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By R. S. Silo

A new process for leaching oxidized copper ore (CuO) is presented. Its principle advantage is that it requires low cost raw materials. For large operations the only materials used are sodium chloride (NaCl) and calcium carbonate (CaCO3). In those operations of medium size, sulfur, which is abundant in the North of Chile, is used. However the process may also be applied to small copper plants provided low cost sulfuric acid is available as a substitute for sulfur. That is, it may be applied to those small capacity plants where large additional installations for the regeneration of the leaching solution are not needed. The method is comprised of six stages, namely: Crushing, Leaching, Washing of the Solution, Precipitation, Regeneration of the Leaching Solution, and Fusion. A flow diagram for this process in a large or medium-sized plant is given. LEACHING This process requires hydrochloric acid as the leaching solution for treating copper ores. This is easily produced from sulfuric acid and sodium chloride as follows: A small excess of NaCl is advisable to avoid the presence of free sulfuric acid. The experiments reported here were performed with 36 grams of HC1 per liter of solution to obtain a free acidity equivalent to 50 gpl of H2SO4 (the usual leaching solution concentration). Hydrochloric acid leaching may be done by either of the usual methods; i.e. percolation or agitation. The method selected depends on the characteristics of the ore. No matter which method is chosen, low pressure air can be used either as an air lift for circulation of the solution, or for agitation of the pulp with "Pachuca" tanks. In either case, there are no problems with respect to oxidation. Leaching by agitation produces good recovery; but at times, the problem of high consumption of leaching solution or the overproduction of grinding slimes which interfere with contact between phases negates this advantage. The percolation method was used in this study. Percolation took place in four 15-liter containers, 11 1/2 in. diam. by 12 in. height, having hemispheric bottoms. Each container was fitted with a wooden bottom having 1/4 in- holes. The air lift was a 3/4 in. plastic tube 10 in. high. Air at 6 psi was supplied from a rotating laboratory compressor. 10 kg of ore were charged to the container and counter-current leaching was used. The leaching solutions were fed through the center pipe in order to use the ascending solutions to reject the air in the charge. The solution circulated through the air lift in order to facilitate the movement according to the increase in density produced by the reaction between the phases present. Specific observations made in this report cannot be generalized because the leaching characteristics are dependent on the nature of the ore used, the method of leaching, and the production of primary or secondary slimes while crushing or leaching.

Jan 1, 1967

"Nestling in a little valley, right under the shadow of the rugged peaks of the Rocky Mountains and just over the great Continental Divide on the Pacific Slope, are Columbia Gardens, Butte's one rare beauty spot. Here purling brooks, fed from springs of snow-water course through the grounds to lend their aid later in making the great Columbia River. It is a question which has done more to make this oasis the charming place it is, nature or man, for both appear to have put forth their best efforts. The inspiring scenery surrounding the gardens is found in close association with the consummate art of the trained landscape gardener. The most delicate flowers, nurtured in large greenhouses, in the pleasant months of early spring and summer are transplanted into outdoor beds and in many instances woven, as it were, into beautiful designs. Green trees and grass on every side rest the tired eyes.Butte owes this delightful breathing spot to former Senator W. A. Clark, who owns and maintains it. A decade ago there were five large smelters belching forth their obnoxious fumes upon the city, making it impossible for vegetation to flourish within the confines of the town, a condition which fortunately no longer prevails. Primarily with a view of furnishing the children with a healthy playground, other than the muddy or dusty streets, Mr. Clark bought and developed the land upon which these grounds are situated. Upon numerous days in each month during the summer season, when school no longer demands attendance, his street railway carries the little folks to and from this ideal spot, free of all charge. ""Children's Day"" at the gardens presents a scene of life and happiness which once seen can never be forgot."

Jan 1, 1913

T.P. 1958 D. H. DAVIS.*-Mr. Carris has ably pre¬sented the problems of coal preparation, particularly those brought about as the result of increased mechanical loading. Many mines are now crushing the run-of¬-mine raw coal through 12 or 15 in. immediately after it is dumped from the mine car and before it is handled by conveyors. At certain mines the removal of large slate mechanically has been solved by the installation of scalping screens consisting of bars or rails set at spacing of 12 to 15 in. on the top deck of the main raw-coal sizing screen. At the plants where these are in use, the plus 12 or I5-in. raw material contains 60 per cent or more free rock or slate, so that it is easier to pick coal than to pick rock. After the screening at 12 or 15 in. is accomplished, the oversize material is diverted to one side of the shaker, where a picker allows the refuse to pass off the shaker into a chute and guides the coal back onto the shaker. After the large rock has been removed, it is then advisable to reduce the size of rock by crushing before putting it onto a conveyor. A great saving in picking labor has been made by the use of such scalping screens, which in addition has maintained the plant capacity when handling a dirtier feed. The great increase in percentage of coal under 1/4 or 3/8 in., coupled with a greatly increased percentage of free impurities in this size, is the most serious problem that has been brought about by mechaniced loading. Many plants that formerly prepared good quality 1/4-in. to o or 3/8-in. to 0 slack by air¬cleaning are faced with installing facilities for wet-cleaning mechanical and heat-drying and water clarification. The change to wet prepa¬ration of fines usually affects the marketing problems for many coal companies. There will also be problems involving wastage of fine solids and stream pollution. Much work will be necessary for improvements in present practice. Pneumatic and electrostatic methods for cleaning fine coal should receive consider¬able attention in an attempt to avoid wet¬cleaning of fines. The preparation supervisor and the plant personnel should not be satisfied merely to run the cleaning-plant machinery and assume that the job will be done for them. Coal is a heterogeneous substance and in many instances is constantly changing. This is more true when full-seam methods are in use. Only persons trained to observe closely and make the necessary changes in plant operation will be able to solve the many problems that will be imposed on the preparation plants. The plants will require skillful and observant operating men. With full-seam mining methods, seams of roof coal will often be mined. Under the former mining systems these strata were not mined and frequently they contain a high per¬centage of bony and banded partings. The mining of this coal will greatly alter the washability and specific gravity characteristics of the feed to the plant. Often the percentage of 1.40 to 1.60 sp. gr. increased from 3.5 to 7.5 per cent, or nearly a 1.0 per cent increase in the ash content of the 1.60 sp. gr. float coal. Thus the cleaning problem is much more difficult, and it is unlikely the same ash content of cleaned coal can be produced as before without a decrease in recovery or the produc¬tion of a "middlings" product. Mr. Carris had this in mind when he said "The quality of the

Jan 1, 1946

By J. C. Bokros

At temperatures above 950°F, zirconium which has been strained a critical amount will experience critical recrystalli-zation. The large grain size thus formed can result in a reduction in the fatigue life by a factor of 2 to a factor of 9 at both high and low temperatures. The critical strains for zirconium vary from 15 pct at 900°F to about 2 pct at 1125°F, while those for zircaloy III vary from 15 pct at 1050°F to 5 pct at 1200°F. Zircaloy II ,experiences no critical recrystallization up to 1200°F. ZIRCONIUM has become increasingly important for nuclear applications and is being employed in reactors at temperatures where recrystallization can occur. Recent work' on the fatigue properties of zirconium has shown that coarse-grained structures developed in zirconium during recrystallization have much lower fatigue lives than fine-grained material. The development of these large grain sizes under such conditions is well known to be the result of critical recrystallization.2-4 Briefly, critical recrystallization occurs when a metal is strained a critical amount and annealed in the recrystallization range. The critical strain is defined as that minimum strain necessary to promote nucleation in the time unit and temperature considered. The maximum grain size occurs at the critical strain, since at this strain the fewest stable nuclei per unit volume grow into new grains. Recrystallization is not evident below this; strain since the nucleation rate is vanishingly lolw, and metal strained more than the critical amount has a higher nucleation rate per unit volume which results in a finer grained structure. This paper describes the critical recrystallization observed in reactor-grade zirconium, zircaloy 11, and zircaloy I11 as a function of annealing temperature and temperature of strain. EXPERIMENTAL The zirconium used was hafnium-free, double arc-melted sponge obtained from the Bureau of Mines. The ingots were forged and hot reduced to 0.08 to 0.10-in. sheet and subsequently cold reduced to 0.035-in. sheet with intermediate and final anneals at 1200 OF for 15 min. The zircaloy II and zircaloy III used were 0.035-in. sheets in the annealed condition. Compositions of these materials as tested are given in Table I. To determine the critical strain at a given temperature, tensile specimens having a0.065-in. taper in a 2-in. gage length were machined from the sheets parallel to the rolling direction. The specimens were polished, etched, and examined metallographically to ensure that all of them were strain-free, initially. Tukon indentations were made every half millimeter along the gage length of each specimen. These served as fiducial marks enabling the plastic strain to be measured with a microscope and micrometer stage. The specimens were pulled to failure at a rate of 0.002 in. per min in an Instron tensile-testing machine. Three temperatures were used for straining: room temperature, 500 ºF, and 900 ºF. The 500º and 900 ºF tests were run in an argon atmosphere. Since the rate of work hardening changes with temperature, a different critical strain was obtained for each temperature of strain. Specimens, prepared in the manner described, were annealed in vacuunl at various temperatures ranging from 900" to 1200 F for up to 1000 hr, after which they were examined metallographically. The critical strain and the recrystallized grain size as a function of strain were determined for each specimen. Results for the same temperature and time indicated that the critical strain measured was reproducible to within 5 pct of each other. RESULTS AND DISCUSSION Since increasing the time of anneal increases the probability of the nucleation of a new grain, the critical strain decreases with time at a decreasing

Jan 1, 1961

By B. A. Shaw

Historically, microwave tubes have been fabricated from massive metal and ceramic components. The current trend is to lighten tibes for airborne applications. The reqciiremenls of light weight and also reduced cost have created a novel approach to tube structure in which thin-film technology plays a major role. Although the electrical requirements of thin-film circuits in microwave tubes differ from those required or se,niconductor integrated circuits. the technology is basically similar. The stringent requirements of the micvowave tube have created sophisticaled thin-film techniques thut are of interest to the integrated-circuit industry in general. This paper describes a nunzber of thin-jilm techniques recently developed and discusses in detail the application of the technology in microwave tubes. The particular areas of interest are: 1) ceramic mounted thin-film slow-wave structures; 2) thin-film secondary emitters; 3) suppression of tube environnental multipactor by semiconducting' thin films; and 4) age-hardenable and dispersion-hardened thin metal films. SEVERAL thin-film techniques specifically applied to microwave power tubes are discussed in this report. There are two reasons for this work. One is the necessity of reducing weight and cost of microwave tubes and the other is related to overcoming problems in the tube operation by the use of applied thin-film technology. The major emphasis of this work has been on tube slow-wave structures. Other work in the area of secondary emission, either its suppression or its enhancement, is continuing; the most satisfactory results to date have been by utilization of thin-film technology. The requirements of high thermal and electrical conduction together with greater strength than normally obtained with elemental materials have led to the development of dispersion-hardened films. The paper will discuss: 1) ceramic-mounted delay-line microwave tubes; 2) multipactor and secondary emission; 3) hardened films. I) CERAMIC-MOUNTED THIN-FILM SLOW-WAVE STRUCTURES In a conventional crossed-field microwave tube, the slow-wave or delay-line structure is produced from two carefully machined components. One half of the structure is shown in Fig. 1. The other half is the mirror image of the first but is rotationally offset by a half a period. The combined structure now forms an interdigital type of slow-wave structure and is the anode of the tube as shown in Fig. 2. The period and finger length of an interdigital slow-wave structure are prescribed by the desired dispersion characteristics. The typical design is as shown in the first figure; it can be noticed that the finger width is several times greater than the finger thickness. Even assuming that it were mechanically possible to produce free-standing fingers of extremely small cross-sectional dimension, for example, 0.002 in. thick by 0.005 in. wide by 0.500 in. long, decreasing this finger width would increase the tube efficiency but would also decrease the thermal-conduction path, causing an increased temperature rise from intercepted rf current which in its extreme could easily cause finger melting. Hence, for free-standing lines of this type, the design is a compromise between mechanical capabilities, tube efficiency, and thermal dissipation. These structures are also expensive and tend to be heavier than purely electrical considerations would demand. In the present approach, we have transposed the three-dimensional structure previously shown into an essentially two-dimensional structure as shown in Fig. 3. The linear structure is used here for clarity of detail. The support member is a ceramic material and the line is deposited copper. The final tube design is shown in Fig. 4. Because of the backwall sup-

Jan 1, 1967

By K. Mukherjee

A quasi-thermodynamic calculation is presented for estirt~ating vacancy Parameters in fcc metals. For fcc metals the equilibrium vacancy concentration at the melting point can be approximated by a constant mole fraction. The Gibbs free energy of formation of the vacancies can then be expressed as a simple function of the absolute melting temperature alone. From this description the formation energy Ef, the vibrational entropy Sv, and the formation volume of a vacancy can be calculated in terms of known thermodynamic parameters. The calculated values are in good agree-rnent with available experimental results. IT appears that many of the physical parameters associated with lattice defects can be empirically related to thermodynamic melting parameters.'-7 Besides the implicit correlations between melting phenomenon and point defects, the melting temperature itself at atmospheric pressure can be used as a reference temperature for the purpose of comparison of vacancy concentrations in a given crystal class. The concentration at the melting point then corresponds to the maximum vacancy super saturation in the crystalline state at a fixed pressure. For pure fcc metals such as Au, Cu, Al, Ag, Pb, and Pt the mole fraction of vacancies at the melting point8 is of the order of 10*"3 to 10"1. The equation expressing the equilibrium vacancy concentration at the melting point contains three parameters: the formation energy, the vibrational entropy, and the absolute melting temperature, see Eq. [2]. Since these three parameters cover a wide range of values8 in the above-mentioned metals, it can be assumed that in other fcc metals, for which no reliable data are available, the mole fraction of vacancies at the melting point most likely lies in the range 10~3 to lO"4. This is then the basis of the calculations described in this article. Within this range the mixing entropy can be linearized and the vibrational entropy, the formation energy, and the vacancy formation volume can be calculated in terms of known thermodynamic constants. 1} LINEARIZATION OF MIXING ENTROPY The Helmholtz free energy of a crystal containing n vacancies at the melting point can be writteng as where Ef, T,, k, and S, are the formation energy of a vacancy, the absolute melting temperature, Boltz-mann's constant, and the vacancy formation entropy, respectively. After applying Stirling's approximation in Eq. [l] and minimizing with respect to n where (n/N), is the equilibrium vacancy concentration in mole fraction at the melting temperature at 1 atm pressure. If instead of setting (6~/6n) = 0 immediately after Stirling's approximation in Eq. [I], the configurational partition function is simplified, then some useful and significant results can be obtained by utilizing the experimental inforrnation After applying Stirling's approximation and rearranging is plotted as a function of (n/N) in Fig. 1. The points, not all of which are shown, are fitted by a straight line substituting from Eq. [5] into Eq. [I] and minimizing with respect to n combining Eqs. [6] and [2] It must be emphasized that Eq. [7] is only a crude approximation based on an oversimplified model of

Jan 1, 1967

By Dwight H. Seely, Louis R. Records

A process for low-temperature dehydration of natural gas utilizing Joule-Thomson effect in expansion through a throttling orifice has been tested in a full-scale field installation. The results of these tests are presented in the form of performance curves from which the process may be easily evaluated. The effect of separation temperature on condensate recovery from the process is also shown. INTRODUCTION The transportation of natural gas from producing well to the consumer has always encountered the problem of hydrate prevention. This problem has become increasingly important in the past ten years due to the rapid increase in produced gas volumes, production pressures, transportation pressures and distance from producing wells to consumer. Natural gas, as normally produced from gas or gas-condensate wells, is saturated with water vapor at well-head conditions of temuerature and pressure. The solution of the hydrate problem require; but one basic process — dehydration of the gas to a water content which will result in a water dew-point below the minimum temperature to be encountered from the producing well to the point of consumption. Much of the recent development of gas and gas-condensate reserves in the Gulf Coast Area has been in locations which are accessible only by water. High well-head pressures, pipeline construction and maintenance costs and the desirability of final central gas-condensate separation facilities have stimulated the development of dehydration equipment which can be installed at each well and which will permit hydrate-free transportation of both gas and condensate in the same line to central facilities. There are four types of natural gas dehydration processes now used: 1. Adsorptive processes. 2. Absorptive processes. 3. Chemical reaction processes. 4. Refrigeration processes. The first three of these processes are indirect in that they require use of adsorbents, absorbents or reactive chemicals. These materials require regeneration and part of the total gas stream is consumed in the regenerative process. Indirect processes have a wide range of flexibility as defined by allowable operating pressure and temperature, but most are not easily adapted to automatic operation. The refrigeration process described in this paper was designed for installation at the producing well-head. It requires no regenerative cycle and with normal well-head temperatures no external source of heat. The flexibility of this process is limited only by the pressure drop which may be allowed between well-head and transportation line. THEORY There are three basic physical concepts involved in the low temperature dehydration process. These are: 1. Formation of hydrocarbon hydrates. 2. Joule-Thompson effect resulting from the expansion of gaseous mixtures through a throttling orifice. 3. The equilibrium composition characteristics of water vapor and gaseous hydrocarbon mixture.. The chemical composition and physical structure of hydrate; have been described by several investigators.3,4,5,10 Specific conditions of temperature, pressure and composition as well as the requirements for turbulence and presence of free water necessary for hydrate formation have been described by Katz.6 Natural gas hydrates, as they are found in plugged gas pipe lines, have the appearance of packed snow. The mass of these hydrates has low continuous porosity and permeability. Joule-Thomson effect. or the reduction in temperature which occurs when natural gas is throttled throusll a restrictive orifice, is the basic phenomenon which permits efficient use of refrigeration for the purpose of dehydrating natural gas. Joule-Thomson coefficients for gafeous mixture; of methane with ethane and with butane have been reported by Buder.-I~olzer, Sage and Lacey.2 Brown1 predicted temperature drops for pressure drops from enthalpy-entropy calculations. Aside from this work there were no fundamental data found which would be applicable to natural gas mixtures of varying spe-

Jan 1, 1951

By Dwight H. Seely, Louis R. Records

A process for low-temperature dehydration of natural gas utilizing Joule-Thomson effect in expansion through a throttling orifice has been tested in a full-scale field installation. The results of these tests are presented in the form of performance curves from which the process may be easily evaluated. The effect of separation temperature on condensate recovery from the process is also shown. INTRODUCTION The transportation of natural gas from producing well to the consumer has always encountered the problem of hydrate prevention. This problem has become increasingly important in the past ten years due to the rapid increase in produced gas volumes, production pressures, transportation pressures and distance from producing wells to consumer. Natural gas, as normally produced from gas or gas-condensate wells, is saturated with water vapor at well-head conditions of temuerature and pressure. The solution of the hydrate problem require; but one basic process — dehydration of the gas to a water content which will result in a water dew-point below the minimum temperature to be encountered from the producing well to the point of consumption. Much of the recent development of gas and gas-condensate reserves in the Gulf Coast Area has been in locations which are accessible only by water. High well-head pressures, pipeline construction and maintenance costs and the desirability of final central gas-condensate separation facilities have stimulated the development of dehydration equipment which can be installed at each well and which will permit hydrate-free transportation of both gas and condensate in the same line to central facilities. There are four types of natural gas dehydration processes now used: 1. Adsorptive processes. 2. Absorptive processes. 3. Chemical reaction processes. 4. Refrigeration processes. The first three of these processes are indirect in that they require use of adsorbents, absorbents or reactive chemicals. These materials require regeneration and part of the total gas stream is consumed in the regenerative process. Indirect processes have a wide range of flexibility as defined by allowable operating pressure and temperature, but most are not easily adapted to automatic operation. The refrigeration process described in this paper was designed for installation at the producing well-head. It requires no regenerative cycle and with normal well-head temperatures no external source of heat. The flexibility of this process is limited only by the pressure drop which may be allowed between well-head and transportation line. THEORY There are three basic physical concepts involved in the low temperature dehydration process. These are: 1. Formation of hydrocarbon hydrates. 2. Joule-Thompson effect resulting from the expansion of gaseous mixtures through a throttling orifice. 3. The equilibrium composition characteristics of water vapor and gaseous hydrocarbon mixture.. The chemical composition and physical structure of hydrate; have been described by several investigators.3,4,5,10 Specific conditions of temperature, pressure and composition as well as the requirements for turbulence and presence of free water necessary for hydrate formation have been described by Katz.6 Natural gas hydrates, as they are found in plugged gas pipe lines, have the appearance of packed snow. The mass of these hydrates has low continuous porosity and permeability. Joule-Thomson effect. or the reduction in temperature which occurs when natural gas is throttled throusll a restrictive orifice, is the basic phenomenon which permits efficient use of refrigeration for the purpose of dehydrating natural gas. Joule-Thomson coefficients for gafeous mixture; of methane with ethane and with butane have been reported by Buder.-I~olzer, Sage and Lacey.2 Brown1 predicted temperature drops for pressure drops from enthalpy-entropy calculations. Aside from this work there were no fundamental data found which would be applicable to natural gas mixtures of varying spe-

Jan 1, 1951

By A. F. Witt, A. M. Gaudin, A. K. Biswas

Finite contact angles in the rutile-water-organic liquid system are traceable to contamination or are due to addition of a surface-active agent. Finite contact angles are invariably accompanied by hysteresis.1-7 Besides surfactant concentration and pH, the nature of the organic liquid is found to be a factor influencing the magnitude of contact angle hysteresis. In a recent paper the authors have reviewed principles and applications of measurement methods for contact angles and their hysteresis.22 In this paper, these methods are applied to a system consisting of rutile, an organic liquid (benzene, decane, or dode-cane) and water. Surfactant (dodecylamine hydro-chloride) was used at various concentrations and various pH values. MATERIALS A synthetic rutile crystal supplied by the Linde Co. was used. It is a cylinder 1/2 in. diam, with faces cut perpendicular to the c-axis. The crystal is stated to be alumina-free and to be 99.9% pure. Rutile is a high surface energy solid, its calculated average field strength being 2.7 x 105 e.s.u.,9 its dielectric constant10 is 114. The zero point of charge of rutile was measured11 and found to be at pH 6.0. The atomic distances and bond angles of the tetragonal crystal of rutile have been precisely determined.l2 The organic liquids were specially purified. Reagent grade benzene was repeatedly shaken with concentrated sulfuric acid to remove thiophene, then neutralized with sodium hydroxide solution, rinsed with distilled water, dried overnight over anhydrous calcium chloride and filtered. The refractive index of this chemically purified benzene was 1.4977 (at 25°C) - very close to that of pure benzene (n25 1.4979).13 Both n-decane and n-dodecane were washed with aqueous sodium hydroxide, concentrated sulfuric acid (repeatedly, until the acid layer was colorless) and again with alkali, to free the organic hydrocarbon from fatty acids and unsaturated hydrocarbons. The organic phases were subsequently washed with distilled water and dried over anhydrous sodium sulfate. The filtered hydrocarbons were then distilled under vacuum (9-10 mm pressure). Decane, thus purified, showed traces of unsaturated and of carboxylic compounds. On gas chromatographic analysis the purified n-dodecane showed the presence of two impurities. However, the relative retention times of these components did not change substantially when measured on a polar or a nonpolar column. This indicates that the compounds were probably in the same polarity class, i.e. the components were nonpolar like dodecane. Conductivity water has always been one of the liquids. Conductivity of the water used was 10-6 ohm-' cm". Dodecyl ammonium chloride was prepared from pure amine (supplied by Armour and Co., Chicago), by Li in the MIT Mineral Engineering Laboratory.14 The critical micelle concentration at 25°C is known, 0.0138 mol per liter15 or 3.06 gpl. All our experiments have been done at concentrations lower than the critical micelle concentration. The glass vessels, glass drop holder and the rutile crystal were all cleaned with hot chromic acid followed by distilled water, concentrated hydrochloric acid, and again distilled water, and conductivity water. During the experiments, a nitrogen atmosphere was maintained. For this purpose, commercially purified nitrogen was further purified by passing it over hot copper wire at 450°C, then through columns of acidic chromous chloride solution, concentrated alkali solution and distilled water. APPARATUS AND METHODS Hysteresis was produced by the "captive drop" or constant volume drop method as well as by the "expanding-contracting drop" or variable volume drop method. The image of the drop while it is expanding, contracting or moving is projected on a screen and photographed. The developed film is projected through an enlarger and the contact angles measured with a protractor.

Jan 1, 1964

By R. M. Asimow

Both smith1 and wells2 have shown that the dif-fusivity of carbon in austenite increases rapidly with increasing carbon concentration. Smith has shown, in addition, that part but not all of this increase can be attributed to the concentration dependence of the activity coefficient of carbon in austenite. From the work of Eshelby', it is known that, because of the image displacements, there is a uniform dilatation of the material in a body containing random centers of dilatation. It is thus tempting to explain the enhanced diffusivity as resulting from this apparent negative pressure caused by the interstitial carbon atoms.* That is, the activation free energy for diffusion is not directly a function of concentration if we consider that the alloy is subjected to a concentration-dependent pressure. To proceed with a quantitative solution, it is necessary to determine the activation volume AV for the diffusion process. An exact calculation of AV is quite a difficult problem and does not appear to have been solved as yet. A simpler procedure is to use the semiempirical, macroscopic theory of seyes' which relates the activation free energy AG to AV. Keyes has shown that for many types of diffusion processes the following relationship is valid Where p is the Gruneisen constant and x the compressibility. This relationship is based on the assumption that AG can be identified with strain-energy terms. In general there will also be contributions to AG due to a change in the energy of the valence electrons of the metal; thus the relation must be considered largely empirical. Surprisingly, for self-diffusion where it is well-known that the electronic contribution is quite important,' the Keyes relation works quite well for many systems. For interstitial diffusion where it might be expected that the relationship is on a firmer theoretical basis, the limited experimental data available is not in particularly good agreement as can be seen from Table I. However, it must be remembered that besides the uncertain basis of the Keyes formula there is considerable uncertainty in some of the experimental values of AV. The only real justification for using the Keyes formula in the present analysis is that it gives a result which satisfactorily solves the problem at hand and, further, there are no more reliable procedures for calculating AV available. The coefficient 3 in Eq. [I] is determined such that the room-temperature value for x is to be used. The activation entropy AS is estimated as 8.95 x 10"3 kcal per OK mole using the values in Table I1 and the Zener" relation AS = PAHIT, where p is a dimensionless thermal coefficient of Young's modulus which is to be evaluated at low values of T/T,, aH is the activation enthalpy, and T, is the melting temperature of the alloy. The resulting value of AG at 1000°C is 25.6 kcal per mole. The Gruneisen constant (p = 3cup/XC,), where p is the density, is evaluated from the room-temperature data in Table I1 after calculating C, from the relation. A value of p = 8.32 g per cu cm based on the value of a. in Table I is used. The result is C, = 5.0 x lo6 erg per g, H = 2.32, and AV = 3.41 cu cm per mole at 1000°C and infinite carbon dilution. It is assumed that the activation volume is not a function of carbon concentration. The theory could be refined to consider AV a function of concentration, but due to the uncertainties in the parameters there seems little justification for this. Carbon dissolved in austenite forms a nonideal solid solution, so that in writing an equation for. the diffusivity of carbon it is necessary to take into account the change in activity coefficient with concentration. The resulting equation is16

Jan 1, 1964

By M. J. Marcinkowski, K. S. Sree Harsha

A detailed numerical analysis has been made of the equilibrium configuration of partial dislocations in a blocked deformation twin under an externally applied stress. Twins made up of both pure screw and pure edge partials have been considered. The components of stress in the vicinity of the twin tip associated with each of these configurations have been plotted. It has been found that at some critical degree of oblateness the shear stress fields of the blocked screw or edge twin can both sPontaneously nucleate slip, whereas only the component of stress oxx about the edge twin can nucleate and propagate cracks. TWINNING becomes a predominant mode of plastic deformation at low temperatures and/or high strain rates. Fig. l(a) shows what must be the first step in the formation of a deformation twin, namely the formation of a loop of imperfect dislocation bounding a stacking fault. In an fcc crystal the partial dislocations have Burgers vectors of the type 1/6 a,(112) and the fault is of the intrinsic type while in the bcc crystal the partials have Burgers vectors of the type ao(lll). The stacking sequence of (111) planes in a perfect fcc crystal is given by ABC ABC, and so forth, and in one which contains a twin by ABCABACBA, and so forth. It is apparent that the stacking fault and twin give rise to no mistakes associated with adjacent close-packed planes; however, with respect to second-neighbor close-packed planes the faulted crystal has twice as many mistakes as the twin. The energy of the twin boundary may thus be taken to be one-half that of the intrinsic fault boundary. In the case of the bcc crystal the stacking sequence of (112) planes is given by ABCDEFABCD, and so forth, in a perfect crystal, by ABCDCDEFA, and so forth, in a crystal which contains a fault, and by ABCDCBAF, and so forth, in one which contains a twin. An analysis similar to that applied in the fcc crystal shows that both the fault as well as the twin involve no neighbor violations across adjacent planes. However, there are twice as many violations across second-neighbor (112) planes associated with the fault as compared to that of the twin. Thus once again the energy of the twin boundary may be taken as one-half that of the fault. It is important to note that, unlike the fcc, the faults in the bcc crystal involve first nearest-neighbor violations and are thus expected to be of much higher energy than those in fcc crystals. A more detailed analysis of the material discussed above can be found in Ref. 1. To a good approximation then, the lenticular twin shown in Fig. l(b) can be generated by adding partial dislocation loops on successive (111) planes for fcc crystals or (112) planes for bcc crystals in the manner shown, with no additional expenditure of chemical energy other than that required for the fault shown in Fig. l(a). In practice, deformation twins are much more extended than that shown in Fig. l(b) and more closely resemble one shown schematically in Fig. l(c). It is readily apparent that the free energy of the twin and matrix are identical. In those cases where the partials lead to a structural change, the free energy of the material contained within the dislocation array is lower than that of the matrix and we have the so-called martensite transformation. The present investigation is the first in a series of five major theoretical-experimental efforts which will deal with the static and dynamic behavior of twin nucleation and growth. There has been a recent surge in activity pertaining to the equilibrium shapes of twin lamellae2'3 and

Jan 1, 1969

By T. M. Kegley, J. H. Frye, D. L. McElroy, M. L. Picklesimer, E. E. Stansbury

Measurements of rate of growth, thermodymmic quantities, and partitioning of Mn are reported for high-purity eutectoid Fe-C and Fe-C-Mn steels for the auistenite-pearlite reaction. Evaluztion of the cotnstants of a derived-rate equation with these data indicate that Mn additions cause the decrease observed by increasivg the activation energy and apparent activation entropy or the movenment of complexes at the interface. A diffusion-controlled mechanism is not required. Appreciable partitioning of Mn to cementite occurs entirely behind the austenite-pearlite interface for more than 30°C of subcooling. ThE growth of pearlite from austenite has been extensively studied over a period of years. but the rate-controlling step in the process is not known nor is the mechanisrn of the effect of alloying elements understood. A comprehensive review of the subject has been given by Mehl and Hagel. The present study has been concerned with further considerations of the effects of alloying elements on the rate of growth of pearlite. Analytical relatioriships for the rate of growth of pearlite have been considered by Zener.2 Turnbull,3 Machlin,4 Cahn.5 Frye,6 and Frye et a1.7 The derived expressions in each case involve the free energy of the transformation. the interlamellar spacing. and some rate term of the nature of the diffusion coefficient. mobility or frequency of occurrence of some rate-determining step. The treatments. of course. differ in detail. Further consideration is given in the present paper to the equation of Frye, Stansbury. and McElroy which was derived from modified absolute rate theory without in any way specifying the mechanism of the reaction. This equation is r=c ? T ? F exp -?E*/RT [1] where r = rate of growth in mm/sec c = a constant AT = equilibrium transformation temperature minus actual transformation temperature "C ?F = free energy per mol of austenite minus that of pearlite ?E* = activation energy R= gas constant ?F in Eq. [1] is computed from the following: ?F=?H?T/To - ?T' dT' ?T' ?CdT"/T" [2] To To where AH is the enthalpy per mol of austenite minus that of pearlite at the equilibrium temperature, To, and AC is the difference in specific heat between austenite and pearlite per mol. Subsequently, Darken, Fisher, and Galligan8 have reported that a layer of ferrite separates pearlite from austenite at the growing interface (i,e., the advancing face of Fe3C is in contact with ferrite, not austenite) and the ratio of the thickness of this layer to the spacing of the pearlite has not been found to vary with alloy content or transformation temperature. This observation does not require any alteration in the above equation: however, it may require that a different significance be attached to the factor, AT. The AT term appears in Eq. [I] as a consequence of a factor for the amount of growth per complex transformed at the interface.* It is based *This is not the sole reason for expecting such a relationship. See Ref. 7._______________________________________________________ on a l/2 ?T dependence of the interlamellar spacing. Zener2 has developed a theory which leads to Soa 1/?V where So = the pearlite interlamellar spacing. This relation is as consistent with the data on interlamellar spacing as other relationships, although, as pointed out by Mehl and Hagel,1 the data are not sufficiently precise to consider the relationship as confirmed. The work of Darken, Fisher, and Galligan8 requires that the above be written where f = the thickness of ferrite layer between austenite and pearlite. The present paper is concerned with iron-carbon-manganese eutectoid alloys and reports experimental measurements of the following kinds: 1) the effect of

Jan 1, 1961

By R. S. Rickard, M. C. Fuerstenau

Anodic polarization curves for iron dissolution and cathodic polarization curves for copper deposition and ferric and hydrogen ion reduction were studied. These results were used to predict the relative rates of the reactions: The rates of the first two reactions were found to be first order with respect to the reacting ion, and the rale-controlling step was diffusion of the ions to the callzode surface. The rate of hydrogen ion reduction in an oxygen-free solution is dependent on the reciprocal of the square root of the hydrogen ion activity. In solutions containing oxygen, the rate of hydrogen reduction becomes dependent on the square root of the partial pressure of oxygen. At equal concentrations copper precipitation occurs about twice as fast as ferric ion reduction. In an air-saturated solution containing 0.01 M cupric ion at pH 2, the rate of hydrogen ion reduction zs about 10 times slower than that of copper precipitation. At pH values below 3, the rate of hydrogen reduction in oxygen-free solutions is very slozu. COPPER cementation has been utilized industrially for many years as a means of recovering copper from aqueous solutions. There are many different types of cementation plants, but all simply provide a means of contacting iron with relatively dilute copper solutions. In the past little or no attention has been paid to rates or mechanisms of the reactions involved. As a result, this and other studies'-3 have been undertaken recently to establish the important parameters in this system. The reactions involved in copper cementation by iron are: Since transfer of charge is involved in every case, these reactions should be considered from an electrochemical point of view. In any electrochemical system involving electrolytic conduction, passage of electrons necessitates ion transfer to the respective electrodes according to Faraday's law. The current in the system will be proportional to the rate of ion transfer, and, therefore, when the current in the galvanic cell is known, the rates of the reactions involved can be determined. Galvanostatic electrode measurements5" are applicable for these electrochemical studies, in that with this technique polarization curves (current density vs electrode potential) are established by impressing a constant current through an electrode and measuring the electrode potential. Once the current density, electrode potential, and reacting area are known for each reaction in this cementation system, the rates of the iron-consuming reactions can be determined. EXPERIMENTAL MATERIALS Several metal electrodes were used in this investigation; they are shown in Table I. Solutions were made with reagent-grade salts and conductivity water. Air, nitrogen, and oxygen were employed. All of these gases were saturated with water and degreased prior to use. EXPERIMENTAL PROCEDURE The experimental work was divided into two general areas. The first area involved galvanostatic measurements, which were used to determine the rates of reactions as a function of various parameters. The second area comprised actual cementation experiments to check the rates predicted from the electrode measurements. Galvanostatic Electrode Experiments. Polarization curves were obtained using a standard galvanostatic technique5'= with the apparatus shown in Fig. 1. The various electrode polarization experiments were run the same way except for changes in solution composition, polarity, and type of measured electrode. The general procedure involved the following steps: 1) a solution was made 0.5 M in sulfate ion and to the desired cation concentrations; this solution was placed in a constant-temperature bath and saturated with the desired gas; 2) the electrodes were cleaned and placed in the electrode holder; 3) the previously cleaned apparatus was assembled and immersed in a constant-temperature water bath (temperature controlled to ± 0.05"C); 4) the electrode was then positioned; the solutions were introduced, and the polarization meas-

Jan 1, 1969

By J. L. Fitch, B. G. Hurd

The presence of gypsum in samples subjected to standard core analysis introduces serious errors in the measurement of water saturation and porosity. The magnitude of these errors, depending upon the type of analysis procedure used, has been evaluated experimentally and theoretically. Water-saturated pore volumes determined by vacuum distillation or retort procedures may be too high by as much as 48 per cent of the volume of gypsum present. The maximum error in this value determined by Dean-Stark extraction with toluene is 36 per cent of the gypsum volume. If pore space is measured by a Boyle's law type porosimeter the maximum erorr due to gypsum is 38 per cent of the original gypsum volume present. The conscientious core analyst may eliminate the errors caused by gypsum by either of two methods. He may apply suitable corrections for the water of crystallization removed from gypsum, or take special precautions to prevent dehydration of gypsum during core cleaning and alzalysis procedures. These alternatives are discussed and methods for obtaining reliable core analysis data are proposed. Gypsum (CaSO4 . 2H2O) occurs as a common mineral in many of the world's sedimentary basins. In addition to its presence as primary bedded evaporitic deposits, it is often found as secondary replacement zones and pore-fillings in host rocks. That it may cause false indications in porosity, both on neutron logs and in standard core analysis, has been generally recognized. False porosity interpretations from neutron logs result because the chemically bound water in gypsum attenuates neutrons as effectively as free water. Errors in core analysis result when gypsum is dehydrated prior to or during the analysis. Vacuum retort procedures used by many laboratories to determine fluid saturation and porosity effect a complete removal of water of crystallization from gypsum. The crystal water, distilled and collected with free water from the sample, is counted as water-sat11rated pore space. Dehydration of gypsum results in a decrease in volume occupied by calcium sulfate and a corresponding increase in pore volume. Thus, if gypsum is dehydrated by sample cleaning and drying procedures, subsequent porosity measurements with gas expansion or compression instruments will be high. The qualitative effect of gypsum on porosity determinations by retort procedures was discussed in a recent article by Bynum and Koepl3. They concluded that since false porosity was interpreted as being water saturated, determinations of oil content were not affected. Others in the industry, however, have pointed out that porosity values are often used with values of water saturation determined independently, e.g., from electric resistivity logs in making reserve estimates. Values of water saturation calculated from the formation resistivity using the Archie equation, S4= are actually low if values of are high due to gypsum. In this case, false porosity values due to gypsum could cause serious errors in calculations of oil-in-place. This investigation was made to determine quantitatively the effect of gypsum on porosity values determined by different core analysis procedures. EXPERIMENTAL PROCEDURES Dehydration of Gypsum The extent and rate of removal of water of crystallization from gypsum under conditions encountered in core analysis procedures were studied. Taken for the experiments were three types of relatively pure, naturally occurring gypsum, viz. selenite, satin spar and massive gypsum. Although all samples probably contained trace chemical impurities, each type lost the theoretical amount of water upon complete dehydration. An automatic recording thermobalance, similar to one described by Mauer2, was used to obtain dehydration rate data for samples heated in dry air. Water

By D. Weinstein

Yieldilzg in annealed arc-cast molybdenunz in torsion was studied as a function of strain rate and tem-perature. The temperature dependence of the yield point for different strain rates was used to calculate a heat of activation for the yield point. The heat of activation was not a constant but was approximately a linear function of the stress at yield. It is proposed that the rate effect in yielding is determined in part by a site place-change of C (or other interstitial atom) in the metal. THE low-temperature embrittlement phenomenon in metals and alloys has been known to exist for a long time. Although a transition from ductile to brit-tle behavior has been observed in some close-packed hexagonal metals1 and a face-centered cubic alloy, the most common class of metals exhibiting this be-havior has a body-centered cubic lattice structure. For example, a ductile to brittle transition has been observed in iron,3 molybdenum,4 chromium,5 colum-bium,6 and tungsten.7 In the present investigation, molybdenum specimens were tested in torsion over a wide range of temperatures at three widely separated strain rates, and the temperature for onset of embrittlement was determined. Characteristic of body-centered cubic metals and closely associated with plastic deformation is the appearance of a sharp upper and lower yield point. Theoretical explanation of the yield point in iron and low-carbon steel is due to Cottrell,8 who attributes the phenomenon to the pinning of dislocations by the formation of impurity atmospheres around the dislocations. These atmospheres tend to lock the dislocations and make them more difficult to move. The stress required to move a dislocation and thereby cause plastic deformation is greatly increased, and thus an upper yield point is observed. In addition, theoretical analysis,9 as well as experimental observations, show that the upper yield point is strongly a function of temperature. The upper yield point is observed to decrease with an increase in testing temperature, and above a certain temperature (-700° K in iron) it no longer appears. This is consistent with the concept that thermal vibrations will help free a dislocation from its atmosphere, so that the external stress required to free a dislocation from its pinning atmosphere decreases with increasing temperature. Furthermore, with increasing temperature the equilibrium concentration of impurity atoms around a dislocation decreases exponentially with the result that the dislocation is less firmly pinned. In Cottrell's theory of yield point a static model is visualized in which the pinning atmospheres, particularly interstitial atoms, are immobile, and the dislocations are anchored to stationary positions in the lattice. However, experiments1,7 show the upper yield point to be time-dependent or a function of the rate of straining, a high strain rate causing a high upper yield point. Present theory does not adequately account for the rate dependence of the yield point, and the exact function of the interstitial atom is not under stood. Nevertheless, observation of the temperature dependence and rate dependence strongly suggests that the upper yield point phenomenon is due to the interaction between dislocations and pinning atoms, and that a diffusion mechanism is important in determining the yield point.

Jan 1, 1962

By G. K. Manning, E. R. Stein, E. E. Underwood

Columbium, carbon. and nickel additions were made to iron-base alloys with 20 pct CY. The effects on microstructure, precipitation-hardening characteristics, and High-temperature properties were investigated by means of metallographic, hot-hardness, and magnetic measurements. An austenitic alloy consistilzg of Fe-20Cr-14Ni-0.8C-2.5Cb had higher hot-lzaciness at 1700°F than the other alloys investigated. Its favorable standing is attributed to an enhanced interaction of Cb and Cr4C particles dispersed within a stable austenitic matrix. FOR the past 20 years, cobalt- and nickel-base alloys have been used for the more stringent high-temperature applications because of their excellent creep resistance. Although their performance is quite satisfactory, other base materials must be considered for large tonnage, low-cost applications such as for the automotive gas turbine. Iron-base alloys are also used extensively, but at somewhat lower temperatures, primarily because of the instability of particles or because precipitation occurs at relatively low temperatures. Since unusual stability has been reported for Fe-Cb and Cb-C compounds.1-3 it was hoped that effective amounts of these compounds could be taken into solution at temperatures just below the melting range, then precipitated upon reheating. Actually, strengthening was found to occur by both precipitation hardening in some alloys and by phase transformations in others. Among the alloys investigated, that with the best high-temperature properties owes its strengthening to a combination of carbide particle interaction and a relatively stable austenitic matrix. EXPERIMENTAL PROCEDURES Small preliminary melts of about 100 g were made in a vertical Glotube furnace, using alundum crucibles and an argon atmosphere. Alloys weighing 35 lb were melted in a basic-lined induction furnace, also under argon. The compositions of the alloys are given in Table I. The nickel-free alloys were usually ferritic, while those containing nickel were generally austenitic. Depending upon the particular heat treatments, or the combination of alloying elements, two-phase alloys of ferrite and austenite could be obtained. In the following text, however, the nickel-free or nickel-bearing alloys are referred to simply as either ferritic or austenitic alloys respectively. The small ingots were swaged at 2000°F, in steps, to rods of approximately 3/16-in. diam. The large ingots were forged at 2100°F to 1-in. sq bars. No difficulties were encountered in swaging or forging any of the alloys to as much as 90 pct reduction in area. For heat treating at temperatures above 2000°F, specimens were sealed in quartz tubes under a partial pressure of helium. No special precautions were found to be necessary at lower temperatures. Intermetallic compounds in the preliminary alloys were identified by means of X-ray diffraction measurements. Correlation of these results with micro-structural characteristics (such as color, shape, size, and location) of the compounds aided in their identification. Magnetic susceptibilities were also obtained at room temperature with a Magne Gage instrument after the various heat treatments. To

Jan 1, 1962

By Milton E. Wadsworth, T. D. Chatwin

Bulk density variations can usually be minimized by properly mixing the material before moisture measurement. The measuring of moisture on material being with- drawn directly from storage bins requires some form of bulk density correction. In Bethlehem's pellet plants continuous automatic bulk density correction and uniform feed-rate control are obtained with Bethlehem's patented Bin Level Control System. With this sys- tem a single probe, suspended or inserted in the bin, senses whether material is at the proper level in the bin and automatically regulates filter speed to control the filter-cake discharge rate to maintain this level. The level of concentrate in the filter-cake bin can thereby be controlled to within ± 1/2 in. of the point of contact between the concentrate and the probe. Material thickness on the conveyor does not have to be controlled accurately and mix compositions can vary widely as long as they do not contain variable amounts of water-soluble electrolytes. In sinter plants, errors caused by changes in normal feed rate and bed height are minimized by counter-weights that permit the free-floating to maintain a uniform contact pressure on the mix. Large changes in mix resistance can be taken care of either by resetting the control point or by adjusting the calibration control.

Jan 9, 1968

By H. F. Webster, C. G. Dunn

Rolling md annealing procedures are described for developing the (110) preferred orientation in tantalum for use as a thermionic-emission materinl where electrodes of a uniform high work function are needed. The development of a (110) [001] annealing texture is also reported. A preferential growth process due to low (110) gas-metal surface energy is considered in explanation of the observed growth of (110) grains. ThE growth of (110)-oriented grains in thin strips of rolled zone-refined tantalum, previously discussed briefly,' is reported together with more recent information on the formation of a (110)[001.] annealing texture, i.e., one where the [001] direction of each grain lies close to the rolling direction. The development of tantalum sheet with a (110) preferred orientation (position of [001 ] directions unspecified) is of importance as a thermionic-emission material in thermionic-energy converters. Since therm ionic-emission properties of cesium-coated crystals vary over a wide range depending on (hkl) a2-7 a single (hkl) preferred orientation is more useful than either several preferred orientations or none. Furthermore, the (110) preferred orientation yields the highest thermionic-emission density for a cesium coverage of less than a monolayer.5-7 A consideration of the stability of the grain structure needed at high operating temperatures suggests that the preferred orientation itself should be produced by annealing processes. Information on annealing textures in tantalum, however, is rather limited. Pugh and Hibbard 8 obtained (111)[112] and (lll)[112] components in a 1400°C recrystallization texture in 95 pct cold-rolled foil; these components were enhanced on annealing at 2500°C. Muller9 rolled 99.97 Ta to 90 pct reduction in thickness in the final stage and noted only a slight sharpening of the rolling texture, with some intensification of the (111)[112] component upon annealing at 1200°C. The experimental procedure followed in the present work stemmed from the idea of using possible differences in (hkl) surface energies to provide a small driving force for growth of grains having the lowest (hkl) surface energy.l0* This would mean using high-purity tantalum processed into thin sheet form and annealed at high temperatures either in a noncontaminating atmosphere or in one producing additional sample purification. EXPERIMENTAL Zone-Refined Tantalum. National Research Corp. tantalum in the form of 1/8-in.-diam rod and of 99.98 purity (53 ppm 0, 15 ppm N, and 8 ppm C) was zone-melted four times. The traversing speed was 4 mm per min. Such treatment increased the resistance ratio, R293k/R20K , where R293K is the resistance of the specimen at 20°C and R20K the re-resistance at liquid-hydrogen temperature, from a value of 25 for the initial rod to 175 for the zone-refined rod (the increase in the resistance ratio provides a measure of purification11,12). Part of a zone-refined rod was rolled unidirec-tionally to a strip 0.003 in. thick and 0.28 in. wide. Samples were given anneals in the range 1300" to 2100°C using ac conduction heating in an oil-free vacuum system. Recrystallization to small grains appeared to be complete at 1300°C. Large grains were formed at higher temperatures, but these were not entirely strain-free, some grains showing asterism in Laue X-ray patterns and some displaying a range in orientation. Part of the difficulty was caused by thermal expansion of the tantalum strip as it was held between fixed supports. However, in a different arrangement with the tantalum freely suspended in a tantalum can, high-frequency induction heating in vacuo at about l0-6 Torr produced

Jan 1, 1964

By S. T. Yuster

An analysis has been made of the factors responsible for tilted fluid contacts in petroleum reservoirs. The factors are static and dynamic with the former being controlled by those variables responsible for the capillary rise of fluids, and the latter include rate of formation tilt and hydraulic circulation. The explanation that rate of formation tilt may be responsible for tilted contacts appears untenable. The role of some of these factors in the migration, fractionation. accumulation and possibly the prospecting for oil is indicated. INTRODUCTION While it is generally considered that the segregation of gas, oil, and water in a petroleum reservoir results in approximately horizontal planes separating these phases. there are factor; which modify this simplified picture to a very great extent. Some of these factors are static. and the departure of the fluid interfaces from horizontal may represent a static equlibriun. Some of these factors may be dynamic and the interface positions may be non-equilibrium and represent a steady .state condition. Of course combinations of these two situations may also exist. The reasons most commonly given for this behavior are hydraulic circulation of fluids, change in character of the formation, and a rate of tilt of the formations more rapid than the rate at which the fluids may re-establish an equilibrium. Russell's Principles of Petroleum Geology' contains an extensive discussion of tilted fluid interfaces and their importance in the migration and accumulation of petroleum. Russell cites examples of tilted water tables at Lance Creek, Wyo.; Rock River, Wyo.: Cut Bank. Mont.; Cushing, Okla.: and Graham; Okla. Also given was the Wasson Field of West Texas which has saucer shaped oil-water and gas-oil interfaces with the saucer being deeper in the case of the oil-water contact. The Bradford Field in Pennsylvania has a tilted water table. San Ardo. Coalinga None and some other California field.; have tilled contacts. A recent paper by King Hubbert discuses the effect of hydraulic circulation of the water underlying the oil in a given stratun and it- implications in the accumulation of and drilling for the oil. The foregoing would indicate that tilted fluid interfaces are not uncommon and that it would be of importance to underbtand the forces which are responsible. Further. it would be of interest to examine certain idealized models of situations which may cause tilting with the thought in mind of deriving relatinnships between the important variables. These relationships may only hold exactly for the model* assumed but the results may apply semi-quantitatively to actual formations and at least indicate trends. The discussion will be divided into the effect of static factors and the effect of dynamic factors. STATIC FACTORS It has already been mentioned that one reason given for tilted contacts is a variation in formation properties. Specifically this is a change in the pore size of the formation capilaries. If the internal surface of the reservoir is preferetially wet by water, capillarity will cause the water 10 rise to a greater extent above the free water table in a small capillary than in a large one. Consequently the water-oil contact will be higher in the lower permeability sands than in the higher permeability sand.;. The free water table may be defined as the position the oil-water interface would take if capillarity were absent. Since the phenomenon is the capillary rise of water in an oil environment, a derivation of this shold give a relationship between the variables. Fig. 1 is an idealized model of the situation with a uniform bore circular capillary ubstitttting for the tortuous non.circular formation pore. The upward force.; on the column of water will be equated to the forces downward to give the equilibrium situation. forces upward = force downward where r is the radius of the capillary in ceritimetera. a is the interfacial ten4on oil-water in dynes per centimeter, 0 is the

Jan 1, 1953

By B. F. Decker, D. Harker

The recrystallization reaction in OFHC and spectroscopically pure copper has been followed by X ray diffraction determinations of the amount of material with the cold-worked and recrystallized textures in specimens which had been given various heat treatments. The heats of activation for recrystallization are found to be: 29.9 kcal per rnol for OFHC copper and 22.4 kcal per rnol for spectroscopic copper. A reliable and speedy method for measuring the amount of recrystallized material in a piece of rolled metal, together with a new scheme for low temperature heat treatment, have made possible a determination of the activation energy for recrystallization in rolled copper. This method for studying recrystallization rates is different from others reported in the literature.' Oxygen free, high conductivity copper—OFHC copper—of purity 99.98 pct gave an activation energy for recrystallization of 29.9 kcal per mol with recrystallization data taken in the temperature range 208-245°C. Copper of purity 99.999 pct from the American Smelting & Refining Co. gave an activation energy for recrystallization of 22.4 kcal per mol with recrystallization data taken in the temperature range 43-135°C. The great change in activation energy for recrystallization as the small amount of impurity in the metal is decreased suggests that the motion of grain boundaries is conditioned by the impurities which must be concentrated in them. Thus the OFHC copper recrystallizes with an activation energy of the order of magnitude to be expected for the diffusion of the kind of impurities likely to be present. The high purity copper, on the other hand, recrystallizes with a much lower activation energy, in accord with the notion that the grain boundaries need not wait for the impurities to diffuse with them. Copper when strongly cold-rolled has a well-defined crystallite texture which can be described by saying that the [111] direction of the face- centered cubic crystals is aligned approximately in the cross-rolling direction and that faces of the form {110} lie approximately in the rolling plane. When such rolled copper is completely annealed the crystallite texture is quite different: the [loo] direction is in the cross-rolling direction and faces of the form (100) are in the rolling plane. At intermediate stages of annealing, the copper contains both textures. If a Geiger counter X ray diffraction spectrometer is set up so as to measure the intensity of the (200) Bragg reflection from the rolled surface of a piece of copper strip, this intensity increases from a very small value in the cold-worked state to a maximum as the specimen is annealed. The same would be true for (200) reflections from planes normal to the rolling or cross-rolling directions. In view of this fact, the amount of material in the copper which has recrystallized can be measured by comparing the intensities of one of these reflections just mentioned with the intensity from a similar specimen after complete annealing. In much the same way the intensity of (111) reflections from planes normal to the cross-rolling direction could be used to measure the amount of unrecrystallized material in the specimen. In the work to be described here the amounts of recrystallized and unrecrystallized material in partly annealed rolled copper specimens were determined in this way. Experimental Procedure Samples of oxygen free high conductivity (OFHC) copper, cold-rolled 99.7 pct to 0.002 in. thickness, were subjected to heat treatments for various chosen times at four different temperatures, and high purity copper samples, cold-rolled 98.0 pct to 0.0015 in. thickness, at six different temperatures. Each sample, after treatment, was placed in an orientation sample holder for use with a Geiger counter X ray spectrometer and a reading was taken of the intensity of the (200) reflection from planes perpendicular to

Jan 1, 1951