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By S. F. Reiter

The paper presents isothermal recrystallization curves for 0.08 and 0.15 pct C steel at subcritical temperatures following small amounts of plastic deformation. The effects of deformation, temperature, and aging on nucleation and growth rates ore described. The free energy of activation for grain boundary migration in steel is given. SEVERAL excellent reviews of the literature have appeared concerning the recrystallization of metals.'-' The present investigation follows the approach advanced by Mehl, Stanley, and Anderson,6-7 in which the rate of recrystallization was analyzed in terms of N, the rate of nucleation, and G, the rate of growth of recrystallization nuclei. Two lots of low carbon, capped steel of the analysis given in Table I were studied. Each lot consisted of a 150 lb coil which had been hot rolled to 0.083 in. and then cold rolled to 0.042 in. at the mill. Strips 0.930 in. wide were sheared perpendicular to the rolling direction. Both steels were normalized before studying their recrystallization characteristics. The strips were cleaned, painted with a magnesia-acetone paste, and made into packs of equal weight, wrapped in 0.002 in. copper foil. The packs were placed in a salt bath at 900°C for 30 min and air cooled. A relief anneal followed in a second salt bath for 15 min at 650°C. The relief anneal was found necessary from early tests in which a longer incubation period and slower rate of recrystallization were observed in relief-annealed lot A steel than in similar material which was strained and recrystallized directly after being normalized. This effect, which indicates the presence of transformation and/or cooling stresses in steel air cooled from above the A, temperature, has also been observed by Samuels8 and Masing.9 Figs. 1 and 2 show the microstructure of lot A and B materials and illustrate the rather uniform No. 8 ASTM grain size produced by this heat treatment. Winlock and Leiter10 observed that strip specimens which had their sharp edges removed elongated more uniformly than those which were not polished. Similarly, when the sheared edges were removed on a belt grinder, it was found in the present investigation that such samples recrystallized more uniformly than did unpolished strips. Therefore, all strips were carefully rounded prior to their extension. The approximate strain limits for the production of large recrystallized grains are from 6 to 12 pct extension." It was found that for the purpose of this investigation, 8 and 9 pct elongation were suitable deformations. The strain rate employed was 0.01 in. per in. per min and produced a yield point elongation of 4 pct. Winlock and Leiter found that mild steel of No. 8 ASTM grain size gave the same yield point elongation when extended at 0.012 in. per in. per min. All of the lot A and B strips extended in tension developed a straight, stretcher strain line at each grip when the upper yield point was reached. The lines were parallel and made an angle of 55" with the edge of the strip. They approached each other with increasing strain and met near the center of the sample at the end of the yield point elongation. Immediately thereafter, a small drop in load was observed and then the load increased in a regular manner with increasing extension. The grips were initially 8 in. apart. After extension, the 6 in. gage length was carefully cut into 1 in. samples. The remainder of the strip was discarded. After a flash pickle in hot 50-50 hydrochloric acid, six samples, each of which had been taken from a different strip, were placed in a basket and submerged in a lead pot for isothermal recrystallization. Although no recovery effect was observed, strain aging did occur after extension. Therefore, samples were always recrystallized within 24 hr after their cold deformation. After recrystallization, the samples were etched with a solution comprised of one part by volume of nitric acid with three parts of water. Bromide printing paper was exposed directly at low magnifications and later used with a mask to measure the desired quantities. First, the average diameter of the largest grain visible in each sample was determined using dividers. Next, the number of recrystallized grains per unit area was counted and recorded as n. Then, for each sample, the combined area of the recrystallized grains was measured by transcribing the grain outlines to standard graph paper. Many determinations of the area of the recrystallized grains were repeated five times and indicated a standard error that was not greater than 25 pct. The average area for six samples was divided by the area of the mask to yield the percentage recrystallized. Recrystallization of 0.08 Pct C Steel The progress of recrystallization at 670°C after 8 pct elongation of lot A steel is shown in Fig. 3, a through f. The shapes of the growing crystals are approximately equiaxed, as is assumed in the

Jan 1, 1953

By E. T. Turkdogan

This is a compilation and a critical review of the data on the Fe-Ca-0 ternary system. Using the results on the reductiorz-equilibria, an oxygen potential diagram is drawn for the greater part of the system. A number of univariant systems and invariant points, not determined experimentally, are evaluated by making use of the theorem on univariant curves intersecting at an invariant point. The formation of solid solutions and ternary compounds and the crystal structures of some of the phases in the composition-diagram are given for a feu! temperatures. DURING the past thirty years there has been a continued interest in the study of the Fe-Ca-0 system. A detailed literature survey made by white1 in 1943 indicated that further work was required to clarify the phase relationships; in fact, the work carried out in the subsequent years, reviewed by Burdese2 in 1954, made a valuable contribution to a better understanding of this subject. Most of the data were obtained by the step-wise reduction of mixtures of iron oxides and calcium ferrites. However, there is some uncertainty about the phase relationships in this system, arising mainly from insufficient use of thermodynamic concepts in the construction of phase diagrams. In this paper an attempt is made to establish the invariant points from the available data. OXYGEN POTENTIAL DIAGRAM Schenck and coworkers3,4 were the early investigators who studied part of this system by the step- wise reduction method and suggested the formation of two ternary compounds, CaO.FeO.Fe2O3 and 2Ca0.5Fe0.2Fez03, the latter being referred to as point X. They also deduced from their results that the phases Y (8.74Ca0.32.5Fe0.8.74Fe2O3 and Z (2.02CaO-97.98FeO) were formed near the w?stite corner of the system. Martin and voge15 postulated the existence of the compounds CaO.9FeO and 4Ca0.3Fe3O4; the former is very close to the composition of point Z and the latter to that of CaO.FeO-Fe2O3. The most valuable contribution to the presen knowledge on this system was made by Cirilli and Burdese6-8 who showed by X-ray and chemical anal yses that there were two ternary compounds, CaO-Fe0.Fe2O3 and CaO.3FeO-FezO3; the former is the same as that suggested by Schenck et al. and the latter is close to their point X. The results of Cirilli and Burdese show that the phases Y and Z postulated by Schenk et al. are solid solutions of calcium oxide in w?stite. In most of the above-mentioned reduction-equilibria measurements carbon monoxide-carbon dioxide mixtures were used and in a few cases hydrogen-water vapor mixtures were employed. Using the

Jan 1, 1962

By D. J. McAdam, G. W. Geil, D. H. Woodard, W. D. Jenkins

INTRODUCTION IN a series of papers, the authors and their associates have shown the influence of four important factors on the technical cohesion limit.3-16 By "technical cohesion limit" is meant the technically determinable resistance to fracture. The four important factors are the stress system, plastic deformation, temperature, and the strain rate. The influence of any one of these factors may be represented by a curve of cohesion limits, although only one point on the curve may represent actual fracture. As the term "fracture stress" has come into general use with the same significance as technical cohesion limit, the authors are here using the shorter term with the understanding that it does not always refer to actual fracture. The previously-mentioned series of papers contains ample evidence that plastic extension increases the fracture stress of any polycrystalline metal. In a recent paper of the series,15 moreover, it has been shown that the effect of plastic deformation on the fracture stress cannot be attributed to reorientation of internal flaws but is a work-strengthening effect, similar to the effect on the flow stress.[$] Plastic deformation of steels, however, may not only cause work hardening, but may result in additional hardness because of strain aging. Some evidence that strain aging affects not only the flow stress but also the fracture stress, has been presented in a recent paper.14 In that paper, a study is made of the influence of plastic deformation at room temperature on the fracture stress of ferritic steels at -188°C. The study is based on the results of two-stage tests. In the first stage each specimen was extended a predetermined amount at room temperature; in the second stage the specimen was tested to fracture in liquid air. In most of these tests the specimen remained in the testing machine during the interval of about one hour between the first and second stages, it was kept under a tensile load of about 500 lb and maintained at liquid air temperature. The effects of various amounts of plastic deformation on the fracture stress were thus determined and curves were obtained to represent the influence of plastic deformation at room temperature on the stress at brittle fracture in liquid air.14 Two specimens of ingot iron, however, were removed from the testing machine at the end of the first stage and several days elapsed before the specimens were tested to fracture in liquid air. As shown in Fig 8 of that paper," the points representing fracture of these specimens are far above the curve representing the results of two-stage tests without a rest interval between the stages. The evidence thus indicated that the fracture stresses of these two specimens were increased not only by the work-strengthening, but also by strain aging. The present paper presents results of further investigation of the influence of strain aging on the fracture stress. There are two kinds of aging of steel.

Jan 1, 1948

By Adrien Berton

For nearly a century, the Corocoro deposit has been renowned among geologists from the fact that it shares with the Lake Superior deposits of the United States the distinction of being the only important copper districts where native copper is worked commercially. The Corocoro district, named after the city of Corocoro, the capital of the Province of Pacajes (Department of La Pas, Bolivia) is situated towards the western edge of the Bolivian high plateau, at an altitude of a little over 13,000 ft. The most interesting part of the district is that immediately surrounding the city of Corocoro, at a distance, by railway, of 65 miles from La Paz and 210 miles to the Chilean port of Arica on the Pacific Coast. The climate of the region is that of the semi-desert, dry and relatively cold, with big differences of temperature between day and night. The rainy season begins in December and ends in March. The cupriferous lodes of Corocoro have not attracted as much interest as the silver mines of Potosi but they have been known for a long time. In the precolonial period the Indians were using the charquis, or natural native copper sheets, to make small brass objects, and the beautiful pale green brochantite of the outcrops as a source of green pigments. During the colonial period, the oxidized ores of the outcrops were worked for copper, which was used by the mint at Potosi for making currency. The native copper ores were neglected because the Spanish miners were at a loss how to concentrate and smelt them. About 1830, work by rudimentary processes, which were improved little by little, was begun on the native copper ores. The total production of native copper in the following hundred years amounted to 100,000 tons. This native copper, which was remarkably pure, was much appreciated on the European markets before the introduction of electrolytic copper. It was useful for making special ornamental brass or bronze and the granular concentrates of native copper, called barrilla, containing 80 to 85 per cent copper were suitable for making copper sulfate by direct oxidation and subsequent leaching with sulfuric acid.

Jan 1, 1937

By C. W. Nicolson

The Tri-State zinc and lead-mining district is in the northeast corner of Oklahoma, the southeast corner of Kansas and the southwest corner of Missouri. The area throughout which active mining has been conducted is about 45 miles long and about 5 miles wide, extending northeasterly from Commerce, Okla., to Alba, Missouri. Although the lead ores were mined on a very small scale in the vicinity of Joplin, Mo., as early as 1848, nothing of any importance was done in the district until 1870, since when both mining and smelting have been prosecuted with considerable vigor. In the beginning the lead ores only were exploited, but within a few years extensive deposits of zinc ores were found and since that time the production of zinc ore has far exceeded that of lead. Both the surface and mineral rights in Missouri and Kansas were under individual ownership by the time ore was discovered. Although some of these rights were purchased by mining companies, most of the mining has been done under leases covering small areas, usually 40 acres, although in the past many leases were given on much smaller tracts. In Oklahoma most of the mineral land had been alloted by the Government to various Indian tribes and although the title to some of these lands had been acquired by various white men before the discovery of the rich Picher field, the title to most of the land has remained with the Indian tribes and the leasing of the mineral rights has been done by the Federal Government for the benefit of the Indians. The Indian allotments were of 200 acres each and some of the mining leases covered entire allotments, although many leases were granted for only 40 acres or even less. Practically all of the leases granted in the past required the erection of a concentrating plant on each lease, a condition that has had a pronounced effect upon the mining and milling methods of the district, since the apparent ore reserves on each tract were too small to justify large and elaborate mining and milling plants. Most of the leases were

Jan 1, 1940

By K. I. Savage, S. C. Sun

This paper describes a process developed to recover coal, clays and pyrite from coal wastes. The process consists of fine grinding followed by coal and pyrite flotation which leaves the clays in the flotation pulp. A bituminous coal refuse containing 10% sulfur and 30% carbonaceous material was treated by this method to yield a coal product containing 4% sulfur, 10% ash; a pyrite product containing 45% sulfur (84% FeS2), 1% carbonaceous material; and a clay product containing 2% sulfur (3.5% FeS2). The coal yield was about 89%. The pyrite yield was about 77%. The process steps may be entirely flotation, or gravity separation (hydrocycloning) may be used to increase the pyrite : coal ratio in the flotation feed. Cost estimates for the process show a profit of $2.28 per ton of low pyrite grade refuse, but these do not include labor, maintenance, overhead and plant depreciation. The development of this process consisted of three parts: (1) exploratory tests, (2) op-timazation tests and (3) confirmatory tests. The objectionable qualities that sulfur imparts to coal have been commented upon from early times, and they have become more objectionable as the uses of coal have grown. In whatever form coal takes — raw, carbonized or gasified —the sulfur content remains objectionable, and therefore its compounds are removed as completely as possible. It has long been known that sulfur occurs in coal in different forms. In 1861, sulfur was said to exist in the state of sulfuric acid in combination with a base; in combination with iron as iron pyrites; as bisulfides of iron; and in combination with the organic elements of coal.' Pyritic sulfur is a term loosely used to cover the sulfur associated with iron in its various forms. The mineralogically recognized forms are pyrite (FeS2), pyrrhotite (Fe 1-x S) and marcasite (FeS2). The particle sizes of pyrites vary widely. Isolated grains of marcasite smaller than 15 microns have been found disseminated through coal.2 Hair-like "veins" of pyrite filling cracks in vitrain have been found. At the other extreme, lumps or nodules of pyrites large enough for removal by hand picking have been encountered. Organic sulfur, unlike pyritic sulfur, does not exist as discrete particles, but is instead intimately associated with the coal structure and thus it is impossible to remove it or reduce its concentration by physical or mechanical means.2 In the preparation of coal for its various markets, the pyrite minerals (pyrites) are separated from the raw coal feed. This separation process concentrates the pyrites in the tailings or other waste products. It would be desirable to recover these pyrites for three reasons: (1) Pyrites are potential sources of sulfur and iron. In 1967, for the fifth consecutive year, Free World consumption of sulfur exceeded production.3 Propelled by the shortage, the domestic price of sulfur has risen from $24 to $38 per long ton (bright). (2) The refuse, when placed in piles, becomes ignited. The pyrites (FeS2) bum, giving off SO,. Thus, the pyrites are a cause of air pollution. (3) Also, the pyrites undergo chemical reaction when exposed to air. The refuse is leached by waters which result in stream pollution due to the water-soluble iron and acidic reaction products. Coal refuse also contains coal minerals and clay minerals. Therefore, any process for recovering the pyrites must successfully separate them from the coal and clay minerals. In the study discussed here, ten different bituminous coal refuse samples were successfully upgraded in pyrite content. These samples represented a wide variety of coal waste materials from Pennsylvania and other states. The variabilities of the sulfur and coal contents are shown in Table I. The extremes are Sample J, a high sulfur-low coal, and Sample B, a low sulfur-high coal. Definitions of some of the symbols or terms used in this report are given below: Mesh size—Tyler standard mesh screen sieves with an opening based on the square root of two. Fe —Indicates iron, as determined by a stannous reduction-dichromatic oxidation method. S—Indicates sulfur, as determined by the ASTM "Eschka" method for sulfur in coal.

Jan 1, 1969

By R. G. Aspden

Crystals with an (001) [loo] initial orientation of an iron-base alloy containing 3 pct Si were cold rolled with and without the use of constraints. A major difference in the rolling and annealing textures was observed between crystals rolled with and without constraints. These data show that the contribution of constraints at grain boundaries in a poly crystalline sheet should be considered in applying textural data on single crystals to grains in an aggregate. SILICON-iron alloys with a cube texture have been recently developed and their magnetic characteristics reported.1-4 Of interest in the development of this texture were the textural changes of single crystals accompanying rolling and annealing and the influence of constraints at grain boundaries in an aggregate on the behavior of individual grains. The present study was primarily concerned with the effect of constraints during rolling on the textures of 3 pct Si-Fe crystals initially (001)[100]. Barrett and Levenson5 were among the first to observe an influence of constraints at grain boundaries on the textural changes of individual grains during deformation. They tested Taylor's6 theory of plastic deformation of face-centered-cubic metals in which deformation textures were predicted. About one-third of the grains in poly crystalline aluminum did not rotate as predicted. Grains of the same initial orientation were observed to rotate in different directions under the influence of applied stress and anisotropic flow of neighboring grains. Recently, the various inhomogeneities of flow of crystals in an aggregate have been studied7'8 and reviewed.9-11 Barrett and Levenson" rolled (001) [loo] iron single crystals inserted in close-fitting holes in copper to limit lateral flow and to simulate rolling of grains in an aggregate. Deformation bands were formed after a 90 pct reduction in thickness, and the cold-rolling texture contained two components described by rotating the (001)[100] about 35 deg in both directions around the normal of the rolling plane. No annealing textures were reported. Chen and Maddin13 rolled molybdenum single crystals initially (001) [loo]. The crystals were mounted between two hardened silicon-iron plates and 96 pct reduced in thickness by rolling at a low rate of reduction, about 0.0001 in. per pass. The deformation texture had the mean orientation of (001) [loo], and the azimuthal spread included orientations described by rotating (001) [loo] about 35 deg in both directions about the pole of the rolling plane. The presence of deformation bands were not reported by Chen and Maddin or detected in subsequent work of Ujiiye and Maddin.14 The ideal orientation of the annealing texture was (001) [loo]. Recently, Walter and Hibbard 15 reported on the textures of 3 pct Si-Fe alloy crystals initially near (001) [loo]. Each crystal was in an aggregate cut from a columnar ingot. After 66 pct reduction by rolling, the texture consisted of two symmetrical components which had the orientations described by rotating (001) [loo] about 30 deg in both directions about the pole of the rolling plane. Annealing texture was near (001) [loo]. In the above work, the textures of body-centered-cubic crystals were studied after rolling under the influence of constraints. The deformation textures varied from (001) [loo] to near the (001) [110] type and appeared sensitive to the manner in which the crystals were rolled. No textural data were available on the effect of rolling (001) [loo] crystals with and without constraints. The purpose of the present work was to evaluate the influence of constraints during rolling on the textures of 3 pct Si-Fe crystals initially (001) [loo]. Rolling and annealing textures were studied for a) crystals rolled with no constraints at different rates of reduction, and b) crystals rolled with constraints imposed by neighboring grains and by plates between which a crystal was "sandwiched". PROCEDURES AND EXPERIMENTAL TECHNIQUES Data are presented on four crystals which are representative of several crystals studied. The orientation of each crystal prior to rolling was (001) [loo] as determined by the Laue X-ray back-reflection method," i.e., each crystal had an (001) within 3 deg of the rolling plane and [100] within 3 deg of the rolling direction. These crystals were obtained from two iron-base alloys containing 3 pct Si by weight which were prepared by vacuum melting electrolytic iron and a commercial grade of silicon. Crystals 1, 2, and S-1 were cut from a large single crystal grown from the melt of one alloy by the Bridgman technique17 in an apparatus described by

Jan 1, 1960

By F. J. Schuh

The drilling industry long has been plagued by failures in the bottom few joints of surface and intermediate casing strings. This paper presents an analysis of the various possible causes of failure and concludes that failures are caused by short-lived, high-energy torque impulses delivered from the drill string through the bit while drilling out the cementing plugs, cement and floating equipment. The magnitude of these torque impulses is shown to be a function of the rotational momentum of the drill string, and a method is derived to calculate the magnitude of these impulses. The available methods of strengthening the bottom joints are reviewed. It is concluded that, while present methods are ineffective, a combination of improved procedures for strengthening and minor restrictions on drillout practices will prevent failures. Introduction In most cases, failure in the bottom few joints of casing strings is not discovered until electric logs record that the bottom one, two or three joints have parted from the casing string and slipped down the hole. However, in some cases the parted section of casing uncovers a high-pressure or lost circulation zone, or shifts laterally restricting the passage of drilling equipment. In these instances extensive remedial work is required to realign the parted pieces and seal the exposed formations. Several methods used to strengthen the bottom joints of casing strings include locking set screws in the couplings, putting wedges in special collars, welding straps across the couplings, welding the couplings and, most recently, using epoxy resin-based, thread-locking compounds. Since none of these techniques has eliminated the problem, this study was initiated to find the cause of failures and to evaluate the available methods of prevention. Mechanics of Casing Failures An analysis of the various possible causes of failure indicates that the casing is unscrewed rather than broken and that therefore failure must occur before the shoe is drilled. Since there is no general agreement as to the causes of casing failure, some possible mechanisms were ATLANTIC RICHFIELD CO. DALLAS, TEX. considered in this analysis. Failure of the bottom joints of casing can occur by only one of three types of stress: tension, torsion or bending. The possible mechanisms of failure were evaluated by determining the forces required to cause casing failure by each of the stresses; and, where applicable, the possibility of failure by fatigue was considered. For casing to part under tension requires a downward load of more than the tensile strength of the casing. The lightest API weight H-40 grade casing requires a bit load on the bottom of the casing of 27,000 to 34,000 Ib per inch of bit diameter (Table 1). Since maximum drill collar weights seldom exceed 10,000 Ib per inch of bit diameter, it is apparent that casing strings cannot be parted by the downward load of the drill string. The second mechanism considered was failure by bending. This mechanism requires that the lowermost casing joints be free to be deflected laterally until the bending stress exceeds the strength of the pipe. To fail, the casing (at a height L above the shoe) requires a force and deflection' at the shoe of To deflect the casing shoe with the drill string obviously requires a dog-leg at the casing shoe. This dog-leg must have a rate of change equal to or greater than the change in curvature of the deflected casing, which is given by

Jan 1, 1969

By A. T. Chatas

A description of the geometrical characteristics of spherical reservoir systems, a discussion of unsteady-state flow of such systems and examples of engineering applications are presented as backgmund material. The fundamental differential equation, a description of average spherical permeability and the introduction of the Laplace transformation serve as theoretical foundations. Engineering concepts are investigated to indicate particular solutions of interest, which are analytically obtained with the aid of the Laplace transform. These are numerically evaluated by computer, and presented in tabular form. INTRODUCTION A tractable mathematical analysis of unsteady fluid flow through porous media generally requires incorporation of a geometrical symmetry. The simplest forms include the linear, cylindrical (radial) and spherical. Most analytical endeavors have concentrated on cylindrical symmetry because it occurs more often in petroleum reservoirs. Nevertheless, some reservoir systems do exist that are better approximated by spherical geometry. Review of technical literature revealed but a single reference to unsteady spherical flow in petroleum reservoirs.l The motive and purpose of the present work was to remove this gap in technical information, and to provide the practicing engineer with some useful analytical tools. The mathematical details associated with the particular solutions of interest involved use of the Laplace transformation. Hurst and van Everdingen previously demonstrated the efficacy of this operational technique, and in many respects the present treatment was patterned after their earlier work.2 PRELIMINARY CONSIDERATIONS GEOMETRICAL CHARACTERISTICS Geometrically, a spherical reservoir system is defined at any instant of time by two concentric hemispheres whose physical properties of interest vary only with the radial distance. Every physical property is thus restricted to be a space function of only one variable: the distance along a radius vector emanating from the center. Such a system is composed of an outer region and an inner region, separated by a defined internal boundary. The inner region simply extends inward from this boundary, whereas the outer region extends outward from it to an external boundary. The position of the internal boundary is presumed fixed, so that the size of the inner region remains constant. On the other hand, the position of the external boundary at any given instant of time is determined by the distance into the system that a sensible pressure reaction has occurred, Thus, the external boundary may change position with time. It initially emerges from the inner region and advances outward to its ultimate position. When this ultimate position coincides with a geometric limit, the reservoir system is said to be limited. When it coincides with points subject to pressure gradients furthest removed from the internal boundary, yet short of a geometric limit, the system is said to be unlimited. In this investigation two different boundary conditions are imposed at the ultimate boundaries of limited systems. The first requires that no fluid flow occur across this boundary; the second that the pressure remain fixed at this boundary.3-5 UNSTEADY-STATE FLOW In a strict sense virtually all flow phenomena associated with a reservoir system are unsteady-state. The transient behavior of these phenomena requires accounting, however, only when time must be introduced as an explicit variable. Otherwise, steady-state mechanics may be used. Analytically, steady-state conditions prevail in a reservoir system only over that portion of its history when this relation is satisfied:

Jan 1, 1967

By G. E. Pellissier, P. H. Salmon Cox, B. G. Reisdorf

Banding that occurred in plates rolled from the early production heats of 18Ni(250) maraging steel is described and related to the segvegation of certain alloying elements (nickel, molybdenum, titanium), the extent of which was quantitatively evaluated by means of electron-microprobe analysis. The effect of banding on mechanical properties is discussed, with particular reference to observed directional differences in plane-strain fracture toughness of plates. It is shown that banding originates as interdendritic segvegation during ingot solidification and persists in some degree through normal soaking and hot reduction to plate. The results of the study showed that heating sections of small laboratory-cast ingots at 2200°F for 4 hr was sufficient to markedly reduce microsegregation and to considerably improve mechanical properties. Hot rolling of 7-in.-thick ingot sections to 1/2-in.-thick plate effected a similar reduction of microsegregation, but resulted in even greater increases in ductility and toughness than that obtained by homogenization treatment alone. DURING the past few years, considerable attention has been directed towards the low-carbon, high-alloy maraging steels and in particular towards the 18Ni-8Co-5Mo-0.4Ti alloy. The steels of this group, having an excellent combination of high strength and toughness, have a number of advantages over their more conventional medium-carbon low-alloy, quenched-and-tempered counterparts. In the annealed condition, the maraging steels are in the form of a ductile marten-site; aging at a relatively low temperature, typically 900°F for 3 hr, increases greatly the strength through the precipitation of intermetallic compounds. One problem in the early production heats of maraging steel was that the finished plate frequently displayed a banded structure. Previous work on other steels1-' had established that banding in wrought products is either a direct or an indirect consequence of chemical segregation, which occurs during solidification and persists to some extent through normal thermal and mechanical treatments. For example, Smith and others: in a study of low-alloy steel, were able to correlate the severity of banding in the wrought product with the degree of interdendritic segregation of nickel and chromium in the as-cast ingot. The effect of banding on the mechanical properties of steels is usually considered to be detrimental, although there is only limited evidence to suggest that a marked improvement in properties can be obtained with less heterogeneous structures. Comparison of the longitudinal and transverse tensile properties of banded and of homogenized 4340 steel showed that only the transverse ductility was improved by homogenization, but even then the improvement was not commercially significant.' Conversely, homogenization of through-the-thickness tension specimens of quenched-and-tempered steel plate, containing 1.47 pct Mn, increased the strength by as much as 10 pct and the tensile ductility by at least a factor of twos5 This improvement was related to the elimination of manganese-rich bands, which also are one of the factors responsible for cold cracking in the heat-affected zone of metal-arc welds.7 In the present study the nature and severity of banding in early commercial 18Ni(250) maraging steel plate and in laboratory-melted 18Ni(250) maraging steel plate was determined. The effects of banding on plane-strain fracture toughness and the effects of thermal homogenization treatments on the strength, tensile ductility, and toughness of 18Ni(250) maraging-steel as-cast ingots and rolled plate were evaluated. In addition, the effects of hot deformation by rolling on the mechanical properties of ingots were determined. 1) STUDIES OF BANDING IN EARLY PRODUCTION PLATE The chemical composition of the steel (A) used in this part of the investigation is shown in Table I. Banding was not clearly evident in either as-rolled or annealed* plate, but annealed and agedc** plate had a banded structure. The typical banded condition, Fig. 1, consists of layers of unetched austenite (white) and dark-etching martensite in a light-etching martensitic matrix. X-ray diffraction measurements showed that this steel contained more than 6 pct austenite. An electron-probe X-ray microanalyzer (using a focused beam of electrons) was used to determine the composition of the bands and of the material between the bands with respect to the main alloying elements— nickel, molybdenum, titanium, and cobalt. The recorded X-ray intensities were converted to concentration values with the use of a standard of similar composition. To facilitate probe positioning, all analyses were conducted on specimens that had been given a light etch. The influence of this etching on the analytical results was negligible; analyses made on the identical area before and after etching yielded essentially the same concentration values. The results of the electron-microprobe analyses at selected points revealed that the layers of austenite and adjacent dark-etching martensite contained greater amounts of nickel, molybdenum, and titanium than did the surrounding matrix, Table 11. The austenite layers

Jan 1, 1968

By Ben-Zion Weiss, Melvin R. Meyerson

Chromium diffusion coatings on commercial Armco iron lead to carbide precipitation at the grain boundaries in and below the coatings. High compressive stresses are introduced into the coating and, as a result, tensile stresses are introduced into the base material below the coating. In coated samples, fatigue cracks form at the grain boundaries below the coating after only a limited portion of the total lifetime (5 to 10 pct). Residual tensile stresses and a stress concentration caused by precipitated carbides seems to be responsible for early crack nucleation. Stage I of Propagation may be divided into two substages: I-a in which the crack Propagates along grain boundaries, and I-b in which the crack propagates along slip boundaries according to a shear mode. In uncoated samples, the cracks form at slip bands after 40 to 50 pct of the total lifetime. In coated samples the Propagation process takes longer than in uncoated samples because of the moderate rate of crack extension until the crack breaks through the coating. The chromium-diffusion coating causes little if any increase in fatigue life. CHROMIUM diffusion is one of the most popular processes used to apply coatings to iron alloys. This popularity stems from the fact that the diffusion treatment is comparatively easy to carry out, and it improves certain surface properties such as corrosion and wear resistance as well as some other properties. Very little effort has been devoted to the investigation of the effect of chromium-diffusion coatings on mechanical properties and particularly on fatigue properties. Since the chromium coating usually represents a small fraction of the total volume of the base material it is generally assumed that the macro properties are dependent principally on the base material rather than the coating. Insofar as fatigue is concerned, there are indications that the fatigue life of the chromium coating is not less than that of the basic material and the fatigue properties are generally not reduced by it.' But chromium diffusion causes drastic structural and chemical changes in the region of the material surface2-4 which introduce additional residual stresses. Such changes must affect fatigue crack nucleation and may sometimes affect the initial stages of propagation. Furthermore, it is conceivable that the secondary stages of the crack propagation could be influenced by some irreversible structural changes in the core of the material, which stem from the long-time heat treatment at high temperatures required to apply the coating. This paper analyses the structural and compositional changes produced in commercial Armco iron by a chromium-diffusion coating and the effect of the coating on fatigue crack initiation and propagation. EXPERIMENTAL PROCEDURES The investigations were carried out with commercial Armco iron. The chemical composition of the iron, the number of specimens tested, the grain size produced during chromizing and heat treating, and the thickness and microhardness of the chromized layers are shown in Table I. Samples were chromized by a gas diffusion process. The temperature and time of the diffusion coating process were chosen according to a previous grain growth study. It had been found that at a temperature of 970°C and a holding time of between 3 and 9 hr there are practically no changes in grain size. To describe the grain size more accurately the ASTM method5 was supplemented by a statistical analysis of the mean volume diameter as outlined by Fullman6 and The The mean volume diameter was deter- mined from D = p/2m where D is the mean volume diameter, and m is the mean reciprocal value of grain diameters as seen on the micrograph. The shape and the size of the asymmetrical sample, see Fig. 1, were chosen so as to facilitate the study of fatigue crack initiation. Before coating, the samples were machined and the surface of the groove was polished. After chromizing, the two side surfaces were machined and polished so as to retain the coating only on the top surface of the groove. Residual stress in the chromized layer was measured on the top of the grooved section of the specimen after the diffusion process. The inclined incident X-ray beam procedure was used.9'10 The computations were performed with the initial assumption of a zero surface normal stress component. An electron microprobe analyzer was used to obtain the relative amounts of chromium and iron con-

Jan 1, 1970

By C. W. Nicolson

The Tri-State zinc and lead-mining district is in the northeast corner of Oklahoma, the southeast corner of Kansas and the southwest corner of Missouri. The area throughout which active mining has been conducted is about 45 miles long and about 5 miles wide, extending northeasterly from Commerce, Okla., to Alba, Missouri. Although the lead ores were mined on a very small scale in the vicinity of Joplin, Mo., as early as 1848, nothing of any importance was done in the district until 1870, since when both mining and smelting have been prosecuted with considerable vigor. In the beginning the lead ores only were exploited, but within a few years extensive deposits of zinc ores were found and since that time the production of zinc ore has far exceeded that of lead. Both the surface and mineral rights in Missouri and Kansas were under individual ownership by the time ore was discovered. Although some of these rights were purchased by mining companies, most of the mining has been done under leases covering small areas, usually 40 acres, although in the past many leases were given on much smaller tracts. In Oklahoma most of the mineral land had been alloted by the Government to various Indian tribes and although the title to some of these lands had been acquired by various white men before the discovery of the rich Picher field, the title to most of the land has remained with the Indian tribes and the leasing of the mineral rights has been done by the Federal Government for the benefit of the Indians. The Indian allotments were of 200 acres each and some of the mining leases covered entire allotments, although many leases were granted for only 40 acres or even less. Practically all of the leases granted in the past required the erection of a concentrating plant on each lease, a condition that has had a pronounced effect upon the mining and milling methods of the district, since the apparent ore reserves on each tract were too small to justify large and elaborate mining and milling plants. Most of the leases were

Jan 1, 1940

By Nicholas J. Grant, Michio Yamazaki

Cast copper alloys containing 10, 20, and 30 pct Ni and 0.75 to 0.80 pct Al were machine-milled into chips, then comminuted in a rod mill to fine flake powder utilizing a number of processing variables. The powders here internally oxidized, mostly at 800°C, in a low-pressure oxygen atmosphere. The consolidated powders were hot-extruded into bar stock. Room-tenmperature tension tests, stress-rupture tests mostly at 650°C, but also at 450° and 850°C, and hardness measurements after various annealing temperature treatments to study alloy stability were perfomted. Excellent room-temperature strength, high rupture strength at 650°C, and resistance to recrystallization at 1050°C were obtained. Problems in optimizing conditions for internal oxidation of Cu-Ni base alloys are discussed. THE interesting high-temperature properties of SAP' have stimulated considerable effort in the study of more refractory alloy systems where the potential for high-strength alloys at high temperature is great.2-13 A number of methods have been utilized to produce the desired fine, hard particle dispersions, of which internal oxidation2,9,7 of dilute solid-solution systems offers considerable promise by virtue of the potential for producing ultrafine, well-dispersed oxides. While most of the published works are concerned with pure metal matrices, a number of investigators have studied the effects of solid-solution strengthening.10,19 Use of more complex alloy matrices (for example, aging systems) has been unsuccessful because overaging still occurs at high temperatures in the oxide-containing alloys.14.15 Solid-solution strengthening is, however, effective at very high temperatures9,10 and might be expected to contribute importantly to the strength of oxide-dispersion strengthened alloys. For this study, internal oxidation of solid-solution alloys of copper and nickel, containing small amounts of aluminum, was chosen as the method of alloy preparation. PREPARATION OF ALLOYS Three copper alloys containing about 10, 20, and 30 pct Ni and each containing 0.75 to 0.80 pct A1 (enough to yield about 3.5 vol pct alumina) were prepared as air-cast ingots measuring 2.5 in. diameter by 6 in. high (see Table I for the analyses). Processing steps for all the alloys were as follows (also see Table 11): 1) Homogenization of the ingot at 982°C (1800°F) for 45 hr in an argon atmosphere. 2) Machine milling of ingots into fine chips. Average thickness was about 0.1 to 0.2 mm. 3) Hydrogen reduction of chips at 593°C (1100° F) for 1 hr to reduce copper and nickel oxides. 4) Rod milling of chips to finer powders. 5) Hydrogen treatment of powders as in step 3. 6) Internal oxidation of the powders. 7) Hydrogen treatment of oxidized powders as in step 3. 8) Hydrostatic compression of evacuated powders. 9) Sintering of compacts in hydrogen. 10) Hot extrusion. Variations in processing among the alloys were made in steps 4, 5, and 10 (see Table 11). In the past, two methods were utilized to internally oxidize alloy powders. Preston and Grant3 surface-oxidized dilute Cu-Al powders to obtain the necessary amount of oxygen to oxidize the solute metal (aluminum and silicon), and then permitted the formed copper oxide to diffuse and react with the solute in an argon atmosphere. Bonis and Grant4 exposed Ni-A1 and other nickel alloys to an oxygen pressure derived from the decomposition of nickel oxide at a preselected temperature, in an argon atmosphere. Both methods are applicable and can be modified to generate a range of oxygen pressures for oxidation of the solute but not the solvent metals. Procedure I: Surface Oxidation of Alloy A3, Cu-10Ni-0.76A1. Powders of -20 to +28 mesh were surface-oxidized at 500°C (932°F) to obtain the desired amount of oxygen for oxidation of the aluminum to alumina; the powder was then sealed in Vycor and heated at 900°C (1652°F) for various times up to

Jan 1, 1965

By A. N. Chirico

This paper reviews the three major distillation processes: multiple effect (LTV) evaporation, multi-stage flash distillation and vapor-compression forced circulation evaporation. Scale preventative measures are discussed for all saline water applications. Operational data is presented on the Freeport, Texas, demonstration plant, which is the first government facility to produce one million gallons per day of fresh water for a municipality. There has been much publicity concerning the water crisis that confronts many peoples today. There is little doubt that the arid regions - which include the Middle East, parts of Africa and the Caribbean — have suffered to no slight extent for the lack of this most precious commodity. But what about our own country? Government experts have extrapolated demands and flatly predict that by 1980 we will be faced with a shortage of 80 billion gal per day. The validity of this prediction has been disputed by others; however, it appears certain that there will always be a natural abundance in some areas, a shortage of supply in other areas. Distributing our total natural water resource equitably would be impossible. Transmission of water by means of aqueducts can be an expensive undertaking. The controversial Feather River Project in Calif. is an example. The estimated cost for this venture is a staggering three billion dollars. As our population continues to increase and our standard of living rises, agricultural and industrial requirements will be proportionate. What can be done to avoid a crisis? We can conserve and use our water for industrial and irrigation purposes more judiciously: we can attempt to eliminate pollution of our natural resources from sewage and industrial wastes; we can develop, while there is time, saline water conversion processes for the massive production of low cost fresh water. The scope of this paper will be limited to only the distillation type processes that are commercially feasible. The first step in making potable water is to find a source of raw material. An inexhaustible supply is provided by oceans in coastal regions, but the supply of water is more critical in the inland communities of our country. The source of raw material in these. regions is brackish well water and this must be utilized. There is a significant process difference when handling brackish water compared to seawater and this brings out an important fact: No single conversion method can be universally applied to solve all the water problems. Composition of the raw water and degree of distillate purity are factors which must be considered before a particular process is selected. Local conditions at the plant site, fuel costs, labor costs, disposal facilities, etc. are other equally important factors which must be evaluated. WATER CONVERSION PROCESSES Conversion processes commercially feasible today are: 1) multiple effect evaporation, 2) multiple flash distillation, 3) vapor compression distillation and 4) electrodialysis. The first three are distillation processes which take potable water out of the raw water, while the fourth is a membrane process which takes out the salt. In addition to the above there are a good number of other promising methods for production of potable water, many of them in the basic research stage. Freezing is another promising process with commercial potential. This process hinges upon the formation of ice crystals which are free of salt occulsions. Separation and washing of the crystals are problems that must be solved before this process can be considered commercially feasible. Freezing processes have several advantages mostly attributable to the low temperature of operation. This low temperature reduces the scaling and corrosion problems encountered in higher temperature operations. Several different freezing processes are being considered and will be tested in the pilot plant at Wrightsville Beach. One process is a flash freeze process, a second uses a secondary refrigerant such as butane for freezing, and a third process employs a secondary refrigerant particularly controlled to produce large ice crystals. Of the above processes, only the distillation processes are reliable when water of high purity is re-

Jan 1, 1963

By C. S. Matthews, M. J. F. Rosenbaum

The purpose of thir work wax to lcarn it~lzut infori~lation could he obtained from various typs of pilot water floods and to attempt to find the optunum pilot patter11, for a revervoir which had previously been depleted by a solution gas drive. The study was made in the laboratory with mathemetical methods a dynamic analog and a potentiotnetric analog. Results werp tested against the field llistorics of a nrrnlber of pilot water floods. At a reasonable valrre of currzulative injection, the total production rate for the one-injector five-spot should reach about 6.5 per cent of injection rate, and for a four-injector five-spot, about 9 per cent. Accurate estimates of ultimate recovery cannot be made on the basis of such snzall prorluction rates. However, with a pilot composed of nine ir1jector.s and 16 producers the production rate is approximately 50 pcr cent of injection rate at a reasonable value of camulative injection. Sonle inforn~ation for extended performance predictions might he obtained from such a large pilot. These conclusions were drawn on the basis of results obtained for unit mobility ratio, and a sturly using tlre potentiometric analog was made of the effect of other mobility ratios to determine the range of applicability of these predictions. For the four-injector, five-spot pilot with the ratio of production to injection rate (before water breakthrough) is about twice that for with it is about two-thirds; and with M0= 10, it is about one-third For high mobility ratios, it was found that the production rate increased considerably as water-cut increased. These result can be used to modify, qualitatively, the inter.pretntions based on curves for the unit rnobilit\. ratio CaSeS. It was found that the maximum ratio of production rate to injection rate obseriled in field pilot floods was of rhe scime order as that prerdicted by these methods. The time required to reach thisr maximum did not generally agree with the time predicted for a homogeti~orir reservoir. The differcrlce between predicted and observed time of response gives an indication of the permeability profile and of the condition of the producin,g wells. Pilot water floods of the pattern type are generally carried out in reservoirs which have been depleted by solution gas drive and are at low pressure. Under these conditions, oil and water can be considered incompressible. It is assumed that, as the water is injected, an oil bank forms ahead of it and that there is a distinct interface between the water zone (or bank) and the oil zone (or bank) and between the oil zone and the region ahead of the oil zone. It is further assumed that only gas is mobile in the unflooded (gas) region, only oil is mobile in the oil bank and only water is mobile in the water bank. The saturations and the mobilities associated with each zone are assumed uniform. We idealize our reservoir to be homogeneous, horizontal and of constant thickness. Effects of gravity within the producing layer are assumed negligible. If the actual time-dcpendent flow problem is approximated by a acries of steady-state problems. the potential and stream function in the oil bank and water hank satisfy Laplace&apos;s equation in two dimensions. We can therefore use a poteiitiometric analog of this system. Potentiometric models have yielded uscful results in this laboratory&apos; and clsewhere in the study of a variety of secondary recovery problems. For the case where M = I, we generally prefer to use theoretical mcthods as well as a simpler dynamic analog. Except where otherwise noted, the ratio, side of five-spot/wellbore radius. is taken to be 3,600. a figure which corrcsponds to a normal-size wellbore in a 10-acre well spacing. THEORETICAL EVALUATION OF VARIOUS PILOT PATTERNS, Mw0 = 1 <&apos;he theoretical models which we used to examine the performance of various pilots are shown in Fig. 1. Image theory was used to determine the ratio of production rate to injection rate as a function of the volumc of the flood. The ratio of production rate to injection rate was chosen because this is an easily measurable quantity which is characteristic of a pilot

By L. C. Michels, O. G. Ricketts

The disorientations between s?nall grains, whose growth has been arrested at an early stage of recrys-tallization, and the deformed matrix in cold-rolled aluminum single crystals were determined using transmission Kikuchi line and electron diffraction patterns. The orientations of the recrystallized grains were found to be random, and the disorientations of these grains with the matrix weve found to be intermediate to large. This leads to the conclusion that the observed vecrystallization began in small areas of large disorientation present in the cold-worked structure. heavily cold-worked thin sections of aluminunz single crystals and of polycrystalline aluminum and nickel were produced directly by a mechanical technique. The specinlens thus prepared were heated with the electron beam to bring about vecrystallization during observation in the electron microscope. Motion pictures taken du.ring heating and the electvon, microg.raphs taken both before and aftev heating allowed the recrystallization process to be traced to its ovigin. Re cvystallized grains originated in very s,mall regions of the cold-worked structure and developed through rapid migration of high-angle boundaries. The boundaries either were present as such in the matrix or were formed out of dense dislocation networks. SIGNIFICANT advances have been made in recent years in the study of nucleation of recrystallization using the technique of transmission electron microscopy of thin metal foils. Bollman1 in a study of heavily rolled polycrystalline nickel found support for the Cahn-Cottrell2,3 theory of nucleation. According to this theory nuclei form by the initially slow growth of subgrains formed through polygonization. During this initial period of slow growth (the incubation period) the migrating boundary of the subgrain increases its disorientation with the cold-worked matrix and thereby increases its mobility to become a rapidly migrating high-angle boundary. Bailey4,5 investigated the annealing behavior of several metals deformed both in tension and by rolling and concluded that recrystallization took place through the migration of high-angle boundaries. With low deformations these boundaries were present in the metal before deformation. With high deformation it was not possible to tell whether the boundaries were pieces of the original grain boundaries or were produced either during deformation or by polygonization during ameal- ing. Direct observation during heating of metal foils indicated that subgrains form by polygonization and grow at an uneven rate. The grain size obtained decreased with decreasing foil thickness indicating that the foil surface resists boundary motion. Votava,6 in heating stage experiments on rolled copper, observed nuclei to appear suddenly and grow in jumps of differing magnitude. However, he found no special dislocation configurations where the nuclei appeared. Fujita,7 as a result of a study of subgrain growth in heavily worked aluminum, concluded that the boundary of a recrystallized grain initially forms from the boundary of a group of subgrains. This occurred by a process of deposition of vacancies and dislocations in the group boundary as the boundaries within the group disappear. HU8,9 directly observed a similar process in heating stage experiments on 70 pct rolled Si-Fe single crystals. The growth of subgrains appeared to proceed by a coalescence mechanism. The observed fading away of the boundary between two subgrains was explained by the moving out of dislocations from the disappearing boundary into the connecting or intersecting boundaries around the subgrains. The subgrain size and degree of disorientation with the surrounding structure were thus increased. With the increase in disorientation occurred a corresponding increase in boundary mobility, which eventually allowed the boundary to migrate rapidly. This process was observed to occur within "microbands" consisting of parallel narrow segments disoriented by a few degrees present in the as-rolled structure. The conclusion of Rzepski and Montuelle10 that growth is preceded by the coalescence of blocks through disappearance of their common boundaries supports this view. In contrast to Hu&apos;s coalescence model for nucleation were the conclusions of Walter and ~och.""~ Working with the same material as Hu, of the same orientation and rolled to the same reduction, they concluded that nucleation occurred by the Cahn-Cottrell mechanism. They observed, in agreement with Hu, that recrystallization began in the "microband" regions which they referred to as "transition" bands. Bartuska13 studied subgrain growth in heavily rolled nickel using a beam heating method in the electron microscope. He concluded that nuclei for recrystallization form from the largest most perfect subgrains present in the cold-worked structure by rapid intermittent migration of parts of subboundaries. In rare instances he observed subgrain growth by coalescence. EXPERIMENTAL PROCEDURE The materials used in this study were 99.999 pct A1 supplied by A.I.A.G. Metals, Inc., and 99.999 pct Ni supplied by Johnson and Matthey and Co., Ltd. The Hitachi HU-11 electron microscope, with uniaxial

Jan 1, 1968

By J. E. Flinn, S. A. Duran

The steady-state creep behavior of poly crystalline cad mi inn was studied over a temperature range of (1.56 to 0.94 Tm. Two distinct mechanisms were found to occur over this temperature range. They were described by: where and represerqt the minimum strain rates corresponding to the low- and high-temperature regions, respectirely. The two regions of constant acti11ation energy were connected by a transition region where the strain rate was controlled by both mechanisms acting in parallel. At temperatures below a transition temperature of about 0.7 Tm the agreement between the activation energy value for creep and that for self-diffiision suggests a rate-controlling mechanism of dislocation climb. For cadwzium, steady-state creep at temperatures above 0. 7 Tm appears to be controlled by another mechanism, perhaps involving the behavior of dislocation jogs. FRENKEL et al.1 studied the high-temperature creep of polycrystalline cadmium and reported an activation energy of 21 kcal per mole for the 0.5 Tm < T < 0.8 Tm range. Based on observations of creep rate at only two temperatures, a value of 22.1 kcal per mole was determined by Medbury. These two investigations were for the purpose of showing agreement between the activation energy for creep and that for self-diffusion, reported3 as 18.2 and 19.1 kcal per mole, respectively, for diffusion parallel and perpendicular to the hexagonal axis. Gilman4 investigated prismatic glide in single crystals of cadmium over a higher-temperature range of 0.72 to 0.93 Tm, and found an activation energy of 29 kcal per mole. He also reported5 an activation energy higher than that of self-diffusion for prismatic glide in zinc single crystals deformed at temperatures near the melting point. This value was in good agreement with those found for an equivalent temperature range by Flinn and Munson6 and by Tegart and sherby7 for polycrystalline zinc. These two independent studies also disclosed at lower temperatures another value of activation energy near that for self-diffusion. It would be expected from the creep results on zinc and single-crystal cadmium that creep studies on polycrystalline cadmium, extended to temperatures near the melting point, might yield an activation-energy value higher than the 22 kcal per mole value found in earlier studies. The purpose of this paper is to report the steady-creep behavior of polycrystalline cadmium over a temperature range of approximately 0.5 to 0.9 Tm EXPERIMENTAL METHOD The cadmium used in this study was obtained in the form of as-cast rods, 0.5 in. diam, through the courtesy of the Bunker Hill Mining Co. The material was of 99.995 pct purity, as determined by spectro-chemical analysis. The creep specimens, which were 0.250 in. diam by 0.400 in. long and annealed at 300°C for 45 min to produce a stable average grain diameter 0.25 mm, were tested in compression using an apparatus similar to that described by Sherby.8 The specimen temperature was controlled to within ±0.5°C with the help of appropriate constant-temperature baths. The applied stress was maintained within 1.0 pct of the desired value by the additions of lead shot at fixed strain increments. No barreling was observed over the strains encountered during testing. Isothermal creep tests9 were used in the study with only a few differential temperature tests10 run for comparison purposes. Steady-state creep data were obtained over a temperature range of 60 to 287°C (0.56 to 0.94 Tm) at five stress levels ranging from 28.1 to 140.6 kg per sq cm. RESULTS The minimum or steady-state creep rate may be described by an equation of the following form:" where i is the minimum strain rate, S is the structure factor, F is a stress function, Qc is the energy of activation, T is the absolute temperature, and R is the gas constant. The minimum strain rates obtained in this study for cadmium were recorded on a semilogarithm plot as a function of the reciprocal absolute temperatures for the various stress levels, as shown in Fig. 1. This figure shows a characteristic transitional behavior" with a parallel interaction of two mechanisms. It is obvious that the activation energies corresponding to the individual processes are insensitive to stress because the curves are parallel. The discrete activation-energies values for the low- and high-temperature regions for the various stress levels are reported in Table I, and were determined by the least-mean-square method. For the low-temperature region, an activation energy of 20.7 ± 0.6 kcal per mole was obtained, and for the

Jan 1, 1967

By R. J. Burgess, A. R. Ramey, A. R. Adams

During interpretation of pressure buildup tests on gas wells in a tight dolomite gas reservoir, peculiar behavior was noticed. Two straight lines were apparent. Effective permeability to gas taken from either straight line was about the same, and the Miller-Dyes-Hutchinson dimensionless time check for the straight line was proper for both straight lines. Geological data indicated the likelihood of scattered trending fractures in the reservoirs. Since the first straight Iine yielded permeability values close to the geometric mean permeability from core analyses, it was postulated that the reservoir model was that of an acidized well completed in the tight dolomite, but that widely scattered hairline fractures caused the mean permeability of the reservoir distant from the well to be higher than the matrix permeability. Because all other studies of fractured reservoirs to the authors&apos; knowledge assumed that the fracture matrix was dense enough to communicate directly with the well, no interpretative methods were available. The Hurst line-source solution for a radial change in permeability for interference between oil reservoirs was adapted to pressure buildup testing. The result indicated that the first straight line should yield the proper matrix permeability and wellbore skin effect. The second straight line may be extrapolated to obtain static pressure. The time of bend between the straight lines was used to estimate distance to a fracture. Application to field test data is shown. It is believed that the methods developed and the case history presented will add to present tools available for pressure buildup interpretation. Introduction Since the pioneer studies by Miller, Dyes, and Hutchin-son1 and Horner&apos; in 1950 and 1951, well test analysis has become recognized as one of the most powerful tools available to both production and reservoir engineers. Well test analysis serves as a logical basis for well stimulation and completion analysis, and for long-term reservoir engineering. Since the early 19501s, much effort has been placed on the development of well-test analytical methods. Reservoir and well conditions of increasing complexity have been considered systematically to provide the analyst with a catalog of causes and effects. Matthews and Russella state that some 200 papers dealing with this subject have been published in the last 35 years. Developments in well test analysis appear to have originated in one of two ways. Either a physically realistic field condition was anticipated and analytical solutions for the condition achieved, or anomalous field test behavior was recognized and interpretative methods sought for the anomaly. In recent years, it has appeared that the latter has inspired an increasing number of studies. The analyst today finds an increasing number of known cause and effect studies available for well test analysis, the classic of which is that of finding the specific flow problem that generated the answer — the well behavior. Although it may be impossible to achieve this goal uniquely, the analyst often is able to select a useful interpretation that combines all known performance and geologic data — or to show that various logical alternatives would not significantly affect the interpretation. During a recent reservoir study, we observed gas well test behavior that did not appear to fit behavior described previously. Although it cannot be said that we have found a unique interpretation, we shall present in this paper the peculiar behavior observed, and describe the reservoir and interpretative methods developed. Reservoir Description The subject gas reservoir is a 9-mile-long, narrow dolomite reservoir lying within a limestone of Ordovician age. (See Fig. 1.) The dolomitized rock in the field consists of dark brown to buff, dense to coarsely crystalline, vugular dolomite containing numerous hairline fractures, many of which may have been closed in the reservoir and parted when cores were brought to the surface. Larger fractures are also apparent in core, but usually are filled and sealed with euhedral dolomite crystals. Portions of the north flank of the reservoir are known to be cut by a sealing fault downthrown to the north. Gas wells located near the fault have higher open flow potentials than those more distant from the fault. This is believed to be a result of higher permeability near the fault due to more extensive and open fractures. Detailed coring and core analysis have been performed on several of the wells in this reservoir. Fig. 2 presents permeability variation&apos; plots for both horizontal and vertical

Jan 1, 1969

By H. Kazemi

An ideal theoretical model of a naturally fractured reservoir with a uniform fracture distribution, motivated by an earlier model by Warren and Root, has been developed. This model consists of a finite circular reservoir with a centrally located well and two distinct porous regions, referred to as matrix and fracture, respectively. The matrix has high storage, but low flow capacity; the fracture has low storage, but high flow capacity. The flow in the entire reservoir is unsteady state. The results of this study are compared with the results of the earlier models, and it has been concluded that major conclusions of Warren and Root are quite substantial. Furthermore, an attempt has been made to study critically other analytical methods reported in the literature. In general, it may be concluded that the analysis of a naturally fractured reservoir from pressure transient data relies considerably on the degree and the type of heterogeneity of the system; the testing procedure and test facilities are sometimes as important. Nevertheless, under favorable conditions, one should be able to calculate in-situ characteristics of the matrix-fracture system, such as pore-volume ratio, over-all capacity of the formation, total storage capacity of the porous matrix, and some measure of matrix permeability. INTRODUCTION The analysis of flow and buildup tests for obtaining in-situ characteristics of oil and gas reservoirs has received considerable attention in the past decade. Most of the available techniques result in reliable conclusions in macroscopically homogeneous reservoirs or in the homogeneous reservoirs with only certain types of induced and/or inherent heterogeneity (such as wellbore damage, etc.). In general, the greater the degree of heterogeneity, the less the reliability of the information deduced from the pressure transient data. A commonly encountered heterogeneous system is a naturally fractured reservoir where two types of distinct porosities occur in the same formation. The region containing finer pores may have high storage and low flow capacities. This is called the matrix. The remaining region may have high flow capacity with low storage. The latter region is generally the set of interconnecting fractures and fissures of the rock, and for this reason it is called the fracture. Ordinarily, we wish to obtain the permeability and porosity of each region and perhaps the frequency of the fracture distribution in a reservoir. Such information is necessary for reservoir engineering. Other information, such as wellbore damage, will be useful in evaluating possible remedial work for such fields. Few authors have suggested theories to aid in calculating the in-situ characteristics of a naturally fractured reservoir similar to what we have described above. Pollardl suggested that a naturally fractured reservoir contained three distinct regions: a damaged or an improved region surrounding the wellbore, and the two remaining regions the same as described earlier. He suggested that the flow was taking place from the tight matrix into the highly conductive fractures, then into the we wllbore region and finally into the well column. He concluded that the average pressure buildup in each of these distinct regions can be expressed approximately in terms of an exponential decay function of time. He also hypothesized that the decay coefficients for each of these functions were significantly different from each other; consequently, each of these functions became dominant in turn, in the process of pressure buildup. Thus, by a proper graphic plot of the logarithm of wellbore pressure differences vs buildup time, each of these functions could be determined (see Fig. 1). Pollard suggested methods of determining the wellbore damage and fracture volume. Later Pirson and Pirson2 extended

Jan 1, 1970

By O. R. Wagner, R. O. Leach

Immiscible displacement tests were performed in a consolidated sandstone core over the interfacial tension range from less thdn 0.01 to 5 dynes/cm to better define how interfacial tension (IFTJ reduction can lead to increased oil recovery. Data obtained were displacement efficiency at breakthbrough vs IFT for both drainage and imbibition conditions. These tests simulate water flooding under oil-wet and water-wet conditions, respectively. Results of the study have shown that displacement efficiency under both oil-wet and water-wet conditions can be markedly improved by a sufficient reduction in IFT. In the particular porous media used and for the low pressure gradients employed, the IFT must be reduced to a value less than about 0.07 dynes/cm to achieve increased recovery at the time of breakthrough of the injected phase. Below 0.07 dynes /cm, further small reductions in IFT result in large increases in displacement efficiency. Observed increases in recovery were obtained at pressure gradients which are well below those which can exist in the interwell area of a reservoir under water flood. The effect of pressure gradient on recovery is discussed. INTRODUCTION A residual oil saturation remains in rock which has been water flooded because, under usual reservoir conditions, the driving force which can be generated is inadequate to expel oil trapped by capillary forces. Since these capillary forces can be reduced by reducing the IFT a frequently studied method of increasing oil recovery has been the use of surfactants to reduce the water-oil interfacial tension. Mungan l observed improved recovery in both water-wet and oil-wet systems at 1.1 dyne /cm IFT, finding that the amount of improvement was greater in oil-wet systems. Moore and Blum,2 working with visual flow cell micro-models, con- cluded that recovery cannot be improved in water-wet systems by injecting surfactant solutions. They calculated that, for a pressure gadient of 1 psi/ft in their model, the IFT must be reduced to 0.03 dynes/cm to release oil trapped under water-wet conditions. Berkeley et al.3 indicated that, at representative field flooding rates, the IFT must be reduced to 0.001 dyne/cm to improve recovery, Thus, there is a wide variation of opinion about the IFT levels needed to improve recovery under field conditions. These previous investigators all have used as their experimental method the addition of surfactants to the injected water. The use of surfactant solutions to reduce IFT creates two experimental problems: (1) the loss of surfactant through adsorption on reservoir rock can obscure the true IFT value which exists at the displacement front, and (2) at very low values of IFT emulsifica-tion of oil and water commonly occurs. It is difficult, therefore, to determine whether the increased recovery is caused by IFT reduction as such, or is instead caused by emulsification. Also the properties of the available surfactants limit the IFT range which can be studied. In the present study the purpose is to better define how interfacial tension reduction can lead to increased oil recovery. A matter of great interest is the amount of recovery improvement potentially achievable in this way. The study was made using very low pressure gradients which was well within the range achievable by water flooding in the interwell region of petroleum reservoirs. A unique experimental approach was chosen to avoid adsorption and emulsification problems, and to allow convenient control of IFT. The fluid phases used were the equilibrium vapor and liquid phases of the methane-n-pentane system. The interfacial tension level was varied by changing the equilibrium pressure of the methane-pentane system over the range from 1,200 psia to near the critical pressure (2,420 psia). All tests were performed at a controlled temperature of 100F. The IFT-vs-pressure relationship for the methane-pentane system was based on the data of Stegemeier and Hough,6 and on new data obtained in this study. With this experimental approach it has been possible to study displacement at lower values of IFT than have been previously investigated.

Jan 1, 1967