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By Walter Miller

ALTHOUGH confident of its ability to meet any demands which may be made, the petroleum refining industry is not complacent about the situation and realizes that the quantities of petroleum products to be furnished are so enormous and so far beyond what was previously estimated that the full co-operative effort of the industry must be exerted. Establishment by the President in May of the Office of Petroleum Coordinator for Defense with Secretary of the Interior Ickes at its head, plus the formation of the Petroleum Industry Council for Defense, in November, provide the channels for united endeavor within the industry and the means for gearing that endeavor within the industry and the means for gearing that endeavor in full harmony with the nation?s needs. Great strides have been made and a rapid understanding of the situation and the magnitude of the task is being attained by all concerned.

Jan 1, 1942

By Bradley Stoughton

AT THE meeting of the Board of Directors on May 20, the resignation of Bradley Stoughton as Secretary of the Institute was presented and regretfully accepted by the Board. The letter of resignation follows : Gentlemen: About two years ago, I indicated to the President and some members of the Board my belief that the office of Secretary of the Institute should not be a permanent one. It is my observation of events, not only in our own Institute, but also in several sister societies, that too long a tenure of office by the Secretary inevitably leads to a situation which is not good either for him or for the society. After submitting this in writing to the Directors on February 17, 1920, I was overpersuaded by members of the Board to defer resignation until a more convenient time for the

Jan 1, 1921

K. T. Aust and J. W. Rutter (General Electric Research Laboratory)—We find it difficult to reconcile the activation energies determined by Gifkins with his general conclusion that "migration during both creep and grain growth can thus be treated on the basis of the same model" (that of Lucke and Detert). Gifkins finds the activation energy for grain boundary migration during creep to be 24.5 kcal per rnol and that for grain boundary migration during grain growth to be 7.5 kcal per mol. The calculation carried out by Gifkins of the activation energy for grain boundary migration during grain growth, using the Lucke and Detert model, gives a value of 20 to 24.5 kcal per mol, rather than his experimental value of 7.5 kcal per mol. The theory of Lucke and Detert was developed to account for the rates of migration of grain boundaries in the presence of impurities during grain growth. The theory does not take into account the effect on the boundary migration of another, simultaneous process such as creep deformation and would be expected, therefore, to be applicable only to migration during grain growth. The fact that Gifkins measured a different activation energy for boundary migration during grain growth (7.5 kcal per mol) from that during creep (24.5 kcal per mol), although the specimens were of the same composition, shows clearly that such an effect exists under his experimental conditions; the presence of a simultaneous creep deformation markedly affects the boundary migration process in comparison with what would be observed under the same conditions but without the creep deformation. The failure of McLean's equation (Eq. [4] of Gifkins' paper) to give a satisfactory dislocation density difference for boundary migration during creep is not surprising, since the activation energy which must be used in this equation refers only to the elementary atom transfer process of grain boundary migration. This activation energy value is approximately 6 kcal per mol for zone-refined lead, as determined in both the grain boundary migration experiments of Aust and Rutter31, 32 and the grain growth experiments of Bolling and Winegard.33 Using this activation energy value, McLean's equation gives reasonable agreement with observed migration rates for grain boundaries moving free of the influence of impurities.31, 32 The value of 24.5 kcal per mol is probably associated with the presence of impurity atoms, as Gifkins suggests. It should be noted, however, that this value was obtained using lead of only one composition and measurements at only two temperatures. The work of Aust and Rutter3"' on the effects of tin, silver, and gold on grain boundary migration in zone-refined lead in the temperature range from 320" to 200°C, as well as the work of Bolling and Winegard34 on the effect of silver and gold on grain growth in zone-refined lead, shows that the measured activation energy is markedly dependent upon the kind and amount of solute present. Gifkins' work does not permit evaluation of the effect of the 8 ppm of impurities other than oxygen present in his specimens. One incidental point: the symbols used to designate the experimental points of Fig. 6 appear to be in incorrect order in the figure caption. As the caption is printed, it would indicate that larger grain sizes were obtained after annealing at 47°C than at 100°C, which does not agree with the text (point M, p. 1019). Finally, it seems clear from Gifkins' results that any serious attempt to determine whether grain boundary migration and grain boundary sliding during creep occur with the same activation energy, as Gifkins suggests and McLean rejects, must take into account the effects of impurities on these two processes, Although the work of Weinberg35 indicated that adding small amounts of copper, iron and silicon to aluminum did not affect the grain boundary shear behavior, it should be noted that his starting material contained approximately 60 ppm of impurities. Gifkins' results indicate impurity effects at an impurity level of 8 ppm, suggesting strongly that the most significant impurity range to be investigated lies substantially below that value. R. C. Gifkins (author's reply) — As Drs. Aust and Rutter suggest, the results under discussion may have to be reinterpreted in the light of their own work on grain boundary migration, which was not available to me when the paper was written. Because of their work, Aust and Rutter attach more importance than I did to the activation energy for grain boundary migration during annealing (7.5 kcal per mol) obtained from a "direct" plot of log-rate against the reciprocal of absolute temperature. At the time it was obtained, this value seemed rather low, although it was similar to the value obtained by Bolling and Winegard.36 It was then, and still is, difficult to accept this value because of the low value of the index in the power law for grain growth, which seemed to indicate the influence of impurities. It was also concluded that the low value of the activation energy might have arisen from the manner of selecting rates of grain growth which were truly comparable at the two temperatures. There were many other indications in these experiments and those on recrystallization during creep3? that an impurity, probably oxygen, was of importance. The model for grain-boundary migration which Lucke and Detert had proposed was an obvious possibility and its use yielded an activation energy for boundary migration during annealing of 20 to 25 kcal per mol.

Jan 1, 1961

By R. E. Ogilvie, E. T. Peters

The X-ray Kossel-line method has been used preaioz~sly for measuring lattice parameters to accuracies of 1 part in 100,000.5 A second application of this method is described for determining the crystallographic orientation of a randomly positioned single-crysta1 spherical volume that can he as small as 50 µ in diameter, within accuracy limits of ±1/2 deg. The theory, experimental procedure, and interpretation of Kossel-line patterns and an experimenta1 verification of the predicted orientation relationship of the cph k and fee a Cu-Si phases are presented. This orientation relationship can be described as (111)a, (00.1)k; [110]a [11.0]k. In addition, the lattice parameter of the a phase was found to he a. = 3.62154 ± 0.00014Å. The Kossel-line method when used in conjunction with electron microanalysis is shown to he capable of providing a complete chemical and structural analysis of a given crystal. THE most easily accomplished methods for determining the orientation of a single crystal are variations of the Laue X-ray diffraction method. Although certain materials can be oriented to within ± 1 deg accuracy by observation of exterior macroscopic features, such as etch pits, cleavage faces, or growth features, the Laue method is generally preferred for routine laboratory application. Both back-reflection and transmission patterns are coordinated by appropriate reference charts and are plotted in terms of reflection plane poles (normals) on a stereographic projection. Orientation is deduced by relating the pole distribution (which is fixed by the crystallographic symmetry of the specimen) to two specified external reference directions. The Laue method has several limitations. 1) Orientation can rarely be determined to better than ±l deg accuracy. Principal errors involve inaccuracy in specimen-to-film distance, measurement confidence of individual Laue spots, and stereographic plotting. 2) Because of the indeterminacy of the X-ray wave length diffracted to a given spot, it is not possible to determine supplementary crystallographic data, such as interplanar spacings and lattice parameters. 3) The method is generally limited to specimens of cubic symmetry or to specimens of high symmetry and known structure. 4) The relatively large cross-sectional area of the incident X-ray beam generally precludes the measurement of relative grain orientation in a polycrystalline material.* _____ Several of these limitations can be overcome by application of the Kossel-line method, which has been previously employed for precision lattice-parameter determinations.'-= For this method, a point source of divergent monochromatic X-rays is generated within the crystal by means of an incident electron beam. The divergent X-rays which fulfill the Bragg law are diffracted by the specimen and are recorded on a film placed either in transmission or back reflection. Analysis of the film yields a direct measurement of orientation and lattice-spacing values to an accuracy of ±1/2 pct. As analyses can be obtained from spherical specimen volumes as small as 50 µ in diameter, the method provides a means for structural analysis of second-phase or impurity precipitates within a given matrix. The primary limitation of the Kossel-line method is the requirement for an electron microanalyzer or similar apparatus capable of producing a finely focused electron beam. This paper is designed to present the theory, experimental procedure, and geometrical interpretation of Kossel patterns. The experimentally determined orientation relationship between the k and a phases occurring in the Cu-Si system and a precision measurement of the a lattice parameter are presented as a practical application of the method. THEORY OF KOSSEL LINES Divergent X-ray beam photography utilizes an effective point source of characteristic X-rays which, when diffracted from a single crystal, form numerous diffraction and absorption cones that are recorded on film.7 The cones generated from a source lying within the crystal are called Kossel lines.' Although the X-ray scattering from a divergent point source contained within a crystal is described in terms of Laue dynamical theory,9 the directions of the diffracted spectra can be ade-

Jan 1, 1965

By William J., Coulter

IN the early days of Colorado mining, between 1880 and 1900, when Leadville, Kokomo, and Robinson were boom mining camps, the entire area around Climax for a matter of fifteen miles was overrun with prospectors, so the mineralized outcrop at Climax was not unknown. The principal interest in minerals during this period was in gold, silver, and lead, and since the Climax outcrop showed none of these it drew little attention. Geology played an important part in bringing prospectors to the very edge of the Climax deposit. The Mosquito fault, which crosses near the base of Bartlett Mountain, continues as an important geological structure, at least as far as Leadville some twelve miles distant, and at the base of Bartlett Mountain the vertical throw on the fault is estimated to be between 2000 and 5000 ft. The sedimentary beds known to the Leadville district are all present on Bartlett Mountain to the north of the Mosquito fault, which cuts them off abruptly, and exposes the Pre-Cambrian rocks that underlaid them, so the prospectors, who were searching for gold, silver, and lead in the sediments

Jan 1, 1946

By J. A. Berger, G. W. Wiener

Several transition metal nitrides have been prepared and their saturation magnetization determined. On the basis of an atomic model of ferromagnetism involving a consideration of nearest neighbor interactions and the assumption that all atomic moments of the metal point in the same direction, it appears that the nitrogen interacts with d-shell of the transition metal in such a way as to reduce the magnetic moment. THERE is a large class of materials having metallic properties which are formed by a combination of hydrogen, boron, carbon, oxygen, or nitrogen with the transition metals. Several attempts have been made to establish the type of metal-nonmetal bonding in these interstitial alloys because it is believed that many of the physical properties of these materials are determined by the characteristics of this bond. Several of these alloys are ferromagnetic, and thus a powerful method is available for investigating the structures in a direct manner by measuring the saturation magnetization. The latter is a fundamental property of ferromagnetic metals and alloys which depends primarily on the electron distribution surrounding the atom. For the first row of transition metals, this refers specifically to the 3 d-shell. Since bonding involves the electronic configuration between atoms, there is reason to suppose that a relationship exists between ferromagnetism and bond type. In the case of the interstitial structures studied in this work, bonding will refer to the distribution of electrons between the transition metal and the nonmetal. Since these alloys have metallic properties, it is further proposed that any bonding interactions will involve the outer p-shell of the interstitial element and the incomplete d-shell of the transition metal. If this is the case, then the relationship between ferromagnetism and metal-non-metal bonding is established qualitatively. In order to investigate the subject quantitatively, certain transition metal nitrides were chosen because they have simple crystal structures, are ordered alloys, and are ferromagnetic. They also have sufficiently high saturation magnetization to be of technical interest. Currently there are two major theories of ferromagnetism, each of which has been applied to the interpretation of the saturation magnetization in terms of atomic structure. They are usually referred to as the band theory and the atomic theory. The former has found widespread application to the study of pure metals and certain solid-solution allays. However, it has not been applied to the interstitial structures or ordered alloys because it does not interpret the properties directly in terms of the crystal structure. The atomic theory on the other hand is especially suited to the study of interstitial structures because it permits an interpretation of ferromagnetic phenomena in terms of the crystal geometry. As has been pointed out previously, the nitrides have simple ordered crystal structures and, therefore, the choice of the atomic theory for the interpretation of the data is a natural one. One of the prime difficulties with the atomistic theory is that its mathematical justification is much more difficult, and for this reason its general acceptance will depend to a large extent on the value it has in explaining and predicting the results of experiment. Before the presentation of the theoretical basis for understanding the metal-nonmetal bond, it is useful to review the ideas existing prior to this work. Four different interpretations have been given to the metal-nonmetal bond. These are summarized as follows: 1—acceptance of electrons by the nonmetal from the incomplete d-shell of the transition metal, 2—transfer of electrons from the nonmetal to the incomplete shell of the transition metal, 3—no exchange of electrons between the two atoms, and 4— a resonating type of bond involving the p electrons of the interstitial atom giving rise to half bonds. Zener'-4 in a recent series of papers has proposed a new theory of ferromagnetism and has developed an explanation of the observed saturation magnetization of iron nitride (Fe,N) using the concept that nitrogen accepts electrons from the 3d-shell of iron. Jack," on the basis of atom size considerations in iron carbonitrides, has proposed that nitrogen transfers or donates electrons to the inner 3d-shell. He found that the effective size of the carbon atom was less than that of nitrogen and thus suggested that the interstitial atoms give up electrons. Kiessling" has studied the borides of several transition metal atoms and proposed that boron loses one p electron to the transition metal. He postulated that the additional electron added to the metal lattice compensates for the loss in metallic properties which results from the increased metal-metal atom separation. GuillaudT3" has proposed similar arguments from some recent magnetic studies he had made on manganese nitride. However, he did not base his conclusions on a quantitative argument. Pauling," in a recent paper, discussed electron transfer in in-termetallic compounds. He classified nitrogen as a hyperelectronic atom which can increase its valence by giving up electrons. He classified the transition metals as buffer atoms which are capable of either accepting or giving UP an electron. He pointed out that two factors are operating which promote electron transfer because they lead to increased stability. The first is an increase in the number of bonds, and the second is a decrease in the electric charges on the atoms. These ideas when applied to the interstitial nitrides would indicate a viewpoint favoring electron transfer by nitrogen to the transition metal. Hagg7s arguments in favor of no exchange are adequately summarized by Wells." Implicitly, Hagg

Jan 1, 1956

By Harold V. Pearce

(Chattanooga Meeting, October, 1908.) THE fire which occurred in the fall of 1906, at the works of the Boston & Colorado Smelting Co., Argo, Colo., destroyed entirely the gold- and silver-refinery of the plant; and in view of the development of modern practice in the refining of copper-mattes, etc., the management decided that it would be inadvisable to rebuild that part of the works for the continued use of the process which had been conducted therein for so many years as a metallurgical secret. This decision probably removes altogether from the sphere of practice the " Pearce " method for the separation of gold. At all events, it removes the business reasons which have prevented hitherto the publication of the principles involved. At the suggestion of Dr. Raymond, Secretary of the Institute, my father, Richard Pearce, the former manager of these works, has requested me to prepare a brief description of this process for the benefit of our members. Since I severed my connection with the Boston & Colorado Smelting Co. some time ago, I am indebted for some practical details to the present superintendent, Charles Rees, whose friendly assistance I would gratefully acknowledge. With regard to the history of the inception and development of this process by its inventor, Richard Pearce, I cannot do better than quote freely from his own notes and papers. HISTORY OF THE PEARCE PROCESS.' "In 1874 my entire time was directed to the improvements and additions to the plant at Black Hawk. The changes which I had made in the construction of the furnaces at Black Hawk proved so beneficial that I was requested to introduce the improvements at the branch works at Alma. These changes were carried out as speedily as possible, and proved of great advantage as compared with the old system. "The separation and refining of the gold from the matte now engaged my attention, and since previous experience in the treatment of gold-bearing matte and

Feb 1, 1909

By W. V. Green

Creep of tantalum was measured at temperatures from 0.6 to 0.89 of the absolute melting temperature. The creep curves include first, second, and third stages. Steady-state creep rate depends on the fourth power of stress. The activation energy for creep throughout this temperature range is approximately 114 kcal per mole, measured by the aT technique. Subgrain formation occurs as a result of creep strain, and pile-up dislocation arrays are observed in etch-pit patterns. BECAUSE of its high melting point-which is exceeded only by those of rhenium and tungsten—and its high room-temperature ductility compared to most of the other high-melting-point metals, tantalum will undoubtedly be utilized in an increasing number of high-temperature applications. Alloying studies directed toward increased high-temperature strength must use data on tantalum itself as a base line in order to evaluate the effectiveness of the alloying additions. However, to date, no systematic study of creep of tantalum at temperatures above one-half of its melting point has been reported in the literature. Conway, Salyards, McCullough, and Flagella1 have measured linear creep rate of tantalum sheet as a function of stress, but at only one temperature, 2600°C. This paper describes a relatively thorough study of the high-temperature creep of tantalum. METHOD Material Tested. The commercially supplied, l/2-innch-diameter tantalum rod used for this work was electron-beam-melted, cold-forged, rolled, swaged, cleaned chemically, and vacuum-annealed for 1 hr at 1000°C, all by its manufacturer. The vendor's analysis included 60 to 170 ppm C, 3.4 to 4.2 ppm H, 60 to 80 ppm 0, 15 ppm N, and a hardness ranging from 66 to 81 Bhn and averaging 76 Bhn. Creep eimens Used. Two creep-tested specimens are shown in Fig. 1. The 1/4 in.-diameter gage section was 3/4 to 1 in. long, and terminated either at shoulders 5 mils high or at 20-mil-diameter tantalum wires spot-welded to the circumference of the gage section. Both kinds of shoulders served equally well as fiducial marks for optical strain measurements. The spot welding did not alter the creep behavior in any detectable way; the 5-mil- high sharp shoulders did not result in any detectable localized effect on the strain. Before testing, each tensile bar was first mechanically polished -id then electrochemically polished according to the method referred to by Forgeng2 as the "Thompson Ramo Woolridge" method, which was suitable for tantalum after small adjustments of technique were made. Two tensile bars tested at low stresses had 1/8-in.-diameter gage sections and utilized only the weight of the bottom grip for the applied load. Although these diameters were smaller than were desired for other reasons, applied loads were known with high precision in the tests in which they were used. Testing Procedure. Two different constant-load creep-testing machines were employed, one of which has been described by Smith, Olson, and Brown.3 In both, the tensile bar is held vertically on the axis of a cylindrical tungsten tube or screen heater by threaded tungsten grips. The tensile bars and associated grips are heated by radiation from the incandescent heaters, which are heated by their own electrical resistance. Both testing machines use pins to hold the bottom grips in place. The load is applied to a tensile bar through hanging weights, a constant force-multiplication lever, a pull rod sealed to the chamber lid, and a top grip threaded to the pull rod at one end and to the tensile bar at the other. In one machine, the vacuum seal is a bellows with a low spring constant; in the other, the seal involves a rotating "0 ring". With the latter, rotation is converted to translation with a crank shaft, so that elongation of the tensile bar is accommodated with no change of tensile load. The incandescent tensile bar is viewed by an external optical system through slots in the radiation shields and heater, and an enlarged image is projected on a ground-glass screen. Gage-length measurements are made on this image with cathetometers on traveling microscopes. With regard to creep-test results, the two machines were identical. Thorium oxide coatings were applied to the threaded ends of the tensile bars, to prevent diffusion welding of the tensile bars to the grips during testing. Specimen temperatures were measured with an L. & N. optical pyrometer which had been calibrated against a standard carbon arc, and were corrected fir window absorption by calculation from the measured spectral transmittance of the quartz observation windows. Longitudinal temperature gradients in the tensile-bar gage length and temperature drifts during testing were detectable but small, and were estimated to be 10°C or less. Accuracy of temperature measurement was confirmed by comparing the temperature measured on the surface of a special

Jan 1, 1965

By R. S. Busk

Niels Engel (University of Alabama, University, Ala.)— In this paper it was pointed out that the electron-gas and energy-band theory accounts for the fact that the lattice parameters exhibit a sudden change when the electron concentration (number of bonding electrons per atom) exceeds a certain number around two. This statement is said to support and prove the electron-gas theory. But this theory is not able to account for a series of experimental data. Also several expectations, deduced from this theory, are not found to exist. In Figs. 6 and 7 the energy bands of the second and third periods are given as they must be assumed in order to account for the electrical properties of the elements in these periods. In Figs. 6 and 7 the electron-gas and energy-band theory is compared with the electron-oscillator hypothesis in accounting for the properties of the elements in the second and third periods. Fig. 6 shows the second period, The energy-bands are overlapping and separated to be in agreement with the electrical conductivity of the elements. The oscillator hypothesis explains conductivity due to electron vacancies. In graphite there is a closed s-shell in every other atom and two vacancies in the others. Conductivity is therefore only maintained by migration of s-electrons in graphite. In boron there are no s-electrons. The diatomic molecules of nitrogen and oxygen and the paramagnetism of oxygen can be accounted for by a similar behavior as the s-electrons of the bonding electrons. But this explanation will deviate too much for the purpose of this discussion. Fig. 7 shows the third period. In the energy-band picture about two s-electrons are assumed in magnesium and aluminum, but only one s-electron is assumed in silicon. The diamond lattice is assumed to be controlled by a sp3 hybrid. However the electron distribution develops ideally according to the oscillator hypothesis. Only sodium, magnesium, and aluminum exhibit electron vacancies and conductivity. To account for the insulator properties in Si, P, and S in the third period it must be assumed that the four last added p-electrons must be taken up in bands containing only one electron per band.' (Compare the electron band picture in Hume-Rothery.' Hume-Rothery does not consider the insulator properties of the nonmetals.) In the second period already the first p-electron must have entered a single electron band. Based on the energy-band picture in Figs. 6 and 7, the following questions must be asked: 1—Is it consistent with the energy-band idea that electrons of the same kind (p-electrons) can be divided into separated bands? 2—Is it consistent with the energy band idea that single electron bands can exist? 3—Why are the first two p-electrons (in boron and diamond) separated into two single electron bands in the second period, but overlapping in the third period (aluminum)? 4—Why are s-electrons and d-electrons taken up in continuous overlapping bands, while p-electrons are divided into single electron bands? 5—Why do the peaks and valleys (y and w and further x and z) of the energy band below four electrons per atom not show up in the electrical conductivity of alloys? For example consider the Li-Mg system or the alloys between Mg and three electron metals where the mentioned discontinuity in the lattice parameter is found. 6—Why does the beginning of the p-electron band (x) not show up in the lattice constants similar to the filling up of the s-electron band (z) ? In magnesium alloys the electron-gas theory postulates the first Brillouin zone to be filled at about two electrons per atom. This is claimed to explain the sudden change in lattice spacing and c/a values of several magnesium alloys when the electron concentration exceeds a few percentage points over two electrans per atom. This was emphasized in the paper by Busk. If the electron-gas energy-band theory is correct a sudden change in electrical conductivity and possibly other properties .should be expected when the same electron-concentration or temperature is exceeded. A sudden change in lattice spacing or other properties should also be expected when the filling degree is such that p-electrons are introduced into the p-band, for example at x in Figs. 6 and 7. Such phenomena are at found by experiment. and If the number of electrons should vary with the energy level depending on the average number of bonding electrons per atom, the electrical conductivity should be expected to vary in accordance with the energy band layout (Figs. 6 and 7) caused by different numbers of conducting electrons at different filling up degrees. Nothing indicating such a behavior is observed. In addition to these discrepancies between the electron-gas and energy-band theory and measured data, the theory violates the principles developed along with the Bohr theory of atomic structure. According to these principles a filled shell is saturated and therefore unable to form bonds. Therefore two S-electrons per atom should form a closed or saturated shell, which has been pointed out as accounting for the inability of helium to form bonds. Beryllium, magnesium, or calcium atoms with two s-electrons should be expected to form inert atoms with properties almost like the helium atoms. Several other inconsistencies and disagreements with measured data of the energy-band theory can be mentioned. Some of these are discussed with reference to other papers. 8 Because the electron-gas and energy-band theory seems to fail on several points, I have developed another theory which can account for all the phenomena the electron-gas theory is able to account for. This new theory is further able to account for things which are impossible to explain by the electron-gas theory at the present state.

Jan 1, 1953

By A. O. P. Casbarian

An analytical method is developed to determine the variation of the ultimate lateral resistance of a plate in a cohesionless soil with depth. This analysis is based on a modification of Rankine's classical earth pressure theory and the theory of plasticity as applied to soils. The ultimate resistance is defined as the product of the effective stress at the midpoint of the plate, the area of the plate and a dimensionless variable termed the ultimate resistance factor. This variable has been plotted us the depth ratio: i.e., the ratio of of the depth of embedment us the height of the plate. The resistance of a plate may then be calculated using the values af the ultimate resistance factor from the chart provided or the equation may be programmed for use in an analysis of anchor systems in cohesionless soils. It is emphasized that the analysis is semitheoretical. The theory has been compared with experimental results reported in the literature and results indicate general agreement. Actual field tests are necessary to further verify this theory. INTRODUCTION With the exploration for oil offshore in waters all over the world, it is of importance to determine the behavior of the various soils in relation to their ultimate resistance to deformation. Examples of such problems are the holding capacity of anchors and the lateral resistance of piles. Very little information is available in the published literature on the design and performance of anchors, in either cohesive or cohesionless soils. The analysis developed in this report is the first step in obtaining a solution for the determination of anchor holding capacity in a cohesionless material. DISCUSSION The theory used in the analysis is based on the ultimate strength of the soil and is the maximum resistance developed by the plate against further movement. In such a state the elastic deformations are disregarded in comparison with the plastic deformations. Hence, the plate can be considered as completely rigid. The theory of plasticity determines the three unknown stresses at any point by means of two equilibrium conditions for a small earth element in combination with the failure condition. However, the exact solutions can only be carried out in a few simple cases such as, for example, when the rupture or failure lines are straight (Rankine theory) or with spiral and straight rupture lines (Prandtl theory).l Kiitter 2 derived a single equation expressing the variation of the stress in any given rupture line. To utilize this equation, it is necessary to know the stress in the rupture line at a certain point. Unfortunately, this is difficult to obtain unless the rupture line intersects the free surface at a certain angle or when the earth is cohesion-less and unloaded. A method to overcome this is to consider only the boundary conditions at both ends of a rupture line without investigating the equilibrium of the earth above the rupture line. This assumes that the rupture lines meet the surface at statically correct angles, so that boundary stresses may be determined. As Kiitter's equation furnished a relation between these stresses, the unit earth pressure may be calculated at the point where the rupture line meets the wall. Another way in which Kotter's equation may be applied is in investigating the equilibrium of a soil mass above a rupture line. This method assumes that the failure or rupture line is known and that the boundary stresses in the rupture line at the ground surface can be determined. In this case it is possible to determine the earth pressure from the equations of equilibrium.

Jan 1, 1967

By W. T. Cardwell

Physically absurd, triple-valued saturations appear in the straight-forward solution of the Buckley-Leverell equations for the displacement of oil by water or gas. From an engineering viewpoint, the triple value causen no difficulty. It is well known how it may be compensnted in order to obtain physically meaningful, numerical results. From a scientific viewpoint, the question still arises: What did the triple value mean? This paper explains how and why the triple value arose in non-capillary Buckley-Leverett theory. The discussion should serve as a background for the understanding and use of the modern method of characteristics in di.~pkzc(>ment theory. INTRODUCTION Displacement theory was introduced to petroleum technologists in 1 941 by Buckley and Leverett.' Their first equation, which they wrote down without derivation, was equivalent to the following: ?s/?t= - qr/F ?f/?r (1) where S = saturation of displacing fluid (a fraction) r = time q,. = total volumetric velocity of both the displacing phase and the phase being displaced (usually, but not necessarily, assumed to be a constant) F = porosity (a fraction) f - fraction of the total volumetric velocity that is the volumetric velocity of the displacing phase (assumed to he a function of S only x = distance. Buckley and Leverett called Eq. I "a material balance equation". Actually it is derived from both a continuity equation, or material balance equation, and Darcy's law. Buckley and Leverett jumped from their Eq. 1 immediately to their Eq. 2, which was the equivalent of the following: (?x/?t)x = qr/F df/ds = qr/F f'(s) (2) The jump from Eq. 1 to Eq. 2 involves apparently simple mathematics, but in that apparently simple mathematics lies a subtle point that is part of the key to the meaning of the triple value to be discussed here. Eq. 2 may be readily interpreted as saying that a point of constant saturation (on a saturation-vs-dis-tance curve) moves with a constant velocity that is proportional to the total volumetric rate, inversely proportional to the porosity, and is otherwise a function of the saturation itself. So that if one knows the derivativc with respect to saturation of the fractional flow function, f(S), for each saturation, one knows the velocity of each point of the moving saturation-vs-distance curve. The function f(S) can he determined experimentally and its derivative f'(S) can be calculated. It turns out that the experimentally derived f'(S) is not a monotonic function of S, but instead it has a definite maximum and declines away at both high and low saturations. This in turn means, in accordance with Eq. 2, that on a moving saturation-vs-distance curve, ccrtain intermediate saturations will travel faster than the saturations either higher or lower. The result is indicated in Fig. 1. In Fig. 1, the abscissas represent distances along a column of porous medium, which column is assumed to be uniform in cross-section perpendicular to the ab-scissal direction. The ordinates represent fractions of pore space occupied by the displacing phase, which may be either water or gas. It is assumed that the saturation is uniform over all planes perpendicular to the abscissal direction. The saturation is a function only of time and one space variable. Time variation of the saturation is represented by change in shape of a curve such as curve AGJ, which represents the initial saturation-vs-

By W. Mitchell, B. H. Bergstorm, C. L. Sollenberger

A unique compression testing machine was constructed to load individual 1/8 to I-in. spheres of glass, etc., at rates from 100 to 100,000 lb per min. During loading the applied load was continuously plotted us the deformation of the sphere-platen system. The load-deformation curve conforms to the theory of elasticity. The spheres were surrounded by steel retaining rings or by gelatin (to prevent secondary fracture). The product size modulus was determined from screen analyses. The data shows: 1) Energy input per unit mass is inversely proportional to the product size modulus (or directly proportional to the surface area per unit mass). 2) Increased loading rates slightly increase the energy input per unit mass required for fracture without affecting the preceding relationship. Theory and experiments show that much of the input strain energy is transformed into kinetic energy of fragments at fracture, this being a reason efficiencies based on "surface energies" are exceedingly small. This large kinetic energy component is usually dissipated as heat but may be partially reclaimed because impact of fragments against the surface of steel retaining rings causes additional comminution. There are currently several theories of crushing, all of which can be derived from the general energy equation of Gillilandl as was pointed out by Mitchellet al in 1954'and more recently by Rose and Sullivan. If the exponent of the equation dE-x-"dx is assigned values of 2,1, or 3/2, one obtains by intergration between suitable limits, the equations of Rittinger, kick,' and Bond,' respectively. Other investigators prefer to let the exponent be a variable parameter. To help resolve the controversy, the Allis-Chal-mers Research Laboratories set up a series of carefully controlled experiments in which the level of energy input required to induce the comminution of a single particle by slow compression loading was very accurately measured. The energy input requirement, in conjunction with the size analysis of the fragments produced at fracture, yielded an accurate energy-product size relationship for the conditions studied. APPARATUS The experimental apparatus was designed to apply a compressive load on opposite sides of an "ideal particle." Spherical shapes were chosen, because point contact loading is typical of the mechanics of conventional crushers. The bulk of the experimental data was obtained with glass spheres because glass is a fairly homogeneous, brittle material for which the properties follow definite statistical distributions. The spheres ranged from 1/8 to 1-in. diam. The compressive load was applied to the specimen at a uniform rate by a loading mechanism (Fig. 1) which acted through a system of levers. The uniform rates, ranging from 100 to 100,000 lb per min, were obtained by metering water into a bucket suspended at the end of the secondary level. Point contact was made with the sphere through tungsten-carbide platens. This latter material is extremely hard and has a high modulus of elasticity, thereby having a minimum of distortion when loaded. The actual load on the sphere was measured independently of the lever system by a load cell, Fig. 2, which was designed so that the voltage output of the load cell would be proportional to load. The deformation of the specimen was indirectly measured by a pair of transformers which were attached to opposite edges of the upper platen. The cores of the transformers, which were attached to the lower platen, moved relative to the transformer so that the voltage output was proportional to the deformation of the sphere-platen system. The load was plotted against the deformation on an X-Y recorder. The area under the curve, as shown on Fig. 3, was proportional to the energy input of the

Jan 1, 1961

By A. M. Sarem, J. M. Campbell

Molecular refraction is introduced as a new and improved third parameter for prediction of the PVT behavior of hydrocarbon systems. This parameter, characterizing the complex as well as the pure hydrocarbon systems (1) is a direct measure of London dispersion forces which affect the PVT behavior; (2) can be measured directly, accurately and easily for complex as well as pure hydrocarbon systems; (3) varies significantly between the reference substances thus allowing accurate interpolation of PVT properties; and (4) has a fundamentally sound basis. Molal average molecular refraction was used with the pseudocritical mixing rule proposed by Leland and Mueller to predict the molal volume of liquid and vapor for 84 published data points on nC4-nCI0, Cl-nC5, Cl-nC4-nC10 systems in the region of coexisting vapor-liquid and at the critical point. The same technique was applied to predict the densities of liquid hydrocarbon mixtures in the two-phase and single-phase regions near the critical point for seven different systems each having different properties of the heptanes-plus fraction, but all simulating the fluids of either gas-condensate or volatile oil reservoirs. A modification of the Leland-Mueller mixing rule for the determination of pseudocritical properties is also presented which yields more accurate liquid density predictions than the original form when used with the proposed third parameter. INTRODUCTION The PVT behavior of multicomponent systems has received widespread attention in the literature in recent years. A large portion of the reported work has stemmed from attempts to overcome the inherent difficulties encountered when using the standard compressibility-factor chart which shows 2 as a function of reduced temperature T, and and reduced pressure p,. This chart assumes that z, is constant for all systems. The error in this assumption is not pronounced for pipeline-type gases high in methane and low in heavy ends, particularly when contained at moderate pressures. For such gases the error in the calculated z is usually less than 2 to 3 per cent. However, the reliability of this approach becomes somewhat nebulous for gas condensate and volatile oil systems at high pressure. One logical approach has been to recognize the variation of 2,. This idea was first suggested by Meissner and Seferianl and used by Lyderson, Greenkorn and Hougen2 to prepare extensive tables of thermodynamic properties. Other third parameters have been proposed by Stockmeyer, Kihara, Riedel, Lightfoot, Bloomer and Pitzer. These were tested by Satter and Campbel13 for many gas mixtures and it was shown that they were inter-related. All of these third parameters have a common fault — they cannot be directly evaluated for the heptanes-plus fraction. Consequently, one necessary requisite of an improved method for predicting the density of multicomponent hydrocarbon systems, was development of a third parameter that could be evaluated for that fraction. PREVIOUS MULTICOMPONENT DENSITY PREDICTION METHODS Sage and Lacey4 suggested a method of using partial molal volumes for computing the density of hydrocarbon gas mixture for pressures to 3,000 psi. In this technique, they approximate the complex multicomponent gaseous mixtures by a quarternary system of methane, ethane, propane and butane. Sage, Hicks and Lacey5 suggest a method of using partial molal volumes for computing the density of hydrocarbon liquids. The results agree within 3 per cent of the experimental values. However, the composition range is limited to about 10 per cent by weight of methane. Consequently, this correlation does not cover the low-molecular-weight liquid similar to natural gasoline and high-pressure gas condensates.

Jan 1, 1966

By Charles Camsell

MORE than one-third of all Canada is embraced in the federal domain known as the Northwest Territories. Its most northern point, Cape Columbia, on Ellesmere Island, is only 500 mi. from the Pole. It includes parts of the main physiographic divisions of the North American continent. In the West there is a strip of 30.000 sq. mi. lying in the Cordilleran region, where peaks in the Mackenzie Mountains rise as high as 8500 ft. East of this strip and extending roughly to a line through Great Bear and Great Slave lakes to the Arctic coast is a section of the interior plains. This section, known as the Mackenzie Lowlands, contains the great artery, the most striking feature of the Northwest Territories-the Mackenzie and Slave river waterway impressive in its width, almost two miles in places, and in it's navigability for 1357 miles without obstruction to the sea. Adjoining the Mackenzie Lowlands on the East is the greater portion of the mainland of the Territories, which, as well as a large share of the island area, is in the Canadian Shield.

Jan 1, 1937

By C. W. Binckley, F. R. Burgess, E. R. Haymaker

A method of establishing stabilized back-pressure curves for gas wells producing from formations of extremely low permeability is presented. Actual well performance under many different operating conditions is shown by the stabilized back-pressure curve. By use of the method. it is possible to conduct back-pressure tests with a critical-flow prover on wells that stabilize slowly, and save approximately 88% of the gas ordinarily vented to obtain satisfactory test data, with a great reduction in time required for testing. INTRODUCTION The reasons for establishing dependable back-pressure curves on gas wells have been pointed out by previous publications. The publication most referred to. of course, is the United States Bureau of Mines Monograph 7, titled "Back-Pressure Data on Natural Gas Wells and Their Application to Production Practices". The technique generally established therein has been accepted and used by many engineers; and, when proper tests are conducted, the results can be used for the analysis and solution of several practical problems concerning field operation and development. Even where formations of low specific permeability are encountered, the determination of a well's actual performance by the back-pressure test method permits the engineer to analyze many problems in individual well operation and also to predict necessary future field development. Such problems as the determination of the ability of a well to produce into a pipe line at a predetermined line pressure, the design of gas gathering systems and meter settings, and the determination of the time and the number of wells required to be drilled to meet future market obligations, can be solved, in part., by the use of a reliable back-~ressure curve. In addition, the computed well delivery rates determined by data from backpressure tests ordered by state regtilatory bodies, when compared with the true back-Pressure curve, permit the operator to ascertain whether such data represent unstable or relatively stabilized delivery rates for given pressure conditions of the well. The technique of back-pressure testing, as described in this report, was developed by Phillips Petroleum Company engineers from data obtained during a testing program that started in 1944 and has been continued to date. Three hundred and eleven back-pressure tests were conducted on 299 wells located in the southern part of the Hugoton Field. The gas-bearing zone is composed of several dolomitic formations of the Permian Age; the important ones are the Herington, Upper Krider, Lower Krider, and Winfield. The average bottom-hole temperature is approximately 91 °F.. and the initial wellhead shut-in pressures range from 400 to 440 psig. The spacing pattern is 640 acres per well with each well located near the center of the section. The range of back-pressure potentials on wells tested was from 500 to 23,000 Mcfd. All gas wells were acidized, and the quantity of acid used, expressed in 1574 hydrocloric acid, varied from 12,000 to 22,000 gallons per well. The quantity and concentration of each treatment depended on the stage, the formation being treated, and experience gained from previously completed wells. The gas in the Hugoton Feld is a "dry" gas. It has a gasoline content of approximately 0.25 gallons per thousand cubic feet, as determined by charcoal test, and its specific gravity averages about 0.71 as compared to air (air = 1.00 at 60°F.). Of the wells tested, 71 were completed with 7" casing, 3 with 9 5/8" casing, and 1 with 6%" casing set on top of the upper producing formation with the well bore through the gas bearing formations being open hole. Two hundred and twenty-four were completed with 5 1/2'' O.D. casing set through the gas bearing formations and perforated. For the purpose of establishing reliable back-pressure curves in the area, Phillips Petroleum Company personnel has computed data on the basis of 24-hour flows per point. Early in the program, many tests were actually permitted to flow 24 hours to obtain data for each plotting point, at great expense in man power and time. Presently, however, such tests have been replaced by tests of short duration flows which can be made to effect results that correspond to the tests obtained by flows of much longer duration. METHOD When a gas well producing from a reservoir of low permeability is opened for production through a constant size orifice, both the rate of flow and working pressure decline. first at a high rate and later at a lower rate until after several hours the decline becomes difficult to ascertain. In this paper the rae of flow and working pressure are considered to be stabilized when it becomes difficult to observe changes in working pressure during a period of three hours by the use of a deadweight pressure gage. Stalibization of pressure in the literal sense is never obtained in a producing gas well. In formations of low permeability. such as those in the Hugo-ton Field, most wellhead working pressures approach stabilization closely enough to be used satisfactorily in the determination of a back-Pressure potential curve after flow periods of 24 hours. We shall therefore describe the backpressure curve calculated from ohserved rates of flow and working pressure at the end of 24-hour flow periods.

Jan 1, 1949

By E. R. Haymaker, C. W. Binckley, F. R. Burgess

A method of establishing stabilized back-pressure curves for gas wells producing from formations of extremely low permeability is presented. Actual well performance under many different operating conditions is shown by the stabilized back-pressure curve. By use of the method. it is possible to conduct back-pressure tests with a critical-flow prover on wells that stabilize slowly, and save approximately 88% of the gas ordinarily vented to obtain satisfactory test data, with a great reduction in time required for testing. INTRODUCTION The reasons for establishing dependable back-pressure curves on gas wells have been pointed out by previous publications. The publication most referred to. of course, is the United States Bureau of Mines Monograph 7, titled "Back-Pressure Data on Natural Gas Wells and Their Application to Production Practices". The technique generally established therein has been accepted and used by many engineers; and, when proper tests are conducted, the results can be used for the analysis and solution of several practical problems concerning field operation and development. Even where formations of low specific permeability are encountered, the determination of a well's actual performance by the back-pressure test method permits the engineer to analyze many problems in individual well operation and also to predict necessary future field development. Such problems as the determination of the ability of a well to produce into a pipe line at a predetermined line pressure, the design of gas gathering systems and meter settings, and the determination of the time and the number of wells required to be drilled to meet future market obligations, can be solved, in part., by the use of a reliable back-~ressure curve. In addition, the computed well delivery rates determined by data from backpressure tests ordered by state regtilatory bodies, when compared with the true back-Pressure curve, permit the operator to ascertain whether such data represent unstable or relatively stabilized delivery rates for given pressure conditions of the well. The technique of back-pressure testing, as described in this report, was developed by Phillips Petroleum Company engineers from data obtained during a testing program that started in 1944 and has been continued to date. Three hundred and eleven back-pressure tests were conducted on 299 wells located in the southern part of the Hugoton Field. The gas-bearing zone is composed of several dolomitic formations of the Permian Age; the important ones are the Herington, Upper Krider, Lower Krider, and Winfield. The average bottom-hole temperature is approximately 91 °F.. and the initial wellhead shut-in pressures range from 400 to 440 psig. The spacing pattern is 640 acres per well with each well located near the center of the section. The range of back-pressure potentials on wells tested was from 500 to 23,000 Mcfd. All gas wells were acidized, and the quantity of acid used, expressed in 1574 hydrocloric acid, varied from 12,000 to 22,000 gallons per well. The quantity and concentration of each treatment depended on the stage, the formation being treated, and experience gained from previously completed wells. The gas in the Hugoton Feld is a "dry" gas. It has a gasoline content of approximately 0.25 gallons per thousand cubic feet, as determined by charcoal test, and its specific gravity averages about 0.71 as compared to air (air = 1.00 at 60°F.). Of the wells tested, 71 were completed with 7" casing, 3 with 9 5/8" casing, and 1 with 6%" casing set on top of the upper producing formation with the well bore through the gas bearing formations being open hole. Two hundred and twenty-four were completed with 5 1/2'' O.D. casing set through the gas bearing formations and perforated. For the purpose of establishing reliable back-pressure curves in the area, Phillips Petroleum Company personnel has computed data on the basis of 24-hour flows per point. Early in the program, many tests were actually permitted to flow 24 hours to obtain data for each plotting point, at great expense in man power and time. Presently, however, such tests have been replaced by tests of short duration flows which can be made to effect results that correspond to the tests obtained by flows of much longer duration. METHOD When a gas well producing from a reservoir of low permeability is opened for production through a constant size orifice, both the rate of flow and working pressure decline. first at a high rate and later at a lower rate until after several hours the decline becomes difficult to ascertain. In this paper the rae of flow and working pressure are considered to be stabilized when it becomes difficult to observe changes in working pressure during a period of three hours by the use of a deadweight pressure gage. Stalibization of pressure in the literal sense is never obtained in a producing gas well. In formations of low permeability. such as those in the Hugo-ton Field, most wellhead working pressures approach stabilization closely enough to be used satisfactorily in the determination of a back-Pressure potential curve after flow periods of 24 hours. We shall therefore describe the backpressure curve calculated from ohserved rates of flow and working pressure at the end of 24-hour flow periods.

Jan 1, 1949

By J. O. Brittain, E. P. Lautenschlager, D. A. Kiewit

Compression tests were run in the temperature range of 700° to 900°C ox 0' phase NiAl intermetal-lic alloys of several grain sizes. At these temperatures the minimum strengths were observed at the stoichiometric composition. While significant increases in strength occurved in both the low-nickel (vacancy) and high-nickel (substitutional) regions, the highest strengths were found in the high-nickel region. During deformation serrated flow was sometimes observed in the low-nickel alloys. After deformation transgranular cvacking and deformation striations were observed in all compositions tested. AS part of a general investigation of the properties of NiAl inter metallic compounds, a preliminary study of the role of point defects upon plasticity was made by high-temperature compression tests on ß' NiAl specimens of several grain sizes and compositions. ß' NiAl is an intermetallic compound having a CsCl structure and a rather wide range of composition from A1-45 at. pct to 60 at. pct Ni.1 According to Bradley and Taylor2 and to cooper,' it possesses a defect lattice in which departures from stoichiometry in the direction of decreased nickel content lead to the presence of vacant nickel sites (although Cooper's work indicates that a small amount of substitution also occurs) whereas departures on the high-nickel side lead to substitution of nickel on aluminum sites. NiAl forms congru-ently from the melt at approximately 1650°C,1 and thus has a higher melting point than either of its component elements. Up to this time, although this and other high-melting intermetallic compounds have been suggested for elevated-temperature usage,4 only the hardness4 and a few tensile-strength measurements5 have been reported for NiAl at high temperatures. In the present investigation the effects of composition upon the compressive-strength properties in a range of 700° to 900°C have been measured for NiAl of several grain sizes. EXPERIMENTAL PROCEDURES The alloys were made as described elsewhere6 from an A1-46.8 at. pct Ni master alloy furnished by the International Nickel Co. with additions of high-purity nickel and aluminum. The charges were vacuum-induction-melted in A12O3 crucibles with small amounts of helium added to the atmosphere to suppress vaporization. They were cooled slowly from the melting temperature to achieve uniform grain size. In order to refine the as-grown grain size a special rolling technique was developed. Alloys were packed into 0.10-in. wall-type 302 stainless-steel tubes which were partially filled with magnesium oxide to prevent bonding between the alloy and the steel jacket. The ends of the tubes were closed by hot forging, and the packets were then hot-rolled. The alloys with greater than 50 at. pct Ni were rolled at 1100°C, but it was found necessary to increase the temperature to 1350° C before alloys with less than 50 at. pct Ni would roll without cracking. With these temperatures, reductions as high as 48 pct were achieved in a single pass. The rolled alloys will hereafter be referred to as "fine grained" whereas the as-grown material will be designated "coarse-grained''. The compression specimens were made by cutting square cross-sectional pieces, approximately 3/16 by 3/16 by 1/2 in., with a water-cooled diamond cut-off wheel from the as-grown or the rolled alloys. Specimens were ground to their final dimensions by polishing through 3/0 grit silicon carbide papers. The final shape was a rectangular parallelepiped of square cross section having a height-to-width ratio of 3:1. Compression testing was carried out in a compression rig of our own design mounted on an In-stron Floor Model. The specimen chamber could be heated to 1000°C and was controlled within ±2°C. The compression rig was enclosed within a bell jar and was maintained at a 50 µ of mercury vacuum throughout the duration of the test. The test cham -ber was heated from room to test temperature within 15 min. Specimens were then held at the test temperature 30 min prior to testing. Previous experiments indicated that no grain growth would occur within this time. An Instron Variable Crosshead speed unit was used to adjust for small variations in specimen lengths in order to have a constant initial strain rate, €, for all specimens of a group. For the fine-grained specimens the strain rate was changed rapidly at constant temperature by a factor of 10 with the speed lever on the Instron. For a given € the compression data was analyzed in terms of true plastic strain (E) and true compressive stress (0).

Jan 1, 1965

By W. C. Ellis, M. E. Fine

WHEN certain binary Fe-Ni alloys are worked cold and then stabilized by a stress-relief anneal, their Young's moduli are nearly invariant over a substantial temperature range determined by composition and work-anneal history.' In the present investigation addition of molybdenum to such alloys (besides increasing the yield strength) was found to diminish the sensitivity of the thermal coefficient of Young's modulus to composition changes. Such alloys are of interest for applications requiring 1 a metal with controlled, low temperature coefficient of Young's modulus and substantial magnetic permeability.' Young's modulus ordinarily decreases with rising temperature. In ferromagnetic alloys a change in modulus on heating due to loss of ferromagnetism modifies the .temperature dependence. Far below the Curie temperature ferromagnetism alters the modulus in two ways: a—Addition of the energy of magnetization, a function of interatomic distance, changes the relation between interatomic energy and distance.' This lowers the modulus in the Fe-Ni and Fe-Ni-Mo alloys of this investigation. b—An applied stress changes the ferromagnetic domain arrangement so that linear magnetostriction contributes to the strain and further lowers the modulUs.~ Since in the alloys of this investigation both effects lower the modulus, loss of ferromagnetism on heating changes the slope of the modulus-temperature curve in a positive direction. With increasing temperature the slope of the modulus-temperature curve, due to progressive loss of ferromagnetism, becomes less negative, goes through zero (the modulus is minimum), becomes positive, and resumes its normal negative value above the Curie temperature.' The increase in modulus and decrease in curvature in the modulus-temperature curve occurring on work hardening have been attributed to a reduction in effect (b).'. Vn the absence of ferromagnetism work hardening through introduction of residual strains would be expected to decrease the modulus.' Alloy Preparation—Test Methods Four series of alloys having nominal molybdenum contents of 5, 7, 9, and 10 pct and containing 47 to 58 pct Fe (the analyzed compositions are given in Table I) were melted in air and cast as bars weighing from 2 to 6 lb. The charge consisted of electrolytic nickel, Armco iron, molybdenum (99+ pct) or ferromolybdenum (62 pct Mo), manganese, and aluminum as a deoxidizer. The bars were swaged cold to the desired diameters with intermediate anneals. Alloys in this composition range are reported" to be face-centered cubic and ferromagnetic at room temperature. The Curie temperatures" decrease with molybdenum. For example, keeping the Ni/Fe ratio at unity and increasing the molybdenum from 0 to 17 pct decreases the Curie tempera- ture from approximately 500°C to room temperature. (The 17 pct Mo alloy requires quenching to retain a single phase.~) Young's modulus at a series of temperatures from —50" to 100°C was determined by a dynamic method previously described.', " In this method Young's modulus is calculated from the resonant frequency (in this case approximately 50,000 cycles per second) of a rod sample (approximately 2 in. long) vibrating longitudinally in the first mode. The densities of the samples at room temperature, Table I, were determined by the standard method of weighing in air and reweighing in redistilled bromobenzene. The linear coefficients of expansion, Table I, needed to calculate the sample length and density at the temperature of measurement, were obtained by observing the change in length (22" to 100°C) of an 8 in. gage distance with a two microscope cathetometer. The values of density and coefficient of expansion in the few samples checked are independent of treatment to the accuracy reported. This was assumed to be general for all the samples. The modulus values are accurate to &0.05x101' dynes per sq cm. However, values of thermal change in modulus are accurate to 20.005~ 10" dynes per sq cm. Young's Modulus Values at 25°C: The modulus values of O', 5, and 10 pct Mo alloys at 25 °C are plotted in Fig. 1 as functions of nickel. After working cold, the samples were either recrystallized at 950" to 1000°C or given a low temperature stabilizing anneal at 400° C. The 400°C anneal does not reduce the hardness nor cause recrystallization. Annealing at 400 °C does

Jan 1, 1952

By H. S. Wang, Y. P. Gupta

Diffusion of zinc and germanium in liquid silver is measured in the temperature range 975" to 1400°C by use of the capillary-reservoir technique. The ex-perinzental results are discussed in terms of the fluctuation and the "hole" theories of liquid diffusion, assunzing the solute as a point charge equal to the difference in the valences of the solute and solvent atoms. The additional coulombic interaction term due to the excess solute charge is evaluated in terms of the Thomas-Fenni approximation. The theoretical and experimental results agree with both the fluctuation and "hole" theories of liquid diffusion. No perceptible effect on solute diffusion in liquid silver of the size difference between the solute and solvent atoms/ions is apparent. DIFFUSION in liquid silver of electropositive solutes indium, tin, antimony, and homovalent gold has been previously reported by Leak and Swalin1 and Gupta,' respectively. These solutes have nearly the same atomic size but differ principally from one another in excess valence (+2, +3, +4, respectively). The observed differences in the temperature dependence and the rate of solute diffusion were explained in terms of an added coulombic interaction between the solute and the solvent atoms. In the case of diffusion of gold in liquid silver, the data were found to be consistent with an effective valence for gold of -0.85, as proposed by Le Claire.3 Recently, Wang and Gupta4 have reported a study of diffusion of ruthenium, iron, and cobalt in liquid silver. The results of diffusion of these solutes and their temperature dependence were found consistent with the hole theories and the fluctuation theories of liquid diffusion, if ruthenium, iron, and cobalt were diffusing in liquid silver with relative valences -2, -1.3, and -0.5, respectively, instead of -3, -3, and -2 as suggested by the relative position of these elements in the Periodic Table of Elements. Furthermore, the predicted valences for these solutes were observed to be consistent with the sparsely available information on the magnetic properties of some of the dilute alloys of copper and silver with these solutes. In theoretical calculations of solute diffusivity, the solute was assumed as a point excess charge equal to the difference in the valences of the solute and solvent atoms. Both the assumption of a point excess solute charge and the use of the Thomas-Fermi approximation to calculate the potential of a solute charge are less precise for the case of electronegative solutes. Therefore, it was not possible to infer from the data on ruthenium, iron, and cobalt an effect, if any, on solute diffusion of the relative differences in either the Period or the size of the solute and solvent atoms or the solute atoms themselves. A study of the diffusion of Period 4 elements, specifically zinc and germanium was, therefore, undertaken since zinc and germanium, respectively, have relative valences of +1 and +3 in liquid silver and the data obtained on diffusion of these solutes could be compared with the available data on diffusion of Period 5 electropositive solutes, indium, tin, and antimony in liquid silver. From such a comparison, it was hoped to learn something about the effect, if any, of the ion size or the structure of the ion core on impurity diffusion in liquid silver. EXPERIMENT The diffusion of tracer zinc and germanium in liquid silver was studied by the capillary reservoir technique, modified adequately for use at high temperatures. In principle, capillaries containing liquid silver

Jan 1, 1970

By L. H. Robinson

Triaxial compression tests on Indiana limestone indicate that chemical additives in the pore fluids can increase or decrease the strength in plastic failure but not in brittle failure. Tests using a series of the sodium salts of dicarboxylic acids show that odd-number carbon-atom chains decrease the yield strength as much as 3.0 x 10 3 psi, and even-number carbon-atom chains increase the yield strength as much as 9.0 x 102 psi. ,The most effective chemical (sodium citrate) decreased the yield strength of Indiana limestone from 16.0 x 103 to 12.0 x 103 psi. The chemical additives investigated have no influence on microbit drilling rate when drilling with zero differential pressure. However, when drilling at a 2.0 x 103-psi pressure differeniial and using an odd-number carbon chain compound as the circulating fluid, the roller bit drilling rates were slower than with water whereas the drag bit drilling rates were faster. One even-number carbon chain compound added to the circulating fluid produces the opposite effect: the roller bit drilling rate is slightly faster than with water and the drag bit slower than with water. INTRODUCTION A Russian book by Rehbinderl published in 1944 generated much interest in the possibility of aiding and accelerating the destruction of solids by the action of a liquid in which the solids are deformed. This book describes a process in which microcracks are generated during elastic deformation. To describe this process, the rock is divided into three zones: (1) the zone in which the destruction takes place, (2) the predestruc-tion zone (an affected area immediately below the destroyed zone) and (3) the undisturbed specimen. Consider a load applied normally to a surface of an infinite slab of rock. Immediately below the point of application of the load, the rock is destroyed by compression or shear forces. Below this area of destruction, because of a great number of discontinuities ranging from defects to weak points in crystals of discontinuities in crystal latices, very small cracks are created in or between the crystals (often referred to as microcracks). Upon removing the load, the broken rock in the destroyed zone could be removed. In the lower predestruction zone, however, the microcracks in and between the crystals could disappear by the process of rehealing, i.e., the molecular attraction from one side of the crack to the other side being sufficient to completely eliminate the crack. Thus, a large number of these microcracks possibly exist only for a relatively short period of time. The concept of small cracks being generated within the crystals of a rock is not unreasonable. If the rock matrix is deformed below the yield point, some of the defects present within the crystalline structure could start small cracks through the interior of the grains. Upon removal of the load, these microcracks reheal (or the newly generated surfaces come back together) so that all evidence of cracks completely disappears. Under various types of loading, and in various types of fluids, the rehealing of these cracks would be time dependent. If a liquid adhered to the surface of a rock, it could penetrate into the microcracks and thus delay or prevent the rehealing process. This suggests that the prevention of healing of the microcracks may be dependent upon the wetting characteristics of the solid. Thus, rocks which are water-wet should be more easily destroyed in water than in nonpolar hydrocarbon liquid. Adsorption of a liquid could also reduce the free surface energy which could explain the decrease in strengths of materials under nonrepetitive-type loading. Rehbinder's work prompted Boozer, Hiller and Serdengecti 2 to examine the effects of pore fluids on the deformation of rocks subjected to triaxial compression over a range of confining pressures, temperatures and strain rates. Fluids which strongly adsorbed on the rock grain surfaces decreased the strength of sandstone and limestone, which deformed plastically. For certain strain