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By Edward A. Loria

Vanadium is one of the materials being considered for use in fast-breeder nuclear reactors. It is a good heat conductor and nearly transparent to radiation, properties regarded as ideal for nuclear fuel containers. The problem has been the metal lacks ductility needed for forming. In our program at Reno Laboratory the effects of the U.S. Bureau of Mines (previous affiliation) the effects of oxygen, nitrogen, and carbon have been reported21,22 nd most recently the effects of boron and boron with carbon.23 The continuing study by the Ames Laboratory of the effects of hydrogen, the most subtle and fugitive element in its relationship to structure and properties, is commendable. The solubility of oxygen, nitrogen, and hydrogen in vanadium (and other bcc metals as well) is related to material purity. With the available limit on metal purity and the interaction (clustering) of hydrogen with the other interstitial and substitutional elements present in their base metal, would the authors comment on the tolerance of hydrogen in relation to oxy- gen that will avoid intergranular fracture and above what content or how seriously harmful in oxygen at various carbon levels? Understanding the true effects of hydrogen (and other interstitial impurities) in vanadium depends on knowledge of the amount present under various conditions and its distribution between various possible positions. Significant amounts of hydrogen may be in "thermo-dynamic" solution, but not as individual atoms in interstitial positions. It may be in grain boundaries, in subgrain boundaries, in vacancies, or in dislocations. Some of the hydrogen may be paired or in complexes with impurities in substitutional solid solution in vanadium. This makes the analysis of the effect of hydrogen vastly more difficult. It should not be expected that hydrogen in grain boundaries will affect slip in the same manner as hydrogen in interstitial positions, nor will the complexes react to heat treatment the same way as hydrogen in dislocations. It is gratifying that the authors have quoted results from two of our inestiations,' but neglected one2' which applied the Petch theory to electrorefined vanadium of high purity and analyzed the effects of oxygen, nitrogen, and carbon on the ai and ky values obtained by the extrapolation and grain size methods. Details can be found in the paper. Briefly, we obtained a ui value of 10,300 psi (t = 5150 psi) at 273°K. The metal also exhibited profuse twinning with high ductility at 123" and 77°K. Nitrogen was more effective than oxygen in increasing ui, the increase being about twice as much for the same impurity level. Carbon additions resulted in only minimal changes in Ui. The corresponding ky increased as oxygen and nitrogen increased, with nitrogen being more effective. Carbon additions resulted in little change. Although the difference in yield strength of vanadium was explained on the basis of the Cottrell-Bilby model of the tearing away of dislocations from the impurity atoms,

Jan 1, 1970

By Jack R. Elenbaas, Donald L. Katz

A radial turbulent flow formula has been developed which permits the computation of the pressure drop for radial flow in gas wells whether the flow is laminar, turbulent, or partially laminar and partially turbulent. Using the formula a complete back-pressure curve has been calculated and analyzed by a comparison with existing back-pressure curves. A procedure is presented for computing the permeability of the porous media when the porosity, sphericity and average particle diameter are known. Introduction Recent studies on the flow of fluids through porous media have provided new methods for computing flow under turbulent conditions. The present study was initiated as an investigation of pressure -drop computations for flow through porous sands in gas wells and as an analysis of present-day back-pressure tests. Although laminar flow exists in the producing formation of gas wells under normal flow rates, turbulent flow does take place adjacent to the well bore. As the flow rate is increased, turbulent flow exists further and further into the producing formation and under open-flow conditions in relatively deep wells a considerable portion of the flow through the sand will be turbulent. In order to calculate a complete backpressure curve for relatively deep wells without resorting to extrapolation of curves drawn from data obtained in back-pressure tests or calculations made in the completely laminar region, it was necessary to have some means of calculating pressure drop for flow through porous sands under turbulent conditions.4.6 As a result, a radial turbulent flow formula was derived from the equations recently presented by Brownell and Katz.1 A rigorous solution of this equation involves a trial and error graphical integration. By making the assumptions of average viscosity, temperature and compressibility factor of the flowing gas, it was possible to graphically integrate the relation for the general case of radial flow of gases through the porous sand of gas wells. A chart has been prepared relating the value of the integral to the radius of the well bore and to the Reynolds number of the flowing gas. The chart actually performs the graphical integration and the solution of the formula is then reduced to a simple trial and error calculation. A typical back-pressure curve is calculated to show the transition from laminar to turbulent flow. This paper will briefly describe the pro-cedurcs for computing flow through porous media, including a method for predicting sand permeability from porosity and grain size and shape. Flow through Porous Media Brownell and Katzl recently reported a correlation for computing flow of fluids through porous media by the use of an enlarged Reynolds number and friction factor in which the porosity of the bed is included as an additional prime variable. The enlargcd Reynolds number com-

Jan 1, 1948

By Donald L. Katz, Jack R. Elenbaas

A radial turbulent flow formula has been developed which permits the computation of the pressure drop for radial flow in gas wells whether the flow is laminar, turbulent, or partially laminar and partially turbulent. Using the formula a complete back-pressure curve has been calculated and analyzed by a comparison with existing back-pressure curves. A procedure is presented for computing the permeability of the porous media when the porosity, sphericity and average particle diameter are known. Introduction Recent studies on the flow of fluids through porous media have provided new methods for computing flow under turbulent conditions. The present study was initiated as an investigation of pressure -drop computations for flow through porous sands in gas wells and as an analysis of present-day back-pressure tests. Although laminar flow exists in the producing formation of gas wells under normal flow rates, turbulent flow does take place adjacent to the well bore. As the flow rate is increased, turbulent flow exists further and further into the producing formation and under open-flow conditions in relatively deep wells a considerable portion of the flow through the sand will be turbulent. In order to calculate a complete backpressure curve for relatively deep wells without resorting to extrapolation of curves drawn from data obtained in back-pressure tests or calculations made in the completely laminar region, it was necessary to have some means of calculating pressure drop for flow through porous sands under turbulent conditions.4.6 As a result, a radial turbulent flow formula was derived from the equations recently presented by Brownell and Katz.1 A rigorous solution of this equation involves a trial and error graphical integration. By making the assumptions of average viscosity, temperature and compressibility factor of the flowing gas, it was possible to graphically integrate the relation for the general case of radial flow of gases through the porous sand of gas wells. A chart has been prepared relating the value of the integral to the radius of the well bore and to the Reynolds number of the flowing gas. The chart actually performs the graphical integration and the solution of the formula is then reduced to a simple trial and error calculation. A typical back-pressure curve is calculated to show the transition from laminar to turbulent flow. This paper will briefly describe the pro-cedurcs for computing flow through porous media, including a method for predicting sand permeability from porosity and grain size and shape. Flow through Porous Media Brownell and Katzl recently reported a correlation for computing flow of fluids through porous media by the use of an enlarged Reynolds number and friction factor in which the porosity of the bed is included as an additional prime variable. The enlargcd Reynolds number com-

Jan 1, 1948

By J. W. Freeman, D. N. Frey

Fundamental reasons for the improvement in creep resistance of an austenitic alloy by cold working were investigated mainly by X-ray diffraction. The creep resistance was found to be improved by the internal stresses in the lattice of the alloy induced by the cold work. THIS investigation was concerned with the fundamental reasons for improvement in creep resistance of an austenitic alloy as a result of cold working. Also, the investigation was carried out to elucidate the conditions under which cold working could be expected to improve the creep resistance. To achieve these ends, creep resistance and internal structure were correlated for a variety of cold-worked conditions. Since the aim of the investigation was not to obtain specific and extensive information on any one alloy, creep testing was done with a single stress at 1200°F. Structural studies were carried out primarily with X-ray diffraction characteristics. The alloy used, low carbon N-155, was selected on the basis of being representative of at least some of the alloys used in gas turbines. Low carbon N-155 alloy in the form of %-in. sq bar stock was used in this investigation. The chemical composition, in percent, was: C, 0.13; Mn, 1.43; Si, 0.34; Cr, 20.73; Ni, 18.92; Co, 19.65; Mo, 3.05; W, 1.98; Cb, 0.98; N, 0.14; and Fe, balance. The bar stock was produced from a 13-in. sq billet, finished to 7/s in. round cornered square between 2060" and 1910°F. Prior to use in this particular investigation, the bar stock was solution-treated 1 hr at 2200°F and water quenched. This procedure was used in order to put the stock in a condition where effects of prior processing were minimized. Experimental Procedure The specific approach to the problem was twofold. First, the influence of cold working, under various conditions, on the creep rate under a single stress at 1200°F and on the internal structure was in part determined. Second, the effect of annealing at various times and temperatures on the creep rate and internal structure of the cold-worked samples was in part evaluated. The first step was basic to the investigation—creep resistance and structure were to be correlated. The second step was taken to see if the annealed samples showed some internal changes which could also be correlated with changes in creep resistance. This it was felt would facilitate solution of the basic problem. The creep and structural studies were carried out on samples reduced approximately 5, 15, and 40 pct at room temperature and 15 pct at temperatures up to 2200 °F. Annealing of various of the samples was done at 1200°, 1400°, 1600°, and 1800°F for time periods up to 1000 hr. Studies of the annealed samples were concentrated on materials rolled approximately 5, 15, and 40 pct at room temperature and 15 pct at 1400°F. The creep tests were carried out at 1200°F under 40,000 psi, the latter being approximately the 1000 hr rupture stress of the material

Jan 1, 1952

By D. R. Shreve, L. W. Welch

An analysis for predicting the behavior of reservoirs exploited by a combined gas drive and gravity draintrge mechanism is presented. The method allows the prediction of gas-oil ratio, oil production rate, and cumlulative oil recovery for high relief pools in which pressure is maintained either by gas injection in the crest of the structure or by a combined gas and water injection program. The reservoir is represented by a model of communicating vertical prisms, with production or injection at the upper or lower boundaries of each prism. The theory of macroscopic gravitational segregation of two fluids within a reservoir is discussed in detail for all ranges of saturation. A description of an application of the analysis to a typical field problem is also presented. INTRODUCTION The importance of gravity drainage as a producing mechanism has become more evident during recent years. However, many of the reservoir engineering methods which have been used in the past for predicting the behavior of reservoirs producing by this mechanism have required such drastic, simplifying assumptions that the calculated performance in some cases does not resemble the actual pool behavior. The mechanism of fluid displacement in porous media has been described by Buckley and Leverett,1 and a simplified "one zone" method based on this development has been used by engineers to evaluate the performance of gravity drainage pools. Welge2 has modi- fied this approach so that the calculation time has been markedly decreased. In addition, many other authors3-9 have analyzed various phases of the gravity drainage producing mechanism during the past several years. In a high relief reservoir in which gravity may affect the recovery mechanism, there are two main types of exploitation programs which can be employed: 1. Reservoir pressure is maintained by injecting gas into the upper portions of the reservoir. In this case gas is not released from solution and, if dynamic pressure drops are small compared to the total pressure of the system, the gas and oil may be considered to be immiscible and to have constant fluid characteristics. 2. Reservoir pressure is not maintained and a "natural depletion" mechanism prevails. The term "natural depletion" can be used to describe the production history of a reservoir in which a gradual decline of average pressure and the associated release of solution gas continue throughout the producing life. In this mechanism gas is released throughout the reservoir and there is a continuous change in the characteristics of both the gas and the oil phases. It is the purpose of this paper to present the results of mathematical developments by which a method has been devised for evaluating the performance of reservoirs which are depleted by the first type of exploitation program discussed above. It should be mentioned that, although throughout the analysis gas and oil represent the two fluids existing in the reservoir, the method is equally applicable to gravity drainage in water-oil systems. STATEMENT OF PROBLEM In reservoirs of pronounced structural relief, where the closure of the oil section is great or the angle of

Jan 1, 1957

By Stephen Royce

[Stephen Royce.. I .......................... E. S. Moore.. 9 .......................... E. L. Bruce.. 10 ......................... J. E. Hawley.. 11 ........................ L. M. Scofield.. I 2] STEPHEN ROYCE, * Crystal Falls, Mich.Having examined and reported upon the Steep Rock Lake property and vicinity on several occasions for clients, and having kept in touch with the operation from 1938 on, the writer offers the following discussion of the valuable paper by Messrs. Roberts and Bartley, which was so kindly prepared in response to the writer's earnest request, made as a member of the Committee on Mining Geology. ORIGIN OF THE ORES The writer wishes to express complete agreement with the authors that the origin of these deposits was replacement action by hot ascending sulphide solutions of igneous origin, gaining access via the limestone and dolomite breccia channels, and acting mainly to replace the dolomite and limestone breccia with hematite and hydrated hematite. Some replacement in adjoining greenstones and tuffs by the same solutions may also have taken place, but the latter occurrences may represent replaced iron formations originally bedded in with the volcanics. Iron formation in the same relationship to volcanics is extensively developed on the western Menominee Range of Michigan, in the Middle Huronian belts; also appears in similar relations on the Vermilion Range; and is abundantly exposed in the same stratigraphic position no farther away than the southeast arm of Steep Rock Lake itself. Furthermore, the writer's classification of drill cores, made June 11, 1938, on the prop¬erty, contains the following, for hole 8, in the original strike of the A ore body: "332-342 ore; 342-350 much-leached sugary chert with thin ferruginous slate bands." This is a typical iron formation. The ore in this first group of holes (Numbers 6 to 13, incl.) is described in the writer's 1938 notes as follows: "The ore is hard, massive hematite with some limonite, and shot through with many small vugs." The breccia forms in the float ore and in the drill samples were also noted. As a field classification this does not check badly with Professor Schwartz's microscopic work. Notes supplied by Mr. Neeland, then geologist at the exploration, show: "Hole 23 has some iron formation, not logged yet." It appears therefore that there is some iron formation at the exploration, much iron formation in similar stratigraphic position in the vicinity, and iron formation similarly located as to volcanics on the Vermilion and western Menominee Ranges. Certain of the holes, notably Holes 25 and 27, showed some specular hematites resembling those known to be formed from cherty iron formation elsewhere. Hence the writer concludes that at least a small part of the Steep Rock ores results from replacement of iron formation. By far the greater part of it is, as the authors say, clearly a replaced limestone and dolomite breccia, with the breccia outlines still preserved in much of the ore, and all of the replacement is by hot ascending waters. The authors' citation of the neighboring Atikokan pyrite, pyrrhotite and magnetite

Jan 1, 1943

By A. H. Duane, A. E. Miller

The high-temperature allotropy of some heavy rare-earth metals and their alloying behavior with magnesium in the 0 to 50 at. pct Mg region was studied by thermal, microscopic, and X-ray methods. Examination of a hcc phase retained upon quenching alloys of different magnesium content confirmed the existence of a bcc high-temperature allotrope in pure gadolinium, terbium, dysprosium, holmium, erbium, thulium, and lutetium. The lattice constants of the pure metals were determined from a Vegard's Law extrapolation and .found to be 4.05, 4.02, 3.98, 3.96, 3.94, 3.92, and 3.90 + 0.02 A, respectively. In all of the systems studied, the high-temperature bcc phase decomposed eutec-toidally, when slowly cooled, into a hexagonal rare earth-Mg solid solution and a simple-cubic peritec-tic AB-type compound. In 1956, Spedding et al.' observed high-temperature resistivity anomalies in the light rare-earth metals and made several unsuccessful attempts to retain the high-temperature form of these materials at room temperature by quenching the pure metals from temperatures near their melting points. High-temperature X-ray techniques were used by Spedding et a1.' in 1959, to investigate the high-temperature allotropy of the rare-earth metals. This study showed that lanthanum, cerium, praseodymium, neodymium, ytterbium, and possibly gadolinium are bcc at temperatures near their melting points. Discontinuous changes in resistivity at elevated temperatures were also observed for pure gadolinium, terbium, dysprosium, holmium, and lutetium, thus indicating the possible existence of a high-temperature crystalline transformation in these metals. However, due to experimental difficulties encountered in the high-temperature X-ray analysis of these metals, their allotropic form was not identified. Spedding et a~.~ in 1960 observed that yttrium displayed a continuous solid solubility with lanthanum at elevated temperatures, thus showing the high-temperature structure of yttrium to be the same as that of lanthanum, i.e., bcc. Similarly, the high-temperature alloying behavior of gadolinium with yttrium showed gadolinium to be bcc at elevated temperatures. The bcc nature of the high-temperature form of yttrium was again recognized in 1960 by Eash and carlson4 in their study of the alloying behavior of yttrium with thorium. Gibson and Carlson, in a similar study of the alloying behavior of yttrium with magnesium, found that by quenching Y-Mg alloys from within the 0-solid solution region, Fig. l, they were able to retain the allotropic form of yttrium. It was the present authors' intention to use this method to show the existence of a bcc high-temperature form of the heavy rare-earth metals gadolinium, terbium, dysprosium, holmium, erbium, thulium, and lutetium. Simultaneous with the present work, Beaudry and Daane' have shown the bcc nature of the high-temperature form of scandium. EXPERIMENTAL PROCEDURES Materials. The rare-earth metals used in this study were prepared by the calcium reduction of the fluoride and were further purified by vacuum distillation. The magnesium was obtained from the New England Lime Co. and was also purified by distillation prior to its use in the preparation of the rare earth-Mg alloys. The results of chemical and spec-

Jan 1, 1964

By H. H. Keller, E. J. Couch

Damage to production wells subjected to the high temperatures associated with in-situ combustion projects has been a problem since the advent of this thermal recovery technique. Injection of water down the annulus of hot wells has been successfully utilized for cooling and prolonging the life of such wells. A mathematical model that is suitable for predicting the effectiveness of cooling water in a particular application is developed. Typical results for practical ranges of the various parameters involved are presented. INTRODUCTION In the normal course of in-situ combustion operations, highly damaging conditions develop in the production wells as the combustion zone approaches, and these wells are subjected to high temperatures (up to 1500F). The resulting well damage is recognized as one of the more serious operating problems unique to the in-situ combustion process. Even in operations where well completions have been specifically designed to cope with this problem, the question arises as to how this destructively high temperature can be kept within tolerable limits. A simple and economical approach to this problem is to circulate cooling water down-hole. This method has been used with some success in shallow reservoirs. At greater depths, however, the heat exchange with the overburden surrounding the well and between the fluids in the tubing and the annulus tends to equalize the temperatures of the two fluid streams so that the cooling capacity delivered to the bottom of the hole decreases with well depth. This method would provide no appreciable control over the bottom-hole temperature at great depths. In order to delimit the condition under which cooling by water circulation is effective, the wellbore temperature must be related to the water inlet rate and temperature; to the reservoir depth, production rate, and initial temperature; and to the combustion at at bot tom-hole depth. A model that meets these requirements and that will offer an approach for developing engineering solutions to practical design and operating problems is described in this paper. MATHEMATICAL MODEL Previous studies of temperature distributions include those for flowing wells1p2 and those for hot fluid injection. Adams and Haddenhorst 6 presented solutions for the down-hole circulation of hot oil in the treatment of paraffin-deposition problems. In this paper the thermal model presented by Ramey 4 is adapted to the flow system shown schematically in Fig. 1. Water at temperature Ti is injected at a rate wi and flows down the annulus outside the tubing. It mixes at bottom-hole depth D with the fluids produced at race w from the hot reservoir at temperature T. This mlxtureJ. of injected water and reservoir fluids flows up the tubing and is produced at the surface at TI,. In order to describe the temperature response in this system, we make use of the usual conservation of

Jan 1, 1969

By Wallace W. Key

Chalk is a natural calcium carbonate occurring as the remains of soft, friable, minute marine organisms. Whiting can be either finely ground calcium carbonate prepared from chalk, marble, or limestone or the product obtained by chemical precipitation from a solution or suspension containing lime. Until relatively recently, whiting made from limestone was termed "whiting substitute," but it is now usually designated as limestone whiting. Precipitated calcium carbonate, sometimes called "precipitated whiting" or "precipitated chalk," is a finely divided calcium carbonate product obtained by chemical precipitation from a solution or suspension containing lime. Considerable quantities of precipitated calcium carbonates are produced from many chemical processes. Naturally occurring calcium carbonate in a variety of crystalline forms and in all degrees of chemical purity forms a substantial part of the earth's crust. Exactly where a chalk grades into a marl or calcareous shale through increase of clay or silt or into a hard limestone through consolidation and crystallization is difficult to determine because no rigid specifications have been promulgated for classifying them. Composition and Properties Once considered to be amorphous, chalk was later found to be cryptocrystalline. In the pure state it consists entirely of CaCO3, but many deposits are impure. When impurities are removed and the material is reduced to a finely divided state, it is known as chalk whiting. Much confusion attends the use of the term "chalk" as well as the classification of whiting materials. For instance, blackboard chalk is not necessarily chalk but is sometimes plaster of paris or a form of talc. Colored "chalks" may be true chalk colored and compressed with a binder but are probably such materials as hematite, clays, or carbonaceous matter. The term whiting was applied exclusively to the product derived from true chalk before World War I. Chalk imports were difficult to acquire during World War I, and whiting substitutes, a term applied to the products derived from natural rock deposits and precipitated calcium carbonate, were introduced. Substitute whitings were not acceptable at first, but it was found that blending true chalk with substitutes often created an improved product; eventually by selection of limestone and finer grinding, products not only acceptable, but for some uses superior to chalk whiting, were developed. Gradually the term "substitute" was dropped because chalk whiting had lost its importance, being largely supplanted in the United States by other whiting materials. Whiting is now made in ever-increasing quantities from limestone, marble, dolomite, marls, vein calcite, oyster-shell, as well as primary and byproduct precipitated calcium carbonates. Distribution of Chalk Europe-In England, France, Belgium, Denmark, and other European countries highpurity chalk occurs in extensive beds. The Cretaceous period, or the "age of chalk," in geologic history receives its name from the great deposits of chalk exposed on either side of the English Channel. It has been estimated that oceans in which chalk and allied deposits were formed covered more than 500,000 square

Jan 1, 1960

By J. D. Livingston

THE hardening of alloys by the precipitation of a second phase has long been an important technological process. One approach towards improving our understanding of this phenomenon has been a correlation of mechanical properties with such parameters as particle size and inter par ticle spacing.' Several reviews of such data have appeared.2-4 A major limitation to this approach has been that for most alloys the particles are submicroscopic in size in the range of optimum hardness. Precipitation-hardening copper-cobalt alloys, therefore, are of interest, because the ferromagnetic properties of the precipitate make it possible to measure particle size, number of particles, and so forth, from magnetic measurements alone.5, 6 Livingston and Becker7 have applied these techniques to a study of precipitation hardening in an alloy of 2 pct Co in copper. It was found from magnetic measurements that nearly all the cobalt to be precipitated was out of solution within a few minutes at 600°C, whereas the peak in tensile yield stress was not attained until a much longer aging time. Thus during the first 1000 min of aging time at 600°C the Yield stress was increasing while a constant volume of precipitate was coarsening, i.e., while particle size and interparticle spacing were increasing. Peak yield stress was reached at an average particle radius of about 70A. The earlier study was confined to one alloy at one aging temperature, so that the volume fraction of precipitate was fixed and, therefore, particle size and interparticle spacing could not be independently varied. The work has now been extended to several alloys of varying percentage cobalt in copper, and to aging at various temperatures. It was hoped that such a study might clarify the relative importance to precipitation hardening of particle size, interparticle spacing, and volume fraction of precipitate. EXPERIMENT The alloys studied contained 0.7, 1.3, 2.0, and 3.2 wt pct Co in copper. They were prepared from electrolytic copper and electrolytic cobalt in a vacuum -induction furnace, worked to 3/8-in.-diam rod, and machined into tensile specimens with a gage section 1 1/2 in. long and 3/16 in. in diam. All specimens were given a solution treatment consisting of a 30-min anneal in nitrogen at 1000° C followed by a quench into iced brine. Subsequent aging was done in nitrogen and followed by a water quench. Average grain diameter was approximately 0.01 in.

Jan 1, 1960

By T. E. Ockershauser

The Southwest Antioch Oil Field located in T2&3N - R2&3W, Garvin County, Okla., was discovered in February, 1946, by The Globe Oil & Refining Co. and The Vickers Petroleum Co. at their Melinda Gibson No. 1. Oil production was encountered at a depth of 6,525 ft in 14 ft of lower Pennsyl-vanian sandstone. The producing sand, locally called the ."Gibson" or "Third Deese," is a sand bar deposit strung along the west flank of the Pauls Valley uplift in a northwest-southeast direction. The oil reservoir is defined to the east by the edge of sand deposition along the uplift and to the west by the gradation of sand into shale. Within the Antioch Unit, the sand dips from 150 to 400 ft per mile southwesterly and has a pay thickness varying from 10 to 55 ft and averaging 28 ft. Several areas of Gibson production have been developed, including the Katie pool on the south, the Elmore Area of the Southwest Antioch Gibson Sand pool. the Southwest Antioch Gibson Sand pool proper, the Southwest Maysville pool and the New Hope pool on the north. Production extends over a belt 22 miles long by about two miles wide and is continuous except into the Katie and New Hope pools. It appears that drilling will soon prove these intervening areas productive. To March 1, 1950, approximately 18,000 acres have been developed with 450 Gibson wells. It is likely this count will ultimately reach 32.000 acres with 800 wells. RESERVOIR The natural production of oil from the Gibson reservoir is primarily due to solution gas expansion though gravity also plays a part. There is no indication of water drive or evidence that an initial gas cap existed. Gibson oil has a stock tank gravity of 43" API and was saturated at the original reservoir pressure of 2.925 psi. It contained 1,3440 cu ft of gas per bbl in solution and had a high shrinkage of 70 per cent. Connate water amounts to 15 per cent. Reservoir temperature is 130°F. Porosity averages 15.5 per cent and permeability ranges from less than one md to over 1.000. Based on meacurement of 400 core plugs from 15 wells, 78 per cent of the permeabilities fell within the 10 to 1,000 md bracket and averaged l67. Primary oil recovery is estimated at 140 bbl per acre-ft or 22 million bbl for the present 137-tract unit. Due to unitization

Jan 1, 1951

By T. E. Ockershauser

The Southwest Antioch Oil Field located in T2&3N - R2&3W, Garvin County, Okla., was discovered in February, 1946, by The Globe Oil & Refining Co. and The Vickers Petroleum Co. at their Melinda Gibson No. 1. Oil production was encountered at a depth of 6,525 ft in 14 ft of lower Pennsyl-vanian sandstone. The producing sand, locally called the ."Gibson" or "Third Deese," is a sand bar deposit strung along the west flank of the Pauls Valley uplift in a northwest-southeast direction. The oil reservoir is defined to the east by the edge of sand deposition along the uplift and to the west by the gradation of sand into shale. Within the Antioch Unit, the sand dips from 150 to 400 ft per mile southwesterly and has a pay thickness varying from 10 to 55 ft and averaging 28 ft. Several areas of Gibson production have been developed, including the Katie pool on the south, the Elmore Area of the Southwest Antioch Gibson Sand pool. the Southwest Antioch Gibson Sand pool proper, the Southwest Maysville pool and the New Hope pool on the north. Production extends over a belt 22 miles long by about two miles wide and is continuous except into the Katie and New Hope pools. It appears that drilling will soon prove these intervening areas productive. To March 1, 1950, approximately 18,000 acres have been developed with 450 Gibson wells. It is likely this count will ultimately reach 32.000 acres with 800 wells. RESERVOIR The natural production of oil from the Gibson reservoir is primarily due to solution gas expansion though gravity also plays a part. There is no indication of water drive or evidence that an initial gas cap existed. Gibson oil has a stock tank gravity of 43" API and was saturated at the original reservoir pressure of 2.925 psi. It contained 1,3440 cu ft of gas per bbl in solution and had a high shrinkage of 70 per cent. Connate water amounts to 15 per cent. Reservoir temperature is 130°F. Porosity averages 15.5 per cent and permeability ranges from less than one md to over 1.000. Based on meacurement of 400 core plugs from 15 wells, 78 per cent of the permeabilities fell within the 10 to 1,000 md bracket and averaged l67. Primary oil recovery is estimated at 140 bbl per acre-ft or 22 million bbl for the present 137-tract unit. Due to unitization

Jan 1, 1951

By J. B. Cohen

EARLY investigators1-4 reported that additions of beryllium to silver caused embrittlement. The in-termetallic phases which are now known to exist5,' were not known at the time. Solidification appeared to occur by a simple eutectic reation.4,7 (The primary beryllium-rich phase appeared globular, when the liquidus temperature was near the melting point of pure beryllium, and angular when the liquidus was much lower; in discussion of Sloman's work,4 it was suggested that this difference was due to an intermetallic compound which was not revealed by the polishing technique.) In the investigation reported here, it was found that if the compounds now known to exist were avoided, certain beryllium-silver alloys containing large amounts of the primary beryllium phase possessed sufficient ductility to be cold formed. Alloys containing 14 and 20 at. pct Ag were prepared from vacuum-cast beryllium containing 1.0 to 1.2 pct impurities and silver, 99.99+ pct pure. The elements were melted together by induction in beryllia or alumina crucibles under argon at less than 1 atm pressure. The cooling rate was adjusted by regulating the temperature of the melt and by reducing the power to zero without stopping the water flow in the induction coils, which were in contact with the crucible. Ingots were about 0.75 in. in diam with a grain size of 0.12 to 0.25 in. Microscopic investigation of transverse or longitudinal sections of an ingot cast from a temperature well above its melting point showed that, in general, the compounds did not form, presumably because of rapid cooling; the alloys consisted of beryllium-rich particles in a silver-rich matrix as shown in Fig. 1. A eutectic structure was not observed, probably .due to the low beryllium concentration of the eutectic composition and eutectic divorcement. Within a given grain, the small globules of the primary phase were all oriented in the same direction, as indicated by examination under polarized light; the orientation varied from grain to grain. This suggested that the globules were branches of the same dendrites. If cooling was too slow, a third constituent was observed in the microstructure; because it formed around the primary beryllium-rich globules it was Fig. 1—Ag-Be alloy, 18.6 at. pct Ag, as-cast. Bright field illumination. Etched with an aqueous solution of NH,OH and H2O2. X500. Reduced approximately 21 pct for reproduction. probably the 6 compound. A thin ring around an ingot often contained this constituent. When this compound was present in large quantities, or the silver segregated so that large regions occurred with the beryllium-rich globules in contact, sections from the ingot were brittle. When the compound was initially absent, it was possible to carry out reductions in thickness of 50 pct by cold rolling with only limited edge cracking; failure did not occur until reductions of 80 pct. A typical cross section after cold rolling is shown in Fig. 2. After simple bend tests, microcracks were found; these apparently were difficult to propagate in the two-phase structure, as the specimens continued to behave in a ductile manner after the cracks appeared. Similar cracks would probably be closed during rolling. It is apparent in Fig. 2 however, that the primary beryllium particles undergo extensive plastic deformation. Hardness values of the alloys indicated that some work-hardening occurred during cold working. Fig. 2—Ag-Be alloy, 18.6 at. pct Ag, reduced 83 pct in thickness by cold rolling. Bright field illumination. Etched with an aqueous solution of NH,OH and H2O2. X500. Reduced approximately 21 pct for reproduction.

Jan 1, 1961

By R. F. Ashton, D. S. Thompson

In reporting results of precipitation hardening experiments, it is customary to include such conditions as solution heat-treatment temperature, specimen size, and quench medium as well as the aging time and temperature. One portion of thermal history that is often overlooked is the effect of the heating rate employed to achieve the aging temperature. It is the intent of this note to demonstrate the importance of the rate of heating to aging temperatures. This work was carried out on the aluminum alloy 7075 aged at 162oC, a temperature commonly used to obtain stress corrosion resistant tempers. A 2 in. thick plate of 7075 was quenched into 24°C water after solution heat-treatment for 2 hr at 470°C. Approximately 13 in. around the periphery of the plate was discarded to minimize quench rate variations, and the remainder was divided into 0.5 by 1.8 by 2.0 in. blocks which were held at room temperature, 24oC, for 4 days. This aging, or incubation period, at room temperature allowed a copious supply of GP-zones to form. Blocks were then heated at various rates to 162oC using the practices shown in Table I. Both single- and two-step aging practices were employed for each heating rate. The single step consisted of heating directly to temperature at the indicated rate while the two-stage practice included an interruption of heating for 7 hr at 107°C. In the case of the two-stage 100°C per min heating rate experiment, the specimens were returned to room temperature after 7 hr at 107°C where they were held for 16 hr be-fore finally heating at this rate to 162°C. This devia-tion in practice is not considered to be significant. Blocks were removed after various times at 162oC, and aging curves were determined from duplicate R. F. ASHTON and D. S. THOMPSON,Member AIME, are Senior Scientists, Metallurgical Research Division, Reynolds Metals Company, Richmond. Va. Manuscript submitted December 2. 1968. IMD Table I. Aging Practices Two-step Single-Step Heating Rate* Aging Aging Heating Method oC per Min A B Programmed Air Oven 0.23 * 0.01 C D Programmed Air Oven 0.93 ? 0.03 E F Air Oven at Temp -10 G H Oil Bath at Temp ˜100 *Heating rate was measured with a thermocouple at the center of a specimen. An average value between the starting temperature and 3°C below the aging temperature is reported for practices E-H. PRACTICES 70 — A B C E and G 50 - 2 4 6 810 20 40 60 HRS.AT 162°C Fig. 1—The influence of processing variables on 7075 aging curves. Fig. 2—7075 aged according to practice H (single-step aged, fast heating rate) for 3 hr. Magnification 100,000 times.

Jan 1, 1970

By J. H. Keeler

The tensile characteristics of Zr-Fe binary alloys containing up to 5 atomic pet Fe are reported for the temperature range —195o to 500°C. A linear relation between stress at constant strain and volume fraction ZrFe2 was found. The coincidence of data from unalloyed zirconium with zero volume fraction ZrFe2 indicated little or no solid solution in IL-zirconium, in agreement with Hayes, Roberson, and O'Brien.' The absolute increase in strength due to particle strengthening, although decreasing with increasing temperature, was a greater percentage at high temperature. ZIRCONIUM is of interest for use in nuclear reactors because of its low neutron absorption, good corrosion resistance, and high melting temperature. The alloying of zirconium with iron has been considered as a means of increasing the mechanical strength of zirconium without seriously increasing the neutron absorption " over that of unalloyed zirconium. The Zr-Fe system has a eutectic at 934°C and 23.7 atomic pet Fe and a eutectoid at 800°C and 4.0 atomic pet Fe. The zirconium-rich end of this system determined by Hayes, Roberson, and O'Brien' is shown in Fig. 1. The intermetallic phase coexisting with a and ß-zirconium has been reported as Zr2Fe3,1 with a,, - 7.04A, and as ZrFe2,2 face-centered-cubic, the phase being of the MgCu, type (C-15). It was more recently agreed to be ZrFe33 and face-centered-cubic. This intermetallic phase is essentially insoluble in a-zirconium, the hexagonal-close-packed modification; and the lack of solubility makes the system particularly interesting metallurgically. The system is strengthened almost exclusively by particles of in-termetallic phase, and there is very little solid solution strengthening to complicate the analysis. The Bureau of Mines, in its survey of zirconium-base alloys,' reported the tensile properties of Zr-Fe alloys made from chloride process zirconium, induction melted in graphite crucibles, and swaged at 850°C in iron sheaths. Additional data on these ZrFe alloys were given by Hayes, Roberson, and O'Brien.' Chubb and Muehlenkamp% have recently reported the strength of Zr-Fe alloys containing up to about 1.25 atomic pet Fe. These alloys were made from crystal bar zirconium, hot worked at 820°C, annealed at 700°C, and tested both at room temperature and at 316°C. Experimental Procedure The materials used in this investigation were high purity zirconium made by the iodide process and electrolytic iron. The composition of the zirconium as obtained by spectrographic analysis and the nominal composition of the iron are given in Table I. Alloy ingots weighing 100 g were made by are-melting under argon in water-cooled copper crucibles in a multihearth furnace."

Jan 1, 1957

By B. K. Larkin, H. K. van Poollen, H. C. Bixel

A detailed treatment is given of the transient pressure behavior of a well located near a linear discontinuity. On either side of the discontinuity, the values of permeability, viscosity, compressibility, and porosity are uniform, but may be different from those on the other side of the discontinuity. These results generalize previously published works which assumed the permeability ratio for media on different sides of the discontinuity was zero, one, or infinity. One application of this material would be to facilitate detection of facies changes or fluid-fluid contacts by transient testing. Solutions, presented graphically, show pressure decline for constant rate fluid production. The range of variables examined includes dimensionless time from 0.1 to 100, rnohility ratio from 0.001 to 1000 and specific compressibility ratio from 0.001 to 1000. For dimensionless tinze less than 0.4, the pressure behavior is essentially that of a well in an infinite reservoir. Thus, reservoir properties near the well may be estimated in the usual manner. Using an overlay technique to match an experimental curve with one of the theoretical curves, it is possible to estimate the distance to a discontinuity by substituting the actual time t and the corresponding dimensionless time , at which a match occurs into the equation where is the diffusivity near the well, and may be estimated from data taken at early time. Because of both the complexity of the solutions and limited computer facilities, well interference problems were not examined extensively. However, it was found that well interference may be masked by the discontinuity in some cases. By superposition of the results of constant rate fluid production, the problenz of pressure buildup may be treated. Such results show that for early shut-in times correct values for the transnzissibility are obtained from conventional semilog plotting. However, erroneous values of the static reservoir pressure are obtained unless data at large shut-in times are taken. INTRODUCTION Transient well testing has yielded estimates of such reservoir parameters as static reservoir pressure, permeability. porosity, and well bore effects. In most tests, it was assumed that the reservoirs were homogeneous and iso-tropic. Anisotropic media' and radial discontinuities were considered.'.' Various studies have been made on multiple-layer reservoirs." ' Linear discontinuities have been described for problems of one-dimensional flow.' In the present paper, a mathematical treatment is given for a well located near a linear discontinuity in an otherwise infinite medium (see Fig. 1). An actual reservoir analogy would be a well in a relatively thin reservoir near a fluid-fluid contact, or a well located in a reservoir exhibiting a sudden change in rock and formation characteristics, such as thickness, porosity, or permeability. A sudden change in porosity or permeability may be caused by clay fill or other types of facies changes. Sudden thickness changes niay be the result of such geological formations as buried shore lines and channel deposits. In otherwise uniform formations, a linear discontinuity may be caused by fluid-fluid interfaces such as oil-water contacts. 3s-oil contacts, or gas-water contacts.

By A. T. Sweet, C. E. Plummer, H. W. St. Clair, S. F. Ravitz

The ammonium sulphate process for recovering alumina from clays was proposed by Rinman, Buchner, and others many years ago, and more recently various modifications have been investigated both here arid abroad.l-Is The process, as it is being investigated by the Bureau of Mines, involves the following essential steps: (I) sulphating the alumina in the clay by baking with ammonium sulphate at approximately 4m°C., (2) leaching with water to extract aluminum sulphate and ammonium sulphate, (3) crystallization of ammonium alum, (4) conversion of the alum to aluminum hydroxide by the ammonia gases given off during the baking, and (5) calcining the aluminum hydroxide to alumina. The over-all reaction between kaolinite (the most important alumina mineral in most clays) and ammonium sulphate during the baking step may be expressed as follows: Al2O8.2SiO2.2H2O + 4(NH4)2SO4 = (NH4)2SO4.A12(SO4)3 + 6NH3(g) + SH2O(g) + 2SiO2 [i] There is definite evidence. as is shown later. that the aluminum occurs in the baked product as anhydrous ammonium alum rather than as aluminum sulphate, provided the baking temperature is not much above 4o0°C. It is probable that the reaction takes place in the following steps: (NH4)2SO4 = NH3 -(- NH4HSO4 [2] Al2O3.2SiO2.2H2O + ;}NH4HSO4 = A12(SO4)3 + 3NH3 + 5H2O + 2SiO2 [3] A12(SO4)3 + (NH4)2SO4 = (NH4)2SO4.A12(SO4)3 [4] In onc modification of the process, the ammonium sulphate is first decomposed according to Eq. z, and the clay is treated with the resultant ammonium acid sulphate. Reaction I is highly endothermic. On the basis of the best available data, the following values have been estimated for the changes in heat content and free energy in calories per mol: -AH = 331,040 - 34T -AF = 331~040 - 78.3T log T - 671.8T The heat required' at 25OC is 320,900 cal. per mol, or 5650 B.t.u. per pound of alumina. The theoretical equilibcium pressure of NHa, based on the free-energy equation given above, increases very rapidly as the temperature rises above 3o0°C., and reaches one atmosphere at 43s°C. Ammonium alum solutions are almost ideal for crystallization. A saturated solution of ammonium alum contains 126. grams of AlzOa per 1000 grams of water at 90°C. and only 16.5 at 20 C. Hence most of the alum crystallizes out when the

Jan 1, 1944

By Ervin E. Underwood

IT has been recognized for many years that dis-persed particles have great value in raising the creep resistance of metallic alloys. In fact, some of the most successful high-temperature alloys owe their superiority to this factor above all others. A recent observation by Glen1," indicates that even better high-temperature resistance to deformation results in alloys capable of two successive precipitation reactions. The ramifications of this finding are of great interest. Unfortunately, our understanding of the reasons for such notable improvements has not kept pace with technical developments. In an effort to uncover some of the basic facts governing strengthening by particles, a program was initiated at the Battelle Memorial Institute with the primary goal of comparing creep strengths in single-phase and two-phase (precipitating) alloys. The effects of precipitation from solid solution on the creep properties of alloys are generally such that the resistance to creep is increased. However, if alloys are heat treated to different degrees of hardness before creep testing, it is often found that those possessing the maximum hardness initially do not necessarily have the maximum creep resistance. Depending on the stresses and temperatures involved other structures may prove more desirable. Considerations of the above nature indicate the importance of defining the initial state of the alloy. Here, it was decided to start with quenched single- phase alloys in which precipitation and creep deformation proceed concurrently. Equipment and Experimental Procedures Preparation of the Specimens—Four 25 lb ingots were prepared from 99.999 pct Cu and 99.996 pct Al to compositions of 1, 2, 3, and 4 wt pct Cu. Spec-trographic and chemical analyses are listed in Table I. After heat treatments and intermediate reductions, the alloys were cold rolled to 1/8 in. thick sheet. The final cold reductions amounted to 50, 40, 20, and 10 pct for the 1, 2, 3, and 4 pct Cu alloys, respectively. The specimens for creep testing were machined into tensile flats 7 in. long, 3/4 in. wide (at the shoulders), and 1/8 in. thick. The reduced sections were 1/4 in. wide and 21/2 in. long. After heat treatments at 540°C to an ASTM grain size of 1 1, the specimens were quenched into water at room temperature, then electropolished in a glacial acetic acid and perchloric acid solution. The gage marks were Knoop impressions placed 2 in. apart on the reduced sections. Blanks of 1 x 1 in, were cut from the same sheets for the age hardening runs and were given the same grain size heat treatments. The specimens and blanks were stored in a refrigerator at —40°C until needed for testing. Creep Measurements—Creep tests were conducted in a constant temperature room which was maintained at 26° ±1°C. A split-type, hinged, vertical-tube furnace was mounted on a horizontal track so that the specimen could be enclosed suddenly. Thus, it took about 15 min for the specimen to come within 5°C of the test temperature. The temperature variation along the specimen was controlled to about

Jan 1, 1958

By J. G. Richardson

The performance of laboratory water floods is compared with the flooding behavior calculated by the Buckley-Leverett techniques from steady-state relative permeability-saturation relations. Both the steady-state and unsteady-state experiments were conducted on the same sand-packed column. Relative permeabilities were calculated by the Welge technique from the unsteady-state waterflooding displacement experiments and compared with those measured by steady-state techniques. An evaluation of the various calculation procedures was made. It was demonstrated that steady-state relative permeabilities could be used to calczcJate waterflood performance. INTRODUCTION To calculate the waterflooding behavior of a given reservoir, relative permeability-saturation relations of the reservoir rock are required. These relative permeabilities are commonly measured on core samples by steady-state experiments such as the Penn State technique.' The relative permeabilities obtained in steady-state experiments are calculated from oil and gas flow rates and pressure drops measured under conditions of equilibrium distribution of oil and water in the pore spaces with slow approach to equilibrium. On the other hand, in water floods the water saturation at a given point changes rapidly with time as the flood front passes. Extensive research2 has shown that the steady-state relative permeabilities to oil and water are independent of the rate of flow and the fluid viscosities. Research has also demonstrated that the waterflooding performance of homogeneous sands uniformly contacted by water is independent of rate when capillary pressure gradients, which are important in short laboratory columns, are made negligible. However, there is little experimental data in the literature comparing relative permeabilities calculated from steady-state flow experiments with those calculated from flooding experiments. In this paper, the production data of two water floods and the relative permeabilities calculated from a series of steady-state experiments on an unconsolidated sand column are presented along with the comparisons calculated by the Buckley-Leverett and by the Welge techniques. The purpose of this study was to determine if steady-state relative permeabilities could be used to predict the waterflooding performance. This study also permitted an evaluation of the Buckley-Leverett and Welge calculation procedures and allowed an insight into the nature of microscopic displacement of oil by water. EXPERIMENTAL APPARATUS AND PROCEDURE The apparatus used in this investigation was a Lucite column 1 ft long and 11/2 in. in diameter. A drawing of the apparatus is shown in Fig. 1. Six pressure taps were evenly spaced along the top of the column to measure the oil pressures. Three pressure taps fitted with small porous disks were spaced along the side of the column to measure water pressure. Water was admitted to the inflow face of the sand through a porous disk while oil was admitted through a hole in the porous disk and distributed to the face of the sand by grooves machined in the porous disk. Retainer screens of 325-mesh stainless steel were cemented over the inlet and outlet ports and the pressure taps to prevent loss of sand. The column was packed with a clean dry sand all of which was finer than 200 mesh. Next, the sand was saturated with a solution of 150,000 ppm sodium chloride solution. The column was weighed dry and water-saturated to obtain data for the calculation of the pore volume. A 151-cp oil was then injected into

Jan 1, 1958

By R. H. Brown, F. Keller

Because of the extensive use of Alclad 24s alloy sheet in aircraft construction, there is much interest in the metallurgical changes caused by heat-treatment of this product.1, 2 One of these changes is the result of the diffusion of soluble elements from the core into the coating during treatment. This paper deals with the thermal treatments that may influence diffusion and with the practical effects of diffusion on the serviceability of the product. As is well known, Alclad 24s-T sheet has a core of high-strength alloy combined with surface layers of relatively pure aluminum. The microstructure of a cross section of this product is shown by Fig. I. Not only does the relatively high-purity coating have a high resistance to corrosion, and hence serves as a mechanical barrier between the core metal and the corroding environment, but in addition this coating exerts electrochemical protection over areas where the core may be exposed, such as cut edges. In addition, the coating affords electrochemical protection to projecting heads of A17s-T, 17s-T and 24s-T rivets, or attached members made from these alloys. Under some conditions of heat-treatment, however, diffusion of copper into the coating will alter the electrochemical relationship between the coating and the core to the extent that only partial protection will be obtained under some corrosive conditions. The reason for the electrochemical protection lies in the fact that the coating layers of pure aluminum are anodic to the alloy core. The addition of copper to aluminum produces alloys in which the potential is lower than that of the pure metal. Moreover, as the amount of copper in solid solution in 24s alloy is increased, the potential of the alloy becomes more cathodic. When heat-treated at 920°F. and quenched in cold water, 24s-T is about 0.16 volt cathodic to pure aluminum. However, copper will diffuse from the core into the coating, and if it reaches the surface the potential will be altered in a cathodic direction. Thus the potential difference between the core and coating may be less than 0.16 volt, depending uponIthe thickness of the coating, and the time and temperature of heat-treatment. Of the methods available for determining the extent of diffusion of copper from the core into the coating of Alclad 24s-T, two are generally used; namely, the metallo-graphic and the solution potential methods.3 Metallographic Methods Metallographic methods will reveal the progress of diffusion of copper into the coating. For instance, the diffusion zone in the coating intermediate between the coating surface and the core is shown in Fig. I. This photomicrograph is of a polished and etched cross section of 0.040-in. Alclad 24s-T sheet. Diffusion proceeds into the coating more rapidly along the grain boundaries than through the body of the grains. Consequently, the diffusion zone is not of uniform width

Jan 1, 1944