficiently low permeability zone in its travel upward, then it can accumulate and form a secondary gas cap. If no zones are encountered which are tight enough to hold gas against the gravity forces, then the gas travels on until it reaches the top of the sand or the main gas cap. Numerical simulation of multiphase flow in reservoirs is generally performed with time steps such that the flow of a fluid into or out of a block in one time step is a fraction (considerably less than one) of the total amount of that fluid present in the block. Use of a time step where the time step's

Jan 1, 1969