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Henry Louis, Newcastle-upon-Tyne, England (communica, tion to the Secretary): I have been much interested in Mr. Schmitz's description of the copper-ore bed in the Permian formation of Texas. He compares it with the Mansfeld Kupferschiefer; but it seems to me to present closer analogies with a small deposit on the same side of the Atlantic, in Nova Scotia, which I examined in 1877. I quote entirely from my fieldnotes, made then, and from specimens still in my possession. These copper-deposits are known in several places; but I examined them at the village of New Annan, on the banks of the French river. This district has been determined by Sir J. W. Dawson as being of Permian age, and this determination seems to have been confirmed as recently as 1891 by the operations of the Canadian Geological Survey. The following is the section, very imperfectly exposed in a few shallow levels, described in ascending order: Red sandstone, moderately fissile and markedly false-bedded. Lower nodule-bed, 1 inch to 6 inches thick, of fissile mica, ceous sandstone, containing obscure plant-remains converted into anthracite, chalcopyrite, chalcocite and iron pyrites. Very coarse grit or, in places, red sandstone; thickness and character variable. Upper nodule-bed, 6 inches to 2 feet thick exceptionally, generally about 10 inches. Soft, gray, friable shaly sandstone, with nodules of copper-ore. Red sandstone. All these strata lie flat, in places quite horizontal, in places dipping towards the river at 5° to 10°.

Jan 1, 1897

By L. D. Jaffe

From data found in the literature, a method has been derived for calculating hardenability of titanium alloys from their composition. A single graph gives the contributions of each alloying element. These are simply added to a base hardenability for unalloyed titanium. Results agree satisfactorily with measured harden-abilities. RECENTLY the importance of hardenability of titanium alloys in permitting attainment of high strength and hardness has become apparent. If a titanium-base alloy has adequate hardenability for the section size and quenching practice used, it can generally be heat treated to high strength and hardness either by simple quenching or cooling from temperatures near the ß transus, by quenching and tempering (aging), or perhaps by direct isothermal transformation of ß1,2 If the hardenability is inadequate, high strength cannot be attained. Preliminary charts translating hardenability requirements for shapes quenched in various media into terms of Jominy end quenched hardenability specimens or ideal round sizes are now available for titanium alloys." The method proposed in 1942 by M. A. Grossmann for calculating hardenability of steels from composition has proved to be of great practical value.' It appeared worthwhile to see whether, using information available in the literature, a corresponding method for calculating hardenability of titanium-base alloys could be derived. Data No systematic experimental study of the hardenability of titanium-base alloys has yet been made. There is available, however, a considerable quantity of scattered data bearing on hardenability. Some investigators determined Jominy curves on one or several alloys. Others reported as-quenched hardness for specimens of a few alloys cooled at various rates or in various media. Still others gave the as-quenched hardness for systematically varied composition, using one or several cooling mediums. The measurements utilized in this work were limited to hardness. Strength measurements were not used because a low strength may reflect high hardness combined with brittleness. Since, in general, the hardness of titanium alloys goes through a peak as the cooling rate is varied from extremely fast to extremely slow, the cooling conditions at which peak hardness was found were taken as the measure of hardenability.1,2 When as-quenched hardness was found to drop as the content of an alloying element (believed to increase hardenability) was raised, this was taken as an indication that the cooling rate was faster than that giving peak hardness; otherwise, the hardness should go up because of solid solution hardening. Also, if the hardness increased on tempering at low temperatures, this was again taken to indicate that the cooling rate had been faster than that giving peak hardness. Many of the data did not indicate precisely the cooling conditions for peak hardness but merely set a maximum or a minimum bound, or a bracket. Since the sizes of specimens quenched and the location of the hardness readings were not always given, it was occasionally necessary to estimate reasonable limits for them. Only the nominal compositions were available in some cases. As quenching from below the ß transus is equivalent to starting with a mixture of a and ß phases, whose individual composition would differ from the overall composition of the alloy, only measurements after quenches from above the ß transus were used. Hardness measurements on samples heated during metal-lographic mounting were also discarded. Because of their bulk, the data used will not be reproduced. They have been or will be published elsewhere.5-22 Approach All data were first translated into terms of ideal round size. For conversion from Jominy or quenched round or sheet, the author's graphs were used." For a few furnace cools or helium quenches where cooling rates were given, conversion was made on the basis of equal cooling coefficient.23 Plots of ideal round size for peak hardness against percentage of alloying element were next made for

Jan 1, 1956

By G. R. Smithson, John E. Hanway

This paper, the first of two papers covering the development of a metallurgical process for the treatment of a complex ore, describes the bench-scale experimental Program undertaken as a basis for initial process design. The results of using various potentially applicable process steps are detailed and the basis for selecting certain of these steps for Pilot-plant development is outlined. A process consisting of the steps of sulfate roasting, leaching, copper recovery, solution purification, zinc electrolysis, and brine leaching for lead recovery was recommended for further study. THIS paper describes the bench-scale development of a sulfate roasting process designed to recover copper, lead, and zinc from a complex ore. The extrapolation of the bench-scale results to pilot-plant design and the results of pilot-plant operation will be described by Lund, et al.' in a subsequent paper. Several years ago, the research divisions of the St. Joseph Lead Co. became responsible for the development of a metallurgical procedure to treat a complex sulfide ore containing copper, zinc, and lead sulfides. The primary objective was to devise a procedure which would permit economic recovery of the nonferrous values. As could logically be expected, the study of conventional flotation procedures was undertaken; in addition, however, because the physical nature of the mineral association in the complex ore indicated that physical methods of ore beneficiation might not prove to be entirely satisfactory, a program also was established to investigate alternative methods of direct metallurgical treatment for recovery of the metal values. Exploratory test work by the St. Joseph Lead staff led to the conclusion that a sulfate roasting technique represented the most attractive approach for a direct metallurgical process. Sulfate roasting would provide for the selective conversion of the nonferrous values to forms soluble in conventiona1.1 leaching agents and would permit their efficient separation from the insoluble iron and other gangue materials. It should allow efficient utilization of the thermal energy available from oxidation of the sulfide raw material, and might provide an opportunity for recovering byproducts such as iron and sulfur. The decision to evaluate a selective sulfation procedure as a basic processing step also was influenced by the excellent results obtained by the St. Joseph Lead Co. in using this procedure for the recovery of cadmium from zinc sulfide concentrates. The choice of selective sulfation as a major processing step served as a basis for an extended experimental investigation of the process with bench- and pilot-scale equipment to prove its feasibility. St Joseph Lead Co., aware that Battelle Memorial 1nstitute had participated in the development of several fluidized-bed sulfate roasting procedures, asked Battelle to undertake the bench-scale development of a suitable sulfation process. This paper describes the procedure used and the results obtained at Battelle in the treatment of the complex sulfide ore. EXPERIMENTAL WORK Nature of the Raw Material. The sulfide ore deposits of interest are essentially a massive sulfide, with the indivudual ore minerals being extremely fine grained and intimately intergrown with each other and with the associated gangue. The zinc in the ore is present mainly as sphalerite (ZnS), the lead as galena (PbS), and the iron either as pyrite (Fes2) or as pyrrhotite (FeS). Table I shows the chemical analysis of various individual samples of the ore. These analyses illustrate the variability of the ore body and impose a rather severe requirement on any type of metallurgical process—that of being able to tolerate probable wide variations in the assay of the head ore. The tentative flowsheet designed to serve as a guide for the initial experimental investigation of

Jan 1, 1962

By Leo Horvitz

Microanalysis of near-surface soils for hydrocarbons is the basis of a method for locating gas and oil deposits. To substantiate this technique, evidence of vertical migration of hydrocarbons from petroleum accumulations is presented. Tabulated data relevant to hydrocarbon surveys conducted in several petroleum provinces are included. PEROLEUM and natural gas are composed principally of the saturated hydrocarbons ranging from methane, the lightest, to nonvolatile liquids and solids containing approximately thirty-five carbon atoms. A technique for locating buried accumulations of these hydrocarbons before drilling obviously requires that some of the hydrocarbons leave the deposit and migrate toward the surface of the earth where they may be detected in their original form. Earliest attempts to link near surface hydrocarbons to petroleum at depth were apparently made by Laubmeyer' in Germany and by Sokolov in Russia. These investigators collected samples of soil air from boreholes one to two meters deep and analyzed them for traces of hydrocarbons. They found that soil air over producing areas is richer in these constituents than is soil air over barren areas. Since 1936 work on petroleum exploration techniques of this type has been going on in this country. However, instead of determining hydrocarbon content of soil air collected in the field, investigators analyze samples of the soil itself for adsorbed and occluded hydrocarbons, which are released by suitable treatment and found in larger amounts than are the quantities reported for soil air. Difficulties often encountered in collecting gas samples in the field, moreover, are eliminated when soil is used as the sampling medium. Field Procedure: Sample locations are first surveyed over the area to be investigated. Care is taken to locate the stations at considerable distances from roads, pipelines, drilling wells, and other sources of contamination. The borehole pay be dug with a bucket-type hand auger or with mechanical drilling equipment. Lubricants are avoided in either case. When the desired depth is reached, a sample is brought to the surface, placed in a pint glass jar or can, and securely sealed. Sample containers are carefully labeled and delivered to the analytical laboratory. Generally a satisfactory sampling depth range is 8 to 12 ft. In some regions, however, satisfactory data are obtained from samples collected at much shallower depths. Such is the case, for example, in areas of west Texas where the limestone and caliche near the surface occlude hydrocarbons and prevent their rapid escape to the atmosphere. In carrying out broad reconnaissance surveys in search of large features, considerable time is saved by first taking samples one-fourth to one-half mile apart along profiles about one mile apart. If the analytical data indicate a hydrocarbon anomaly of interest, additional samples are taken to produce a more dense and uniform sampling pattern within the interesting area. This sampling program is particularly adaptable to areas that are sectionized. In areas covered with a network of roads, sampling along these roads facilitates the reconnaissance survey. Actual sampling density used depends upon areal extent of features expected. When flanks of piercement-type domes where accumulations may be only several hundred feet wide are sampled, stations are often no more than 200 ft apart. Analytical Technique: Of the hydrocarbons composing petroleum, only the more volatile would be expected to reach the surface of the earth. The analytical technique, therefore, was developed to determine only those constituents that exert a vapor pressure at room temperature. Actually, in near-surface soils, only a very small part of the hydrocarbons are heavier than pentane. Details of the analytical technique have previously been reported. Only a brief description of the methods will be presented here. A weighed portion of the sample, about 100 g, is first treated with an aqueous solution of copper sulphate and then with phosphoric acid in a partial vacuum. The copper sulphate prevents the reaction of the acid with carbides that may be present because the sample has been contaminated by auger particles. Such a reaction may produce spurious methane. The role of the acid is to decompose any carbonates present, thereby helping to release the hydrocarbons. The carbon dioxide is removed with potassium hydroxide and the flask containing the

Jan 1, 1955

By I. Fatt

A recently developed system for measuring electrical resistivity of liquids without use of electrodes offers some interesting possibilities in electric logging technology. The equipment as supplied by the manufacturer is satisfactory for continuous mud logging on a drilling rig or for measuring mud or filtrate resistivity in the laboratory. A simple modification of the commercially available instrument makes it suitable for measuring resistivity of core samples in the laboratory. The continuous measurement of mud resistivity on a drilling rig is a convenient means for detecting mixing of formation water with the drilling mud. Such information is useful to the geologist, the mud engineer and the logging engineer. However, continuous mud resistivity logging by conventional electrode-type resistivity cells is beset with difficulties. The mud, sand and rock chips abrade the electrodes, thereby changing the cell constant and eventually destroying the cell. Also, additives and crude oil in the mud may poison the electrodes by coating them with a nonconductive material. An electrode-type resistivity cell. therefore, may give erroneous readings under certain conditions. Electric logging companies circumvent the electrode poisoning problem by using a four-electrode resistivity cell for measurement of mud resistivity. In this cell, change in electrode area does not change the cell constant. However, the four-electrode cell is difficult to adapt for continuous reading and does not solve completely the problem of electrode abrasion by the sand and cuttings in the mud. The measurement of electric logging parameters on core samples in the laboratory encounters some of the same problems discussed in connection with mud logging. Ideally, the electrical resistivity of a core sample should be measured by placing platinum black electrodes in direct contact with the plane ends of a cylindrical or rectangular sample. Platinum black electrodes however, are much too fragile and easily abraded to be brought in contact with a rock sample. Also, oil or other constituents in the fluid contained in the sample will poison platinum black. In practice, gold-plated brass electrodes, in an AC bridge circuit operating at about 1,000 cps, are used for routine core analysis. For more precise work in research studies, a four-electrode scheme is used.',' Preparation of the samples for the four-electrode method is much too involved for routine core analysis. An apparatus for measuring resistivity of liquids without use of electrodes was described by Guthrie and Boys3 in 1879. They suspended a beaker, containing the electrolyte, by a torsion wire and rotated a set of permanent bar magnets around the vessel. The eddy currents induced in the electrolyte reacted against the rotating magnetic field to develop a torque, which was measured as a deflection of the torsion wire. In 1879 this method could not be made precise or convenient because of the lack of strong permanent magnets. The writer described a very greatly improved apparatus similar to that of Guthrie and Boys, but it was not suitable for continuous measurements or core samples.' Many electrodeless resistivity devices using radio frequency current are described in the literature.5, 6 These generally are suitable only for noting the end-point in a chemical titration. They do not measure resistivity, instead measuring a complex quantity which includes the dielectric constant and the magnetic permeability. The first description of the apparatus to be discussed in this paper was given by Relis.7 Improvements and modifications are described by Fielden,s Gupta and Hills,> and Eichholz and Bettens.10 DESCRIPTION OF APPARATUS The apparatus used in this study is based on the principle that the solution under measurement can form a loop coupling two transformer coils, as shown in Fig. 1. For a fixed AC voltage applied across Coil A, the voltage appearing across Coil B is a function of the resistance of the liquid-filled loop. The details of the voltage generating and measuring circuits are given in Refs. 7, 8, 9 and 10. A block diagram of the equipment is given in Fig. 7. Special features worth mentioning are the operating frequency of 18,000 cps and the automatic temperature compensation which results in the given resistivity readings being automatically correlated to 25°C. The liquid loop supplied by the manufacturer, shown in Figs. 1 and 2, was modified for use in core analysis (Fig. 3). The core sample under test is substituted for a section of the original loop. As shown in Fig. 3, the unit accepts only plastic-mounted cylindrical core specimens. A Hassler-type sleeve easily can be designed for the unit if unmounted cores are to be measured. EXPERIMENTAL PROCEDURE MUD LOGGING A simulated mud line was set up in the laboratory.

By R. J. Teitel

The Pb-U system has been investigated by X-ray, thermal, and microscopic analyses. Two pyrophoric intermetallic compounds were found; UPb3 and UPb. The crystallographic structure of UPb3 is reported. A phase diagram was drawn for the system showing three eutectic and one syntectic reaction. AS a result of the interest in uranium metallurgy, the Pb-U system has been investigated. Practically no quantitative data appears in the literature concerning this system. Chips were machined from bars of high-purity uranium obtained from Ames Laboratory and the lead was 99.9 pct high-purity grade from Bel-mont Smelting & Refining Co. The chips were pickled in a dilute solution of nitric acid, washed in water and then alcohol, and dried prior to use for alloy preparation. The lead was simply sheared from the pig with no chemical treatment. Lead and uranium were placed in graphite crucibles and loaded into an induction furnace. In order to insure good alloy formation, the lead was loaded above the uranium to wash the uranium chips into the melt. After the charge was held at the desired preparation temperature for 15 to 30 min, it was allowed to cool in the crucible. The entire melting operation was accomplished in an atmosphere of helium (double charcoal refined grade with no further treatment). The procedure was to outgas the furnace by first evacuating it to 10-% m Hg, admitting helium to 8 psi gage and sealing the furnace off. An optical pyrometer focused on the charge through a hole in the crucible cover was employed for thermal measurements. Usually a 50° to 70°C correction had to be added to the instrument value. The most suitable alloy preparation temperature range was found between 1220° and 1280°C. The reason for this is explained by the phase diagram, Fig. 7. Above this temperature range two liquids separate preventing alloy formation upon cooling at a reasonable rate. On the other hand, below this range the uranium was coated with a layer of both compounds and the rate of reaction was diminished by diffusion processes. The fastest reaction rate occurred in this narrow range of temperature because only UPb coats the uranium and it evidently does not protect the uranium as well as UPb,. Apparatus and Procedures The development of apparatus and techniques was determined by the peculiar properties of the alloys. All the alloys were pyrophoric, and, consequently, the alloys had to be protected from oxidation by handling them in a dry box or inert atmosphere furnaces. Other operations performed outside of this equipment had to be done as quickly as possible. Thermal analyses were conducted in a furnace and arrangement similar to that described by the author.' Graphite crucibles having a thermocouple well in the bottom were used to contain the prepared alloy, while a helium atmosphere protected the melt from oxidation. The furnace was outgassed by pumping a 10-3 mm Hg vacuum until the furnace had been heated to 400°C. Then helium was admitted and the furnace sealed under 8 psi gage pressure. Chromel-alumel thermocouples were used for thermal analysis and the accuracy of thermal measurements was judged to be k 5°C. At first, an attempt was made to use platinum-platinum-rhodium thermocouples, but evidently lead vapors attack it at high temperatures forming low melting alloys. These lead vapors had direct access to the thermocouple because the graphite crucible was porous. A differential temperature control was used to regulate thermal analyses. The thermal gradient across an alundum tube placed between the windings and the crucible was maintained constant by a controller.

Jan 1, 1953

By J. B. Cheatham, R. B. Paslay

Rock stresses and steady-state flow rates induced by the pressure gradient associated with the flow of formation fluid into a borehole have been analytically determined for a permeable, elastic material saturated with an incompressible fluid. In this analysis, the material properties and loading are considered to be symmetric about the axis of the borehole and independent of axial position. For Case I the material is assumed to have uniform permeability in the radial direction, whereas for Case 11 the permeability is assumed to have been reduced in a localized region adjacent to the hole by either normal well completion and production operations or deliberate plugging during air drilling. Results of a numerical example indicate that, in the absence of plugging, the rock shear strength must be approximately two-thirds the formation fluid pressure in order to prevent rock failure. The required rock strength is high for small radial zones of plugging and decreases as the region of reduced permeability becomes larger; however, a depth of plugging can be reached beyond which there is no real gain in strength, although the flow rate can be further reduced. INTRODUCTION During normal production of oil from a well, it is often desirable to increase the production rate of the formation fluid by increasing the pressure gradient through the formation adjacent to the borehole. Depending upon the magnitude of this pressure gradient and strength of the rock material, this production-rate increase can cause sloughing of the hole wall. In many cases, the production - rate increase can result in excessive sand production, increased wear of production equipment, lost production time and expensive workover jobs. In addition, the phenomenon of increased rock bit penetration rate with the use of a gaseous instead of a liquid drilling fluid has been observed in oilfield drilling operations and experimentally demonstrated by various investigators for several years. The improvement obtained by employing this technique can be quite significant and offers apromising method for reducing drilling costs. However, air drilling is currently limited to geographical locations where high-capacity water-bearing formations are not encountered. This limitation has prevented widespread adoption of air-drilling techniques, because the water influx into the borehole interferes with efficient removal of the drilling cuttings and usually results in a condition such that the bit becomes "balled-up" or stuck in the hole. In an attempt to remove the water - intrusion limitation from air drilling, various chemical and mechanical water shut-off methods have been proposed. Goodwin and Teplitzl suggested one such proposal whereby the permeability of the water-bearing rock structure was reduced in the vicinity of the borehole. Although the development of a shut-off method based upon this approach would certainly be welcomed by the oil industry, it is conceivable that, under certain conditions of the pressure gradient, strength of the rock material and depth of the modified permeability zone, a stress field can be created that will result in an unstable hole. As part of their study, an analytical solution is given for stresses in an idealized model of a hole and the surrounding rock material. The purpose of the present study is to extend the analysis of Goodwin and Teplitz to gain more insight into the details and consequences of excessive production rates and formation water shut-off. In particular, simplified models of these problems have been analytically examined, which makes possible the evaluation of the type of stress fields that can be anticipated as a result of these production and drilling practices. Both problems solved concern the determination of the steady-state volume flow rate of the formation fluid and the resulting steady-state stress and displacement distribution in a hollow, cylindrical configuration. The cylinder of Case I, corresponding to the production-rate problem, consists of a material with a constant permeability from the inside surface to the outside surface; the cylinder of Case 11, corresponding to the water shut-off problem, consists of a material with a constant permeability from the inside surface to an intermediate concentric cylindrical surface and a second constant permeability from the intermediate surface to the outside surface-

By Thomas E. Garnar

Zirconium and hafnium are curious elements because they are almost always found together in nature. Zirconium was discovered by Klaproth in 1789 and isolated 35 years later by Berzelius. Because hafnium's chemical properties are so close to those of zirconium, it was not discovered until 1923 when Coster and Von-Heresey detected it using x-ray spectrographic analysis. These elements occur most commonly in nature as the mineral zircon (ZrSiO4) and less commonly as the oxide baddeleyite (ZrO2). They also are found as a variety of other silicates. Zircon was identified as a component in alluvial and beach sands in 1895, but it was not produced in any quantity until 20 years later. Zircon is always a coproduct from TiO2 mining and processing. During World War I it was produced as a coproduct of beach sand mining for titanium minerals just south of Jacksonville Beach, FL, and was patented as a refractory. It was not until the 1930s when Zircon Rutile, Ltd. began mining at Byron Bay on the east coast of Australia that zircon was first used as a foundry sand. Later in the 1940s, NL Industries, Humphreys Gold Corp., and E. I. du Pont de Nemours & Co., Inc. began production of zircon sands from fossil beaches in northeast and northcentral Florida. Baddeleyite first became available as a commercial product in 1916, but never in the quantity of zircon. Zircon holds a unique position as an industrial mineral because it is used for both its physical and chemical properties as well as an ore of zirconium and hafnium metals. Australia is the major zircon producer followed by South Africa and the US. Zircon is also produced in India, Sierra Leone, Sri Lanka, Malaysia, China, Thailand, and Brazil. Undeveloped heavy mineral beach sand reserves containing zircon are known to occur in Egypt, Malawi, Senegal, and Tanzania. Locations are shown in Fig. 1. Mineralogy Zirconium and hafnium are always present together in naturally occurring compounds. Most commonly they form as the silicate sometimes containing iron, calcium, sodium, manganese, and other elements. Less commonly they are found as oxides in combination with titanium, thorium, calcium, and iron. Zircon is the most common form. It is extremely resistant to weathering, therefore, often it is present in ancient beach sands and placer deposits. Although resistant to alteration from external sources, it is vulnerable to internal alteration as the result of thorium and uranium substituting for zirconium either in the zircon lattice or in solid solution. Alteration to the metamict state takes place as radioactive emanations from these elements disorder the crystal lattice, accompanied by hydration, reduction in specific gravity, and changes in color. The mineralogy of zircon and baddeleyite and variation of physical and chemical properties are shown in Table 1. The effects of zircon's internal alteration and darkened color can be corrected by heating to 1000°C for 30 min or so. A certain time-temperature relationship makes it possible for decolorization and reordering of the crystal lattice to take place when heating at higher temperatures for shorter periods or at lower temperatures for longer periods. After heating, x-ray diffraction patterns are sharper, the grains may be harder, and except for particles of malacon, the grains will be white or colorless in the absence of grain surface coatings. The color change is only temporary and the particles slowly darken with time. Zircon fluoresces light yellow in shortwave ultraviolet light. If exposed to ultraviolet light for extended periods of time, white (calcined) zircon turns purple. With time the induced color begins to fade and eventually disappears (e.g., calcined Florida zircon exposed to ultraviolet light for 24 hr still retains faint, but discernible, purple color after six months).

Jan 1, 1983

By D. O. Wyble

Five water-driver fields, for which pressure predictions had been made within a few years after discovery, were re-studied when four to five years of additional pressure and production data became available. It was fortnd that forecasts of the pressure in water-dri~fe reservoirs may be subject to considerable unccrtainty. Predictions car be erroneous when there is insufficient presswe history to define the cllaracteristics of the aquifer, and when there are errors in the pressure, production or geologic data. INTRODUCTION The efficient operation of an oil or gas reservoir requires that the important characteristics of the reservoir be determined soon after its discovery. It is especially desirable to evaluate the pressure-production relationship quickly, for this relationship provides a basis for deducing the type of production mechanism that is operative, and for making pressure predictions. The pressure predictions, in turn, provide a basis for calculating efficient rates of production, determining whether water or gas should be injected, etc. The importance of pressure prediction is such that forecasts should be made as accurate as possible, and the limits of error well defined. Historically, pressure forecasts for some fields have proved very accurate, while for others the forecasts were so erroneous that they resulted in the adoption of wrong, or at best, unnecessary production practices. Pressure predictions made for water-drive fields are especially subject to error. Accurate forecasting for these fields requires that much be known not only about the reservoir proper but about the adjacent water-filled rock as well. The water-containing rock, or aquifer, may extend for many miles, and often there is only meager data regarding its thickness, permeability and porosity. Much of the information must be inferred from the previous pressure behavior of the reservoir. A brief pressure history may provide little information about the characteristics of the aquifer. Hence, pressure predictions made early in the life of water-drive fields can be incorrect. The work described in this paper was done to determine the degree of reliability which can be expected of pressure predictions made within a few years after water-drive fields are discovered. Five fields, for which the original pressure predictions had been based on less than seven years' history, were re-examined with the aid of four to five years of additional pressure data. Where the predictions were inaccurate, the reasons for failure were ascertained. The studies were accomplished by use of the electric reservoir analyzer.' The analyzer was first adjusted to repeat the original pressure-production match using the same values for the various parameters as were used in the original study. Then, the actual production rates experienced during the time elapsed since the initial study were set into the analyzer, and the pressure behavior indicated by the machine for this period was compared with that which actually OCcurred. Where the pressure profile traced out by the analyzer deviated from the observed field behavior, the analyzer was readjusted to obtain a better over-all match. The old and the new solutions were compared to determine the reasons for any differences. COMPARISON OF PREDICTED RESERVOIR PRESSURE BEHAVIOR WITH ACTUAL PERFORMANCE Field A The original pressure-production match is entirely adequate as evidenced by the pressure match of the field's history subsequent to Jan., 1952 (see Fig. 1)'.

By D. A. Flanagan, B. L. Landrum, P. B. Crawford, B. C. Norwood

Herern is described a heat conduction model which has been developed to predict the pressure distribution within a reservoir being subjected to rrnsteady-state depletion. Although potentiometric models have been widely used to study reservoir pressure distribution, their application is limited to the study of steady-state cases. Electrical analyzers may be used to study unsteady-state phenomena, but their application and simulation have certain limitations. Much of the now accepted theory of unsteady-state fluid flow in porous media has evolved from previous heat conduction knowledge. An analogy between the flow of fluid in an unsymmetrical reservoir and con-duct ion of heat in a similarly shaped unsymmetrical metal plate is made to show adaptability of the hear conduction principle to transient reservoir cases. A description of the model and necessary instrumenrarion is included. Data show influence of well location on pressure distribution during unsteady-state deple[ion. Application of results is made to a hypothetical reservoir and to a reservoir located in an irregular aquifer. INTRODUCTION Development of methods for predicting behavior of petroleum reservoirs has resulted partially from adaptation of electrical and thermal flow concepts to the flow of fluids through porous media. Extensive investigation of electrical and thermal flow problems has resulted in mathematical solutions applicable to many reservoir problems. The relative ease of measuring electrical flow has brought wide acceptance of the use of the potentiometric model to study certain field problems. Potentiometric models are restricted to the study of steady-state conditions because of the instantaneous response of electrical flow to changes in the applied potential. The electrical reservoir analyzer has been one of our most useful instruments for studying certain phases of unsteady-state behavior1. Other than approximation techniques, no method exists for determining pressure distribution in an irregular reservoir during primary depletion. Heat flow, like fluid flow, is inherently transient. The model described here was developed to use this transient nature of heat flow, measurable in the laboratory, to simulate transient flow of fluids in the porous medium of the reservoir above the bubble point. A metal plate shaped like the reservoir to be studied was heated by a "well" source. Temperature increase in the plate is analogous to pressure decline in the field if the field is being depleted, or pressure increase if fluid is being injected. This study is intended to determine the feasibility of using the transient nature of the heat flow to study the transient behavior of fluid flow. It is hoped that this new technique will aid in the understanding of one of the more complex phases of reservoir engineering. THE FLUID FLOW-HEAT CONDUCTION ANALOGY The similarity of the equations which describe the flow of fluids through a porous medium and the conduction of heat through a solid is well known2. Rate of flow of fluids is given by Darcy's law3. while the rate of flow of heat is given by Fourier', (I,, - KA 4T........(2) Combining Eq. 1 with the equation of continuity for a compressible liquid", i.e.,results in Expressing y in terms of the compressibility, i.e., pr = peey ,..........(5) and by expanding the exponential and neglecting higher orders of cp one can obtain

By K. E. Nelson

The effect of thorium and zinc variations on the strength and 100-hr creep characteristics of Mg-Th-Zn-Zr alloys was investigated. Optimum resistance to creep at 650° and 700°F are attainable within a certain range of thorium and zinc contents. This range does not conform to that which develops maximum tensile properties. RAPID advances have been made during the last few years in the development of magnesium alloys for elevated temperature applications demanding high resistance to creep. The beneficial effect of rare-earth metals on the creep resistance of magnesium alloys has been emphasized by a number of publications1-13 and such alloys are now in commercial production. The use of thorium as an alloying ingredient in magnesium was mentioned by McDonald and also in two Alien Property Custodian patent applications.10,17 The initial observation of Sauerwald that thorium contributes still higher creep resistance to magnesium than is attainable with rare-earth metals has recently been substantiated.'" " In fact, it has been demonstrated that the useful temperature range of magnesium alloys is appreciably extended by the use of thorium. In all cases, it was observed that zirconium must be included in the alloys in order to render them fine grained and more readily castable. Several recent publications:2-27 indicate that a still further improvement in creep resistance and a further extension of the useful temperature range can be realized by the addition of zinc to alloys. The primary purpose of this paper is to present the results of a comprehensive study of the effect of zinc on the strength and creep characteristics of Mg-Th-Zr alloys. Compositions covering the range of thorium content from M to 6 pct and zinc content from 0 to 5 pct have been investigated. The creep characteristics at 650" and 700°F reported in this paper are based on results of tests of 100-hr duration. It is appreciated that creep tests of 100-hr duration might not yield adequate data for design purposes for parts with much longer expected life. However, for the purposes of the present discussion, it is felt that the combination of stresses and temperatures used in the 100-hr creep tests have yielded a clear representation of the compositional variation of creep resistance at the temperatures investigated. Creep tests of 1000-hr duration are now in progress on a few of the most promising alloys. Preparation and Testing of Alloys The alloys studied in this intensive investigation were prepared in 25 lb capacity mild steel crucibles. The thorium, zinc, and zirconium were alloyed and poured as described in earlier publications The thorium was introduced into the melt in the form of a Mg-Th hardener," the zinc added in the metallic form, and the zirconium alloyed in the form of the commercial hardener containing magnesium and 30 to 50 pct Zr.10, 26 Fluxing practices for melting and refining were the same as for magnesium-rare-earth metal-zirconium alloys. The melts were sampled for analytical determinations and poured into separately cast 1/2 in. diameter standard tensile bars. The test bars were given a precipitation treatment of 16 hr at 600°F in laboratory furnaces. It has been shown by other tests that a high temperature solution treatment followed by an aging treatment is unnecessary for the development of optimum properties in Mg-Th-Zn-Zr alloys. The selection of 600°F as the aging temperature was based on an attempt to achieve metallurgical stability without coalescence of the undissolved phases and the attendant loss in strength. The thorium, zinc, and zirconium contents of each melt were determined chemically. The zirconium contents are reported in two parts, "soluble" and "insoluble," referring, respectively, to the portions present in the alloy which are soluble and insoluble in dilute HCl acid. Distinction is being made between these two components of the zirconium content in the alloys because it has been found that only that portion of the zirconium content which is soluble in dilute inorganic acids affects the structure and properties of the alloys. The usual impurities consisting of copper, iron, manganese, and nickel were determined spectroscopically. The analysis for each melt is listed in Table I. A description of the methods of tension and creep testing has been detailed in earlier papers. The tests were performed with the cast skin re-

Jan 1, 1954

By F. F. Schmidt, H. R. Ogden, E. S. Bartlett

Continuing tantalum alloy development studies have been concerned with a more detailed investigation of promising binary, ternary, and more complex tantalum alloys containing Groups IV-A, V-A, VI -A. VII-A, and VII-A metal additions. A primary objective of these studies was to improve the elevated temperature strength of tantalum with minimum degradation of fabricability and low-temperature ductility by alloying. Several alloys were found to exhibit hot tensile strengths in the excess of 25, 15, and 10 ksi at 2700°, 3000°, and 3500°F, respectively, combined with excellent cryogenic toughness and ductility. Particularly outstanding in this respect are alloys in the system Ta-Mo-W. Ternary parameter curves describing hot-strength, low-temperature ductility, recrystallization temperature, weld ductility, and fabricability are presented for the Ta-Cb-V, Ta-Hf-W, Ta-Mo-Hf, Ta-Mo-V, Ta-Mo-W, and Ta-V-W systems. At present, only four metals qualify for large scale structural applications at temperatures above about 1800°F. These are tungsten, tantalum, molybdenum, and columbium. Research and development work on these refractory metals has progressed to the point where efforts are now primarily directed toward the improvement of high- and low-temperature mechanical properties through alloying. High melting point combined with excellent low-temperature ductility, fabricability, toughness, weldability, and high solubility and tolerance for both substitutional and interstitial solutes are important attributes of tantalum. Conversely, its high density and relative scarcity compared with other refractory metals are the major deterrents to the use of tantalum. Early studies in the Battelle alloy development program established base line data on the mechanical and metallurgical properties of high-purity tantalum.' These studies were extended to include a preliminary investigation of the effects of various alloying elements on the established base properties.2,3 Recent studies involved a more detailed investigation of promising binary alloys containing Cb, Hf, Mo, Os, Re, Ru, and W, and ternary Ta-Cb-V, Ta-Hf-W, Ta-Mo-Hf, Ta-Mo-V, Ta-Mo-W, and Ta-V-W alloys. Results of major importance obtained are given in this article. EXPERIMENTAL PROCEDURES Electron-beam-melted tantalum (Wah Chang) and high-purity alloying elements were consolidated as 150-g ingots by multiple nonconsumable arc melting under a partial atmosphere of helium. Homogeneity of the button ingots was checked radiographically. Alloy buttons measured about 1-1/2 to 1-3/4 in. in diam by about 0.35 and 0.50 in. thick. Nominal alloy compositions were checked on each alloy button by weighing after arc melting. In most instances, weight losses were within 3 pct of the total weight charged. Subsequent chemical analyses on a number of selected alloys showed interstitial contents to range as shown below: Range of Interstitial Content, ppm 0 C N H 25-75 50-100 10-50 1-5 Metallic alloying additions were found to agree well with nominal compositions based on weight change data. Fabrication directly from the cast button to sheet was conducted at low (75° to 900°F), intermediate (1800° to 2000°F), or high (3000°F) temperatures, depending upon alloy content and hardness. Evacuated stainless steel or molybdenum packs were used for fabrication at intermediate and high temperatures, respectively. The temperature required to complete recrystal-lization in one hour was determined by hardness measurements and metallographic observations (longitudinal test sections) after vacuum annealing at 180°F intervals in the range 2010° to 2910°F. All mechanical property evaluations were conducted on recrystallized sheet, nominally 0.04 in. thick. Weldability of the various alloys was screened using manual TIG welding techniques. Bend ductility (bend axis perpendicular to weld axis) was the criterion used for evaluation. Tensile specimens employed 0.200 by 1 in. gage lengths, and bend test specimens measured about 1 by 1/4 in. Low-temperature tensile tests were conducted using a crosshead speed of 0.02 in. per min up to the point of yielding, and 0.05 in. per min to fracture. High-temperature tensile tests were conducted in vacuum using a crosshead speed of 0.01 in. per min

Jan 1, 1963

By Edward Hanrahan

September 1981 I'm here today to report on a revolution -- a revolution in the way the Federal Government looks at energy. I'm not talking about a simple change in the relative emphasis on sources -- such as more recognition for coal and nuclear power, with less rhetoric about "soft- technology." Nor am I describing a mere change in focus -- from the demand side to the supply side. And I am not referring exclusively to our obvious goal of budget cuts. No, I'm here to discuss a fundamental change in Federal direction -- one that started as soon as President Reagan was inaugurated, and one that is articulated in the National Energy Policy Plan he sent to Congress in July. That brief policy document was backed up by three volumes of supporting data; but I think I can catch it's flavor for you in just three phrases: * First, various energy forms complete with each other and complement one another. * Second, fair competition among them (which includes honest pricing) will give us the best "energy mix." • And, finally there may be ligitimate arguments about where Federal responsibility in regard to energy spills over into Federal interference; but it's about time we drew the distinction -- and eliminated the latter. This Administration's national energy policy is quite different from any we have had in recent years. It is tuned to human nature and changing times. We are seeking the best practical solutions in the energy -a lot better than the ones we have been offered before, but still something less than perfection. One way we do that is by counting on a fully informed public to guide it's own destiny. And, instead of treating energy as an isolated entity, we recognize it as part of the overall economy. The President's Program for Economic Recovery is as much a factor in energy policy as the specific actions of the Department of Energy. One striking difference from the past energy policy 1s that this policy plan does not say: "In 1985 we will -produce so many hundreds of millions of tons of coal: . . . or . . . "By the end of this century the Nation will be deriving X percent of it's electricity from wind generators." Unfortunately, targets like these are what many people have come to expect from the Federal Government -- and what they think of as energy policy, whether the figures hold up in the long run or not. But . . . think about it! Nether the Department of Energy nor any other part of the Federal Government produces coal, or mines uranium, or manufactures solar collectors. There are only a few sections of the country where the Federal Government generates and sells electricity. So it does not take any great insight to recognize that the amount of energy we will produce or consume as a Nation In the future depends on many factors beyond direct government action. And those future totals cannot be predicted precisely, anyway -- by the Government or by anybody else. According to our way of thinking, the choices should be up to the people. When the free market works within a healthy economy, individuals express their preferences in the marketplace -- adjusting the balance of all energy factors continually in a way that no computer could be programmed to reflect perfectly. So, instead of having the Government issue a rigid set of numerical goals, our main concern simply is that there be enough energy. We want the Nation itself to decide how much that should be, what form it should take, and how that energy should reach consumers. The marketplace decides. Considering the recent past, this is indeed a revolutionary idea. It has some pitfalls, and we won't reach this ideal of free choice overnight. But that is where we are headed. And I'll offer some evidence in a few minutes that the policy has already started working. First, let me give you some of it's highlights: 1) Nobody who appreciates the philosophical underpinnings of this Administration will be surprised that the energy policy shows faith In domestic energy production and the supply side of the economy; but it also recognizes the important role of energy conservation -- the wise and efficient use of energy resources.

Jan 1, 1982

By A. J. Griest, A. P. Young, P. D. Frost

A study was made of the effect of ß grain size on the tensile ductility of a-ß titanium alloys haet treated to strengths in the range 165,000 to 180,000 psi. It was concluded that the primary cause of $ embrittlement is the large grain size which is obtained so rapidly in many a-ß titanium alloys when heated into the ß field. It was also found that grain-boundary a and acicular intragranular a in the microstructure are not necessarily detrimental to the tensile ductility if the prior ß grain size is sufficientlv fine. BETA embrittlement occurs in a-ß alloys when the finish hot-working or stages of the subsequent heat treatment have been done at temperatures in the ß field. In order to avoid this embrittlement, for-gings must be finished at temperatures under the ß transus. For better workability, it would be desirable to forge at temperatures in the ß field. For this reason, research has been conducted to determine the cause of ß embrittlement. Although ß grain size has been considered as a possible contributing factor to ß embrittlement, only limited research has been done to evaluate its effect. The effect of addition elements on ß grain growth in unalloyed titanium has been studied by Liu.' Complete mechanical property data, however, were not obtained for correlation with grain size. Ogden and coworkers2 have investigated the effect of both a and ß grain size and grain shape in Ti-Cr-Mo alloys. Their data indicated that tensile ductility was relatively insensitive to ß grain size at annealed strength levels (140,000 psi ultimate). No study has apparently been made to determine the relationship between ß grain size and ß embrittlement in a-ß alloys heat treated to high strength (180,000 psi ultimate). The high-strength condition is that in which ß embrittlement is particularly severe. Beta grain size is not easily varied through the use of a range of annealing times and temperatures in the ß field, because of the rapidity with which ß grain growth occurs. Short-time heating techniques are needed to obtain the smallest ß grains. EXPERIMENTAL PROCEDURE In this research, the experimental procedure was as follows: 1) Tensile and microimpact specimen blanks were resistance heated to produce a range of ß grain sizes. 2) The tensile and microimpact blanks were then solution-treated in the a-ß field and aged to produce predetermined ultimate tensile strengths in the range 165,000 to 180,000 psi. Tensile and impact ductility were then correlated with a grain size for constant strength levels. Materials—The alloys Ti-6A1-4V, Ti-4A1-4Mn, and Ti-16V-2.5Al are representative of the heat-treatable a-ß types in which ß embrittlement can be severe. The compositions and ß transi of the heats studied are given in Table I. The Ti-16V-2.5Al heat was melted and fabricated to 1/4 in. round at Battelle; the other alloys were obtained as 1/4 in. round rolled from commercial heats. The micro-structures of the as-rolled alloys were fine a-ß mixtures. This structure is typical of titanium alloys hot-worked extensively in the a-ß field. Resistance-Heating Treatments to Establish ß Grain Size—For direit resistance heating, a 1/4-in.-diam s~ecimen was heated with a 3000-watt transformer rated for 1000 amp with adjustable secondary voltage. The apparatus included a spray quench fixture. Both heating and quenching periods could be automatically controlled. For temperature measurements, 28-gage Chromel-Alumel wires were tack-welded to the specimen at its midpoint. A high-speed recorder-controller was used to control the heating cycle.

Jan 1, 1960

By P. C. J. Gallagher

A number of recmt determinations for the ratio of extrinsic to intrinsic stacking fault energy in fcc solid solutions are examined. Some of these arise from incomplete analyses which can yield only approxi?nate values for the ratio. Reliable results, on the other hand, obtained using extrinsic-intrinsic fault pairs, show that the extrinsic and intrinsic fault energies are essentially equal in several materials. There is some reason to believe that this finding is of general applicability to fcc elements and alloys. A wide range of values has been obtained for the relative magnitudes of the extrinsic and intrinsic stacking fault energies (yext and yint, respectively) in recently published studies in a variety of materials. In contrast, Hirth and Lothe' using a central force model have shown that out to tenth nearest-neighbor interactions the perturbation in energy caused by both types of fault is the same. Although the model used is not completely valid in metals, there is nevertheless some indication that marked variations of yext/nnt should not be observed from one material to another. In early work in Cu-A1, Cu-Ge, Ni-Co, and stainless steel all the deformation faults observed in the electron microscope were found to be intrinsic in nature, which led to an attitude that the extrinsic fault energy must be considerably greater than the intrinsic. Extrinsic faulting arising from deformation has, however, more recently been directly observed in Au-4.8 at. pct n;~ Ag-6 at. pct Sn and Ag-8 at. pct sn; Ag-7.5 at. pct In and Ag-11.8 at. pct 1n;"' pure silwer and Ag-0.5 at. pct ~n;' and Cu-22 at. pct Zn, Cu-30 at. pct Zn, and Cu-7.5 at. pct ~1.l' Multilayer loops containing extrinsic faulting have also been observed in quenched aluminum." While peak asymmetries in X-ray faulting probability studies were generally attributed to the presence of twins,Lelel2 has recently reinterpreted earlier X-ray data in Ag-Sb alloysU in terms of the presence of extrinsic faulting. The determinations of yeXt/yint made from the above studies are shown in Table I, with a brief description of the techniques employed. A number of the methods utilized are deficient in one or more respects, and the reliability of the values listed will be discussed. ~ele'~ recognizes that his approximate determinations of yext/yint assumes equal numbers of extrin-sically and intrinsically faulted dislocations. It is well-known, however, that such an assumption is not at all justified since extrinsic faulting has but rarely been observed in samples studied in the electron microscope. The only conclusion that should be drawn from the X-ray results at present is that the total intrinsic scattering cross section (i.e., the product of the width of the intrinsically faulted dislocations with their density) is approximately ten times greater than for extrinsic faulting in these particular samples. An important point is that the relative magnitudes of the energies cannot be inferred from results of this type, unless the intrinsic and extrinsic faults form with equal ease. One must recognize that, although a formation barrier may restrict the amount of extrinsic faulting which occurs, this in no way implies that the extrinsic and intrinsic energies should be different. It is unlikely that a worthwhile estimate of the relative densities of extrinsically and intrinsically faulted dislocations can be made at the high deformations present in X-ray samples. ~oretto,'~ from a statistical argument applied to the nonobservation of extrinsically faulted tetrahedra out of a large sample, concluded that yeXt/yint could not be less than -4.5. However, the present author feels that a high-energy formation barrier as just supposed also explains this finding satisfactorily and that no conclusion can possibly be drawn concerning the actual extrinsic stacking fault energy. The same argument also serves to explain the fact that extrinsic faulting has been relatively little observed in the electron microscope. Extrinsic-intrinsic node pairs and isolated extrinsic nodes were first reported by Loretto~ and subsequently by Ives and Ruff,' Gallaher,' and Gallagher and Wash-burn.' Ives and Ruff' found a wide spread in the ratio of extrinsically to intrinsically faulted area in the node pairs they observed, and drew the very tentative conclusion that yeXt/yint 2 2. They recognized that a straightforward comparison of the size of the faulted areas could provide no more than a qualitative result without a theoretical analysis of the dislocation geometry associated with extrinsic faulting. A theoretical

Jan 1, 1969

By G. L. Kehl, Emilo Jaraiz F., J. S. Brett

The transformation of eutectoid beryllium bronze has been quantitatively investigated at 550° and 592°C, the temperature region where the products of p decomposition are a fine lamellar eutectoid and a coarse lamellar aggregate which replaces the fine eutectoid with prolonged annealing. Metallographic evidence indicates that the coarse lamellar aggregate forms preferentially in the most densely lamellated regions of the fine eutectoid and favors the hypothesis that the development of the coarse lamellar aggregate in the fine eutectoid is due to the occurence of a cellular segregation reaction. WHEN eutectoid beryllium bronze (Cu-94 pct, Be-6 pct) is isothermally transformed at high temperatures in the and y region after quenching from the fl field, the principal initial decomposition process is G one of growth of approximately spherical nodules composed of a number of lamellar colonies of the a and y phases. After the initial reaction has proceeded substantially or completely, depending on the transformation temperature, a second reaction occurs wherein the fine lamellar eutectoid is replaced by a coarser lamellar aggregate composed of the same oand yphases.' This reaction is not simply a spheroidization of the initial fine eutectoid but the nucleation and growth of a coarser, structurally different, and more stable distribution of the @and yphases. Fig. 1 illustrates the replacement of the initial fine lamellar structure by a coarse lamellar aggregate. The a phase is the dark mottled constituent; the light constituent the y phase. The phase diagram for the copper-rich end of the Cu-Be system2 is shown in Fig. 2. The a phase has the face-centered cubic structure characteristic of copper-rich solid solutions. The B phase is a disordered body-centered cubic structure, while the y phase is body-centered cubic, ordered (CsC1, B2 type). A. viswanathanS investigating Debye patterns of Cu-6 pct Be discovered that a transitory phase appeared on very rapid quenching from the /3 region which was absent when the quenching velocity was moderate. The phase could be assigned a body-centtred cubic structure with a lattice parameter of 2.876. Tempering at 100°C for 2 hr after quenching resulted in complete disappearance of the phase. The work of Fillnow and Mack' is the only previously published study of the isothermal transformation of eutectoid beryllium bronze. Their study elucidated the nature of decomposition at various subcritical temperatures in an exploratory fashion. The purpose of the research reported in this paper was principally to obtain quantitative information on the isothermal decomposition of the fl phase and to clarify the relationships existing between the fine lamellar eutectoid and the coarse lamellar aggregate. EXPERIMENTAL PROCEDURE The material used in this investigation was an almost eutectoid Cu-Be alloy bar furnished by D.J. Mack. The alloy had been melted under a protective carbon cover and centrigugally cast into a graphite mold preheated to 490 "C. Segregation was minimized by violent agitation during melting and pouring. The analysis of the casting was 93.85 pct Cu, 5.60 pet Be with traces of Si, Mg, Mn, Co, and Al. To determine the minimum soaking time necessary to insure specimen homogeneity, a number of specimens were held in the P region at 788OC for times fron 1 min to 12 hr and isothermally transformed at 550°C. Specimens betatized less than 12 min exhibited partial transformation at times shorter

Jan 1, 1961

By F. G. Miller, T. D. Mueller, L. B. Davidson

A mathematical model of reservoir behavior during one cycle of the intermittent steam injection process is presented in this paper. A cycle of the process is considered to be composed of three stages: injection, condensation and production. The model concentrates on behavior during the production stage. The influence of several parameters on production improvement is described, using the results obtained with a numerical equivalent of the model. Reservoir system parameters considered are thickness, reservoir thermal conductivity, oil viscosity, solution gas-oil ratio and the change in oil effective permeability with temperature. Operating parameters investigated are heat injection rate, steam temperature and cumulative injection time. In the face of considerable uncertainty, the model appears to give a fair prediction of the behavior observed during an actual test. This makes the model a useful means of selecting projects. It is shown that the model may also be utilized to select an optimum set of operating conditions for a particular project. Results of this study show the extent to which production improvement depends on each of the parameters investigated and give an indication of the range of system conditions within which the process would be effective. INTRODUCTION In recent years the intermittent steam injection or steam soak process of oil recovery has become a popular method of improving recovery in reservoirs bearing high-viscosity hydrocarbons. Production improvement due to the process results from heating the reservoir near the wellbore. The process is applied on an individual well basis and is executed in a series of cycles, each consisting of three stages: injection, condensation (the soaking period) and production. During the injection stage, high-pressure steam is injected into the reservoir surrounding the well-bore. This study assumes that injection is carried out over the entire vertical section of the reservoir rock that can be exposed to fluid injection. The condition of steam entering the reservoir is considered to fall within the following limits: (1) steam pressures less than 1,000 psig, (2) steam temperatures between 300 and 700F and (3) steam quality less than 90 percent. The last restriction is due to equipment limitations. Normally, injection re maintained for less than 3 weeks. After termination of injection, the condensation stage begins. The well is shut in for several days, supposedly to make certain that the injected steam condenses. This condensation would insure the retention of injected heat. The production stage is initiated when the well is opened again. Reservoir response during this stage determines the effectiveness of the process (response is defined as the oil production rates, the water production rates and the wellbore temperatures observed during the entire production stage). The immediate response of the reservoir is sometimes quite good. Sets of case histories by Longl and by Owens and Suter2 give some typical figures for response. Duration of the production stage is equal to the time needed for the oil production rate to decline to some predetermined value. This usually requires 4 to 6 months. Termination of the production stage coincides with the start of the next cycle. The process is continued, cycle by cycle, until it becomes unprofitable to continue. One simple model2 and two more sophisticated models3,4 of the process have been presented. These are based on fundamentally different assumptions than those used in this investigation. Although the three models might be modified to fit the assumptions used in this study, it is felt that greater rigor would result by developing a

By Jei Y. Choi, P. G. Shewmon

Using a scratch smoothing technique, the magnitude and the ratio of the surface diffusion coefficients (D,) in two orthogonal directions have been measured on copper for over 100 different surface orientations. Anisotropy was found for all surface orientations except those lying near the (100) and (111); however, these anisotropies were rarely greater than 2.0. The direction of maximum D, appears to coincide with the direction of step edges on any given surface, and if no such steps exist, no anisotropy is found. Thus the jump frequency along a step edge is shown to be faster than the frequency of a jump over the step. The values of Ds and AH for the (100) and the (111) orientations agree quite well with those obtained earlier by the grain boundary grooving technique. It is proven that the directions of maximum and minimum D, (the principal axes) for any surface orientation are known if the perfectly ordered plane corresponding to the given surface orientation possesses a plane of mirror symmetry. Thus the principal axes of D, for orientations lying along the sides of the unit stereo-graphic triangle are always known independent of the extent of thermal disorder or impurity adsorption. The merits and shortcomings of King and Mullins' recently published equations relating Ds to the rate of scratch smoothing are discussed. 1N an earlier paper the authors have reported the variation of the surface diffusion coefficient (Ds) with surface orientation on copper.' In that study Ds was determined from the rate of growth of grain boundary grooves on symmetric bicrystals. This gave values of Ds from 850° to 1070°C in a given direction on each of the six surfaces. It was found that the activation energy for surface diffusion was essentially the same for all six surfaces. The theory developed to explain these data assumed that the free energy of any given type of surface site depends only on the number of nearest neighbors the atom has. This same theory predicted that on any given surface Ds should be independent of direction. The primary aim of this study was to check the validity of this prediction for a wide range of surface orientations on copper. The growth of grain boundary grooves is ideal for studying Ds in a given direction on a given surface over a range of temperatures, because the same specimen can be repolished and used again. However, there is considerable work involved in growing a symmetric bicrystal, and for a survey of Ds in two or more directions on many surface orientations, the technique would be arduous. A better technique appeared to be the scratch method used primarily by Mykura. 2 If a scratch is placed in a surface whose surface tension is independent of orientation, the surface will smooth out in time under the influence of surface tension. To determine D, from this flattening, Blakely and Mykura2 used an approximate solution which was assumed to describe the rate of flattening. Recently King and Mullins3 (hereinafter K and M) have given a more exact analysis of the flattening of an isolated scratch. A second aim of this paper was to check the validity of this newer analysis and compare the values of Ds determined thereby with the values obtained from grain boundary grooving techniques. EXPERIMENTAL PROCEDURE In an effort to work with a particular predetermined surface orientation, light orthogonal scratches

Jan 1, 1963

By Carl Wagner

AT elevated temperatures. most metals react with oxygen, sulphur, or halogen rather rapidly, although a coherent layer of the reaction product is formed and separates the two reactants from each other. The reaction proceeds, since one of the reactants or both dissolve and diffuse across the reaction product. In many cases the rate is diffusion-controlled as is indicated by the validity of the parabolic rate law of Tammann' and Pilling and Bed-worth. wott and Gurney' have suggested that diffusion processes also play an important part in the case of reduction reactions. This is confirmed by observations reported below. In general, however, the rate of reduction reactions is determined not exclusively by diffusion processes. Reduction of Silver Sulphide Above 179°C silver reacts with liquid sulphur very rapidly. Since the volume of silver sulphide is much greater than that of the equivalent amount of silver, a coherent layer of silver sulphide is formed in accordance with a rule established by Pilling and Bedworth.' According to Wagner','' silver ions and electrons migrate from the Ag-Ag,S interface across the silver sulphide layer to the Ag,S-S interface where the following chemical reaction takes place: 2 Ag +2 e + S Ag,S If silver sulphide is reduced by means of hydrogen, the equivalent volume of the reaction product, silver, is less than that of the initial substance. Accordingly, no coherent layer of silver is formed. Instead, fine filaments of silver grow from the silver sulphide surface into the ambient gas. This phenomenon has been investigated by many authors, especially by Kohlschiitter," who has also reviewed previous literature. Kohlschiitter has interpreted the observed phenomena by migration of "silver" dissolved in silver sulphide. According to Wagner,' silver ions and electrons are the migrating particles. The sequence of consecutive steps involved in the reduction of silver sulphide is shown in Fig. 1. Every- where at the silver sulphide surface, hydrogen reacts with sulphur so that excess silver ions and electrons are formed, which migrate at random until they are captured by a nucleus of metallic silver. If such a nucleus lies on the surface and material is furnished only from the base, the original nucleus is pushed outward and thus a filament grows. Removal of sulphur and formation of metallic silver may also take place at different points when silver sulphide is reduced by copper. The reaction is usually formulated as: AgL,S + 2 Cu = Cu.S + 2 Ag but the actual reaction products are silver and a solid solution of the two sulphides. Primarily, excess silver and electrons dissolved in silver sulphide are formed. After a certain degree of supersaturation has been reached, nuclei of metallic silver may form. If, however, a silver foil is in contact with the silver-sulphide phase, as is shown in Fig. 2, silver ions and electrons will migrate to the Ag,S-Ag interface where they are captured. To confirm this scheme, a composite sample, with the geometry shown in Fig. 2, was made by pressing silver sulphide tablets 0.6 cm in diam and 0.4 cm high together with a copper cylinder and a silver foil in crucibles of iron, which does not react appreciably with silver sulphide at 400°C. After heating for 3 to 7 hr at 400°C. the specimens were cut normal to the phase boundaries. It was found that the thickness of the silver foil had increased from 0.01 cm as initial value to a maximum value of 0.06 cm. In the interior of the silver sulphide tablets only traces of metallic silver were observed. These observations show clearly that silver ions and electrons may migrate over distances of several millimeters before they form metallic silver. Reduction of Cuprous Sulphide by Iron The behavior of cuprous sulphide is very similar to that of silver sulphide, since the lattices of the high temperature modifications are identical, but in Cu.S there is a variable deficit rather than an excess of metal. To investigate the displacement of copper by iron, cuprous sulphide powder covered by a copper foil was pressed in iron crucibles and heated up to 800 °C for 3 to 7 hr. The thickness of the copper foil increased from an initial value of 0.005 cm to a nlaximum value of 0.029 cm. In the interior of the

Jan 1, 1953

By R. L. Mauger, P. E. Damon, B. J. Giletti

This report includes the lead isotopic dating of a suite of galenas from Arizona and an application of the K-Ar method to the dating of a Laramide porphyry copper deposit, the Silver Bell Mining District. The lead isotopic data supports prior age assignments based upon geologic inference. The Silver Bell study illustrates the necessity of correlative geologic and petrographic investigations for the interpretation of the results of potassium-argon dating. LEAD ISOTOPIC DATING OF GALENAS FROM ARIZONA ORE DEPOSITS A group of galenas from Arizona ore deposits have been analyzed for lead isotope ratios. The results were used to calculate model ages by the. method of Russell, Stanton and Farquhar,l6 in which the age is calculated directly from the Pb206/Pb207 ratio. The use of Pb206/Pb207 ratios eliminates the errors inherent in measuring the abundance of Pb204. The Holmes-Houtermanns model is the other model commonly used for calculating model ages. Both models assume that any lead sample is composed of primeval and radiogenic components and the calculated age is the time at which the lead was extracted from its source area. Using the Holmes-Houtermanns model, a lead is ordinary if its isotopic ratios lie on an isochron. The growth curve that passes through the experimental point determines the U/Pb ratio in the source area. The RSF model assumes the source area for conformable leads is the mantle, that this has a uniform U/Pb ratio, and thus all ordinary leads must lie on a single growth curve, having a mantle U/Pb ratio. The definition of an ordinary lead differs between the models, and differences in age arise mainly from the assumptions made to evaluate parameters in the model equations. These assumptions depend on the hypothesis chosen to explain ore genesis. In the RSF Model, the Pb206/Pb207 ratio is derived as a function of time. The equation contains three undetermined parameters which are evaluated by assuming three known points lie on the curve. These are the following: 1) Primeval lead from the Canyon Diablo and Henbury meteorites, 2) Modern conformable leads which lie on Patterson's zero isochron, 3) Lead from the Bathurst, New Brunswick base metal deposits. The Bathurst deposits are postulated to be examples of "conformable base metal deposits", as proposed by Stanton.l9 A conformable deposit has a particular genetic history and, as a result, the orebody conforms to stratigraphic layering in the host rock. The metals are brought to the surface in volcanic rocks which originated in the mantle. Weathering products of these rocks, including sulfur and metals, accumulate in areas undergoing sedimentation. The formation of sulfide ion in the sediments by the action of sulfate reducing bacteria causes fixation of iron as pyrite. If the pyrite becomes concentrated in favorable stratigraphic horizons, any base metal deposit eventually formed by replacement of pyrite will have a strata bound character. Compaction and expulsion of pore water from the sediments at depth result in upward mobility of solutions containing soluble base metal chlorides. The strata with high pyrite content act as chemical traps for the base metal ions and replacement occurs. An important result of this general evolutionary model is that, if complete separation of lead and parent isotopes occurred during accumulation of the sediments, any ore deposit formed solely of metals derived from those sedimentary rocks will contain "conformable" lead. This would be true even if the actual ore deposit were formed at a later date by some epigenetic process. In this case, mineralization would be controlled by local conditions, and need not conform to stratigraphic layering. Also, any ore deposit containing lead derived from a mantle or mantle-like source, even though not conformable in Stanton's sense, will fall on the curve for conformable ores and thus give a meaningful model age. Model ages for Arizona galena deposits are listed in Table 1. Fig. 1 is a location map. Jerome-Humbolt District: Galenas from the United Verde mine at Jerome and the Iron King mine at Humbolt give model ages of 1750 m.y. and 1640 m.y. respectively. Both deposits are massive sulfide bodies in a host rock of older Precambrian

Jan 1, 1965