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By Edward Saibel

The various theories that have been advanced to explain or predict the conditions under which a metal fractures may be divided into two categories: First, there are the macroscopic theories generally used in engineering practice. These are empirical in nature and limited in application. For example, the maximum normal stress criterion, which is quite satisfactory for a mild steel in simple tension at atmospheric pressure,' no longer suffices when this steel is pulled under hydrostatic pressure.2 In all of these empirical theories, the critical condition characteristic of the material and of the loading conditions must be obtained experimentally. Secondly, there are the theories based on interatomic forces,3'4 or on the energy required to form new surfaces.5,6 These have all dealt with the theoretical evaluation of the tensile stress necessary to bring about rupture in a purely brittle manner; that is, without plastic flow preceding fracture. All of these attempts have led to values of the tensile strength of crystals or of polycrystalline bodies that are 100 to 1000 times higher than observed values. On this account, it has been thought necessary by some investigators to conceive of a microcrack structure or distribution of flaws throughout the specimen such that the resulting stress concentrations provide the factor necessary to bring about agree- ment between calculation and experiment. It has been pointed out by several observers' that this point of view is highly unrealistic, in that the weakening effect of these flaws or microstructures must be very uniform from specimen to specimen, since the fracture stresses found for various specimens of the same material tested under similar conditions are so nearly constant. Furthermore, since calculations based on atomic forces or atomic energy are for purely brittle fracture, a condition probably never satisfied in tests, agreement is hardly to be expected. Thermodynamic Theory of Fürth In order to resolve this apparent discrepancy between the theoretical cohesive strengths and the observed fracture strengths, Fürth8 advanced a thermodynamic theory of the tensile strength of isotropic bodies based on work of Born relating to the melting of crystals. Assuming an isotropic material free from imperfections and flaws, behaving elastically up to the breaking point, and assuming a connection between rupture and the melting phenomenon, Fürth obtains an expression for the rupture stress a, in the form where Q is the melting energy per unit mass, p is the density, and is Poisson's ratio. Furth compares fracture stresses computed from Eq I with the fracture stresses of metals as given in the Landolt-Bernstein Tables (1927) and in the Hand-

Jan 1, 1947

By Edward Saibel

The various theories that have been advanced to explain or predict the conditions under which a metal fractures may be divided into two categories: First, there are the macroscopic theories generally used in engineering practice. These are empirical in nature and limited in application. For example, the maximum normal stress criterion, which is quite satisfactory for a mild steel in simple tension at atmospheric pressure,' no longer suffices when this steel is pulled under hydrostatic pressure.2 In all of these empirical theories, the critical condition characteristic of the material and of the loading conditions must be obtained experimentally. Secondly, there are the theories based on interatomic forces,3'4 or on the energy required to form new surfaces.5,6 These have all dealt with the theoretical evaluation of the tensile stress necessary to bring about rupture in a purely brittle manner; that is, without plastic flow preceding fracture. All of these attempts have led to values of the tensile strength of crystals or of polycrystalline bodies that are 100 to 1000 times higher than observed values. On this account, it has been thought necessary by some investigators to conceive of a microcrack structure or distribution of flaws throughout the specimen such that the resulting stress concentrations provide the factor necessary to bring about agree- ment between calculation and experiment. It has been pointed out by several observers' that this point of view is highly unrealistic, in that the weakening effect of these flaws or microstructures must be very uniform from specimen to specimen, since the fracture stresses found for various specimens of the same material tested under similar conditions are so nearly constant. Furthermore, since calculations based on atomic forces or atomic energy are for purely brittle fracture, a condition probably never satisfied in tests, agreement is hardly to be expected. Thermodynamic Theory of Fürth In order to resolve this apparent discrepancy between the theoretical cohesive strengths and the observed fracture strengths, Fürth8 advanced a thermodynamic theory of the tensile strength of isotropic bodies based on work of Born relating to the melting of crystals. Assuming an isotropic material free from imperfections and flaws, behaving elastically up to the breaking point, and assuming a connection between rupture and the melting phenomenon, Fürth obtains an expression for the rupture stress a, in the form where Q is the melting energy per unit mass, p is the density, and is Poisson's ratio. Furth compares fracture stresses computed from Eq I with the fracture stresses of metals as given in the Landolt-Bernstein Tables (1927) and in the Hand-

Jan 1, 1947

By Daniel R. Hull

IN 1026 Genders' reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan,3 and by Phillips and Brick,2 so that no resume is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. VAPOR SEGREGATION There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table I, which represents a [ ] cylindrical billet 7 in. in diameter by 5; in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. The lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps up a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By P. D. Merica, J. R. Freeman, R. G. Waltenberg

Contents Page Constitution of Commercial Aluminum.................. 4 Solubility of CuAl2 in Aluminum at Different Temperatures........ 9 Effect of Magnesium on Solubility of CuA12 in Aluminum ......... 15 Solubility of Mg4Al8 in Aluminum at Different Temperatures........ 15 Solubility of Metals and Metal Compounds in Aluminum.......... 20 Summary and Conclusions......................20 Aluminum and its alloys have been the subject of much investigation1 during recent years, in the course of which the principal features of the constitution of most of the binary alloy systems with aluminum have been determined. Except in the case of a few metals—silicon, bismuth, cadmium, lead, zinc, and tin—an aluminum-rich compound is formed in each binary system, which forms a eutectic with the aluminum or its solid solution with this compound: Thus such compounds as FeAla, CuA12, Mg4Al3, and NiAls are formed, which are found in aluminum-rich alloys of their respective series as eutectics with the aluminum solid solution. These compounds are, in all cases, hard and brittle and their presence affects profoundly the physical properties of the alloys in which they occur. Within the zinc-aluminum system a compound, Al2Zn,, is formed that decomposes at lower temperatures. Silicon and tin each form a simple eutectiferous series with aluminum; bismuth, lead, and cadmium are only partly miscible in the liquid state with it. The extent of the solubility in aluminum, in solid solution, of these compounds or of the elements themselves, in the case of those series in which compounds are not formed, is of the greatest importance in

Jan 1, 1921

[Mining Methods Guy N. BJORGE, Chairman CLYDE E. WEED, Vice-Chairman HARLAN A. WALKER, Secretary Alluvial Mining CLINTON BERNARD O. B. PERRY R. B. EARLING C. M. ROMANOWITZ BENERE H. GRANT J. B. STAPLER CHARLES THURMAN Open-Cut Mining Iron G. E. DIEHL P. G. HARRISON EARL E. HUNNER Copper Louis BUCHMAN W. H. GOODRICH J. H. DAVIS WALTER S. LARSH Underground Mining Iron ROY A. BOWEN S. R. ELLIOTT T. C. DESOLLAR W. A. KNOLL GEORGE H. RUPP]

Jan 1, 1940

Arizona E. P. MATHEWSON, Chairman F. W. MACLENNAN, First Vice-chairman CLYDE E. WEED, Second Vice-chairman E.D. GARDNER, : Secretary-Treasurer Box 4097, University Station, Tucson, Ariz. ARTHUR CROWFOOT G.H. DOWELL HENRY F. EASTER R.D. LEISK Boston Meets first Monday each month, October to May, inclusive GEORGE, W. METCALFE, Chairman ROBERT S. WILLIAMS, Vice-chairman F. LEROY FOSTER, Secretary-Treasurer Rooms G-202, Mass. Inst. of Tech. Cambridge, Mass. FREDERICK K. MORRIS GEORGE A. PACKARD

Jan 1, 1934

Arizona E. P. MATHEWSON, Chairman F. W. MACLENNAN, First Vice-chairman CLYDE E. WEED, Second Vice-chairman E. D. GARDNER, Secretary-Treasurer Box 4097, University Station, Tucson, Ariz. I. H. BARKDOLL HENRY F. EASTER MICHAEL CURLEY R. D. LEISK Boston Meets first Monday each month, October to May, inclusive ROBERT S. WILLIAMS, Chairman GLEN F. JENKS, Vice-chairman F. LEROY FOSTER. Secretary-Treasurer Rooms 6-202, Mass. Inst. of Tech., Cambridge, Mass. HOLCOMB J. BROWN ESPER S. LARSEN

Jan 1, 1936

By A. G. Metcalfe, Koeneman

A study of the structure of chemically deposited nickel by Goldenstein, Rostoker, Scpssberger, and Gutzeit has been reported recently. In this work it was shown that the nickel deposit produced by the catalytic nickel-reduction process was an amorphous solid. Crystallization occurred at elevated temperatures when the original powder pattern which showed only a diffuse ring with a d-spacing of 2.01A became sharp, revealing nickel and nickel-phosphide lines. The phosphide was indexed provision%lly on a tetragonal lattice of parameters a = 9.01A and c = 4.42A, which is in reasonable agreement with the structure of Ni3P proposed by No-wotny and Henglein.3 The transformation from the amorphous to the solid state occurs abruptly (e.g., after 7 min holding at 400°C) with the evolution of considerably more than 1000 cal per gm-mole. A more detailed analysis of these effects requires a knowledge of the solubility of phosphorus in nickel. Konstanti-now3 mapped out the phase diagram in 1908 but did not determine the solid solubility. The eutectic was placed at 11 pct P and 880°C. The purity of typical catalytic nickel deposits is very high.' Spectrographic analysis for heavier elements showed only trace amounts of aluminum, calcium, iron, magnesium, lead, and silicon. The term "strace" is a qualitative definition for less than 0.1 pct and probably less than 0.01 pct. Analysis for the interstitial elements yielded 0.04 pct C, 0.0023 pct 0, 0.0005 pct N, and 0.0016 pct H. Some of this material with 7.5 pct P was used in the present work. EXPERIMENTAL METHODS Alloys were prepared from carbonyl-nickel shot and a master composition containing 7.5 pct P. Cold-crucible, nonconsumable-arc melting was used.

Jan 1, 1959

E. H. Dix, JR., Chairman L. W. M. PEIRCE, Past-chairman R. F. MEHL, Vice-chairman ALBERT J. PHILLIPS, Vice-chairman E. M. WISE, Secretary International Nickel Co., Bayonne, N. J. W. M. CORSE, Treasurer LOUIS JORDAN, Executive Secretary 29 West 39th St., New York, N. Y. Executive Committee W. H. BASSETT, JR. R. H. LEACH' W. H. FINKELDEY W. E. REMMERS2 J. A. GANN H. J. ROAST G. O. HIERS C. S. SMITHS L ZICKRICK

Jan 1, 1936

By Edgar C. Bain

Of the important phenomenon of the hardening of steel, Professor Sauveurl says: It would seem as if the methods used to date for the elucidation of this complex problem have yielded all they are capable of yielding and that further straining of these methods will only serve to confuse the issue, the point having been reached when this juggling, no matter how skilfully done, with allotropy, solid solutions, and strains is causing weariness without advancing the solution of the problem. The tendency of late has been to abandon the safer road of experimental facts and to enter the maze of excessive speculations, in which there is great danger of some becoming hopelessly lost. The conclusion seems warranted that new avenues of approach must be found if we are to obtain a correct answer to this apparent enigma. With some degree of fitness we may say this of other problems. It seems likely that one of the new avenues of approach to many metallo-graphic problems is the study of crystal structure, or more accurately, the atomic arrangement, by means of the x-ray spectrometer. The crystal structure of some materials has been carefully worked out by the mineralogist, but his methods are, in general, unsuited to commercial metals and a method that yields even better information is at hand as the result of work on the diffraction of x-rays by Laue and the Braggs2 and later by HullI3 St. John, and others. It should be understood that the contour of free crystals, which is the subject of measurements by the crystallographer, is the result of the atomic structure and, in general, bears a simple and obvious relation to it. The use of the x-ray spectrometer4 has been described frequently, so the procedure will not be given here.

Jan 1, 1923

By Edgar C. Bain

Of the important phenomenon of the hardening of steel, Professor Sauveurl says: It would seem as if the methods used to date for the elucidation of this complex problem have yielded all they are capable of yielding and that further straining of these methods will only serve to confuse the issue, the point having been reached when this juggling, no matter how skilfully done, with allotropy, solid solutions, and strains is causing weariness without advancing the solution of the problem. The tendency of late has been to abandon the safer road of experimental facts and to enter the maze of excessive speculations, in which there is great danger of some becoming hopelessly lost. The conclusion seems warranted that new avenues of approach must be found if we are to obtain a correct answer to this apparent enigma. With some degree of fitness we may say this of other problems. It seems likely that one of the new avenues of approach to many metallo-graphic problems is the study of crystal structure, or more accurately, the atomic arrangement, by means of the x-ray spectrometer. The crystal structure of some materials has been carefully worked out by the mineralogist, but his methods are, in general, unsuited to commercial metals and a method that yields even better information is at hand as the result of work on the diffraction of x-rays by Laue and the Braggs2 and later by HullI3 St. John, and others. It should be understood that the contour of free crystals, which is the subject of measurements by the crystallographer, is the result of the atomic structure and, in general, bears a simple and obvious relation to it. The use of the x-ray spectrometer4 has been described frequently, so the procedure will not be given here.

Jan 1, 1923

By Northcutt Ely

A year ago the petroleum code was in effect, and Congress had before it bills with powerful backing designed to extend and put on a permanent basis the Federal authority impliedly recognized in the petroleum code. Those men in the industry who were convinced of the unconstitutionality of Federal regulation, who believed in conservation, and who were seeking accomplishment of a conservation compact among the oil-producing states, were at that time encountering difficulties in bringing about such an agreement. Since then there has been a shift in the center of gravity. Today, by virtue of the Supreme Court's Schechter case decision, the petroleum code is not in existence, the industry is not operating under an oil administrator, and the Federal-control bills are not on Congress' calendar. In view of what the Supreme Court has said in the Schechter case and the Hoosac Mills case about the local character of mining and manufacturing, the problem today is not whether the Federal Government or the State Governments ought to regulate oil production, but how effective we can make the devices that are available to us under the constitution for the conservation of the nation's oil resources. The interstate oil conservation compact ratified during the past year by Texas, Oklahoma, Kansas, New Mexico, Colorado and Illinois, approved by Congress, but not yet in effect in California, is the mechanism now at work. Interstate Oil Conservation Compact What is this interstate compact? The basic theory is simple and logical. It has four elements to it. The first point is that in order to effect the maximum recovery of our oil arid gas reserves it is necessary for some governmental authority to regulate the way in which those resources are taken out of the ground, so that the reservoir energy is efficiently used, and used equitably by the various owners of the pool. Second, that the state, as distinguished from the national government, possesses the police power necessary to protect the public interest and to protect the correlative rights of the common owners of the oil pool. Third, that the state governments ought to cooperate with each other through an interstate advisory commission so that orderly production in one state is

Jan 1, 1936

By Northcutt Ely

A year ago the petroleum code was in effect, and Congress had before it bills with powerful backing designed to extend and put on a permanent basis the Federal authority impliedly recognized in the petroleum code. Those men in the industry who were convinced of the unconstitutionality of Federal regulation, who believed in conservation, and who were seeking accomplishment of a conservation compact among the oil-producing states, were at that time encountering difficulties in bringing about such an agreement. Since then there has been a shift in the center of gravity. Today, by virtue of the Supreme Court's Schechter case decision, the petroleum code is not in existence, the industry is not operating under an oil administrator, and the Federal-control bills are not on Congress' calendar. In view of what the Supreme Court has said in the Schechter case and the Hoosac Mills case about the local character of mining and manufacturing, the problem today is not whether the Federal Government or the State Governments ought to regulate oil production, but how effective we can make the devices that are available to us under the constitution for the conservation of the nation's oil resources. The interstate oil conservation compact ratified during the past year by Texas, Oklahoma, Kansas, New Mexico, Colorado and Illinois, approved by Congress, but not yet in effect in California, is the mechanism now at work. Interstate Oil Conservation Compact What is this interstate compact? The basic theory is simple and logical. It has four elements to it. The first point is that in order to effect the maximum recovery of our oil arid gas reserves it is necessary for some governmental authority to regulate the way in which those resources are taken out of the ground, so that the reservoir energy is efficiently used, and used equitably by the various owners of the pool. Second, that the state, as distinguished from the national government, possesses the police power necessary to protect the public interest and to protect the correlative rights of the common owners of the oil pool. Third, that the state governments ought to cooperate with each other through an interstate advisory commission so that orderly production in one state is

Jan 1, 1936

By E. G. Leonardon, C. Schlumberger, M. Schlumberger

In the search for practical geological problems amenable to solution by the potential methods, the geophysicist is led to study mathematically various theoretical cases. In these idealistic discussions, the media under consideration are generally supposed to be homogeneous and iso-tropic. The geophysicist, of course, realizes perfectly that these conditions do not occur in their entirety in reality. However, the assumptions made are justified, because very often they are necessary in order to render possible an exhaustive study of a given problem, which otherwise would be too complicated, and would not lend itself to a complete mathematical analysis. Of the above two assumptions, that concerning the homogeneity of a given geological formation is satisfactorily realized except in so far as isotropy is concerned, since this property is not often encountered in practice. As a consequence, it is very desirable for the geophysicist to have quite an extensive knowledge of the properties of anisotropic formations, and of the laws that govern the propagation of electric current therein. With such principles in mind, he will be able to decide whether the conclusions arrived at in simple, isotropic conditions are still correct in more complex cases, or in what way they must be modified or adapted in order to constitute a sound basis for the interpretation of the results obtained in anisotropic media. On the other hand, the fact that in anisotropic formations the mobility of the ions is greater along the strike than perpendicular thereto can be utilized for determining the direction of the dip by induction measurements. We therefore propose to study in three successive chapters the following points: 1. Propagation of the electric current in anisotropic media. 2. Some consequences of the anisotropy of geological formations with reference to the surface electrical measurements, and their interpretation. 3. Determination of the direction of the dip of anisotropic formations by surface induction measurements.

Jan 1, 1934

By Robert Maes, Robert de Strycker

The solidifzcation reactions in the Cu-Sn-As system were determined by microscopic examination, thermal analysis, and X-ray diffraction. The system presents no ternary compound. There is a quasi-binary section, of a simple eutectic type, between the compounds Cu5As2 and SnAs; the system presents, in addition, one ternary eutectic reaction, one ternary peritectic reaction, and seven transitional reactions. The temp-peratures corresponding to each of these reactions were determined, most of them with an accuracy of *lLC. The isothermal lines of the liquidus surface were also established for almost the entire diagram. NO reference was found in the literature relative to the Cu-Sn-As phase diagram and this is believed to be the first study on this subject. The Cu-Sn diagram was taken from Hansen and Anderko;' it is represented by Fig. 1, with the phase designation which will be used in the remainder of this work. For the Cu-As diagram, the solution proposed by Hansen and ~nderko' must be modified to take account of recent data, principally from Heyding and Despault~ and from Hume-Rothery and Burns; this yields the diagram represented by Fig. 2. As for the Sn-As diagram, it is not established with certainty, particularly so far as concerns the solid solubility of tin in arsenic and the solidification reactions near the compound SnsAsz. For this last point, Hansen and Anderko propose two solutions: congruent melting of Sn3Asz with a eutectic SnsAsZ + SnAs or incongruent melting implying a peri-tectic reaction L + SnAs = Sn3As2. Microscopic examination of the few binary alloys prepared in this composition range made us prefer the second of these solutions, which gives the diagram shown by Fig. 3. EXPERIMENTAL METHODS The experimental techniques used in this work were microscopic observation and thermal analysis; a few X-ray diffraction patterns were taken to verify the

Jan 1, 1967

By D. S. Tomalin, D. F. Stein

The effect of reducing oxygen to low concentrations on the fracture of high-purity iron single crystals has been examined at 78° and 20°K. It is found that iron single crystals grown by the strain-anneal method usually contain a few occluded grain boundaries which may become embittled in the presence of oxygen, thereby nucleating cleavage fractures. High purity with respect to interstitial elements was found to inhibit twinning and evidence is presented for an orientation dependence of the resolved yield stress. Deformation occurred by slip rather than twinning at both temperatures of testing with elongations of as much as 9 pct at 20°K. THE fracture properties of iron single crystals have been observedl-3 to be a function of temperature, orientation, and purity. Allen, Hopkins, and McLennan1 demonstrated that at 78°K iron single crystals became increasingly brittle as the tensile axis approached the (001) pole of the stereographic unit triangle. Iron crystals with the tension axis near a (001) pole were completely brittle and orientations near the (011)-(111) boundary were very ductile, achieving a 100 pct reduction in area prior to fracture. Later work of Biggs and pratt2 and of Edmondson3 demonstrated that by reducing the carbon content of the single crystals the transition between brittle and ductile failure at 78°K could be shifted to orientations nearer the (001) pole. Ed-mondson went further and pointed out that any mechanism which tended to increase the yield strength of the iron (i.e., carbon addition, pre-strain) also increased the tendency for brittle behavior at 78°K. Thus by a reduction of carbon content Biggs and Pratt were able to obtain ductile behavior to within 20 deg of the (001) pole, and Ed-mondson was able to obtain ductile behavior to within 26 deg of the (001) pole. Edmondson's material had a total interstitial content (carbon, oxygen, and nitrogen) of approximately 60 ppm and, although Biggs and Pratt reported no analysis, indications were that their iron contained comparable impurities. Stein, Low, and seybolt4 purified iron single crystals to a total carbon, oxygen, and nitrogen content of approximately 20 ppm. They observed a lowering of the yield stress with this increased purity, and thus one might have expected an observation of increased ductility. Although they tested specimens of orientations which the previous workers had indicated should be ductile, the crystals failed at a 78°K in a brittle manner with little elongation. Stein noted,' however, that about 90 pet of the failures could be traced in origin to occluded grains. Allen et al.1 and Edmondson3 do not report examination of their cleavage surfaces, but Biggs and pratt2 reported that microscopic examination of the cleavage surfaces of many of their specimens revealed the presence of small occluded grains. Honda and cohen6 and Keh7 have also observed the initiation of fracture at occluded grains in iron single crystals. Therefore, the additional complication of occluded grains must be considered in studying the properties of iron single crystals and the origin of fractures determined if the ductility exhibited by the crystals is to be considered meaningful. Various investigators8-12 have studied the effects of impurities on grain boundaries in high-purity polycrystalline iron. Rees and Hopkins10 showed that the addition of oxygen to low-carbon (0.002 pet) iron weakened the grain boundaries, causing a shift from transcrystalline to intercrystalline fracture and a progressive decrease on the brittle-fracture stress with increasing oxygen content. In addition, it has been shown by Low and Feustel11 that the addition of carbon to polycrystalline iron containing oxygen eliminated grain boundary brittleness. Thus, oxygen can embrittle grain boundaries in high-purity polycrystalline iron, but the addition of an appropriate amount of carbon can eliminate the oxygen-induced brittleness. The oxygen content (19 ppm) of the iron "single crystals" employed by Stein el al. was large enough to suspect impurity effects at the occluded grain boundaries. Allen et al.1 Biggs and pratt,2 and Edmondson3 may have masked any occluded grain problem in their specimens considering the relatively high carbon levels they employed. stein13 demonstrated that the addition of as little as 0.9 ppm C to previously purified (less than 5 x 10-3 ppm C) "single crystals" would increase the elongation from a few percent to more than 20 pet at 78°K and the fracture was not associated with grade boundary initiation.

Jan 1, 1965

By Claude H. P. Lupis, John F. Elliott

QUITE generally an increase in the temperature tends to bring a system closer to ideality. It is reasonable as a first approximation to consider that the excess free energy will vary linearly with the temperature, or: where t may be defined as the "characteristic temperature" of the solution, or the temperature at which the system would become ideal if the results at T were linearly extrapolated. It must be emphasized that consideration of this hypothetical property is an appeal to intuition rather than an established physical concept. The order of magnitude of 7 for dilute solutions will depend on the nature of the solvent; a value of 3000° + 1000°K may be suggested for ordinary metallic solutions. In terms of free energy, entropy, and enthalpy first-order interaction coefficients, differentiation of the above equations with respect to composition leads to The concept of t offers a simple and plausible interpretation of Chipman and corrigan's3 recent empirical correlation between and a for a number of groups of ternary systems 1-24. The authors found that in each group the ratio was approximately constant. The corresponding calculated from their data by Eq. [4] are listed in Table I. The expected order of magnitude is obtained for 7. As noted by Darken,4 if a regular solution is not assumed, thus if utj) # 0, Chipman and Crrigan's results imply that, as T is increased, ultimately changes in sign, Fig. 1. Clearly Eq. [4] is valid only in a limited range of temperatures since at the temperature 7 at which the system becomes ideal not only should become null but also and . Thus, both and are functions of

Jan 1, 1967

By Harvey T. Kennedy, Erasmo T. Guerrero

In this investigation, the effects of the surface tension of brine and the interfacial tension between oil and brine on the recovery of oil by water flooding of Woodbine sand were studied. Variation of the surface forces was obtained by the addition of small amounts of commercially available chemicals, which did not appreciably change the surface tension of the oil. Fourteen surface-active agents, which were found to be effective in lowering the surface and interfacial tensions, were further investigated to determine the extent of their adsorption by the Woodbine Sand cores. It was found that adsorption was sufficient in all cases to prevent any substantial concentration of chemical at the flood front. The flow system was, therefore, brought to equilibrium with definite concentrations in the flood water by circulation before each test. The data thus have no relation to the results obtainable by using the chemicals in full-scale water floods, but should be helpful in predicting the performance of surface-active chemicals which are not lost by adsorption, if such can be found. Flow tests were made on various concentrations 01 six chemicals selected from the 14 investigated for surface activity and adsorption, with and without the presence of gas in the core. It was found that lowering the interfacial tension had a tendency toward reducing the recovery of oil and that the reduction of the surface tension of the brine had little or no effect. A substantial beneficial effect, however, resulted from the presence of gas in the cores. INTRODUCTION The movement and distribution of crude oil in a porous medium are governed by such factors as surfacc and interfacial tensions, viscosity of the oil, pore size configuration, and wetting characteristics of the medium. The knowledge of the part played by each of these factors is limited. If the oil is assumed to be distributed in droplets whose movement is restricted only by the pore openings, the following equation may be applied: ?P= 2r(1/r1-1/r2) .......(1) In this equation ?P is the pressure drop necessary to force an oil droplet through the construction, r is the oil-brine interfacial tension, r1 is the radius of curvature at the forward and smaller end of the deformed droplet, and r2 is the larger radius. This equation neglects the effects of viscosity, as a static or near static condition is assumed. It would apply equally well for a bubble of gas in liquid if r were taken as the surface tension of the liquid. This relation shows that droplets can be more easily displaced if the interfacial tension is decreased. The displacement of oil from the surface of a sand particle may also be considered from the basis of selective wetting assuming that the oil droplets are smaller than the pore constructions and that the sand surfaces may be considered as planes. A relation of the forces involved can be derived from Dupre's equation to give: Wos = row (1 +Cos?)........(2) where Wos = Work of adhesion between the sand and the oil row = Oil-water interfacial tension 0 = Contact angle ros = Oil-solid interfacial tension This equation would indicate that the displacement of oil from a sand surface is more readily obtained when the water-oil interfacial tension is reduced provided the contact angle remains constant. Evidently. however, the values of Cos 0 may vary along with the water-oil interfacial tension due to changes in the other surfaces of the system. The above theoretical considerations suggest that perhaps even the static behavior of a dispersed oil phase in a porous medium is considerably more complex than may be inferred by the simple systems

Jan 1, 1955

AARONS, J. BOYD, Major. AGNEW, FRANK VANS. ALLEN, HERMAN H., Private, D Co., 8th Reserve Engineers. BANKS, H. R., Lieutenant, Canadian Engineers, B. E. F. BARBOUR, PERCY E., Deputy Supt. (Captain), New York State Troopers; Captain, 22d Regiment, N. Y. N. G. BARLING, H. B., 1st Lieutenant, Engineer Officers' Reserve Corps. BIGELOW, BRAXTON. BLOOMFIELD, E. C., Lieutenant. BORROW, F. K. BROOKS, ALFRED H., Captain, Engineer Officers' Reserve Corps. BROWNE, DE Courser, 1st Lieutenant, Ordnance Dept., Fortress Monroe, Va.

Jan 8, 1917

By J. E. Walstrom

While intensive research continues to promote a more complete understanding of the potential and resistivity measurements that comprise the electric log, it is believed that consideration should also be given to translating these numerous and often widely separated findings into a coordinated and readable body of fundamental facts designed specifically for the petroleum engineer and geologist. Although provision is made through publication for a ready exchange of new theoretical concepts. it is also desirable to provide reviews and appraisals of the more established techniques and methods from the operating standpoint so that an economic and practical application may be realized concurrently with the theoretical progress. With these basic premises as a guide the author reviews the presnt state of electric log interpretation. The paper is directed not so much to the logging or research specialist as to the petroleum engineer and geologist to whom the electric log is only one of the many tools which he employs. Frequently, these persons do not have the time to follow in detail the many specialized contributions that appear and, as a consequence. are not in a position to place these contributions in proper relation to each other, or to the art as a whole. The paper reviews the basic steps in making quantitative determinations from the electric log of the amount of oil or gas present in subsurface formations and also discusses the degree of reliability of these determinations under various conditions. The paper also indicates the trend of future developments in electric logging systems and methods of interpretation. INTRODUCTION The electric log has been used about 20 years as a means for studying the formations penetrated by a well bore. The first half of this period is characterized by the development of suitable logging techniques and equipment. Although progress in this direction is continuing at a satisfactory rate, the last ten years are characterized more by an increasing interest in methods of electric log interpretation. During this period, a large number of fundamental papers have been published, expounding various logging techniques and particular phases of the interpretation problem. Many of these papers represent important contributions, and a few are classic. This paper is an effort to outline as concisely as possible and in simple terms the main course of progress in electric log interpretation. More specifically, it is the purpose of the paper to review the necessary elements and basic steps used in making quantitative determinations of water saturation from the electric log; and to point out the degree of reliability of these determinations under different conditions. It is strongly advised that the operating staffs of the drilling and exploration departments of oil companies cooperate wholeheartedly with both the electric logging service companies and research organizations in the testing and development of new logging systems and interpretation methods. One purpose of the paper is. however, to indicate the degree of caution which must be exercised in placing confidence in new techniques and interpretation methods that have not been thoroughly tested in the field. It is entirely possible to be cooperative in trying new methods and yet reluctant to believe in the results until the methods are firmly established. It is important to define the meaning of quantitative electric log interpretation. In the most general sense, an interpretation of the log has been made when the electrical characteristics of the formations, as portrayed on the log, have been translated into terms describing the formation geometry, rock type, or any other physical characteristics of the formations. The determination that the top of a sand is at a certain depth is an interpretation of the log. Structural determinations made by correlating electric logs from a given area are also interpretations of the logs. The term quantitative interpretation, however, will be used in this paper in the restricted sense to indicate the determination of the water saturation of a formation. This determination defines the fluid content of an oil and gas productive formation only if the porosity is known, and it assumes that the remainder of the pore space contains hydrocarbons. This assumption is believed to be true for most oil and gas productive formations. The quantitative electric log interpretation may he said to be a determination of the fluid content only to the extent which the water saturation, under the conditions given above. defines it. THE BASIC STEPS The fundamental steps in calculating water saturation from the electric log are: 1. Determination of the true resistivity of the formations from the apparent resistivities as recorded on the electric log.

Jan 1, 1952