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By R. H. Pemberton

The principle of airborne electroniagnetic prospecting is well-known. 'The basic geonhysicai texts in inost cases discuss the main elements involved in electromagnetic prospecting. However. there is ceriainlv iittle information available to the public concerning he present types of airborne eiectromagnerlc systenis being flown today by both contracting companies and some of the mining companies which have their own instruments. This is unfortunate since it is difficuit for those people not conducting such operations to understand thoroughly the iarge variation in the electromagnetic instrunlents available. Basically, the aeriai electromagnetic induction method utilizes a primary or transmitting coil through which is generated an alternating magnetic field at a frequents: generally of the range of 100 to 2000 cycies per sec. This primary field links with buried conductors and generates eddy currents within them. These eddy currents in themselves generate a secondary magnetic field of the same frequencv, but generally nut-of-phase with respect to the prinlarv field. This secondarv field is detected above the ground in the pick-up or receiver coil which is tuned to the frequency of the current applied to the primary transmitter coil. One of the main problems in the development of an airborne electromagnetic system is that of maintaining constant coupling between the cransmitting and receiving coil systems. Any variations in the coupling due to relative motion between the two coils will result in an in-phase signal being induced in the receiver coil. [However, any variation in the coupling does not result in an out-of-phase signal change in the receiver coil. The first airborne eiectromagnetic svsteins which were developed utilized a large prlniarv coil set up on the aircraft with the receiving coil being towed behind in a bird, generally at the end of a cable of about 500 ft. in length. It is possible with such a system to record the out-of-phase or quadrature responses more readily than the in-phase re-sponse. One system utilizes a dual frequency method, wnereby the out-of-phase responses at two frequencies are recorded. Another system used today records a single-frequency olrt-of-phase response. Recentlv home companies have succeeded in measuring from ne air both the out-of-phase and the in-phase components. The usefulness of recording in-phase is weil-known, but unfortunately this is difficult to obtain in any towed-bird system. In order to measure the true in-phase signal, the most straightforward system is that in which both the transmitter and receiver coils .Ire affixed in space so that there is little or no relarive motion between the two coils. THE FLIGHT SYSTEM The particular system which Canadian Aero Service is using at present is mounted on a Sikorsky S-55 helicopter (Fig. 1). A record of both the in-phase and out-of-phase responses is made at a frequency of 390 cycles per sec. The transmitter coil is set on a boom mounted in the front of the helicopter; the receiver is set on a tail boom extending back from the helicopter. Separation between these coils is about 65 ft. The two coils are mounted in a vertical co-axial relationship. Having the transmitting coil in a vertical plane ensures that maximurn coupling will occur with vertical conductors rather than flat-lying conductors. Having them mounted as they are in a co-axial relationship on the helicopter ensures that maximum response will occur when the flight direction is orthogonal to the strike direction of a given conductor. The present sensitivity of the Em system is 20

Jan 1, 1961

By I. A. Lesk

The various materials utilized in the construction of integrated circuits, and the resultant materials interfaces, are discussed with emphasis on a materials system that is compatible with all types of integrated circuits and minimizes the number of different interfaces. Problems with interfaces may originate in the silicon, on its surface, and between other materials within the integrated-circuit package independent of the silicon. ThE difference between integrated-circuit theory and practice may generally be spelled out in terms of the difficulties in fabricating a desired structure. There are, of course, problems in forming the requisite materials, of the necessary composition and geometry, where needed. A distinct class of problem, however, is associated with interfaces— generally between different materials, but occasionally between regions of the same material. We require that each interfacial system perform its proper electrical, mechanical, and thermal function, and do so in an unchanging manner with time under the most severe operating conditions. In a practical sense, we deal in nonideal systems, such that it is generally not possible to form an interface exactly the way it was intended, even if we allow for a knowledge of the practical limitations of the fabrication system. Another way of looking at this situation is to realize that, when we form a group of interfaces under apparently the same experimental conditions, there are often differences of important consequence between them. Very high-magnification pictures, such as are obtained by an electron microscope, reveal fine structure that often differs over the area of a given sample, as well as from sample to sample. Low-magnification pictures look better, but don't eliminate the problem. The trend towards integrated circuits, and away from circuits fabricated utilizing separate components, is very strong in many areas of electronics. A typical silicon monolithic integrated circuit, still in place in the wafer on which it was fabricated, is shown in Fig. 1. The increased reliability which is being experienced through the use of integrated circuits can, to a large extent, be credited to the reduced complexity of the interface system that is present in the electronic system. A glance at Fig. 1, however, with all of its epitaxial and diffused p-n junctions, and interconnect system, shows that interfaces have been far from eliminated. Fig. 2, depicting a schematic cross-sectional view of a (partial) typical integrated circuit, illustrates in detail the numerous interfaces that occur in this type of structure. Besides the individual circuit elements, there are interfaces for isolation, and, Fig. 3, even a crossover requires a series of interfaces. What has been accomplished, however, irrespective of whether or not the total number of interfaces in the circuit is increased or decreased, is that the variety of interfaces is very much reduced. This is because there are fewer materials involved. Since the expense incurred in an R & D program to improve reliability is pretty much directly proportional to the variety of interfaces involved, it is economically advisable to work with integrated circuits for highest reliability. That is not to say that circuits built using standard components could not be made as reliable as integrated circuits, but that the expense involved because of the more complex over-all interface system would be much greater. Although electronic performance utilizing integrated circuits with all silicon elements (i.e., transistors, diodes, resistors, capacitors) is adequate for many applications, there are numerous instances where thin-film passive elements must

Jan 1, 1965

By J. T. Dewan

An experimental setup is described whereby the responses of Neutron logging instruments have been determined opposite formations of different porosities and under various borehole conditions. The results of these tests are presented in several charts which show how the Neutron log is affected by the following factors: hole diameter, casing, cement, salinity and weight of drilling mud, and position of logging tool with respect to the wall of the hole. The responses in the case of empty holes are also shown. A chart is furthermore presented which shows the shapes of the Neutron log, as a function of logging speed and time constant, at the boundaries between two formations with different porosities. These were derived mathematically using as a basis laboratory determination of the shape of the curve under static conditions, i.e. at very low logging speed. Corrections for the readings made opposite thin beds are given by these computations. The correction is found negligible under usual logging conditions for beds thicker than about 4 ft. INTRODUCTION The Neutron log is used in borehole surveys both for the delineation of porous formations and for the quantitative estimation of their porosities.1,2,3,4,5 It is common practice to calibrate the response of the Neutron log in terms of porosity values for each given geological unit by means of empirical comparisons between the deflections of the neutron curve and the porosity values given by the core analysis in a sufficient number of wells. Usually, the plots of the porosity values vs Neutron log deflections show a definite trend. It is therefore possible to trace an average line across the plotted points. This average line constitutes a calibration curve which can be used to evaluate the porosities from the Neutron logs in the other wells drilled in the same region. Futhermore, when the porosity values are plotted on a logarithmic scale and the Neutron log deflections on a linear scale, the calibration curve is practically a straight line. Accordingly the calibration curves are often determined by simply tracing a straight line between two points corresponding to two widely different porosities. Different choices are made for these two points, depending on local conditions. For example, one point will be defined by plotting the deflection of the Neutron curve opposite a formation known to be very tight, for which an average porosity value of 1 or 2 per cent is assumed. The other point may correspond to shale sections, to which a porosity of around 40 per cent is ascribed. The information provided by the eletrical logs — in particular the Laterolog, Limestone log or Micro-Latero-log — is also very often a help in the calibration of the Neutron logs. Empirical approaches such as these make possible the derivation of fairly reliable porosity values from the Neutron logs in many cases, at least in open holes and in essentially clean formations. There are, however, several causes of uncertainty which may sometimes entail appreciable errors. On the one hand, the Neutron log readings are influenced by the borehole conditions: hole diameter, presence or absence of casing and cement, presence or absence of drilling mud, characteristics of the mud, and position of the logging instrument with respect to the wall of the hole. The amplitudes of the curves opposite thin beds are furthermore atfected by the bed thickness,

Jan 1, 1957

By W. S. McCain, B. A. Wilcox, A. H. Clauer

The creep and creep-fracture behavior of a Ni-200-2Th0, alloy has been studied over the temperature range 816° to 1038°C and stress range 4000 to 19,000 psi Specimens having their axes either parallel or transverse to the final sheet-rolling direction were tested in air, and the apparent activation energy for creep was found to be 92 kcal per mole, regardless of specinien orientation. The stress dependence 01- the steady-state creep rate, was satisfied by where n depended on orientation; n = 9.7 for rrzaterial transverse to the rolling direction and n = 24.3 for material parallel to the rolling direction. In the latter case, the relation was also valid. The rupture strength of material parallel to the rolling direction was -1.5 times gveater than the transverse rupture strength. Several tests in vacuum revealed that here the creep rate was higher and rupture life lower than for comparable tests in air. THERE is an increased interest today in producing improved dispersion-hardened alloys for high-temperature structural applications. This had led various materials designers to modify existing alloys, such as thoriated nickel. One system that has received considerable attention is based on chromium additions to Ni-ThO2, with the obvious motive of improving the oxidation resistance. Another effect of chromium is that of lowering the stacking-fault energy, y, of nickel. For example, the addition of 30 wt pct Cr decreases y from -225 erg per sq cm for pure nickel1 to -70 erg per sq cm.' This decrease in y could have several effects on the deformation behavior. There is some evidence that cross slip of dislocations around Tho2 particles is a mechanism of tensile3 and creep4 deformation in TD Nickel (Ni + 2 vol pct ThO2) at temperatures below 0.5 the absolute melting point of nickel, T,. A decrease in ? by chromium additions should increase the difficulty of cross slip. Also it has been suggested that the high-temperature (T > 0.5Tm) rate-controlling creep process in "recrystallized" Ni-Tho2 alloys is the climb of edge dislocations over Tho2 particles.5 According to weertman6 a decrease in the stacking-fault energy should decrease the dislocation climb velocity resulting in a decreased steady-state creep rate. Thus, chromium additions to recrystallized Ni-Tho2 alloys would be expected to decrease the creep rate, all other conditions being constant. However, a difficulty arises when the stacking-fault concept is applied to high-temperature creep of dispersion-strengthened metals which are produced on a commercial or semicommercial scale. This occurs because the materials are processed so that they have a high-stored energy of cold work, and the other substructural effects could obscure any influence of stacking-fault energy per se. An example of an alloy with a high stored energy of cold work is TD Nickel bar. This material has a fibrous grain structure (1 I diam by 10 to 15 p long), and the structure is stabilized by the ThO2 particles. Annealing at high temperatures, e.g., 3 hr at 1300°C, causes no recrystallization or grain growth.4 Previous work by the authors4 showed that the high -temperature creep behavior of TD Nickel could not be related to any simple dislocation theory of creep, and this probably was associated with the complex initial structure of the material.

Jan 1, 1968

By W. A. Tiller, W. C. Johnston

The solute distribution ahead of an advancing solid-liquid interface is controlled by varying the momentum boundary layer thickness in the liquid adjacent to the interface. Single pass zone-melting experiments on Pb-Sn alloys are described in which the liquid is caused to rotate in the plane of the solid-liquid interface due to the influence of a magnetic .field rotating in this plane. The variation of the diffusion boundary layer thickness with field strength is determined. DURING the freezing of an alloy a partitioning of solute occurs at the solid-liquid interface, the magnitude depending upon the difference in the solid and liquid solubilities at the interface temperature. Because the diffusion coefficient is so small in the liquid relative to normal freezing rates, either a pileup or a depletion of solute occurs at the interface when the partition coefficient, kO, is either less than or greater than unity, respectively. This solute distribution is completely characterized by i) the solute concentration in the liquid far from the interface, C) the ratio of freezing velocityf, to diffusion coefficient, D, iii) the partition coefficient, ko, and iv) the thickness of the diffusion boundary layer, 6,, at the interface (this assumes that an electric field is not applied across the interface). For a particular system, C ko and D are fixed so that the character of the solute distribution can be changed only by a variation of either f or 6c. As is well known, the freezing velocity can be changed by varying the thermal environment of the alloy. Whereas, the thickness of the solute rich layer can be changed by varying the fluid flow conditions in the liquid. It is the purpose of this paper to describe a technique for controlling the fluid flow conditions in the liquid. During most solidification experiments the driving force for fluid flow arises from either mechanical mixing, thermal convection or electromagnetic mixing. The momentum boundary layer thickness, 6m at the solid-liquid interface, within which negligible movement of the liquid occurs, has been calculated for the special case of mechanical mixing where crystals are solidified by the Czochralski technique.l,2 The calculation of 6m for the case of thermal convection has also been made.3 In some calculations it has been assumed that the momentum boundary layer thickness, 6,, may be equated to the thickness of the diffusion boundary layer 6c, at the interface. However, as may be seen from Appendix I this is only true in very special cases and in general where a is a constant of magnitude determined by the particular liquid alloy. Neither calculations nor experimental data exist for the dependence of upon electromagnetic mixing. In this paper experiments are described in which the liquid is caused to rotate in the plane of the interface due to the torque developed on it by a magnetic field, H, rotating in this plane. The variation of is controlled by the variation of H. A magnetic field rotating in a plane perpendicular to the interface has been used for the purification of aluminum. Experimentally, we determined the variation of 5C with H by using the zone-melting technique of pfann5and a theoretical relationship of Burton et a1.2 pfann5 has shown that, after the passage of one molten zone through a long cylindrical charge of uniform concentration, CO, the solute distribution, C,, in the solid is as shown in Fig. 1. The equation describing this distribution is

Jan 1, 1962

By L. B. Gittinger

Sulfur is a nonmetallic element widely distributed in nature. It constitutes 0.06% of the earth's crust but only a very small portion occurs in sufficiently concentrated amounts to justify mining. Sulfur occurs in practically all animal and plant life. It constitutes approximately 0.09% of the elements in the oceans; it has been found in meteorites. Sulfur was known and used by man before recorded history. The American Chemical Society approved spelling for the element is sulfur. The English spelling sulphur is used commercially in the United States. In ancient times, sulfur was called brimstone, literally "burning stone." Today the term brimstone is used interchangeably with the term elemental sulfur. Sulfur is found naturally in the elemental form in subsurface deposits associated with gypsum and anhydrite in salt domes and sedimentary formations in evaporite basins and in solfatara-type deposits associated with volcanoes and mineral springs. Sulfur occurs also in molecular combination in ferrous sulfides (pyrites and pyrrhotite) and nonferrous sulfides (copper, lead, zinc, and nickel), and in mineral sulfates (gypsum and anhydrite); as hydrogen sulfide contaminant in natural gas; as organic compounds in crude oil and tar sands; and as pyrite and organic compounds in coal and oil shales. Sulfur resources are abundant and exist throughout the world but the extent to which they can be classified as reserves is greatly circumscribed by prevailing prices and technology. Estimates of world sulfur reserves are compiled by the U.S. Bureau of Mines. A compilation of reserves by area and source of sulfur published in 1970 and presented here as [Table 1] totaled 2.47 billion tons (Lewis, 1970). The effect of the decline in prices which has occurred since the earlier estimate is dramatically illustrated by the 1972 estimate of the U.S. Dept. of the Interior which shows world sulfur reserves of only 1.2 billion tons (Anon., 1972d). Sulfur is produced commercially from one or more sources in nearly 70 countries of the world. World production of sulfur in all forms totaled 41.6 million tons in 1971. (Sulfur statistics given in this chapter are long tons.) Native deposits, sulfides and oil and gas contributed, respectively, 31, 41, and 25% of world production (Table 2). Of the sulfur produced from native deposits, salt domes accounted for 54% and evaporite basin deposits, 44%. Volcanic deposits are of little significance except for local consumption. The past two decades have seen important shifts in the world's sulfur sources. In 1950, native deposits and sulfides each supplied about one-half of the world's production. During the 1950s, sulfur recovered from oil and natural gas grew rapidly, representing about 10% of the total by 1960. Since then, the petroleum industry has continued to increase its relative importance as a source of sulfur, representing more than 30% at 1972 year-end. Sulfur is generally classified as elemental or nonelemental for statistical purposes. Elemental sulfur is sulfur produced in the pure, uncombined form. It includes production from native deposits, as well as that recovered in the elemental form from oil and natural gas or other sulfur-bearing materials. When produced from other than native deposits, it is generally referred to as recovered elemental sulfur. Nonelemental sulfur is that which is utilized commercially in molecular combination with other elements, such as sulfides or sulfates. Elemental sulfur is being produced from salt dome deposits in the Gulf Coast region of the United States and the Isthmus of Tehuantepec in Mexico, and from evaporite basin deposits in west Texas, Poland, Sicily,

Jan 1, 1975

By A. E. Worthington, R. F. Meldau

An analog computer study was made of the reduction of the magnitude of the SP by formation geometry and resistivity effects. Practical field .situations were studied. The analog data were converted to the form of departure charts. These charts may he used to determine the reduction in the SP due to the above eflects pith good precision Quantitative interpretation of the SP log in terms of formation water resistivity is presently based on the premise that the observed SP is equal to the electrochemical potential developed across a shale between the mud filtrate and the formation water. This procedure inherently assumes that, first, no electro kinetic (streaming) potential is present, and, second, that the SP is not reduced by resistivity or geometry effects in the formation. When, however, such a reduction of the observed SP does occur, one may write, SP = b,E, b, E, (1) where SP is the observed self-potential opposite the center of the bed under consideration. In this case, E, is the electrochemical potential, E, is the electrokinetic potential, b, is the electrochemical reduction factor, and h, is the electrokinetic reduction factor. The first assumption above is equivalent to assuming E, = O in Eq. 1 and the second assumption is equivalent to h, = b, = 1. Examination of electric logs shows that for many formations of interest the observed SP is reduced below its maximum value. The object of this work is to aid quantitative SP interpretation in at least some of these situations by obtaining values for b, and b, in Eq. 1 as functions of realistic combinations of bed thickness, depth of invasion, and formation resistivity. The only previously published work in this field known to the authors is by H. G. Doll' in 1948. He evaluated b, under conditions permitting exact analytical solution. His work clearly established the importance and qualitative nature of formation geometry and resistivity effects upon the SP, but the necessity of obtaining analytical solutions restricted his study to situations of limited practical interest. In order to extend such studies to practical combinations of formation parameters which do not lend themselves to feasible analytical solutions, the results reported in this paper were obtained by use of a special analog computer. THE ANALOG MODEL The analog model used for this study was the Guyed Analog Computer which originally was designed and built for resistivity log departure curve studies. It consists of a two-dimensional mesh of resistors, with the vertical mesh corresponding linearly to vertical distance along the borehole, and the horizontal mesh corresponding to radial distance from the borehole axis. By proper choice of horizontal resistor values, a three-dimensional, axially symmetric, borehole-formation problem can be modeled with this two-dimensional array. These and other details of the model are contained in a paper by H. Guyod'. The geometry used for the SP studies with the analog is depicted in Fig. 1. This configuration has a horizontal plane of symmetry, and, hence, the model, and the following discussion, need only to be concerned with one quadrant such as shown in Fig. 2. A further simplification arises by considering that both the natural potential sources and those used in the model have fixed internal impedance. Therefore, the current flows produced by these sources can be separated and studied independently ( i.e., the superposition theorem can be applied). SP = SP, i SP, = h,E, + b,E, ,(7)

By S. H. Moll, R. E. Ogilvie

The investigation of solid-state diffusion phenomena may lead to much information concerning binary alloys. In particular, a study of the concentration gradients present in multiphase diffusion couples can lead to the determination of the solubility limits of the single-phase fields in the phase diagram. The specific concentration gradient which results from the heat treatment of a diffusion couple depends not only upon the time and temperature of diffusion, but also upon the number of phases existing in equilibrium at the diffusion temperature. Such concentration gradients possess sharp discontinuities whose terminal points correspond to the solubilities existing at the limits of the two-phase field in the phase diagram at the diffusion temperature. In general, there will be a discontinuity in the concentration curve for each two-phase field which exists in the phase diagram between the concentration limits of the couple. A number of investigators have analyzed the gradients present in multiphase diffusion couples. 1-8 The iron-titanium phase diagram exhibits a y loop in the temperature range from 900" to 1400°C, and the limit of the a + y field lies at some composition which is less than 1 wt pct Ti for any temperature. It was felt that a diffusion study could yield values not only for the diffusion coefficients involved, but also for the chemical solubilities in the phase diagram. The concentration gradients were analyzed by an X-ray absorption technique developed by Ogilvie.6 The absorption of a monochromatic X-ray beam is measured in steps parallel to the diffusion direction and the resulting intensity gradients are transformed into concentration gradients by applying the laws of X-ray absorption in a binary system. This technique has been applied by ogilvie6 to the systems Ni-Au, Cu-Au, Fe-Cr, and Ni-Cr; by Gelles7 to the systems Be-Fe, and Be-Ni and by Hilliarde to the system Al-Zn. Linear X-Ray Absorption Analysis—The use of X-ray absorption analysis as a tool for determining concentration gradients arises from the fact that the beam is absorbed according to the quantity and species of elements present in the sample and not according to their state of aggregation. This method is more advantageous than the chemical analysis of machined layers since it is less time consuming and less expensive and can analyze a very small area. IF a homogeneous binary alloy (A + B) is analyzed with two different monochromatic X-ray beams I0(2) and lo(2) the following relation between the transmitted intensities, the intrinsic absorption coefficients of A and B for the two different radiations and the weight fraction of each element may be derived.' In (I/Io) (a+b) xa(u/p)a(2) + xb(u/p)8(2) Eq. [1] is independent of specimen thickness and density, but requires that either element A or B possess an absorption edge between the wavelength limits of the two monochromatic beams. I, is evaluated for each radiation by measuring the transmitted intensity through a varying number of foils of a suitable absorber. A plot of the natural logarithm of the transmitted intensity as a function of the number of foils, when extrapolated to zero foils, yields the value of I,. If a plot of the ratio in Eq. [ I] is calculated as a function of xA, then a master curve results. From

Jan 1, 1960

By S. Korman, S. B. Tuwiner

THE purpose of this study is to investigate the effect of agitation upon the flotation of chal-cocite. It is believed that the concentration of collector which is required to produce a water-repellent surface upon the mineral is determined among other things by the rate of collector diffusion through an impeding film of more or less stagnant fluid. Its thickness depends upon the intensity of agitation. In the first part of this study a method is developed for determining the thickness of the fluid film upon a polished surface of synthetic chalcocite. The film thickness is then determined as precisely as possible under three readily reproducible condi-tions of agitation intensity. These determinations serve as a quantitative evaluation of agitation. In Part 2 it is demonstrated that in solutions of lime at PH 10.5 and in the absence of air or dissolved oxygen the concentration of collector required to develop water-repellency upon the surface in any given time is a function of the fluid film thickness, and that after about 10 min the relation becomes linear. This points to the possibility that the collector ions may be involved in a diffusional process through the fluid film. In Part 3 it is shown that where air is present more collector is required to produce water-repellency than for the case in which air is excluded. Next, it is shown that for the latter case the most minute amount of sodium sulphide suffices to preclude development of water-repellency. Both oxygen and sulphide are in a sense, therefore, depres- sants for chalcocite in a lime solution at PH 10.5. When oxygen and sulphide are present simultaneously there is a region of minimum critical collector concentration for water-repellency which is very markedly lower than the concentration where oxygen alone or where sulphide alone is present. Moreover, this minimum appears to be identical with the collector concentration which is required where sulphide and oxygen are both excluded. This would appear to indicate that in certain ranges of concentration of oxygen and sulphide, each cancels the effect of the other. The range of concentration of solution for this effect in solutions saturated with oxygen is a function of the agitation intensity. Thus we are led to believe that a chemical reaction involving sulphide and oxygen occurs at the surface of the chalcocite. Part 4 of this study is a further development of this idea and some of its consequences from an electrochemical standpoint, while in Part 5 the disappearance of sulphide from pulps of several minerals is noted with an indication that both dissolved oxygen and the mineral are necessary, the reaction being catalytic or pseudocatalytic. Part 1. Determination of Fluid Film Thickness The Fluid Film Concept: The hindrance to the diffusion of collector to the surface of the chalcocite is a barrier of stagnant fluid in the vicinity of the surface. It is the same barrier that limits the rate of transfer of heat, the rate of solution of dissolving crystals, or any of the other rates pertaining to chemical engineering unit operations in which the film resistance to diffusion plays a principal role.' Fluid films are present upon the surface to an extent which varies with the geometry and intensity of agitation. They result from the fact that in the region within the fluid near a surface, motion is entirely parallel to it. From the standpoint of transfer to or away from the interface the effect is as though the fluid were stagnant. Outside of the film, movement of the fluid may be streamline or turbu-

Jan 1, 1951

By P. Datta, L. L. Handy

For a wetting phase displacing a nonwetting phase from a porous medium the distribution of the residual fluid may depend on displacement conditions. Although this subject has been debated in the literature, only a few experiments have been cited to support the various conclusions. Experimental results presented in this paper show that fluid distributions are dependent on imbibition pmcedures. Results agree qualitatively with predictions from the pore doublet model. If the rate of water imbibition is restricted, the nonwetting phase is trapped preferentially in .the larger pores as expected. But if the rate of water imbibition is unrestricted, trapping occurs somewhat more in the smaller pores. These conclusions were deduced primarily from relative permeability measurements. INTRODUCTION Relative permeabilities are known to depend on the saturation history of the porous medium. For either continuously increasing or continuously decreasing wetting phase saturations, however, they have normally been assumed to be single-valued functions of saturation. Severat investigators have compared relative permeabilities measured by different methods and have reported acceptable agreement.1-5 Studies of simple models of the displacement process suggest that the distribution of residual fluids can be influenced by the displacement method. If this is so, relative permeabilities also should depend on the method of displacement. These predictions have not been supported by experimental data. The object of this paper is to investigate experimentally some of the predictions of these model studies. The particular question of importance is whether steady-state and unsteady-state methods should be expected to give the same values of relative permeability. Much of the reported data showing agreement between steady-state and unsteady-state methods have been obtained on un consolidated sand. Johnson, Bossler and Naumann, however, compared steady-state and unsteady-state results for Weiler sandstone and found no significant differences.5 Levine made a detailed study of pressure and saturation distributions for a laboratory waterflood in a consolidated system but made no attempt to calculate performance from steady-state relative permeability data Bail and Marsden in a somewhat similar set of experiments did attempt a comparison of observations with predictions but the results were inconclusive.7 Excluding gravity, two forces affect the distribution of wetting and nonwetting phases during an unsteady-state, immiscible displacement: viscous and capillary forces. If relative permeabilities are indeed the same when measured by steady- or unsteady-state methods, the fluid distributions at the same fluid saturations must be similar for both methods. Furthermore, the implication is that the relation between capillary and viscous forces is the same for both methods insofar as the effect on microscopic fluid distributions is concerned. Unsteady-state displacements are normally run at high rates to maximize the ratio of the viscous to capillary forces. The objective is to reduce the effect of capillary forces on macroscopic fluid distributions. For floods in which the phase which wets the porous medium displaces the nonwetting phase, capillary forces compete with viscous forces in determining fluid distributions.8 The residual nonwetting phase is discontinuous. Competitive aspects of viscous and capillary forces and the resulting effect on water-oil distribution in porous media have been illustrated in an elementary way using a pore doublet model. This model and predictions from it have been discussed at considerable length by Rose and Witherspoon, Rose and Cleary and by Moore and Slobod.9-13 Rose and Witherspoon show that so long as water invades the model at a rate equal to or greater than the free imbibition rate, the water will move through the larger capillary of a doublet first and trap oil in the smaller capillary. On the other hand, if a negative pressure is applied to the water

Jan 1, 1967

By R. R. Harvey

Recent evidence has indicated that the films forming at crude oil-water interfaces are the result of naturally occurring su,rface-active components in the crude oil rather than oxidation products resulting from exposure of the oil to air. Since the presence of such films may strongly affect the displacement of oil from porous media, a knowledge of their composition and formatiorz is of fundamental importance. In this study, without the assumption of a specific mechanism, film formation is considered to involve the transfer of a weakly surface-active species in solution in the oil to the oil-water interface. The film gas law and the Gibbs adsorption equation may thus he applied to the system. The rigid films which form upon decrease of the oil-water interfacial area are considered a result of the very slow rate of re-solution of the film material into the oil. When the shrinkage of the interface is very rapid, the amount of film material leaving the interface is negligible, and the system may then be treated in the same manner as an insoluble film. The combination of these treatments leads to a new concept of the film factor in which it may he quantitatively related to the concentration of film-forming material at the interface. Suitable experiments can then yield the following information. 1. Original concentration of surface-active species in the oil. 2. The change of concentration with time. 3. Concentration of surface active species at the interface. 4. The change of this concentration with time. 5. Interfacial tension of the system at any time and its variation with time. 6. Equilibriunz concentrations for a given set of conditions. 7. Concentration requirements for solid film formation. 8. Molecular diameter of the adrorbed species. These calculations may be made solely from data taken from measurements on the original oil. While using the pendant drop method of interfacial tension measurement of crude oil-water systems, Bartell and Niederhauser' remarked on the thin, transparent, pliable, solid films or membranes which were often formed at the interface between crude oil and water. As a result of their observations of these films, Bar-tell and Niederhauser concluded: 1. The films are formed by material from the oil adsorbed at the interface rather than by a reaction at the interface. 2. The adsorption of the film-forming material is a rather slow process. 3. There are good indications that the process is reversible; i.e., the film constituents may re-dissolve into the oil. 4. The film will spontaneously spread over any new surface formed. 5. The process of adsorption at the interface is accompanied by a decrease in the interfacial tension of the system. Although they had proved that film formation was not due to a reaction at the interface, Bartell and Niederhauser were unable to demonstrate conclusively whether these film-forming constituents were present in the original reservoir oil or whether they were formed as oxidation products after exposure of the oil to air. Recent evidence seems to point to their presence in the original oil. Although the true nature of the film-forming constituents is still uncertain, these conditions would be fulfilled by the assumption of the presence of a slightly soluble surface-active component in the original oil. This component would migrate to a freshly formed interface because it would thereby lower the free energy of the system. The component at the surface constitutes an expanded monolayer which would become compressed, upon retraction of drop, due to the slow rate of re-solution of the film components into the bulk of the oil. It is possible, by involved extraction processes, to separate or at least concentrate this film-forming fraction. However, using the assumptions made above, the technique of monolayer film study may be applied to reveal much of the nature of the adsorbing material without resorting to an actual separation of the film-forming constituents.

By H. Bartholomew, L. Bernstein

Experirmental bonds of Ag-In SLID to gold, copper, nickel, Kovar, Dumet, nickel-plated molybdenum, ALL-Pt vrzetallizing on ceramic, and nickel-plated Mo-Ti metallizing on Al2O3 ceramic have been made and exalnined. Metallographic taper sections were made of all bonds for Phase identification. In addition, failuve temperatltres were determined for bonds heated undev shear load. Sowe bonds were subjected to electvon-probe microanalysis. The ternary SLID system Ag-In-Sn was similarly evaluated. Plwtonticrogaphs and electron-probe data are discussed and related to over-all phase diagrams , diffusion effects, and wetting properties of the liquid. The rates of diffusion andor compound formation of gold, silver, and copper in indium and In-Sn liquids are found to descend in that order, as measured by the relatzve thickness of phase layers in the interfaces of bonds made at 200to 400°C. It is concluded that the SLID process enables one to produce bonds which are stable at high temperatures, after having been fabricated at low temperatures, and meet most requirements for application in interconnection, silicon bonding, or hermetic sealing of electronic devices. In a previous publication by one of the authors, the theory and principle of SLID bonding in simple binary systems was discussed. SLID bonding can be defined as a joining process using a preform with a laminated structure: a low-melting material clad on a high-melting core. During the bonding cycle a metallurgical transformation occurs such that the resultant structure can withstand, without reliquefying, temperatures higher than those at which the bond was made. The phases present in the joint interface region are high-melting compounds or, if equilibrium is reached, solid solution. Properties will depend on the phases present, ultimately approaching those of the solid substrate core of the SLID preform. The high-temperature strength of bonds made in these systems was correlated to phase identification in the interfacial bond regions from metallographic cross sections and electron-probe X-ray microanalysis data. When complex electronic components are assembled, multiphase systems result at the interfaces of bond regions. In these ternary and higher-order systems very little diffusion and phase-diagram data is available with which to predict the nature of the interfacia1 region that will result from conventional fabrication processes and subsequent field use of the component. Clarke and Rhines did early work in the field using the Al-Mg-Zn system as a vehicle. Guy and co-workers studied a portion of the Cu-Zn-Ni system and some mathematical4 and general5 aspects of multiphase diffusion. irkald' and coworkerse recently studied diffusion in the Cu-Zn-Sn system. No diffusion studies have been made on ternary systems directly applicable to this investigation but some phase diagrams are available: g-u-n, u-i-n, and CU-i-n. I) DESCRIPTION AND EXPERIMENTAL PROCEDURE The elements Au, Ag, Cu, Ni, In, and Sn are found in alloy systems commonly used in fabricating and assembling electronic components. Reference to the appropriate phase diagrams9 and the previous publication will indicate that the binary systems of any of the two low-melting elements, indium and tin, with any one of the other four higher-melting elements are capable of producing SLID bonds. It is not unreasonable to assume that any ternary or higher-order alloy system containing at least one of the elements gold, silver, copper, or nickel and one or both of the elements indium and tin could be used to produce bonds which are stable at high temperatures, after having been fabricated at low temperatures. Indeed, the liquidus contours and isothermal sections of those phase diagrams available7 do so indicate. The parameters affecting the bond and the equipment used in evaluating the bond were described in an earlier paper.' The current investigation used the

Jan 1, 1967

By A. Weiss, W. A. Coster

The search for ore is characterized by a great variety of uncertainties, each of which can be resolved by obtaining information at a cost. Three exploration stages may be distinguished in which information can be obtained, based on inherently different cost structure: 1) the reconnaissance or scanning stage, 2) the examination or screening stage and 3) the project stage. This exploration sequence would roughly coincide with replies to questions as to: where, how, why and how much. As complete information in each stage is too costly to acquire, we must assess the probability that adequate information will be furnished by a limited amount of effort and attempt to maximize the expected value of ore to be found for a given exploration expenditure. Several problems are discussed relative to the mathematical formulation and possible computer procedures for determining the optimum allocation of a total exploration effort. Based on the available literature possible solutions to this problem are indicated. When scanning through published literature on mineral exploration, it seems at first that there is little room for substantial and systematic improvements in the efficiency with which the problem of discovery of new ore deposits is presently being handled by large organizations active in exploration. It appears equally difficult to offer something relevantly new which could generate a break-through in exploration thinking and cause a marked improvement in the ratio of successful undertakings to the total exploration projects started. On the other hand, a number of experts in recent years have urged that the problems in prospecting be analyzed in a more skillful and sophisticated manner than in the past. Their thesis is based mainly on the premise that the cost of finding mineral deposits will increase with increasing technical difficulties. In present large-scale exploration ventures, especially in those regions where outcrops and immediately visible geologic evidence are scarce, older methods of prospecting are increasingly being replaced by more indirect and systematic geophysical and geochemical methods with more emphasis on correct statistical design of exploration patterns. It is perhaps the oil industry which has made the greatest strides in developing statistically, well justified patterns in its search for oil; possibly because oil seepages, as indicators of the presence of oil, left off at an earlier point in time than did outcrops as indicators of base metals. Among the pioneers in the field of statistics and operations research, as applied to mineral exploration, the excellent works of Allais, Slichter, Koop-man, Mickey, de Guhnin, Krumbein, Griffith, Sichel, Krige, de Wijs, and Matheron may be mentioned. It should, however, be pointed out that three subjects of basic importance to the allocation of exploration efforts have so far received only scant attention in published literature, even by the aforementioned authors. In the first place, a more precise definition of the object of the search, i.e., a minimum-size orebody, seems to be outstanding. Secondly, a decision model is not a widely-discussed subject. Thirdly, no concentrated attempt so far seems to have been made to establish probabilities of the occurrence of economic deposits on a regional scale and to arrive at a slightly more accurate knowledge of the probability laws governing the deposition of ore. It is not the purpose of this paper to create new order in the complexity of uncertainties in which our decision processes in exploration necessarily have to be conducted. Rather, we intend to highlight some of the outstanding, hitherto unmapped territory, where diligent compilation and a utilization of present and historic data may statistically improve our chances of success. We hope that the contribution of this paper will lie in bringing allocation problems into better focus and in increasing the mineral industry's realization of the magnitude of the factors involved. THE MINIMUM-SIZE OREBODY The concept of target specifications for what constitute a minimum-size orebody in exploration is a rather variable one and depends to some extent on

Jan 1, 1963

By H. Majima, E. Peters

The oxidation rates of pyrite, pyrrhotite, chalcopy-rite, chalcocite, covellite, bortzite, galem, sphalerite, and stibnite have beet2 carefully compared at 120 oC, using aqueous phosphate solutions buffered at pH 2.7, 7.1, and 11.2 as zvell as in 1.0 M NaOH and in am~onia-containing solutions. Under conditions of these studies, variations in rates of more than a factor of two per unit of mineral surface area were not observed for different minerals in phosphate buffered solutions, except that pyrrhotite showed unusually rapid oxidation rates In acid solutions, and stibnite showed very rapid oxidation rates in basic solutions. In caustic solutions, oxidation vates varied considerably, the most rapid being for pyrite and the slowest for sphalerite. In the presence of ammonia, only copper minerals showed more vapid oxidation rates in neutral solutions. Oxidation rates were measured on the basis of oxygen-consunzption rates per unit surface area of exposed mineral, using equivalent surface areas, mineral mesh sizes, pulp densities, agitation, and oxygen pressure. OXIDIZING pressure leaching of sulfide minerals has been a commercial method of treating concentrates of nickel, cobalt, and copper for over a decade, and recently the treatment of lead and zinc concentrates,' and even the recovery of sulfur from pyrrhotite by such processes, have been shown to be technically feasible.' Furthermore, the leaching of uranium ores by solutions acidified through the oxidation of pyrite and other sulfides present in the ore is commercially practicable.3 5 The mechanisms by which sulfide minerals oxidize in aqueous environments are not yet understood. However, certain generalities can be made for systems containing no unusual reagents, in which oxygen is the oxidizing agent. In acid solutions the oxidation of many sulfide minerals leads to the formation of elemental sulfur.8'7 The attack of some sulfides, notably galena (PbS), sphalerite (ZnS), and pyrrhotite (FeS), at temperatures below about 110°C leads to an almost quantitative conversion of the sulfide mineral to elemental sulfur according to the equation: On the other hand pyrite (FeS2) and copper minerals do not yield elemental sulfur quantitatively. Not more than 50 pct of the sulfur in pyrite is converted to the elemental form in acid oxidation, and this percentage is lowered by higher temperatures and possibly higher oxygen pressures.8'9 Copper minerals sometimes yield elemental sulfurlo'" but, since sulfur can reduce cupric ions with the precipitation of CuS or Cu2S, it is not likely that elemental sulfur is obtained in good yield. In acid solutions sulfur that is not converted to the elemental form always appears as sulfate salts or sulfuric acid. Sulfide minerals that yield elemental sulfur nearly quantitatively on oxidation in acid solutions tend to generate H2S when the conditions are not oxidizing. However, although it has been suggested that H2S is an essential intermediate in the mechanism of oxidation," this is doubtful because it is oxidized very slowly by oxygen. In basic solutions elemental sulfur is never formed, as predicted by thermodynamical considerations, summarized in the form of a potential-pH diagram in Fig. 1. However in neutral and basic solutions, unstable forms of sulfur not shown in the diagram appear during oxidation, notably thiosulfate (SOT-) and polythi-onates (S,O;-, x = 2 to 6).l3,l4 On prolonged oxidation only hexavalent sulfur as sulfate (SOi-) or sulfamate (NHzSO;) is found to remain, the latter appearing only in the presence of ammonia. The oxidation kinetics for thiosulfate by oxygen are the subject of a separate paper,'5 and were studied on the presumption that thiosulfate may, in fact, be a primary oxidation product for sulfide minerals, at least in neutral and basic solutions. A survey of the literature indicated that comparative oxidation rates for different sulfide minerals were needed to establish the role of the mineral structure and its thermodynamic properties on the oxidation rates and mechanisms.

Jan 1, 1967

By I. S. Levy, J. L. Brimhall, B. Mastel

Specimens of' Hastelloy X-280, a low-cobalt version of the solid-solution- hardened nickel-base alloy Hastelloy X, were given a series of thermomechanical treatttzents. They were then Lensile-tested at room temperature and 1350°F. The Microstructures of the specimens tested at 1350°F were studied by electron Microscopy. Microscopy showed that dislocation tangling, caused by the cold working, mas still in evidence after aging-for 24 hr to temperatures as high as 1550oF. (Cr, Mo)23 C6, (Fe, Mo)6 C'. as well us an unidentifiable phase precipitale due to the combination of the thermomechanical treatments and subsequent tensile strain. The room -temperature and 1350°F tensile properties show a general increase ill strength and decreccse in ductility with increusing cold-work level. This is due to the dislocation taangling-. PerLurbatiot~s to this general trend occur- due to solid-solution weakening at the higher cold-work levels as a direct result of the preciplitation reactions. THE requirements for corrosion resistance and high-temperature strength place nickel-base alloys among the more promising materials for advanced nuclear reactor applications. However, when these alloys are irradiated at service temperatures, they generally suffer severe embrittlement'" and reduction in rupture life.3 Certain experimental treatments resulted in improvements in the tensile and stress-rupture properties of Hastelloy X-280, a solution-hardened nickel-base alloy.' To provide a basis for understanding these improvements, unirradiated tensile specimens were examined by electron microscopy. The results are reported in this paper. EXPERIMENTAL DETAILS Material. Hastelloy X-280, a low-cobalt version of Hastelloy X, is a member of the solution-hardened class of nickel-base alloys. The Hastelloy X-280 was obtained from 4- and 1-in: thick plates in the mill -annealed condition. Table I gives the chemical composition of the material as reported by the National Spectrographic Laboratories. ~x~erimental Treatments. Plates of suitable size, 12 by 3 by 1 in., or by + in., were cut under a water jet from the stock material and examined ultrasonic -ally for homogeneity of grain size and absence of voids. The acceptable plates were solution-treated at 2150°Ffor 1 hr and air-cooled. These plates were then reduced in thickness by cold rolling 0, 10, 15: or 20 pct along the original rolling direction. The plates were machined into buttonhead tensile specimens with a gage diameter of 0.125 in., with a gage length of 1.125 in., and with their tensile axes parallel to the rolling direction. The specimens were examined for quality of finish with a penetrant dye, ultra son ically checked for voids, and finally given a dimensional tolerance check with an optical comparator. The acceptable specimens were aged for 24 hr at either 1000" or 1500 F and air-cooled. These specimens were then held at 540°F in a water loop for approximately 18 days to qualify as controls for similar specimens irradiated under the same conditions of time, temperature, water chemistry, and flow rate. Table U summarizes the treatments. These treatments were investigated to establish whether prior precipitation and stabilization of carbide phases at strain sites within the matrix could reduce the amount of carbides available for precipitation at grain boundaries during service. Tensile-Test Conditions. Specimens were tested to fracture at room temperature or 1350 F in air on an Instron tensile-testing machine at a crosshead speed of 0.05 in. per min. The time for the furnace to reach equilibrium at 1350°F was approximately 30 min; soak time prior to testing was 15 min; and test duration was approximately 5 min.

Jan 1, 1968

By L. H. Robinson

A proposed method of drilling utilizes sequential detonation of two types of explosive charges delivered to the hole by a conventional drilling fluid through pipe. A shaped charge first produces a long thin hole. A second charge, called a gauging charge, is pumped into the thin hole, explodes, and enlarges it to full gauge. In one suggested configuration, the explosives are contained in cylindrical capsules 4- to 5-ft long. A drilling head is positioned 2- to 3-ft off bottom. When a capsule is pumped to the bottom of the hole and stops, pressure inside the drill pipe increases and differential pressure detonates the explosive. Primacord along the length of the capsule disintegrates the capsule. The debris circulates out of the hole with the drilling fluid. The gauging-charge action was examined using 2-ft cubes of Berea sandstone. The sandstone (18 per cent porosity) was vacuum-saturated with water and surrounded by concrete. To prevent reflected tensile pulses, the acoustical impedance of the concrete matched that of the sandstone. A 750-psig pressure was applied to a drilling fluid within a shaped-charge-formed hole before detonating the gauging charge. In these tests, 190 gm of rock were removed for each gram of explosive detonated. A similar series of experiments on low-porosity (0.40 per cent) metamorphic limestone provided a more rigorous test. Extensive fracturing from the gauging-charge action prevented an estimate of the volume of the expanded hole. The diameter of the hole was irregular, ranging from about 2 to 4 in, or about fivefold larger than the hole created by the shaped charge. INTRODUCTION In the past, explosives have found a varied but somewhat limited use in the oil field. An early well stimulation technique, still in use today, in vo lves shooting ni troglycerin to en large the borehole and to increase matrix permeability near the wellbore. Bullets and jets are now the conventional method of perforating casing and tubing. Detonations are frequently used to "back off" or "shoot off" stuck pipe and, of course, seismo-graphic work has long depended on explosive-generated pulses to find attractive earth structures. Efforts to use explosives in drilling operations have received limited examinations1-3 which, in one respect, is surprising because explosives offer one way to transmit large amounts of energy directly to the bottom of the hole. Recently, Ostrovskii l described a Russian method of drilling with explosives that utilizes small capsules containing explosives which are pumped into the mud stream to the bottom of a borehole. As the capsules leave the end of the drill pipe, a detonation mechanism is armed. Impact detonates the explosive. In another configuration, two liquids (an oxidizing agent and fuel) in the capsule are separated by a frangible membrane. Separately, the liquids are nonexplosive. Near the bottom of the drill pipe, the capsule passes through a narrow constriction which ruptures the membrane. The mixing of the liquids produces an explosive. Impact is again used to detonate the explosive. About the time Ostrovskii was developing his method, Humble Oil & Refining Co. was independently doing research on another explosive drilling concept based on the sequential detonation of two types -of explosive charges. The proposed technique consisted of alternately pumping a shaped charge and then a "gauging charge" down a well. The shaped charge should drill a long, tapered hole, and the gauging charge should expand it to full gauge. This paper presents the visualized drilling concept and gives results of laboratory work which showed that sequential firing of charges can form hole at an attractive charge-to-rock removal ratio. An important finding was that increased environmental pressure, which is to be expected in wells, increases rock removal efficiency of the gauging charge.

Jan 1, 1966

By E. A. Gulbransen, K. F. Andrew

THIS paper. will present the results of our studies on the kinetics of the gas phase reactions of co-lumbium and tantalum with O2, N2 and H2. Studies on zirconium and titanium have been previously reported.9,11 Due to their high melting points and their many excellent physical and chemical properties, colurn-bium and tantalum have been finding their places as useful metals in science and industry. Chemically the metals are very inert to gas and liquid phase corrosion at room temperature. However, at moderate temperatures of 250°C and higher the metals react readily with oxygen and hydrogen. It is of interest to study the gas phase reactions of these metals for the following reasons: (1) to compare the rates of the several reactions with those of other metals and to correlate the rate data with theory and structure predictions, (2) to add basic information on the practical difficulties of the reduction, refining and working of columbium and tantalum, (3) to anticipate new uses for the metals and (4) to understand the role that the metals play as components in high temperature alloys. Literature Survey A number of papers exist in the literature on the gas phase reactions of columbium and tantalum with O2, N2 and H2; however, only fragmentary data have been reported on the kinetics of these reactions. Although the free energy of formation of the oxide Ta2O520at 25°C has been determined and some thermodynamic work has been reported on columbium and its oxides, the data are not sufficient to make equilibria calculations at elevated temperatures. Oxidation: 1. Kinetics: The rate of oxidation of columbium and tantalum has been studied by McAdam and Geil23 using the interference color method. Tantalum is reported to oxidize more slowly than columbium, zirconium and iron. The amounts of oxidation of columbium after 20 hr in air for several temperatures are reported by the Fansteel Metallurgical Corporation.36 Columbium starts to oxidize in air at about 200°C. The oxide is said to be adherent and prevents further oxidation until the temperature is raised. Columbium is reported not to become brittle on heating in air for short periods like tantalum because the oxide film prevents further reaction. The columbium oxides dissolve into the metal when heated in a vacuum at temperatures between red heat and 1200°C. Above 1200°C the oxides are reported to evaporate. Columbium, in the oxide free state, is an active getter in vacuum tubes. 2. Preparation and Structure: G. Grube, O. Kuba-schewski and K. Zwiauer15 have studied the decomposition of Cb2O5 in argon. They find that CbO2 is formed slowly at 1150° and rapidly at 1300°C. Cb2O5 can be reduced to CbO2 by moist H2. The reduction of this dioxide to the lower oxides is rapid. By varying conditions CbO2, Cb2O3, CbO and Cb2O can be formed. CbO2, CbO and Cb2O have independent lattices while Cb2O3 is a stoichiometric mixture of CbO and CbO2. In a later paper O. Kuba-schewski" has shown that CbO is cubic and that CbO2 has a rutile type of lattice. The most exhaustive work on the oxides of columbium is that of G. Brauer.8 The number and constitution of the solid phases in the binary system Cb-O were investigated by the preparative, analytical and X ray methods. He indicates that only the oxides Cb2O5, CbO2 and CbO exist with limited regions of homogeneity. The solid oxide Cb,O, exists

Jan 1, 1951

By Milton Williams

A comparison is made between the amount of interstitial water found by analysis in cores and that estimated from the resistivity curve of the electric log for the corresponding strata of producing reservoirs. It is shown that while the determined and the estimated water saturations are in good agreement in some cases, this agreement may be due to a fortuitous compensation of errors. Estimates of water saturations made from the electric 1og by use of existing relations should, therefore, be employed with caution. Also presented are data on the variation of salinity of interstitial waters in reservoir sands, and on the effect of variation of salinity and porosity on the validity of estimates of water content made from the electric log. INTRODUCTION Throughout the history of electric logging there have been recurrent cycles of optimism and pessimism as to the value of the electric log in the quantitative estimation of reservoir fluid content. The very early days of electric logging were an optimistic period, in which there was widespread faith in the ability of the resistivity curve to reflect fluid content, and in the ability of the potential curve to indicate textural characteristics. In time the accumulation of exceptions to this idealistic behavior brought about a general disillusionment, and caused the more pessimistic of those dealing with electric logs to believe that the sole importance of the log lay in stratigraphic correlation. Within the last several years optimism as to the quantitative use of the electric log has been revived, primarily as the result of the stimulating work of C. E. Archie' on the estimation of interstitial water in sands from resistivity data. Even though the general trend of thought on the quantitative value of the electric log reflects optimism, it is inevitable that there are some widely divergent opinions of the validity of quantitative estimates based on the electric log. A valid method of estimation of fluid content by means of the electric log and a general knowledge of the textural character of the reservoir rock would be of signal importance, not only in that it would save time and money in securing information on reservoirs now being drilled, but also because it would permit the evaluation of reserves in many fields drilled without adequate core data subsequent to the advent of electric logging. Because of this importance, Humble's Production Research Division, in cooperation with various other company divisions, initiated several years ago series of tests designed to evaluate the reliability of estimates of fluid content made from the electric log. The investigation was limited at the outset to sand reservoirs, since it was felt that the inclusion of limestone reservoirs would entail needless complications. In devising these tests it was immediately apparent that the chief difficulty in evaluating the worth of any method of estimation lay in establishing the true value of fluid content. The results of direct analyses of cores cut with ordinary mud were not sufficient, because of the probability of contamination of the fluids by filtrate from the drilling mud; the results of restored state tests on cores were deemed unsuitable because these results can hardly be said to furnish a primary standard. The method adopted was the direct analysis of cores cut with an oil-base drilling fluid. Such cores, when properly handled, are believed to afford the most precise determination of water content available at the present, and, in addition, lend themselves readily to the determination of various other properties which are pertinent to the estimation of fluid content from the electric log. Since it was desired to compare the fluid contents estimated from the electric log run in ordinary mud with cores cut in the same hole, the use of oil-base fluid necessitated the changing over, after all cores were cut, to a conventional mud. This procedure presented several advantages, one of which was that the use of oil-base fluid permitted

Jan 1, 1950

By T. O. Anderson, E. J. Stahl

Tests to increase knowledge concerning the process of hydraulic fracturing have been performed on three wells in the Allegheny field in western New York. The fracture orientation and its physical appearance at the well-bore was determined by impression packers run at appropriate times throughout the program. Fract~tre azi171uth and its dimensions thus determined were compared to the rock properties and treatment conditions. Logs to provide data concerning rock properties and to improve identification of vertical fractures were run before each step of the fracture treatment. Pressure osc~illu~iot~s were studied after each phase of tile treatments surface pressures during treatment. These measurements show that subsurface pressures exhibit many of the same characteristics as surface pressures during treatment of a well; however, transient pressures are dampened and deelayed in time at the bottom of the well when COmpared with surface pressures. Data obtained from this study provides a means to help locale and determine orientation of vertical fractures made in the open wellbore. Although these rests were performed in only one area, much of the information gained may be applied to fracturing programs in orher areas. INTRODUCTION In this study, various tests were made to provide data to better understand formation fracturing in situ. The reservoir studied is the Richburg oil sand which is a part of a series of predominantly grey sandstones and shales with occasional brown sandstone layers, known as the Caneadea unit of the Canadaway group of Upper Devonian age. Average physical characteristics of 12 cored wells in this area are 13-ft thick gross sand formation, 12-ft thick net sand. 1.7 md permeability, 11 percent porosity, 44 percent oil saturation (before secondary recovery) and 16 percent water saturation (before secondary recovery). This particular area of the Allegheny oil field was originally drilled prior to 1890. The first waterflood secondary recovery attempt was made in 1929. The present sustained waterflood development began in 1951 and is being carried out on a 4.5 to 5-acre spacing. Objectives of these tests were to (I) study fracture azimuth and dimension in relation to rock properties and treating conditions, (2) improve fracture identification techniques, (3) compare surface and subsurface pressure during all phases of treatment and (4) compare the periods of the fluid column oscillations occurring after each phase of treatment. Although the areas of investigation listed appear divergent in purpose, the program was designed primarily to increase knowledge of down-hole conditions leading to rock failure and extension of the fracture thus created. TEST PROCEDURES Wells upon which tests were conducted are designated as Wells 1 through 3. Well 2 was located 440 ft north of Well 1, and Well 3 was located approximately 880 ft west of Well 1. Wells 1 and 2 were completed with cable tools, while the producing interval of Well 3 was rotary cored using fresh water as the drilling fluid to obtain oriented cores. Tests were divided into separate phases on each well as the fracturing program progressed and consisted of measurements performed prior to treatment, during and after the formation breakdown operation. during fracture treatment and after treatment. To verify location and azimuth of the fracture created, and to obtain an impression of wellbore irregularities, a packer was used (Fig. 1). This packer was lowered on tubing into the wellbore opposite the interval under study and inflated in stages to allow the impression material to conform to the wall of the wellbore. A magnetic compass was attached to the tool for orientation reference. Impressions made prior to treatment showed no existing fractures in the wells under study. Impressions made after both formation breakdown and treatment pro-

By R. E. Ogilvie, J. I. Goldstein

The a and y solubility limits in the Fe-Ni phase diagram have been redetermined at temperatures above 500°C. Both a diffusion-couple and a quench and anneal technique were used. The solubility limits were measured with an electron-probe micro-analyzer. The nickel concentration at the phase boundary is increased below 700°C and the a solid-solubility range is much larger than had been previously measured. The solubility limits are also extrapolated to 300°C. It is suggested that the solubility of nickel in a FeNi reaches a maximum in the temperature interval 400o to 500°C. THE equilibrium diagram has been of great use in the field of meteoritics, where the phase relations between kamacite (a) and taenite (?) in metallic meteorites can be described by means of the Fe-Ni diagram. The study of metallic meteorites by electron-probe microanalysis has cast some doubt on the accuracy of the presently available Fe-Ni diagrams.1, 2 Recent thermodynamic studies of the Fe-Ni system also suggest that the diagram may be in error.3 For these reasons the high-temperature (800o to 500°C) part of the diagram was redetermined. INTRODUCTION The currently accepted Fe-Ni diagram is that of Owen and Liu.4 Above 910°C, there is a region of complete solid solubility, ? (fee). Below 910°C, the a (bee) phase is stable in pure iron. The effect of increasing amounts of nickel is to stabilize the y phase. The phases that form when Fe-Ni alloys are heated or cooled bear little relation to the equilibrium diagram. If an alloy is cooled from the y state and held at a temperature within the a + y field, no evidence has been found for the occurrence of the y - a transformation.5 If the alloy is cooled to low enough temperatures the y phase breaks down into a supersaturated bee phase called a2. In fact, in alloys over 27 pet Ni the y phase is retained at room temperature.6 The a, phase has the same composition as the original y. The temperature at which a2 forms, the M, temperature, has been determined experimentally.' A state of equilibrium can be approached by cooling below M, to form a2 and then reheating the alloy into the two-phase region of the diagram. The y phase will then begin to precipitate out of the a2 phase and grow. The growth of the phase, however, is quite slow. Using the interdiffusion coefficients -Da of Goldstein et al.,8 it is estimated that it takes about 1 year to grow a 10-µ-wide region of ? at 700°C in a 5 pet Ni alloy. Owen and Liu4 used the technique just described to form the equilibrium phases. The phases present were determined by means of X-ray analysis. The accuracy of their diagram depends on the number of alloys available near the phase boundary at a given temperature. In this study two different techniques were used to determine the a/a + ? and ?/a + ? solubility limits. The inherent accuracy of both techniques was greatly improved over that used by previous investigators because the phase-boundary compositions were measured with an electron-probe microanalyzer. PROCEDURE The two methods used to determine the Fe-Ni diagram are the diffusion couple (D.C.) and the quench-and-anneal (Q.+A.) techniques. In the first method, diffusion couples whose diffusion path goes through a two-phase region of the phase diagram were used. A description of the technique used for making the diffusion couples has been described in a previous paper.' After the diffusion treatment a discontinuity in the resultant concentration vs distance profile was measured. The nickel concentrations in the a and ? phases at the interface of the discontinuity are the solubility limits of the a and ? phases in the phase diagram at the diffusion temperature. If the interface com-

Jan 1, 1965