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By A. R. Krause, C. Laird

In order to establish whether or not there is a real temperature effect in fatigue (independent of environment) , poly crystalline copper and Cu- 7.9 A1 alloy have been cycled at 298° and 7° K in vacuo and the fatigue lives compared with those in air and in liquid nitrogen. The lives of both copper and the alloy were found to be highly temperature-dependent in the absence of environment. This result casts serious doubt on the validity of the cell structure hypothesis for stage I crack propagation as presently formulated, because it predicts that there should be no such tempevnture dependence. On the other hand, the plastic blunling process is consistent with the result. Effects of environment aside, the homogenization of slip which accompanies testing at low temperature, and at low strains, seems to be the main cause for increased fatigue life. At high strain amplitudes, the fatigue lives of wavy slip materials, typically copper, are independent of temperature.' It is well-known, however, that low-strain lives greatly as as the temperature of testing is decreased. By contrast, the lives of planar slip materials, such as Cu-7.9 pct A1 alloy, increase to an even greater extent with decreasing temperature throughout both the high and low strain ranges.1'2'5 The mechanism of this temperature effect is associated with the earliest stages of fatigue failure,'" crack nucleation, and stage I growth,"' which is slow propagation along slip bands to the depth of a few grain diameters. Such life behavior has been interpreted on at least two different bases. On the one hand, those interested in the temperature effect at high strain amplitudes1 believe that stage I growth occurs by the plastic blunting process of crack propagation.7'9 They explain the effect in planar slip materials by the homogenization of slip* which accompanies fatigue testing at low temper- atures and serves both to delay crack nucleation and to decrease the rate of stage I propagation. On the other hand, Holt and Backofen,2 who have studied the effect in low strain fatigue, believe that stage I growth can be interpreted by a cell structure hypothesis.10-12 They have challenged2 the conclusion that there is a real temperature effect in this regime of fatigue testing and have interpreted the increased fatigue lives almost entirely in terms of the "environmental-protective'' effect of the liquid nitrogen and helium baths used to obtain low temperatures. This interpretation by Holt and Backofen2 may offer a means of discriminating between these two mechanisms as currently formulated and used to explain stage I growth. On the basis of the plastic blunting process applied to stage I crack propagation,7* the low strain fatigue lives of both wavy and planar slip materials should be increased with decreasing temperature. This follows because both materials show increased slip homogenization in this strain regime."13 Consequently, crack nucleation in intensified bands will be delayed and the linking of such small cracks into larger stage I cracks will be difficult. In addition, the blunting process required to lengthen a stage I crack from the order of 2 to 10 (where the strain concentration of the crack begins to overcome the slip homogenization property of the material) will also be retarded. These delays will give rise to longer lives in both kinds of material. In contrast to the blunting hypothesis, no temperature dependence has been predicted on the basis of the cell structure hypothesis, because it is well-known that materials cycled at low temperature show no differences in type of dislocation structure for a given strain amplitude.18"20 If the lives of wavy and planar slip materials do show a temperature dependence when the environment is eliminated as a variable, then it is questionable whether cell structures per se have a fundamental role in fatigue fracture. Accordingly, specimens of copper and Cu-7.9 wt pct A1 have been cycled at 298° and 77°K in vacuo and the fatigue lives compared with those in air and in liquid nitrogen, in order to establish whether or not there is a real temperature effect in low strain fatigue. Since it is difficult to measure the strains in specimens when cycled in vacuo, S-N curves have been used as the basis of comparison. In studying the influence of temperature on fatigue life in ordinary environment, Holt and Backofen2 used the superior basis of E-N curves. However, they also published S-N curves and thus established the relationship between E-N and S-N curves. This relationship is used to support the S-N comparison reported in the present investigation. EXPERIMENTAL Materials. The copper employed in this investigation was of 99.99 pct purity and the cu-7.9 pct A1 was prepared from metals of the same purity. The stock, of 3 in. initial diam, was reduced in size by rolling

Jan 1, 1969

By K. Mukai, M. Ishihara

This report is a brief discussion of the impurity levels both in primary aluminum and super-purily alnminim in connection with raw materials and proc-essing methods. Particularly, truce amounls of im-purities were analyzed by introducing nittss-speclro-gruphy and nenlron-aclivalian analysis techniques. Vanadium and gallium content in primary aluminum metal corresponded to theor amounls in anode coke. but the nickel content in primary aluminum was hide-pendent oj its amount in the anode cake. Sulfur in the anode colic might result in an increase of the iron content in the molten metal in the reduction cell. The content of sodium and calcium increased with increasing bath ratio. In the holding furnacc sodium content decreased rapidly, and nonmetallic inclusions merit separated front the mollen metal. Three-layer elctrolysis was effectire in eliminating many impuri-ties with the exception of copper, aluminum oxide. aluminum nitride, and some rare-earth elements. THE amount of impurities and nonmetallic inclusions in aluminum metal depends on impurities in the raw materials and various production processes. This paper presents an investigation of the behavior of impurities and nonmetallic inclusions in aluminum during the electrolysis process, the period in the holding furnace, and the process of three-layer electrolysis. Chemical analysis and emission spectrometric analysis have generally been used as methods to determine small amounts of impurities in both primary aluminum and super-purity aluminum; however. mass spectrography and neutron-activation analysis have been recently introduced into this field, and trace amounts of impurities can accurately be determined by these latter methods. EXPERIMENTAL WORK Common impurities were determined by means of absorptiometric. polarographic, flame-photometric. and emission-spectrometric methods. However, in the determination of trace amounts of impurities and non-metallic inclusions, the following methods were applied. In the analyses of trace impurities by mass-spec- trographic analysis, samples were exposed in the vacuum spark of double-focus ing Mattauch-Herzog type mass spectrograph (Japan Electron Optics Laboratory, Ltd.). Ilford Q2 photographic plates were used as ion detectors. Fe was used as the internal standard, and the atomic concentration of each element was calculated by the following expression and converted into the weight concentration: where E, and Ei are the exposures (coulomb) when isotopes of the internal standard and impurity elements (on which the estimate is based) show the same density, X is the percent (atomic) concentration of the standard, IF and Ii are the percent abundances of the isotopes of the standard the impurity elements (on which the estimate is based), and Ms and hfi are the mass of the isotopes of the standard and impurity elements (on which the estimate is based). The coefficient of variation in this method is about 40 pct in the range of 0.1 to 1 ppm. In neutron-activation analysis, irradiations were done in the nuclear reactors TRIGA-I1 (neutron flux: 4.7 x 10 11 n per sq cm per sec; Rikkyo University) or JRR-2 (neutron flux: 2 x 1013 n per sq cm per sec: Japan Atomic Energy Research Institute). After the chemical separation, a NaI (3 by 3 in.) scintillator connected to a 256-channel y-ray spectrometer (R.C.L.) was used for counting and recording various activated impurities. The coefficient of variation in this method is about 20 pct. In the analyses of nonmetallic inclusions, aluminum-oxide determination was carried out according to Fischer's method, 3 as follows. A slice of sample was cut off and the surface was cleaned. It was dissolved in bromine-methanol. The solution was filtered and the residue was washed. The residue was fused with potassium bisulfate flux. Then it was dissolved in weak acid, and oxine solution was added. The aluminum oxinate was extracted with benzene. Finally, aluminum was determined absorptio-metrically. Aluminum nitride determination was carried out as follows. A slice of sample was cut off and the surface was cleaned. It was put in the distillation apparatus and decomposed with sodium hydroxide solution. The solution was distilled. Then ammonia was absorbed and

Jan 1, 1967

By L. Kaufman

An equation is derived relating AF a", the difference in free energy between austenite and martensite, to temperature and composition in the iron-chrmnium and iron-chromium -nickel systems. This equation is used to calculate at M,for low-carbon stainless steels. A method for utilizing the energetic equations to calculate M, in stainless steels is suggested. In addition, an explanation is given for the anomalous effect of chromium in forming a y loop concurrent with the lowering of M, in iron-base alloys. It has been demonstrated that the effect of alloying elements on the Ms temperature is strongly dependent upon the influence of the alloying element on the thermodynamic properties of the y and a phases. Notwithstanding the fact that alloying elements affect the Ms temperature by changing the lattice parameters, elastic constants, and inter-facial energies of the a and y phases, their primary role is a thermodynamic one. Thermodynamic analyses have been presented for the iron-carbon'-4 and iron-nickele systems in which equations are derived for Fa and FY, the free energies of the b.c.c. (or b.c.t.) and f.c.c. phases. These equations, which can be obtained with the aid of the equilibrium diagrams, can be used to help predict the Ms vs composition curves. This paper deals with a calculation of the thermodynamic properties necessary to compute AFffLY for iron-chromium alloys. In view of the lack of direct information concerning the activity of chromium in the a and y phases of iron, the regular solution approximationa,g was utilized to bridge the gap. After the necessary equations were derived for the iron-chromium system they were used to calculate AFff— Y for stainless steels by combining them with the previous results obtained for iron-nickel alloys. The results of these calculations offer a means of rationalizing the anomalous behavior of chromium in iron-base alloys. The latter depends on the regular solution approximation in contrast to the explanation offered by zener , which is based upon the "magnetic specific heat effect." THERMODYNAMICS OF THE IRON-CHROMIUM SYSTEM If y represents the atomic fraction of chromium in an iron-chromium alloy, then the free energy of the b.c.c. phase Fa, the f.c.c. phase FY, and the difference in free energy between the f.c.c. and b.c.c. phases of the same composition are given through [3] and Fmy represent the free energies of mixing of the a and y phases; while @era -' and uFea 4Y represent the difference in free energy between f.c.c. and b.c.c. chromium and iron respectively. The values of AEFe0ff4Y in the temperature range between 0" and 900K ( .

Jan 1, 1960

By Persifor Frazer

INTRODUCTION For various reasons I have not specified the locality where the research indicated in the following pages was undertaken. It will suffice to say that it was on the grounds of a villa once remote from, but now completely surrounded by, its neighboring city, and in close proximity to an industrial establishment of great extent and importance manufacturing many kinds of steel articles and employing upwards of thirty chimney-stacks for power and process work. The problem was to discover the cause or causes of the mortality to trees and plants on the place, and to trace these causes to their origin. Before undertaking this experimental work, the bibliography accompanying this paper was compiled and studied. It appears from an examination of the careful scientific work performed by the ablest French, German, and English chemists during the last 25 years that they are unanimous in assigning the principal-in fact, the overwhelmingly predominant-cause of the destruction of vegetation to sulphur oxides, resulting either from direct- oxidation of sulphur in oil of vitriol works, etc., or from the oxidation of the sulphur from the minerals associated with commercial coal. Schröder and Schertel showed in 1884 that the sulphates deposited upon the leaves are not injurious to the plants; and Freytag proved that free sulphuric acid could not be found

May 1, 1907

By Robert J. De Angelis, James H. Barker

An improved method for solving dynawzical dislocation problems using a digital computer is described in this paper. Interactions between two distinct types of dislocations were studied: attractive screw dislocations; and Lomer lock forming dislocations. One dislocation is positioned in the lattice and is initially at rest, while the other dislocation is moved through the lattice on an intersecting slip plane at a constant velocity in the range 0.5 to 0.999C. (C is the transverse velocity of sound.) The results obtained from these computations indicate that screw dislocations account for a small fraction of the total strain over a wide portion of the range of velocities studied. They further indicate that mixed dislocations mainly repel other dislocations in the neighborhood of the active glide plane. From this a possible explanation for cell formation is put forth. The density of Lomer locks expected to exist after a strain of 0.2 was found to be 1.4 x 106 cm-2 which is in good agreement with indirect experimental estimates. IN the past, predictions of favorable or nonfavorable dislocation reactions were based on the associated changes in elastic strain energy. Such considerations take no account of the probability of the two dislocations coming into contact to react. Venables1 was the first to approach these probabilities by considering the interactions between two moving screw dislocations on perpendicular glide planes. Because of the restrictive types of dislocations and glide plane geometry employed, his results have limited application to metallic crystals. The work to be presented here develops a general approach to solving dynamical dislocation problems; either dislocation-dislocation interactions, presented here in detail, or dislocation interactions with any other suitably defined stress field. Two types of dislocation-dislocation interactions common to face centered cubic (fee) materials are considered: those between pure screw dislocations of opposite sign on intersecting slip planes and those between mixed dislocations on intersecting slip planes, that can react to form a perfect dislocation. This latter reaction, referred to as the Lomer reaction, produces a locked product dislocation that finds it energitical favorable to disassociate into two Shockley partials and a stair-rod dislocation. This partial configuration known as a Lomer-Cottrell (L-C) lock plays a major role in work hardening of fee crystals. seeger2 names the L-C lock as the prime contributor to Stage II hardening while Kuhlmann-wilsdorf3 and Meakin and Wils- dorf4 also state that it is a significant contributor to work hardening. However, with a few notable exceptions,5-7 direct observations of the Lomer lock and the L-C lock by electron transmission microscopy are scanty, and even these are subject to other interpretations.5,6 In a study of partial dislocations present in austenitic stainless steel, whelan8 did not observe any L-C locks at the head of pile-up groups. This result contradicted existing work hardening theories and led him to postulate an alternate theory based on the stress required to break away dislocations intersecting a pile-up group, from their stacking fault nodes. Due to the importance of the Lomer reaction in producing L-C locks which are an essential feature in current work hardening theories and because there exist no data giving direct quantitative values for the density of locks, and because there has even been some doubt expressed as to whether this important reaction occurs at all, a study of the dynamic behavior of the mixed dislocations which form the Lomer lock was undertaken. Due to their ability to cross-slip with relative ease, screw dislocations play an important role in the deformation of fee crystals. For this reason, the second type of reaction considered here is between screw dislocations of opposite sign. In addition, computations in volving screw dislocation interactions are relatively simple, thus providing a convenient check on the cornputational scheme employed. DEFINITION OF PROBLEM The force exerted on a dislocation due to a generalized stress field is given by the Peach and Koehler9 equation: Here t2 and b2 are respectively the tangent and Burgers vectors of the dislocation, and T1 is the stress dyadic defining the local stress field. The stress field may be externally applied or generated internally by the presence of a lattice defect, such as a second dislocation, as is the case in this work. Frank10 has shown that an equivalent momentum, P, of a screw dislocation can be defined by: Here, EST is the total energy of a screw dislocation and ESo is its rest energy. The left side of Eq. [2] is the time derivative of momentum and the right side is the position derivative of the energy due to the dynamical nature of the dislocation. The total energy of a dislocation is the sum of the potential and kinetic energies. Weertman11 has developed the expressions which were used here; these give the potential and kinetic energies of uniformly moving edge and screw dislocations in an isotropic medium.

Jan 1, 1969

The following communication has just reached the Institute, from the office of the Provincial Geologist, Department of Lands,-Forests and Mines, Ontario, Canada: During the autumn of 1917 gold was discovered in unsurveyed territory south of Lake Abitibi in northeastern Ontario. This area lies about 70 miles almost directly east of the well known Porcupine area. During the coming summer, the Ontario Bureau of Mines is to make a geological survey of this new gold area. Following the custom of Ontario, this area is being divided into townships, 6 miles square. These townships have recently been given the following names in honor of men well known in the mining and geological world. In alphabetical order the names are as follows: Frecheville-Prof. Wm. Frecheville, Professor of Mining in the Royal School of Mines, London; Past President of the Institution of Mining and Metallurgy. Garrison-Mr. F. Lynwood Garrison, Mining Engineer, Philadelphia, Pa. Harker-Dr. Alfred Harker, F. R. S., immediate Past President of the Geological Society of London.

Jan 6, 1918

By D. W. Fuerstenau

MEASUREMENT of zeta potentials is a useful tool to study the surface chemistry of minerals under flotation conditions.1,2 Because there is continued interest in this approach, the apparatus for obtaining zeta potentials of nonconducting solids by the streaming potential method is outlined here. Fig. 1 illustrates the streaming potential apparatus." The streaming potential cell or plug consists of two 24/40 standard ground joints (4) joined with a piece of pyrex tubing 60 mm long and 12 mm in diam (5). The electrodes are made of bright platinum disks 19 mm in diam and 1 mm thick through which 0.5-mm holes have been drilled (6). To the surface of each is welded a piece of 80-mesh platinum gauze. Each electrode is permanently mounted on the ends of the inner parts of the two standard joints by means of a platinum wire (7) which connects it to the tungsten seal at the end of the cell (8). For ease in cleaning and handling the apparatus, the streaming cell is fastened to the 500-ml reservoir flasks (1) by means of two 18/9 ball and socket joints (2). This particular arrangement permits passage of the solution in either direction through the plug of particles. Flow of solution can be stopped by a stopcock (3). One of the reservoir flasks has a large opening to permit insertion of either a thermometer or a pair of electrodes for measuring pH of solutions within the system. In making the experiments, the plug is filled with 48 to 65-mesh particles, but a layer of 28 to 35-mesh particles is placed at each electrode to prevent any of the finer particles from passing through holes in the electrodes. The assembled apparatus is shown schematically in Fig. 2. To eliminate CO2 from the solutions, all experiments are conducted in a nitrogen atmosphere. Nitrogen, used to drive solutions through the plug, is passed through a bottle of concentrated KOH solution to remove CO2 (9). A 9-liter ballast reservoir (10) is used to maintain a more nearly uniform pressure. A series of stopcocks controls the direction of flow nitrogen to the flasks (11). Tubes of as-carite prevent backflow of CO2 into the system (12). Driving pressure, which can be set at any desired value, is measured with either a water manometer (13) or a mercury manometer (14). Reservoir flasks have side arms for making pressure corrections for the difference in water levels in the flasks. Streaming potentials are measured by the circuit illustrated in Fig. 2. The electrodes from the plug are connected through mercury wells (15) to a reversing switch (16), which reverses the polarity of the electrodes depending on the direction of flow of solution through the plug. The streaming potential is measured with a Leeds and Northrup type K2 potentiometer (17). Proper choice of null instrument is important because Eq. 1 assumes that the current which escapes through the measuring instruments is negligible. An ordinary galvanometer cannot be used to determine the null point because

Jan 1, 1957

By AIME AIME

FIFTY years ago William Bertolette Plank was born in Pennsylvania, in which state he was also educated, winding up with an E.M. from Penn State in 1909, at the age of 23. ' He remained there as instructor for a year, and then went with the Philadelphia & Reading Coal & Iron Co. as mining engineer for three years. During the next four years he was on the staff of the Pittsburgh Coal Co. In 1916 he turned to Government work, going to Pittsburgh as junior mining engineer for the U. S. Bureau of Mines. He became successively assistant mining engineer there, mining engineer at the Bureau's Urbana, Ill., station, and finally Mr. Plank was appointed district mining engineer for the Bureau at Birmingham, Alabama.

Jan 1, 1937

By R. A. Graham, R. W. Rohde

The effect of hydrostatic pressure upon the austenite start temperature of a commercial Fe-28.4 at. pct Ni-0.5 at. pct C alloy has been determined. For pressures to 20 kbar, the austenite start temperature decreased from its atmospheric pressure value of 380°C at the rate of about 4°C per kbar. These data are analyzed by two different thermodynamic approaches; first, considering the transformation as an isothermal process, and second, considering the transformation as an isentropic process. It was found that both these approaches fit the experimental data equally well. The effect of hydrostatic pressure upon the austenite start temperature is best described by considering the mechanical work done during the transformation as that work obtained by multiplying the applied pressure with the gross volume change of the transformation. It is widely recognized1 that strain has an important effect on the initiation of martensitic transformations.* For example, the martensite start tempera- *In this paper, use of the term martensitic transformation implies the reversal of martensite to austenite as wen as the formation of martensite from austenite. ture, M,, may be increased by plastic deformation. Similarly, plastic deformation is observed to lower the austenite start temperature, A,. The effect of uniaxial stress on the M, of iron-nickel alloys has been studied by Kulin, Cohen, and Averbach.2 They found that the martensite start temperature was significantly changed by stresses well within the elastic region. Moreover, the effect of tensile and compres-sive stresses differed. These effects were explained in terms of the interaction of the applied stress with both the dilational and shear components of the transformation strain. The magnitudes of the influence of uniaxial tension, compression and hydrostatic pressure on Ms were measured in 30 pct Ni 70 pct Fe by Pate1 and Cohen.3 Their thermodynamic calculations and similar calculations by Fisher and Turnbull4 predicted the experimental results when the transformation was assumed to occur isothermally at some fixed driving force. This driving force was assumed to be supplied by a combination of the chemical free energy difference between the austenitic and martensitic phases and the work performed during transformation by the applied stress. More recently, Russell and winchel15 reported the effect of rapidly applied shear stress on the reversal of martensite to austenite in iron-nickel-carbon alloys. They performed a thermodynamic analysis of this transformation based upon the assumption that the re- versal occurred adiabatically. They concluded that the applied shear stress did not significantly interact with the transformation strain and thus did not assist in inducing the reversal. Rather they concluded that the reversal was effected by localized strain heating which resulted from the gross local shear deformation of the experiment. In either the adiabatic or isothermal analysis it is necessary to compute the work performed by the interaction of the applied stress and the transformation strains. In the case of hydrostatic pressure this interaction has been treated by two different methods. In either case the applied pressure is assumed to remain constant during the transformation. In one treatment the applied pressure is assumed to interact directly with the dilatational strain associated with the formation of an individual martensite plate.3'4 This local strain has been measured at atmospheric pressure in iron-nickel alloys by Machlin and Cohen.6 In the above treatment this local strain is assumed invariant with temperature and pressure changes. In the other treatment the applied pressure is assumed to interact with the gross volume change of the transformation.7,8 The usefulness of this latter treatment has been demonstrated by Kaufman, Leyenaar, and Harvey7 who calculated the effects of pressure upon the martensite and austenite start temperatures of Fe-10 at. pct Ni and Fe-25 at. pct Ni alloys. Excellent agreement was obtained between their calculations and their experimental data on an Fe-9.5 at. pct Ni alloy. However, this treatment suffers from the fact that the data required to calculate the volume change of the transformation (i.e., the initial specific volumes, the thermal expansion and compressibility data for both the austenitic and martensitic phases) is, in general, not available for any material except pure iron. Thus the calculations of Kaufman et al.7 were necessarily performed by assuming that the volume change of the martensitic transformation in the iron-nickel alloys was that same volume change occurring during the a-? transformation in pure iron. While this approximation may suffice for very dilute alloys it is likely to be inaccurate in high nickel alloys. We have performed measurements of the effect of hydrostatic pressure to 20 kbar on the A, temperature of an Fe-28.4 at. pct Ni-0.5 at. pct C alloy. The composition is similar to the alloy used by Pate1 and Cohen3 to determine the effect of pressure upon the M, temperature. The present measurements permit calculation of the interaction between the applied pressure and the transformation strain. Additionally, measurements have been made which allow precise determination of the gross volume change of the transformation. The data allow direct comparison between the alternate hypotheses of the interaction between the applied pressure and a dilatational transformation strain characterized by either the formation

Jan 1, 1970

By P. S. Kotval, H. Hahell

PRECIPITATION of M23C6 carbides at grain boundaries in austenitic steels and nickel base superalloys has received considerable attention. Hatwell and Berghezan,1 in a study using carbon extraction replicas, observed that dendritic growth of the M23C6 carbide phase occurred at grain boundaries in austenitic steels. Merrick and Nicholson2 have observed that in thin foils of "Nimonic 75" alloy the precipitation of M23C6 carbide was discontinuous at grain boundaries. Lewis and Hattersley3 have suggested that the type of M23C6 precipitation observed in Ni-Cr austenites represented the early stages of discontinuous precipitation. In a more recent study, Singhal and Martin4 have concluded that grain boundary M23C6 precipitation involves the migration of an austenite grain boundary by a mechanism very similar to that proposed by Tu and Turnbull.5 Tu and Turnbull's suggestion essentially involves grain boundary migration under the driving force arising from the difference between the surface free energies of the opposite sides of the plate. Thus, Singhal and Martin's observation4 implies that the first stage of discontinuous precipitation has taken place and that the grain boundary has provided a diffusion short circuit for the sub-stitutional solute atoms (principally chromium) which assist the preferential growth of the M23C6 plate in contact with the grain boundary. However, no evidence of the characteristic cellular morphology typical of discontinuous precipitation was found in Singhal and Martin's studies. Presumably, this is due to the low volume fraction (i.e., low supersaturation of solute) of the precipitating carbide reported by Singhal and Martin.4 Recently, Raymond6 has studied precipitation of the M23C6 carbide in Incoloy alloy 825 and shown that the growth of this phase is perpendicular to grain boundaries at 1400°F and in the plane of the grain boundary at 1700°F. The former aging condition resulting in discontinuous or "cellular" precipitation. Raymond has suggested an explanation for this behavior based on the relative rates of chromium diffusion by volume and grain boundary diffusion at the two different aging temperatures. In the course of a recent investigation on precipitation behavior in several ' strengthened superalloys, precipitation of M23C6 carbide at grain boundaries was studied. Under conditions of a high degree of supersaturation, the M23C6 carbide precipitates in the discontinuous or cellular morphology in Waspalloy (Ni-18.51 Cr-2.0 Fe-3.53 Mo-1.16 Al-2.78 Ti-0.09 C). This note presents electron microscopy observations of this mode of precipitation and its effect on mechanical properties. Specimens of Waspalloy after "solution" heat treatment at 1950°F show essentially single phase matrix with a few residual particles of "primary" MC carbide. In normal commercial heat treatments, precipitation of Ni3(Al,Ti) ordered fcc r' phase occurs throughout the matrix and M23C6 precipitates as globular particles at the grain boundaries. In these commercial heat treatments the degree of supersaturation during precipitation is low. However, if specimens of Waspalloy are quenched from the solution heat treatment temperature of 1950°F and then aged at an aging temperature where the degree of supersaturation is high, discontinuous precipitation of M23C6 occurs. Figs. 1 and 2 show thin foil micrographs of Waspalloy, solution heat treated at 1950°F, water quenched, and aged at 1292° and 1598°F, respectively, for 500 Fig. 1—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 500 hr at 1292°F. Magnification 15,500 times. Fig. 2—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 114 hr at 1598° F. Magnification 13,000 times.

Jan 1, 1970

By P. Breidt, E. S. Greiner

THIS note reports a determination of the melting point of germanium, and the liquidus of the Ge-Ga alloys; lattice constants of the a phase are given. The alloys were prepared by melting germanium (>20 ohm-cm resistivity) and gallium (99.6 pct) in evacuated silica tubes. The materials (50 to 70 g) were heated at 1000°C, held in the liquid state for about ¾ hr, and then cooled rapidly in the tubes. Points on the liquidus were obtained by thermal analysis which consisted of obtaining time-temperature data during heating and cooling the materials in high purity graphite crucibles and a helium at- mosphere. Temperatures were determined with a Pt—Pt-Rh thermocouple protected by a silica sheath. The couple was calibrated against a National Bureau of Standards calibrated couple and also against the freezing points of copper, silver, aluminum, and the 28.1 wt pct Cu, 71.9 wt pct Ag alloy eutectic. The samples for X-ray analysis were prepared by heating small pieces of the ingots in evacuated glass or quartz tubes at temperatures between 600" and 900°C for periods ranging from 2 hr to 22 days, periods deemed sufficient for equilibrium to be attained, followed by quenching in water. The heat-treated samples were ground to powder for X-ray analysis. The lattice constants of the germanium-rich phase (a) were determined with a baok-reflection focusing camera. The X-ray reflections (331 and 422 Cr Ka, 422 and 333 Cr KB) were corrected

Jan 1, 1956

By K. P. Anderko

INVESTIGATIONS of the constitution of the system Mg-Ba were first made by Grube and Dietrich1 between 0 and 47 atomic pct Ba and then by Klemm and Dincke1acker" ver the whole composition range. Klemm and Dinckelacker corroborated intermediate phases of the approximate formulas Mg9Ba and Mg4Ba, and showed a third compound to have the formula Mg2Ba, rather than Mg5Ba, as suggested by Grube and Dietrich. Mg2Ba had been previously recognized by Hellner and Laves3 s a MgZn2 (C14) type structure. The main discrepancies between the results of Grube and Dietrich and those of Klemm and Dinckelacker exist, however, in the liquidus temperatures and solidification equilibria of alloys containing more than about 10 atomic pct Ba. The liquidus temperatures measured by Grube and Dietrich, and the outline of the liquidus of Klemm and Dinckelacker are plotted in Fig. 1 on an enlarged scale. Although there are strong reasons to prefer the results of Klemm and Dinckelacker, it was considered worthwhile to remeasure liquidus temperatures of some alloys in the controversial composition range. The alloys, made up from sublimed magnesium and 99.5 wt pct pure barium, were melted in an Armco-iron crucible in a dynamic argon atmosphere. Thermal analyses were taken using a Speedomax auto- matic recorder. Careful stirring during the solidification process was required in order to avoid segregation. After thermal analysis some of the cast alloys were chemically analyzed. The intended and analyzed compositions of the ten alloys prepared are listed in Table I. Since standard barium determinations cannot differentiate between barium present as element and as oxide, both the barium and magnesium contents of the alloys were analyzed. The fact that the sum of barium and magnesium was close to 100 pct in each case was taken as evidence that no excessive oxidation had occurred. The liquidus temperatures measured are listed in Table I and plotted in Fig. 1. As can be seen, they are in good agreement with the liquidus found by Klemm and Dinckelacker. This leaves no doubt that the thermal results of Grube and Dietrich above 10 atomic pct Ba are incorrect. This work was performed under the sponsorship of the Pitman-Dunn Laboratories of Frankford Arsenal, Philadelphia, Contract No. DA-11-022-ORD-1975. Sponsorship and permission to publish by this organization are gratefully acknowledged.

Jan 1, 1958

By T. D. Mueller, H. Dykstra

This paper describes a method for obtaining compositions of gas and oil phases in equilibrium with each other at a given reservoir temperature and pressure as lean or enriched gas is injected into a reservoir oil not in equilibrium with the gas. The method is based on calculation of equilibrium constants, K, from the equation log Kp = A + B F, where p is pressure and F is component characterization factor. A and B are constants that vary with a composition parameter. The paper explains how A and B could be determined with a minimum amount of data. The method consists of calculating equilibrium constants as a function of liquid composition and using the K's to calculate changes in compositiort of injection gas as it successively contacts original resetvoir oil at the gas-oil front and the change in composition of reservoir oil as it is successively contacted by the injection gas in the vicinity of an injection well. An iterative process is required. Two examples of the method are given which show how oil and gas compositions and properties are calculated with the aid of a computer. INTRODUCTION The calculation of recovery from lean-gas or enriched-gas injection into a saturated or under-saturated reservoir oil requires a knowledge of how phase properties change in a reservoir between injection well and producing well. To determine the phase compositions or properties experimentally would be difficult and time consuming, especially if one wanted to look at the effect of various injection gas compositions. For some fields an engineer would want to make preliminary calculations on the economics of gas injection before he makes the decision to spend a corrsiderable sum of money for laboratory work to obtain the necessary fluid properties. A method for calculatine compositions and properties based on a minimum of laboratory data is described. The minimum amount of data required is injection gas and reservoir oil composition and injection gas solubility as a function of pressure for an undersaturated oil, or the compositions of mixtures of reservoir fluid with two or more enriched gases, which mixtures have a bubble-point pressure that is the same as the expected average displacement pressure. On the other hand, if the economics appear to be attractive, more laboratory data can be obtained in the form of equilibrium constants for three or more mixtures of the reservoir fluid and injection gases. The method is based on the calculation of K's from the equation, log Kp = A + B F, where K is equilibrium constant, p is pressure and F is component characterization factor. This method of plotting K data by means of the above equation is described by Hoffman, Crump and Hocott.1 A and B are constants that vary with a composition parameter. It is shown how experimental data are used to determine how A and B vary with composition. BASIS OF METHOD EQUILIBRIUM CONSTANTS Equilibrium constant (K) data are required for this method. The K of each component is obtained from an equation that gives the product of K and pressure as a function of component characterization factor. The characterization factor F = b(l/Tb — l/T), where b is a constant characteristic of a given component, Tb is the boiling point in OR at atmospheric pressure of the given component, and T is the temperature of the system in OR. This method of plotting K data is described by Hoffman, Crump and Hocott.l The straight-line equation of the log Kp - F plot is log hp = log Kop +BFi, where Kop is at F =0, i designates the component, and B is the slope of the line. The factor F can be

Jan 1, 1966

By G. R. Speich, R. A. Oriani

The rate of coarsening (Ostwald ripening) of copper precipitate Particles in an a-iron matrix has been studied in three Fe-Cu alloys containing 2.3, 4.0, and 5.4 wt pct Cu in the temperature range 730° to 830°C. The kinetics of Ostwald ripening ohevs the law as deduced by Lifshitz and Wagner so that matrix diffusion controls the process. The equilibrium shape of the particles is that of rods with hemispherical caps, and is due to the BOTH Lifshitz and slyozov and wagner3 have recently solved the complex problem of determining the rate of coarsening of an assembly of precipitate particles. Both workers, although using somewhat different mathematical approaches, arrive at the same equation for the relation between the mean radius 7 of a distribution of spherical particles and the bulk solubility co, diffusivity D in the matrix, large anisotropy in the copper/a iron interfacial free energy (y,/y, = 4). A Lifshitz -Wagner equation, modified for both the nonsphericity of the diffusion field and the reformulation of the Gibbs-Thomson equation for the case of nonsphencal particles, is derived. Using the modified equation, the calculated values of the mean radius are smaller than those observed by a factor of about one -half. absolute temperature T, gas constant R, surface free energy y of the precipitate/matrix interface, and the time t of aging: where V, is the molar volume of the precipitate and v is a stoichiometric factor. Wagner's treatment is restricted to the case of spherical particles growing in a liquid matrix where strain energy is not a factor. Lifshitz and slyozov have discussed the effect of anisotropic particle shapes and internal strains on the rate of coarsening. Oriani4

Jan 1, 1965

By H. I. Young

INASMUCH as there has been a great deal of activity in this district recently, a paper of this kind should treat of all the various phases of mining, namely, prospecting, developing and operating. PROSPECTING Where ore is found it a depth of 100 ft. (30 m.) or more, the prospect work is done by churn drilling. Several makes of churn drills are used in this work, both steam- and gasoline-driven machines being used. The drilling is usually started with a 6-in. bit, and the size of the bit is reduced, if necessary, as the hole is advanced. It is general practice to drill from 100 to 400-ft. holes, but this is governed entirely by the location and formation of the ground. In drilling sheet ground, close spacing of drill holes is unnecessary, but in narrow orebodies, the holes are spaced from 15 to 50 ft. (4.6 to 15 m.) apart. Ten years ago, very few assays were kept of the drilling, but during recent years records have been kept very accurately, showing the location, elevation, assays, and also the vertical section of the hole. After the orebody is reached, cuttings are taken every 2 or 3 ft. (0.6 to 0.9 m.) samples being sometimes taken by pouring the water off the cuttings and taking a portion of the coarse material for assay. It has been found, however, that very often the sludge material poured off with the water contains high mineral values. To overcome this, cuttings from each 2 or 3 ft. are put in a container and after the water is evaporated, sample for assay is taken by means of Jones samplers. Permanent records of cuttings showing various formations are kept in glass jars or glued on large cards. Drilling at present is costing from $1.25 to $1.50 per foot. In pre-war times, the drilling costs ran from 75c to $1 per foot.

Jan 9, 1917

By C. R. Breck

THERE has been a running discussion over the past several years with respect to the life and adequacy of our natural gas reserves. Some of the experts agree on one phase of the subject at least-that eventually it will be necessary to augment deliveries of natural gas in the northern markets by the development of a more or less comparable synthetic gas made from coal. The purpose of this paper is to point out: 1. It may be later than a good many people think-the demand for addi¬tional domestic and commercial pipeline gas in at least one section of the North will probably be felt rather keenly before an adequate synthetic pipe¬line-gas project, developed on economic lines, could be completed, even if initiated in the near future. 2. The evidence is considerable that such a project would be technically sound and economically self-supporting, although the margin of profit at first might be so small and the magnitude of an economic enterprise so great -that financing would be impossible without Government aid in some form or other. The part of the country referred to is the heavily populated section in the northeast of the United States. To simplify an examination of the situa¬tion, let us take the potential marketing areas within range to the north and east of the three pipelines: 1. Tennessee Gas Transmission Co. as it enters Erie County, New York state. 2. Texas Eastern Transmission Corporation just before the tap that sup¬plies the general Philadelphia area. 3. Transcontinental Gas Pipe Line Corporation as it enters the state of New Jersey. The sources of gas for these three pipelines are in Texas and Louisiana. The ultimate maximum combined capacity of the three lines at the points stated is approximately 1,200,000,000 cu ft per 24 hr at the maximum load factor probable of attainment in normal operation. The areas supplied by the three lines north and east of the points stated, or assumed as eventual markets, are: 1. Central New York state, from Buffalo to Albany (both inclusive).

Jan 1, 1953

The plans for the activities of the Petroleum Division for the coming year do not differ materially from those of the past several years. The fall meeting is scheduled for Oct. 12 and 13 and is to be held at Tulsa, Oklahoma. The Division, of course, will take part in the annual meeting of the Institute at New York. A fall meeting will also be held in California at approximately the same time as the meeting at Tulsa. A number of papers are to be presented at the two meetings simultaneously. The various committees are at work arranging the programs. The Division will continue to be active in its various fields of endeavor, such as stabilization, production reviews, and economics, but special stress is to be laid on the engineering and research fields. In the past the Division has served as a forum for open and frank discussion of problems confronting the engineers in the oil industry. It is hoped that it will continue to function in this capacity. Papers presenting original ideas and extending the boundaries of knowledge and understanding in the field of petroleum production will be welcomed. Members who have interesting information to contribute should not wait until called upon by one of the Committees, but should offer a paper at the earliest opportunity. The past year has seen a decided strengthening of the control over production, with prospects of even more rigid control in the future. It is essential that production programs under such control be carefully planned and it is highly desirable that petroleum engineers take an active part in the planning, to insure efficient production of oil and minimize the waste of this natural resource. At a time like this, when it is difficult to keep the production of oil within reasonable limits, it may seem unnecessary to improve the efficiency of production methods, but, as has been aptly said, the trouble is not that we have too great a reserve of oil but that we are producing tomorrow's oil today. Therefore it behooves those who are entrusted with the engineering and scientific phases of production to learn how to get the greatest yield economically possible from the present and future fields in order that we may enjoy the advantages of petroleum products for a long time to come.

Jan 1, 1934

By J. M. Smith, G. P. Willhite, J. S. Dranoff

Heat transfer rates were measured in sandstones with flow of gases perpendicular to the direction of energy transfer. Effective thermal conductivities ker ranged from 0.7 to 1.7 Btu/(br)(ft)(°F). The contribution of the solid phase appeared to be the most important in these consolidated materials, although the thermal conductivity of the gas had some effect. The velocity of the gas through the pores of the sandstones had no influence upon ker up to values of 168 lb/(br) (sq ft) in agreement with data obtained for unconsolidated beds of glass beads. The present results indicated that gas mixing, and hence heat transfer by convection in the pores, is less for perpendicular transfer of energy than when fluid flow and energy transfer are in the same direction. HEAT TRANSFER PERPENDICULAR TO FLUID FLOW IN POROUS ROCKS Heat transfer in porous media with pore sizes in the micron range depends upon the fluid in the pores and the geometry of the solid phase. The best characterized system is a bed of solid spherical particles. Heat transfer in this system has been studied extensive1y (Ref. 8 summarizes the literature up to 1959) when the pores contain stagnant fluid. When the fluid is in motion the directions of flow and energy transfer have an effect on the heat transfer rates, as demonstrated by comparing the work of Willhite, et al l3 for perpendicular flow and that of Kunii and Smith9 for parallel flow of energy and fluid. For perpendicular flow, no increase in effective thermal conductivity ke was noted up to mass velocities G of 77 lb/(hr) (sq ft). In contrast, for parallel flow ke, increased with G in the same range of flow rates. These higher values of ke in the direction of flow also have been observed3,4,10 in beds of larger particles, 0.1- to 0.5-in. diameter. For beds of consolidated materials, such as porous rocks, data are not available for these compar- isons, although Adivarahan1 reported results for the parallel case. Hence the primary objective of this work was to measure ke values for perpendicular flow of fluid and energy in porous rocks. Of interest also was the variation in effective conductivity with fluid velocity. APPARATUS AND PROCEDURE In the experimental method, a constant heat flux was applied to the inner surface of an annular section of the porous rock. By cooling the outer wall, a temperature gradient through the annular sample was established and measured with thermocouples placed within the sample at various radial positions, and at three elevations (A,B.C). The location of the 2-in. O.D., 3.75-in. long sample in the apparatus is shown in Fig. 1. Fluid entered the bottom (1) of the 3-in. I.D. (approximate) steel shell, flowed upwards through the sample and out at the top (3). pressure taps (2,4) were used to check the permeability of the sample. The energy flowed radially from the centrally-located electric heater through the sample and was absorbed in the water-cooled jacket. The samples studied were naturally occurring sandstones from different locations with the properties given in Table 1. These materials are identical with those used by Adivarahan 1 for the parallel flow of energy and fluid. Prior to use they were refluxed with toluene to remove hydrocarbons and leached with distilled water to remove soluble salts. Each sample was visually examined and discarded if large nonhomogeneities, such as cracks or stone particles, were noted. Eight copper-constantan thermocouples were inserted in holes drilled radially into the sample with

By C. E. Webber

The economical recovery of the valuable constituents from the effluent of gas-con-densate wells has developed into a problem of balancing the cost of recovery against the cost of compressing the residual gas back into the formation. A possible method of extracting the gasoline and distillate from the natural gas is by oil absorption at high pressures. In order to design and evaluate an absorption plant, fundamental data on the composition of the coexisting hydro- carbon vapor and liquid phases at various temperatures and pressures are essential. A review of the literature indicated that the necessary data for the design of such plants are lacking. The nearest approach to desired published data is that of Katz and Hackmuth,~ who experimentally deter-mined the composition of the coexisting vapor and liquid phases in a natural gas-crude oil system at pressures up to 3000 lb. per sq. in. and at temperatures from 40' to zoo°F. This paper presents the results of the experimental determination of the equilib-rium distribution of the hydrocarbons methane through hexane between natural gas and a typical absorber oil. The ranges of temperature and pressure chosen were from 33' to r8oUF. and from 100 to 5000 lb. per sq. inch. Materials The absorber oil was a typical naturally occurring, Straw-colored distillate that had previously been steam-distilled to an initial boiling point of 300 F. The physical and chemical properties, including the results of an Engler distillation, are presented in Table I. A large volume of this oil was obtained and it was used throughout the complete set of experiments. Table i.—Properties of the Absorption Oil Gravity .......................... . . 32.5' A.P.1. Molecular weight by benzene freezing- point depression.................. 183 Viscosity, poises; at 100°F........... 0.0a80 At 200°F...................... 0.0102 Composition, PeR Cent Aromatics........ 24.0 Naphthenes..... 36.7 unsaturates,Aromatics...... .I24.00.3 1 Parafins Naphthenes.....36.7 39.o EngLeR Distillation Per Cent /ncg. F. Per Cent Dez. P. Initial boilins rmint.. 300 I 60....... 523 5.................. 402 I 70....... 538 10.................. 421 180....... 557 20.................. 462 90....... 570 30.................. 480 1 95....... 623 40.................. 49 .................1 511 Residue, z .o per cent; loss, 0.3 per cent. See refrence I. The n-hexane was obtained from the Ohio Chemical and Manufacturing Co., Cleveland, Ohio. This liquid had a boiling range of from 149" to 152.6'F., with a density of 0.667 at 60°F. and a molecular weight of 85 by benzene freezing-point depression. The propane, isobutane, wbu-tane, isopentane and n-pentane were ob-ta,ined from the Philgas Department of the Phillips Petroleum Co. Certified analyses of these compounds showed their purity to be in excess of 99.5 per cent and they were riot further purified.

Jan 1, 1941

By C. E. Webber

The economical recovery of the valuable constituents from the effluent of gas-con-densate wells has developed into a problem of balancing the cost of recovery against the cost of compressing the residual gas back into the formation. A possible method of extracting the gasoline and distillate from the natural gas is by oil absorption at high pressures. In order to design and evaluate an absorption plant, fundamental data on the composition of the coexisting hydro- carbon vapor and liquid phases at various temperatures and pressures are essential. A review of the literature indicated that the necessary data for the design of such plants are lacking. The nearest approach to desired published data is that of Katz and Hackmuth,~ who experimentally deter-mined the composition of the coexisting vapor and liquid phases in a natural gas-crude oil system at pressures up to 3000 lb. per sq. in. and at temperatures from 40' to zoo°F. This paper presents the results of the experimental determination of the equilib-rium distribution of the hydrocarbons methane through hexane between natural gas and a typical absorber oil. The ranges of temperature and pressure chosen were from 33' to r8oUF. and from 100 to 5000 lb. per sq. inch. Materials The absorber oil was a typical naturally occurring, Straw-colored distillate that had previously been steam-distilled to an initial boiling point of 300 F. The physical and chemical properties, including the results of an Engler distillation, are presented in Table I. A large volume of this oil was obtained and it was used throughout the complete set of experiments. Table i.—Properties of the Absorption Oil Gravity .......................... . . 32.5' A.P.1. Molecular weight by benzene freezing- point depression.................. 183 Viscosity, poises; at 100°F........... 0.0a80 At 200°F...................... 0.0102 Composition, PeR Cent Aromatics........ 24.0 Naphthenes..... 36.7 unsaturates,Aromatics...... .I24.00.3 1 Parafins Naphthenes.....36.7 39.o EngLeR Distillation Per Cent /ncg. F. Per Cent Dez. P. Initial boilins rmint.. 300 I 60....... 523 5.................. 402 I 70....... 538 10.................. 421 180....... 557 20.................. 462 90....... 570 30.................. 480 1 95....... 623 40.................. 49 .................1 511 Residue, z .o per cent; loss, 0.3 per cent. See refrence I. The n-hexane was obtained from the Ohio Chemical and Manufacturing Co., Cleveland, Ohio. This liquid had a boiling range of from 149" to 152.6'F., with a density of 0.667 at 60°F. and a molecular weight of 85 by benzene freezing-point depression. The propane, isobutane, wbu-tane, isopentane and n-pentane were ob-ta,ined from the Philgas Department of the Phillips Petroleum Co. Certified analyses of these compounds showed their purity to be in excess of 99.5 per cent and they were riot further purified.

Jan 1, 1941