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By J. S. Ll. Leach, J. B. Cohen, M. B. Bever

IN the work reported here, the heats of formation of a copper-rich Cu-Sn (a) solid solution and of the Cu.Sn (0 phase were measured by tin solution calorimetry. An approximate determination of the heat effect attending the precipitation of 6 from a supersaturated a solid solution was also made.

Jan 1, 1955

By P. Greenfield, P. A. Beck

The phase is a hard and extremely brittle material with a tetragonal crystal structure, containing 30 atoms per unit cell' It occurs in many binary and ternary alloys of the transition elements. The existence of twelve a phases has been reported in binary alloys of metals from the group vanadium, chromium, molybdenum, and tungsten with metals from the group manganese, iron, cobalt, and nickel. It is a characteristic fact that the composition of the o- phases in the various binary systems is not the same. Rather, there is a gradual shift in composition, for instance in the series of chromium a phases, approximately as follows: CrMn,, FeCr, Cr3Co,. In recent years several ideas have been put forward to account for this variability of composition. SullyZ proposed that a was a type of electron compound, characterized by 1.7 electrons per atom in excess of the number required to fill the Pauling atomic orbitals. These excess electrons were supposed to just fill the first Brillouin zone of the u structure. However, later work indicated that the phase is ferromagnetic at low temperatures, so that a- is unlikely to be a full zone compound.~ Another proposal,* which is also based on the structure of the transition elements advanced by Pauling, and in fact leads to essentially the same a compositions as Sully's theory, suggests that the u phase is characterized by a constant number of electron vacancies per atom. The electron vacancy numbers N,. used were originally the same as those in the Pauling theory, but were later modified empirically vn order to bring about better agreement with data for the p phase in certain ternary systems. For alloys, N,, was calculated on the assumption of simple additivity from the electron vacancy numbers of the components, as follows: N,. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2 (Fe) + 1.71 (Co) + 1.6 (Ni). On this basis a reasonably constant value of N, = 3.4 was obtained for all of the binary u phases and a fairly constant value of N,, = 3.1 for the various p phases. More recently, Bloom and Granta pointed out that a similar correlation with the total number of 3d and 4s electrons per atom is also fairly well fulfilled and concluded that no reference need be made to the Pauling theory. This proposal does not lead to the same binary a compositions as the one described above, so that the relative merits of the two proposals may be determined on the basis of direct comparison with experimental composition data. The purpose of the present paper is to provide such a comparison. Since the experimental data for the composition ranges of several of the known u phases were rather incomplete, it was decided to carry out new experimental determinations for many of the binary systems. Experimental Procedure The alloys were prepared by induction melting in recrystallized alumina crucibles, either in vacuum or in helium atmospheres. Some aluminum was picked up from the crucibles in the alloys of high vanadium content, but this was minimized by keeping the alloys in the molten state for as short a time as possible. The maximum aluminum impurity was 0.13 wt pct by chemical analysis, in an alloy containing over 50 wt pct V. In general, the as-melted compositions agreed accurately with those obtained by chemical analysis. In the case of manganese, however, losses inevitably occurred; consequently all manganese alloys were analyzed. Specimens of all alloys were annealed at temperatures ranging from 1000" to 1300°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. All manganese alloys were sealed in quartz tubes under vacuum before annealing. The specimens were held at temperature for between four and eight days before being quenched into cold water. Alloys were prepared for microscopic examination by mechanical polishing, usually followed by electrolytic etching. X-ray diffraction specimens were prepared by crushing the homogenized alloys, and by reanneal-ing the obtained powders in evacuated quartz tubes for a few hours at the temperature of the lump anneal. X-ray diffraction patterns were made with unfiltered chromium radiation, using an asymmetrical focusing camera of high dispersion. Using microscopic and X-ray techniques jointly, the accuracy

Jan 1, 1955

By A. U. Seybolt

The solubility limit of oxygen in columbium has been determined in the range between 775' and 1100°C by means of lattice parameter measurements and microscopic examination. The solubility is a function of temperature and varies, in the range given above, from 0.25 to 1.0 pct O, respectively. BECAUSE of the marked deleterious effect of oxygen upon the mechanical properties of some of the transition metals, it is desirable to know something about the solubility of oxygen in these metals. The brittleness caused by oxygen in solution is particularly marked in the case of the group VA elements, vanadium, columbium, and tantalum. The solubility of oxygen in vanadium has already been reported in an earlier paper,' and Wasilewski2 has given a value (0.9 wt pct) for the solid solubility of oxygen in tantalum at 1050°C. Brauer3 in 1941 investigated the Cb-0 system up to Cb2O5, but made no real effort to investigate the extent of oxygen solubility in the metal. He made the observation, however, that this solubility must be less than 4.76 atom pct (0.86 wt pct) oxygen. This estimate was made from X-ray diffraction results on the alloys CbO, CbO, and CbO; all alloys consisted of the terminal (Cb) solid solution plus CbO, but the last alloy containing 4.76 atom pct 0 showed only three very weak CbO lines. It is surprising that Brauer, by examining only three alloys, arrived at an estimate of the solubility which agrees very well with the results to be reported herein. Experimental Procedure A columbium strip obtained from Fansteel Metallurgical Products was cut into strips, 0.020x1/2x2 in. Two holes, about 3/16 in. in diameter, were made near the ends of the strips in order to hold them against a flat steel block for mounting in a General Electric X-ray spectrometer for lattice parameter measurements. The same holes were used to hang the specimens inside a fused silica vacuum furnace tube which was part of a Sieverts' gas absorption apparatus. The apparatus and method of adding oxygen gas has been previously described.1 According to the supplier, the columbium obtained had the analysis given in Table I. After degreasing the samples, approximately 0.001 in. was etched from each side of the samples in order to remove possible surface impurities from the last rolling operation. For this purpose the following cold acid pickle was found satisfactory: 8 parts HNO3, 2 parts H2O2 and 1 part HF. Various Cb-O compositions were obtained up to 0.75 wt pct O by the gas absorption and diffusion technique. After the sample had absorbed all the oxygen gas added at 1000°C, an additional 24 hr was allowed for homogenization. This treatment appeared to be adequate, as shown by the linearity of the lattice parameter-composition plot. More concentrated alloys were prepared by arc melting mixtures of Cb and Cb2O5 since it was very time-consuming to make Cb-0 alloys in the neighborhood of 1 pct O, or over, by the diffusion method. When the flat strip specimens were used, they were ready for the X-ray spectrometer after cooling from the Sieverts' apparatus. The cooling rate obtained by merely allowing the hot fused silica furnace tube to radiate to the atmosphere (when the furnace was lowered) was sufficiently fast to keep the dissolved oxygen in solution. Arc-melted alloys were reduced to —200 mesh powder in a diamond mortar, wrapped in tantalum foil, sealed off in evacuated fused silica tubes, and then heat treated as indicated in Table 11. The fused silica tubes were quickly immersed in cold water without breaking the tubes after the heat treatments. The tantalum foil prevented reaction between the fused silica and the sample; there was no reaction between the powdered samples and the foil at 1000°C, but some trouble was experienced at 1100°C. At this temperature level a reaction between the sample and the foil was sometimes observed, which resulted in erroneous parameter values. Experimental Results Hardness Tests: Since most of the X-ray samples were in the form of flat strip, it was convenient to obtain Vickers hardness numbers as a function of oxygen content. Compared to the V-O case,' oxygen hardens columbium much more slowly, presumably because of the larger octahedral volume in colum-bium (about 12.0 compared to 9.3Å3 in vanadium), hence, requiring less lattice strain for solution. The plot of VHN vs wt pct O is shown in Fig. 1.

Jan 1, 1955

By R. E. Maringer, A. Schwope

IT has been recognized that oxygen in minute quantities is extremely detrimental to the room-temperature ductility of molybdenum. Early fracto-graphic studies' of the cast metal indicated that oxides are formed preferentially at the grain boundaries. Additional verification of this preferential segregation has been obtained from internal friction studies on poly crystalline molybdenum (average grain diameter varied from 0.039 to 0.065 mm) and from observations of the effect of oxygen on specimens of extremely large grain size. Specimens A, B, and C, of 0.040 in. diameter commercial molybdenum wire (Lot FW 13-40) were heat treated in the vacuum furnace described by Few and Manning according to the specifications given in Table I. Internal friction studies of these specimens were carried out using a low frequency (approximately 1 cycle per second) torsional pendulum completely enclosed in a vacuum tank. As the pressure of oxygen in the heat treating atmosphere changed, the portion of the internal friction vs temperature curves ascribed to grain boundary relaxation changed correspondingly, Fig. 1. The decrease in the damping capacity at high temperatures as the pressure of oxygen in the heat treating atmos-

Jan 1, 1955

By A. U. Seybolt, R. L. Fullman

THE Hume-Rothery rule relating the relative sizes of the solvent and solute atoms in a substitutional solid solution for moderate to extensive solubility is, of course, well known and much used in the design of alloys. No such rule has been obtained for interstitial solid solutions, although a qualitatively similar relationship would be expected. Among the most common interstitial elements, oxygen, carbon, and nitrogen which can dissolve in important amounts in the transition metals, only in the case of oxygen is there enough solubility data available for an examination of the possibilities of a simple relationship between the extent of solubility and the properties of the metal solvents. Three properties were examined: 1—size of the octahedral space V into which oxygen atoms fit, 2— the elastic modulus E, and 3—the free energy ?F of formation of a low oxide, such as is known to be, or would be expected to be, in equilibrium with the terminal solid solution. The size factor or octahedral volume is so closely associated with the well known Hume-Rothery con- cept of size factor that additional development of this subject is hardly necessary. The octahedral volume used was not corrected to an elevated temperature, as this correction would have made no significant difference. The second factor, Young's modulus E, must be considered, since it is a measure of the strain energy required to force neighboring atoms apart so that an oxygen atom may enter the octahedral volume. The temperature dependence of the elastic modulus of many metals has been reported by Köster,1 but for a rather limited temperature range. Since the

Jan 1, 1955

By E. B. Hunt, T. M. Geffen, C. R. Stewart, V. J. Berry

Laboratory data .show that the gas-oil ratio performance of non-uniform porosity limestones produced by solution gas drive is sensitive to producing rate and to fluid properties. Nan-uniform porosity limestones are those for which laboratcry solution and external gas drive tests yield considerably different relative permeability ratio characterislics. The oil recovery performance by solution gas drive depends directly on the number of gas bubbles formed. Laboratory rates of pressure decline, which are 100 to 10,000 times greater than normal field rates. cause the formation of an unusually large number of gas bubbles. This results in abnormally high oil recovery efficiencies. Since it is impractical to reproduce the number of bubbles formed under field conditions, laboratory solution gas drive data on non-uniform porosity limestones are therefore not directly applicable to field operations. However, certain laboratory data can be used to make a conservative estimate of field performance. The concepts presented in this paper indicate the possibility that increased field oil recoveries may he obtained from non-uniform porosity limestones by rap- idly reducing reservoir pressure for a short interval of time. It has yet to be established that significant improvements in oil recovery from such reservoirs can he realized by varying the pressure decline rate within limits possible in the field. However, the possibility that recovery may be increased in this manner warrants further study. INTRODUCTION Limestone reservoir rocks can be divided into two general classes according to the nature of their pore space. One class has a comparatively uniform pore system composed mainly of voids between grains of the rock (intergranular type porosity). The other class, in addition to having intergranular porosity, has a secondary pore system composed of combinations of solution cavities, fractures, etc., and is considered to have non-uniform porosity. It has been shown in a previous publication' that the laboratory measured gas-oil flow behavior of uniform type porosity limestones is essentially the same for a test simulating a field solution gas drive as for one simulating an external gas drive. For non-uniform porosity type limestones a significant difference in gas-oil flow behavior was found. More efficient behavior was

Jan 1, 1955

By J. Wade Watkins, E. S. Mardock

The accurate evaluation of reservoir-performance characteristics in the secondary recovery of petroleum by water flooding requires use of a water tracer that may be injected into water-input wells and detected at oil-production wells to supplement data obtained from core analyses, wellhead tests, and subsurface measurements. Radioactive iodine has been used successfully as a water tracer in field tests to determine: (I) relative rates and patterns of flow of injected water between water-input and oil-production wells and (2) zones of excessive water entry into oil-production wells. Laboratory evaluations of potential water tracers, previous tracer studies, the value of using a radioactive tracer, general field procedures, and the use of surface and subsurface instruments for the detection of the emitted gamma radiation, are summarized. Data from the field tests are presented graphically and discussed in detail. It is concluded that the radioactive-tracer method, using radioactive iodine, may be used successfully to measure either the relative rates and patterns of flow or zones of excessive water entry into wells under conditions of comparatively rapid transit time between wells. INTRODUCTION Extensive use is made of data obtained from core analyses, wellhead tests, fluid characteristics, and subsurface measurements in evaluating the sweep efficiency of water injected into oil sands for the recovery of oil. Theoretical flow rates and patterns may be calculated from those data using radial-flow formulas, if it is assumed that the physical conditions in the productive formation are homogeneous. Unfortunately, homogeneous conditions rarely, if ever, exist in oil-productive formations. The use of a tracer that may be injected into an oil sand and detected quantitatively, or even qualitatively, at offsetting oil-production wells provides basic data that may be used in determining more accurately the subsurface rates and patterns of flow of injected water between wells than is possible by theoretical calculations based on assumed conditions. Consideration of the data obtained by using a water tracer assists in the application of remedial measures to water-input wells, such as plugging of channels, or selective plugging of highly permeable zones, thereby effecting a more uniform flood and a greater ultimate oil recovery. A water tracer should have the following characteristics: (1) low adsorption on solid reservoir material; (2) high solubility in water; (3) low or negligible solubility in crude petroleum; (4) a wide range of solubility of compounds that may be formed by chemical reactions with ions present in reservoir rocks or waters; (5) high detectability in low concentrations by portable apparatus; and (6) general availability at low cost. Additional desirable characteristics are that the tracer should be nonhazardous in nature under normal working conditions and quantitatively detectable in the well bore, as well as at the surface. Review of Previous Tracer Studies The need for a water tracer has been recognized for many years. As far back as 1906, Dole1 described the use of fluorescein in flow-rate studies made in France in 1901. In 1921, Ambrose" discussed in detail the use of organic and inorganic dyes, chlorides, nitrates, and other anions, lithium salts, and the Slichter electrical

Jan 1, 1955

By W. F. Kieschnick, Eugene Harrison, W. J. McGuire

W. J. McGuire, et al, are to be commended for their undertaking of a mathematical solution of a very difficult problem. Unfortunately, however, a mathematical approach requires the application of several assumptions. These assumptions appear to be unrealistic and lead to answers which do not describe what actually happens when hydraulically fracturing oil and gas wells. Considering laboratory confirmation of breakdown phenomena, the authors appear to have tested their theories only on cement specimens and on samples of Austin limestone, much too small to provide any fracture system. This work resulted in the formation of vertical fractures. If the authors had tried similar experiments on thick walled cylinders made from almost any sandstone cores, they would have found that, using crude oil as the breakdown fluid, horizontal fractures would almost always occur, and at pressures much lower than any calculated. They would also find that by confining the fluid to within the bore (using oil base mud for example) on similar samples, the pressures required to burst the cylinders would be considerably higher and most of the fractures would be vertical. This breakdown pressure behavior has been duplicated in wells in Texas, Oklahoma, Kansas and in Wyoming. Considering field data the phenomena of different breakdown pressures for different breakdown techniques can be further illustrated. Most production and service personnel will agree that a breakdown can be more easily obtained if injection into a formation can be established prior to the occurrence of the breakdown. This is true whether the formation being treated is completed as open hole or as a perforated interval. This is clearly illustrated by a Lakota well in Wyoming, completed open hole at a total depth of 7,358 ft. An attempt to vertically fracture this well failed when a bottom hole pressure of 10,326 psi was insufficient to break down the formation. A non-penetrating type fluid (oil base mud) was in the well at the time the breakdown was tried." The oil base mud was then cleaned out of the well and replaced by a 30" API gravity crude oil. With this oil in the hole the formation breakdown was easily accomplished at a bottom hole pressure of 3,607 psi. This large difference in fracture pressures would be impossible according to the theories presented by McGuire, et al. The authors have used as an example the breakdown pressures experienced when acidizing Permian Basin wells. During acid treatments of limestone and dolomite the "breakdown" (drop-off in pressure) seldom occurs until some injection of acid has been accomplished. In these cases the breakdown is most likely to result from the chemical reaction of acid and rock in already existing vugs and fractures rather than from making a new fracture by hydraulic pressure. If this is true, then results in the Permian basin should not be used to validate the authors' calculations. *** AUTHORS' REPLY to ROSCOE C. CLARK and HENRY F. COFFER The purpose of our laboratory experiments in which thick-walled rock cylinders were hydraulically fractured was to determine the validity of the "thick pipe" formula for brittle materials, and not to predict nor demonstrate directly the orientation of field fractures. Our conclusions concerning field results resulted from calculations involving the "thick pipe" relationship as well as considerations of overburden stresses, rock strengths, and the geometry and dimensions of the field system. Clark suggests that had the models been more porous or contained weak bedding planes, horizontal fracturing would have occurred. This is undoubtedly true provided external stresses similar to those in the earth's crust are nor imposed. However, if we were going to design experiments to represent directly the field case we would impose the proper stresses on the models. It is generally recognized that the vertical compressive stress in the earth's crust arising from the weight of the overburden is approximately 1 psi/ft of depth. Then, as an example, even though a horizontal bedding plane has zero strength, the formation cannot be separated to form a horizontal fracture unless the hydraulic pressure exceeds the stress due to overburden. And in those cases in which the stress resisting vertical fracturing is significantly less than that resisting horizontal fracturing, vertical fractures should result, notwithstanding horizontal plane weaknesses. We agree that breakdown pressure will be less if the fracturing fluid penetrates the formation. In Appendix HI of our paper it is shown that leak-off reduces the pressure necessary to initiate either a horizontal or vertical fracture. It would be difficult to attempt to

Jan 1, 1955

By Charles C. Templeton

Any explanation of the nature of multiphase fluid flow through porous media must ultimately involve a knowledge of the mechanism of such flow through the individual pores of the medium. To provide quantitative information of the latter type, a study was made of gas-liquid and liquid-liquid displacements in single uniform Pyrex capillaries with diameters as small as 4 microns. Quantitative observation of air-liquid displacements with zero contact. angle indicates the adequacy of a model based on Poiseuille's Law and the independence of capillary pressure and interfacial velocity. Consequently, this work discounts previous claims that flow is abnormally retarded in very small capillaries. For the displacement of a very viscous oil by water in a capillary initially filled with water, flow is faster than predicted by the above model. This behavior is probably due to the existence of a thin annular film of water between the oil column and the capi1lary wall as postulated by Yuster. INTRODUCTION The need for experimental observation of the microscopic nature of multiphase fluid flow, to further the understanding of the results of macroscopic flow investigations, has been previously recognized. Chatenever and Calhoun1 in connection with the API Project 47B have extensively studied the flow of fluids through layers of glass or lucite spheres between glass or lucite plates. Lowman2 prepared an interesting film concerning flow in a single capillary, using an apparatus which made a moving interface appear stationary in the field of a microscope. The purpose of the present investigation was to deter- mine what contribution might be made to this field by comprehensive quantitative observation of gas-liquid and liquid-liquid displacements in single capillaries of uniform, very small diameter. The techniques used are similar to those of Lowman but incorporate improvements necessary for quantitative work. Quantitative observations must begin with fluids of simple chemical composition to provide a basis for analyzing the more complex behavior that may be expected with natural reservoir fluids. However, some qualitative observations on systems involving crude oils are presented. Experiments of this sort involve the observation of the velocity of the interface separating two fluids, and have been performed in horizontal or vertical capillaries by several investigators.3,4,5,6,7,8 The most general treatment of their mechanics, by Brittin,9 involves forces due to capillarity, viscous resistance, gravity, an "end-drag" effect, and the rate of change of momentum of the capillary contents. Since the range of pore diameters of interest in petroleum reservoirs is about 0.1 to 100 microns, it was desired to perform these experiments in the smallest capillaries possible, to ascertain whether capillary diameter had any effect on the existing theory based on data from larger capillaries.* It was also important to be able more systematically to vary the direction and rate of displacement than was done by previous investigators. Finally, to concentrate attention on viscous and capillary forces by eliminating gravity as a parameter, this study involves only horizontal capillaries. The work of Eley and Pepper' with a "large" (0.766-mm diameter) horizontal capillary is the previous investigation which is most similar to the present method of quantitative observation. Here capillaries with diameters as small as 4 microns will be studied.

Jan 1, 1955

By C. H. North, L. E. Lynd, W. W. Anderson, H. Sicurdson

D. R. Grantham (Institute of Mining and Metallurgy, London, England)—This paper is a very valuable contribution to our knowledge of ilmenite and its alteration products. Two aspects are not treated in the paper and further information would be valuable. How far are the alteration processes described influenced by the original composition of the ilmenite? The word gangue is used but it is not clear whether this refers to other chemical constituents in the ilmenite, e.g., magnesia, or to other minerals loose or in composite grains. Has the work described been related to specific gravities? Pure ilmenite is stated to have a specific gravity of 4.79. Some varieties range up to over 5.0, while high magnesic varieties have a specific gravity ranging to below 4.2. Alteration to hematite might lower the specific gravity and a porous texture due to the removal of iron and the formation of rutile might also lower it. As specific gravity is a quick method which often gives an approximate indication of composition, data on the above would be valuable. L. E. Lynd (authors' reply)—Because of the way in which beach sand deposits were formed, it is impossible to tell exactly what the original composition of the parent ilmenites might have been. Information on the influence of original composition on the alteration processes must be derived from other sources, perhaps by comparing the alteration products formed from ilmenite in place in a variety of rock deposits, where parent ilmenite and its alteration product can be recognized. No information of this type has yet been brought to our attention. The material referred to as gangue includes all constituents other than oxides of titanium and iron. Nearly all of this was present as separate grains of garnet, augite, hornblende, quartz, feldspar, spinel, or other gangue minerals. Inclusions of gangue minerals within ore grains were rare, and we believe there is little MgO (1 pct or less) or other impurity actually held in the ilmenite structure in any of the concentrates studied. No specific gravity measurements were made on the samples studied. However, the suggestion that alteration involving loss of iron would lower the specific gravity is a very reasonable one, and is in accord with the findings of Creitz and McVay (Ref. 9 of our paper) who reported two magnetic opaque fractions from Trail Ridge, Fla., to have the following specific gravities and pompositions: The specific gravity of this porous, high TiO² alteration product of ilmenite is closer to that of rutile (4.25) than to that of ilmenite. Due to the porosity, it may even be less dense than rutile, although lower in TiO² and higher in iron.

Jan 1, 1955

By W. Seymour

Uranium was cold rolled to a reduction in thickness of 90 pct and the preferred orientation of the grains was determined from X-ray intensity data. Complete pole figures for a large number of atom planes were plotted, and the preferred orientation was found to be duplex (102) [0101 + (012) [021]. These preferred orientations are compared with those reported for many of the hexagonal-close-packed metals. THE preferred orientation of a highly reduced cold-rolled uranium strip was determined in order to obtain additional experimental data which would be useful in further understanding the deformation mechanisms of uranium. The preferred orientations reported herein are not in agreement with those theoretically predicted by Calnan and Clews' for cold-rolled uranium sheets, and differ somewhat from those reported from experiments by Fisher, and Burke and Turkalo. Such variations might be accounted for by differences in the fabrication temperature and the reductions. Experimental Procedure The uranium used in this investigation had been hot rolled to 0.060 in. at 575°C from 0.393 in., and from a 0.060 to 0.020 in. thick sheet at 275°C. From this point the sheet was cold reduced 90 pct to 0.002 in. at room temperature. Three specimens were used to obtain complete pole-figure data. The first was a 1/2 in. square section illuminated by the X-ray beam on the rolling surface. The other two were l/2 in. square longitudinal and transverse sections each made as follows: Approximately 200 1/2 in. square sections of the foil were piled one on top of the other, so that the rolling direction for each piece was kept coincident. A 1/2 in. square by 1/8 in. thick steel section was placed on the top and bottom of a pile and the entire assembly was then bolted tightly together through a 1/8 in. diam hole drilled down through the center. Each pile was then surface-ground from the two proper sides to sections 1/2 in. square by 3/16 in. thick. These specimens were then polished flat and electro-polished to remove 0.005 in. of the surfaces to be examined. It can be shown that uranium is so opaque to a Cu Ka X-ray beam that only a small percentage would be transmitted by one micron of uranium. Therefore, a method of measuring the X-ray intensities diffracted from specimen surfaces was used. The specimens were mounted in a modified Schulz reflection holder' which automatically changed the position of the specimen at a constant rate. The holder, in turn, was mounted on a General Electric XRD-3 Spectro-Goniometer and an automatic record made of the diffracted X-ray intensity vs specimen position. While a specimen moved automatically through 10" inclination, at a rate of l° per min, it simultaneously rotated 360" about a normal to the illuminated surface. (The inclination and rotation angles are referred to as F and a, respectively.) The data were then plotted along the resulting spiral path on a stereographic projection, Fig. 1. Because of defocusing effects on the diffracted beam which occur when diffracting surfaces are in-

Jan 1, 1955

By Bernard York, John J. Reed

J. P. Zannaras (U.S. Tungsten Corp., Congress, Ariz.) —In the investigation described in the paper by Bernard York and John J. Reed, the 8x8x8-in. square block was subjected to compressive forces from three sides, top, side, and rear. Let us refer to the stresses set up by these forces as Sz due to top pressure, Sy due to side pressure, and Sx due to rear pressure. At the section across the 2-in. hole (when failure occurred at 317 psi) the compressive stress Sy was equal to 317 x 8/6 = —422 psi, the top compressive stress S; is of the same intensity, —422 psi, and the rear compressive stress S, equals —317 psi. The true stress is T = Sy — S — S Taking as 0.2,* Taking the case when the opening was ½ in. and failure occurred at 517 psi, 8 Sy - 517 x -----= —537 psi 7.5 8 Sz = 517 x-----= —537 psi 7.5 Sx = —517 psi The true stress T = Sy — Sz — S, T - —537 + 0.2 x 537 + 0.2 x 517 = —327 psi. It can be shown that the above fundamental formula holds good not only for the above two examples but for all sizes of openings used, because when this formula is expressed in terms of the external pressure and size of the opening it agrees perfectly with the experimental results obtained by the authors and given in Fig. 12 of their paper. General formula: T = Sy — s: — S....

Jan 1, 1955

By Glenn C. Waterman

THE diamond drill is a very important tool in exploration and development testing and its use is increasing. In almost all cases results of diamond drilling are analyzed on the basis of grade and tons. A proper evaluation of core and sludge assays is important if drilling results are to be acceptable as a basis for geologic and engineering appraisal. The relatively wide variation in assay averages as calculated by various well-known combining methods indicates that the engineering choice of a method may affect the outcome of the drilling in terms of ore and waste. The problem of combining assay results from core and sludge samples has been discussed many times in conference and in the literature.'" Most writers agree that the field of disagreement in methods is large and that the engineer on the job must consider features unique to his drilling, pick one of several combining methods, and depart from the rules when abnormal results come in. All the discussion to date can be summed up by the admission that as yet there is no fairly simple, generally acceptable combining method that is practicable over a wide range of drilling conditions, ground conditions, and ore occurrence.

Jan 1, 1955

By H. Bernstein

Grain coarsening tests were carried out on AI-4.5 pct Cu and AI-4.5 pct Si alloys. The effects of three variables, melt composition, pour temperature, and mold temperature, were determined. It was found that the macrostructure generally coarsened with increased pour and mold temperatures. Coarsening was extreme in the unrefined alloys but was retarded by the active grain refiners like titanium and columbium. The effect of boron was spectacular in suppressing coarsening tendencies. The results of the investigation support the carbide theory of nucleation as opposed to the peritectic theory. A REVIEW of prior work on the subject of grain refinement in the light metals indicated that, for the most part, it had been concerned with the positive effects of addition agents upon structure. This work produced various theories of refinement. Prominent among them were the peritectic theory and the transition element carbide theory. Certain inadequacies in the former theory appeared to be explained satisfactorily by the transition element carbide theory. In order to appraise these theories further, a study was undertaken of the permanence of grain refinement effects when subjected to thermal or chemical variations. It was considered that a study of this kind would be of practical value, since the light metals are exposed to thermal and chemical variations in the normal course of foundry operations. Accordingly, two alloys of commercial importance were selected for this investigation, the A1-Cu and A1-Si alloys. Experimental Procedure and Results Raw Materials: The base alloys, A1-Cu and A1-Si, were prepared from virgin aluminum and hardeners, induction melted, and pigged for remelting. The grain refiners, including titanium, columbium, zirconium, and boron, were added as master alloys. Analyses of the raw materials and base alloys are listed in Table I. Melting and Casting Practice: The metals were melted in clay-graphite crucibles in a Hevi-Duty pit-type resistance furnace, equipped with a Leeds and Northrup Micromax Recorder and Controller. After melt down of the base alloys, the additions were made. For each casting, approximately 80 grams of metal were poured into a preheated graphite mold held in a transite flask. The mold (Fig. 1) weighed 320 grams. To determine the effect of superheat upon structure, a set of melts was heated successively to four temperature levels, 705°, 775°, 845°, and 915°C, and test specimens were cast at each level. Prior to each pour, the furnace temperature was held constant for 20 min. Next, a set of melts was put through a superheat cycle and test specimens were cast at melt temperatures of 705" and 915°C successively. The crucibles then were cooled in air to 705°C as deter-mined by immersion thermocouple and additional test specimens were poured. The cooling interval was approximately 1 min. Another set of melts was furnace cooled with the cover slightly ajar and test specimens cast as before. The interval in this case was 15 to 20 min, varying with the superheat temperature. The mold temperature for all these tests was 400°C. To determine the effect of cooling rate without superheat upon structure, a set of melts was heated to 705°C, and castings were poured at mold temperatures of 205", 400°, and 540°C. An interval of 15 min elapsed between each pour. Mold temperatures were measured by a direct reading millivolt-meter, using a chromel-alumel thermocouple located at midwall thickness of the mold. To demonstrate the phenomenon of chemical coarsening, agents such as chromium and beryllium, which had acted as coarseners in a previous investigation,' were added to the A1-Cu alloy. Test speci-

Jan 1, 1955

By J. T. Richards

ELASTIC constants, including E-modulus, G-modulus, Poisson's ratio, and compressibility, are affected by temperature, but not necessarily to the same degree nor in the same direction. Theoretical expressions relating the temperature coefficients for the various elastic constants have been introduced by Gruneisen. In considering the thermoelastic characteristics

Jan 1, 1955

By J. W. Whalen

The design, operation and evaluation of an instrumental method for the determination of fluid saturation in porous materials during multiphase flow studies is described. The presence of a magnetic tracer comprising approximately 20 per cent by weight of the aqueous phase is necessary in the utilization of this method. The results of two-phase relative permeability studies on two samples of porous media are presented. The realizable accuracy of the magnetic susceptibility apparatus in fluid saturation determination is estimated to be 2 saturation per cent. The response characteristics of the instrument, together with its simplicity of operation and maintenance are sufficient to recommend its use in routine laboratory studies. INTRODUCTION The problem of fluid saturation determination in laboratory multiphase flow studies characterizing oil recovery processes is one which has been given exhaustive study. Briefly the requirements which are considered essential for a method sewing this purpose are: (1) that the measurement be made external to the porous rock sample under study with no interruption of the fluid flow pattern, (2) the saturation indication must be independent of fluid distribution in the volume scanned by the measuring device, (3) the sensing element should have a small field of definition enabling several independent measurements to be made along the length of a core sample, and (4) the properties of the fluid phases should not be too greatly influenced by required tracer substances. Several methods of saturation determination have found acceptance as meeting most of the above requirements. These include resistivity,1 X-Ray absorption,2,3,4 radiotracers,5,6,7 and neutron8 diffraction The merits of these techniques have been discussed elsewhere in detail and will not be considered here. It may, however. be pointed out that the elaborate instrumentation required by the methods mentioned above, with the exception of the resistivity method (which is undesirable from other standpoints) encourages the development of methods of saturation determination which, while meeting the requirements listed, are simple to operate and maintain. It is the purpose of this paper to describe the instrumentation and evaluation of a technique for the determination of fluid saturation which combines relative simplicity with an accuracy and applicability comparable with methods now in practice. DESCRIPTION OF THE METHOD If the magnetic susceptibility of one of the fluid phases contained within a porous material is sufficiently greater than that of the remaining phases, the fluid content of the material with respect to that phase may be determined by an induction measurement. This may be accomplished by measuring the induced voltage in the secondary of a transformer which contains the porous sample and its interstitial fluids as a portion of the magnetic flux path. Since the fluids used in multiphase flow studies involving petroleum reservoir samples possess uniformly low magnetic susceptibilities, the use of a magnetic tracer in one of the fluid phases is required. In view of the relatively high paramagnetic susceptibility of salts of the transition elements, together with their high water solubility. these compounds become logical choices as tracer materials. Cobaltous chloride, having a specific magnetic susceptibility of 17.5 x 106 cgs electromagnetic units, was used as the tracer material throughout this work, in a concentration of approximately 20 per cent by weight in the aqueous phase. MAGNETIC SUSCEPTIBILITY APPARATUS Basically, the magnetic susceptibility apparatus consists of a transformer serving as the detecting head, a

Jan 1, 1955

By W. R. Clough, M. E. Shank

IT has been noted in a study of the flow and fracture of nodular cast iron under biaxial stress conditions (complete results of which will be published later) that when this metal is subjected to stress it may undergo a striking density change. Such behavior was first determined by strain gage measurements made on tensile test specimens, and has since been substantiated by other types of measurement. The chemical analyses and mechanical properties of several nodular irons to be discussed here are given in Tables I and 11. Tensile data for iron A was obtained from a hollow cylindrical combined stress specimen of the same dimension as those used by L. F. Coffin, Jr.1 in his investigation of gray iron properties. Standard 0.505 in. solid tensile-test bars were used for irons B and C. On each specimen type, A-8 wire resistance strain gages were used—two diametrically opposing gages in the axial direction, two in the tangential or hoop direction. By subtracting elastic strains from the measured strains, the plastic strains could be calculated. By assuming that radial and tangential strains are numerically equal, a measure of permanent volume change can be obtained by summing the plastic strains. This appears to be a good assumption, since the metal either fractured, iron A, or readings were discontinued, irons B and C, long before necking took place. This calculated variation of volume increase with stress is given for irons A and B in Fig. 1. Data for iron C is almost identical with that for iron B. The volume change indicated by Fig. 1 has been substantiated by a more direct type of density measurement. A method developed by S. G. Fletcher and' Morris Cohen,' and completely described in the discussion of their article, has been used. The accuracy of specific volume measurement has been estimated as 0.00002 cu cm per gram. Essentially the method consists of weighing a sample in air and then immersed in water. Measurements were made before and after straining the material. The results shown in Table I11 were obtained by means of half-size (0.252 in. diameter, 1 in. gage length, 3/8-16 threads) tensile specimens. Initial measurements were made on the whole specimen before stressing. After stress-

Jan 1, 1955

By Ingvar Janelid

DURING the last ten years, in the effort to save manpower and costs, methods of drilling and blasting in Sweden have changed and developed in a revolutionary manner. These developments have been accompanied by extensive alterations in methods of tunneling and in mining technique. Since the end of the 1940's there has been a 100 pct change-over in Sweden to the use of tungsten carbide tipped drill steel. Both investigations and practical results have shown clearly that a tungsten carbide chisel bit fastened directly on the drill steel is the most economical for Swedish conditions. This applies to drill steel up to the longest size it is practical to handle. In terms of drilling footage, durability of the drill steel and the tungsten carbide bit is generally the same. In this respect, therefore, a detachable bit offers no advantage over integral steel. Transportation of integral steel to the grinding plant, instead of detachable bits only, involves heavier work, but this is counteracted by placing grinding plants closer together or by grinding at the working place itself. The drilling rate with integral steel is higher, the trouble of changing bits is avoided, and the difficulties which always arise with joints are eliminated. At present steel dimensions are usually 7/8 in. with a shank 41/4 in. long, whereas the international standard shank was formerly 31/4 in. The longer shank renders possible a better guide control of the steel and consequently longer life for the rotation chuck and the water-flushing pipe. After extensive experiments and investigations, agreement has been reached in Sweden on certain series of standards, shown in Table I. Other steel dimensions are, of course, available for special purposes. The standard drill-steel set begins with a 34-mm diam and has a length interval of 2 2/3 ft. On the other hand, for ordinary drifting it has been proved more economical to use greater length intervals on the steel, so only one steel change is required for a 61/2-ft round. Moreover, owing to the relatively close hole spacing necessary in a drift round, it has been possible to reduce the diameters of the tungsten carbide bits. This results in faster and cheaper drilling. As shown by the table, the lengths of drill steels for normal drifting are 33/4 ft and 71/2 ft, with 29 and 28-mm diam bits. During the last few years operators have begun to use 3/4-in. drill steel in place of the 7/8-in. drill steel chiefly employed earlier. This is a valuable development in drilling technique, particularly in view of

Jan 1, 1955

By N. J. Grant, R. Nordheim

An extensive study was made of the aging characteristics of alloys based on the 80 pct Ni-20 pct Cr composition hardened with aluminum and/or titanium, each up to 4 pct. Aging was followed by means of hardness and hot electrical resistance measurements as well as by X-ray and microscopy. Stress rupture tests at 1500°F were utilized as a check on the predicted behavior. THE titanium and aluminum hardened Ni-Cr alloys, exemplified by Nimonic 80 and Inconel X, constitute one of the more important groups of alloys developed to meet the demand for materials retaining their strength at elevated temperatures. For service in the temperature range 1200" to 1500°F, these alloys offer high creep resistance. With increasing service temperature, however, the strength of the simpler Ni-Cr base alloys falls off rapidly so that above 1500°F there is a significant loss of strength. The present investigation was undertaken with the hope that a better understanding of the factors controlling the precipitation hardening of these alloys would make it possible to increase the useful service temperature range. Primarily this investigation involved the study of the effects of titanium and aluminum on the hardening and the subsequent softening at elevated temperatures. The titanium and aluminum contents were each varied between 0 and 4 pct by weight at a constant nickel to chromium weight ratio of about 4:1. (Except when otherwise stated, all compositions are expressed on a weight basis.) The major part of the investigation was confined to alloys with less than 0.06 pct C. Recently several papers dealing with the identity of the microconstituents in the titanium and aluminum hardened Ni-Cr alloys have been published. Using X-ray analysis of the residues from anodic dissolution, Rosenbauml was only able to identify carbides and nitrides in Nimonic 80 and Inconel X. However, since Rosenbaum worked with alloys in the hot rolled rather than in the aged condition, his results are inconclusive. Recently Hignett' reported that the hardening of Nimonic 80 was due to the controlled precipitation of Ni,(TiAl) having the cubic Ni3A1 structure. Taylor and Floydv-" published the results of an investigation of the nickel-rich corner of the Ni-Cr-Ti, Ni-Cr-Al, and Ni-Ti-A1 systems. In the Ni-Ti and the Ni-A1 systems the hexagonal Ni,Ti phase, 7, and the cubic Ni3A1 phase, -y', respectively, exist in equilibrium with the nickel-rich solid solution. The interatomic distances in the basal plane of Ni,Ti and the octahedral planes of the matrix are almost equal, thus explaining the Wid-manstaetten type structure formed when Ni,Ti precipitates from solid solution. When Ni:,Al precipitates from solid solution, it appears usually in globular form, often dispersed along rows corresponding to definite crystallographic directions. The 7 and phases are also the only intermetallic compounds which occur in the nickel ternary alloys with up to 25 pct Cr and 10 pct Ti or Al. Taylor and Floyd found that Ni,Ti takes practically no nickel, chromium, or aluminum into solution. Nial, on the other hand, dissolves a considerable amount of chromium and titanium and some nickel. Up to three out of every five aluminum atoms could be replaced by titanium in Ni,Al. This substitution caused a slight increase (less than 1 pct) in the lattice parameter. With respect to the effect of variation in the titanium and aluminum contents on the high temperature strength of Nimonic 80 type alloys, Pfeil, Allen, and Conway" reported that an 80 pct Ni-20 pct Cr alloy containing 0.20 to 0.30 pct A1 had the highest creep resistance when the titanium content was kept between 1.65 and 2.75 pct. Experimental Procedure The materials used for this investigation were electrolytic nickel, electrolytic or low carbon chromium, sponge titanium and 2s aluminum. The alloys were melted in an indirect carbon arc furnace under

Jan 1, 1955

By N. J. Grant, D. S. Bloom

An investigation of the Cr-Mo-Ni ternary system and attendant binaries has been completed. Some changes in the binary diagrams are shown to be necessary. The 1250°C section of the ternary and the liquidus surface have been delineated. A system of invariant reactions existing above 1250°C has been suggested. BECAUSE chromium, molybdenum, and nickel are important not only as bases for alloying systems but also as major alloying additions for other refractory metals, a study of the phase diagrams is of great interest and importance. In addition there are interesting features of theoretical value, a number of which are of prime consideration in this work. The major aim was to determine the ternary phase diagram of these metals at and above 1250°C, with sufficient attention given to lower temperatures to permit an understanding of the conditions existing at 1250°C and above. To understand ternary systems it is essential that accurate information concerning the binary systems be available, which in turn presupposes thorough knowledge of the constituent elements. On the basis of this investigation not only were significant inaccuracies indicated in the binary systems but much consideration had to be given to one of the elements, that is, chromium. The observation has been made that chromium undergoes a crystal transformation at a temperature near its melting point. Much of the experimental data leading to the detection of this transformation and the effects of this hypothesis on the form of the Cr-Ni phase diagram have already been reported' . and will not be repeated here. The experimental methods employed in the investigation have also been covered.'-" he purity of the molybdenum utilized in this work showed by qualitative spectrographic analysis that chromium, copper, iron, silicon, and tungsten were present in quantities of 0.1 to 0.001 wt pct. During the course of the investigation more than 100 melts were made, weighing from 150 to 200 grams each. Each of these melts was sectioned for chemical analysis and for specimens for examination in the as-cast and various heat-treated conditions by X-ray and metallographic means. All X-ray diffraction patterns reproduced here were made using chromium Ka radiation although iron and copper targets were used on occasions during the investigation. Experimental Results Mo-Ni-System: The most recent comprehensive investigation of the Mo-Ni system was made by Ellinger' in 1942; the diagram as shown in the American Society for Metals Handbook is based on his work. The work done on the system in this investigation substantiated the general form of the diagram although some differences were observed. These are indicated by a comparison of Ellinger's diagram and Fig. 1, the latter showing the results of pertinent thermal analyses made in this research. It can be seen in Fig. 1 that the eutectic composition is

Jan 1, 1955