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By J. B. Clark, F. N. Rhines

THE A1-Mg phase diagram in the composition range from 30 to 60 pct Mg remains uncertain. Four intermetallic compounds are reported in this composition range. All of the published diagrams are in agreement as to the existence of intermediate phases near 37 and 52 pct Mg (Mgl,A1,). Confusion exists, however, as to the number and identity of the intermetallic phases present in the intervening composition range from 37 to 52 pct Mg. Mikheeva and Kurnakovl denote the existence of a phase e near 42 pct Mg. Kawakami," Reiderer? and Laves report a phase near 48 pct Mg. Eickhoff and Vosskuhler, from a critical survey of the literature, composed the diagram shown in Fig. 1, with the exception of the eutectoid horizontal of the e-phase shown at 210°C. RaynorV n a similar survey discounts the existence of the phase proposed by Ka-wakami et al.' at 48 pct Mg and reports a composite diagram similar to that of Eickhoff and Vosskuhler." This uncertainty as to the number of intermetallic phases in the A1-Mg system may be eliminated by annealing a diffusion couple of pure aluminum and

Jan 1, 1958

BUFFALO J R Atkinson, Chairman (Hamilton, Ont, Canada) C E Moyer, Vice-Chairman H A Morlock, Secretary CHICAGO H Erler, Chairman (Gary, Ind ) M E Nickel, Vice-Chairman A M Kroner, Secretary-Treasurer CLEVELAND C W Cravens, Chairman (Cleveland) E J Sobey, Vice-Chairman E Kondas, Secretary Leo Svete, Treasurer

Jan 1, 1958

By A. A. Bauer, H. A. Saller, F. A. Rough, J. R. Doig

among uranium alloy systems are the U-Zr, U-Ti,and U-Mo binary systems, in that an intermediate phase, of limited solubility range, exists in each system. These intermediate phase alloys offer a promising field of investigation, both as binary alloys and as ternary alloy combinations. While a limited amount of work has been done on the binary alloys, none has been done on ternary combinations of these alloys. As a possible prelude to more intensive investigation of these systems, a study of the phase relationships between the 6 phases of the U-Zr and U-Ti systems was undertaken. The solid-state portions of the binary constitutional diagrams for the U-Ti,1 Zr-Ti,2 and U-Zr3 systems are shown in Fig. 1. The solid to liquid transformations are not shown, as these transformations were not studied in the ternary system. The phase designations employed are based upon those shown in the uranium constitutional diagrams. The crystal structures of the various phases are given in Table I. Experimental Materials and Methods The ternary section presented is based upon the results of thermal, metallographic, and X-ray analyses of a series of alloys ranging in composition between the phases of the U-Zr and U-Ti systems (U-74 atomic pct Zr to U-35 atomic pct Ti). After preparation of the alloys, thermal data were obtained. On the basis of these data, specimens were heat treated and examined metallographically. Specimens were then selected from those heat treated for X-ray determination of the phases present in what were considered critical phase regions. Alloy and Specimen Preparation—Alloys for this investigation were prepared from selected as-reduced uranium and crystal-bar zirconium and titanium. For nominal compositions, see Table 11. Charges were arc melted from five to seven times under a helium atmosphere, finally being cast into wire-bar form for fabrication. A zirconium getter button was used to clean the furnace atmosphere prior to melting. The alloys were homogenized 20 hr at 900 °C and furnace cooled. A portion of each bar was then removed for thermal analysis; the remainder was saved for fabrication. Alloys 8 through 14 were placed in steel tubes along with zirconium getter chips and, after flushing with argon, the tubes were welded shut and rolled at 1500 °F to a 50 pct reduction in diam. The remaining alloys were annealed 24 hr at ll00°F to insure transformation of the ? phase to the 8-U2Ti phase and were then hot rolled from a salt bath. Attempts to roll alloys 6 and 7 at 1100 °F were unsuccessful. Following this, attempts were made to roll pieces of alloys 1 through 5, which had cracked rather severely during casting, at 1200 °F, but these efforts were also unsuccessful. These alloys were, therefore, further treated in their cast and homogenized condition. All alloys were pickled to remove oxide formed during rolling. Thermal data were obtained on these alloys by conventional differential thermal analysis at a heating rate of 30C per min, and by a high-speed heating method at rates of approximately 10°C per sec. For the latter method of analysis, a 36-gage Chromel-Alumel thermocouple is spot welded between two slivers of alloy, the sandwich being en-

Jan 1, 1958

By Ralph Hultgren

IN solid solutions atoms of differing sizes occupy the same crystalline lattice, requiring that some of them be compressed and others expanded. The energy involved has been called misfit strain energy and is an important concept of crystal chemistry. If the atomic sizes and elastic constants of interatomic bonds are known, the misfit energy may be calculated,' provided certain simplifying assumptions are allowable. Usually, isotropic crystals are assumed and interatomic distances are taken to be the statistical average determined from X-ray diffraction. Such calculations yield values of the misfit energy of the order of 1 or 2 kcal per atom in alloys such as Au-Cu at compositions of 50 atomic pct. However, evidence has accumulated in recent times that atoms change their sizes with composition of alloys, implying electronic rearrangement of the bonds. The size changes have been found particularly by application of the X-ray method developed by Warren, Averbach, and Roberts.' Thus, Averbach, Flinn, and Cohen3 determined radii in Au-Cu alloys. Oriani4 showed that these new radii led to a calculated misfit energy in disordered AuCu, which was decreased from the values calculated by the usual theory more than twenty-fold, to only 80 cal per g atom. Thermodynamic calculations from the phase diagram5 also show misfit energy to be no more than a few hundred calories per g atom in this alloy. The question of what electronic rearrangements are possible therefore becomes compelling in estimating misfit energy. In the following pages the results of certain calculations on the AuCu tetragonal superlattice are submitted. Conclusions drawn from these should be applicable in large degree to disordered solid solutions. As in all ordered states, bonding distances in the superlattice are individually known, rather than being merely average distances as found from lattice constants of disordered states. Moreover, only the Au-Au and Cu-Cu distances are strained; the elastic constants of these are known in the elementary state. In the usual calculation it is necessary to assume elastic constants for Au-Cu bonds. Misfit energy has thus been calculable without the need of many simplifying assumptions usually made. It is still assumed that equilibrium bond lengths and elastic properties of the bonds are the same in the alloy as in the pure metals. As previously discussed, this is probably not correct. Also assumed is that the bonds are not affected by strain of neighboring bonds. A calculation of Young's modulus from compressibility data shows this to be far from true; extensive electronic rearrangements take place. It would seem that misfit energy cannot be calculated from elasticity data for the elements. The usual methods may, however, give an upper limit which is often much higher than the true value. The question of electronic rearrangement is, of course, a complex one. Pauling's theory gives a simple, approximate treatment of the relation between type of bond and bond distance. This has been applied with some success to the Au-Cu system, as will be shown in a later section. Misfit Energy in Au-Cu Alloys Hume-Rothery and Raynor6 discuss the Au-CU system as a type example of strain energy. The gold atom is 12.8 pct larger in diameter than the copper atom, near the size factor limit beyond which solid solubility is severely restricted. They therefore consider the misfit energy to be large, a conclusion for which they believe they find evidence in the phase diagram. Gold and copper are completely miscible in the solid state, but the alloy has a minimum melting point at an intermediate composition. From this Hume-Rothery and Raynor conclude that the strain energy is nearly large enough to prevent miscibility; the phase diagram tends toward a eutec-tic type. In Ag-Cu, which has almost identical size relationships, solid miscibility is quite limited; whereas in Au-Ag, where atomic sizes are nearly the same, there is complete miscibility without a minimum in the melting point. From their arguments the heat of formation of Au-Cu would be expected to be endothermic or only slightly exothermic, that of Ag-Cu to be endothermic, and that of Au-Ag to be exothermic. Deviations, from Ve-gard's law of additivity of atomic radii support these conclusions, since Au-Cu and Ag-Cu both have pronounced positive deviations, and Au-Ag has a negative deviation. Nevertheless, Au-Cu alloys form exothermically; indeed, considerably more exothermically than Au-Ag, Table I. Hence, strain energy must be much less important in this case than Hume-Rothery and Raynor have supposed.

Jan 1, 1958

By Arthur Tauber, Horst Kedesdy

FERRITES are sintered metallic oxides of the spinel structure type1 and belong to the class of soft ferromagnetic materials. Similar to a ceramic, they can be formed and fired to a dense body, exhibiting a high electrical volume resistivity ranging from 10 90 10' ohm-cm as compared with 10-6 hm-cm for some of the metallic magnetic materials. This high resistivity, with resulting low eddy current losses, finds special application at high frequencies. The dispersive susceptibility of ferrites at microwave frequencies has also led to many applications in this field. Where high resistivity with high permeability is desirable, ferrites are used in low frequency applications. During the last few years ferrites exhibiting rectangular hysteresis loops have been developed for computer and magnetic memory systems. The general formula for ferrites is MeFe2O4 where Me is a divalent metal ion such as Ni, Zn, Mg, Mn, Cu, Cd, and Fe. Only two of these ferrites are nonferromagnetic, namely, those with Zn and Cd. Solid solutions can be formed between different ferrites, and it is of interest to note that solid solutions of a ferromagnetic ferrite with a nonferromagnetic ferrite yield much better magnetic materials than the basic ferrite body. In general, it can be said that the solid solution formation between ferrites has widened the field of ferrite synthesis and has led to methods of preparing materials with a large variety of magnetic properties. During the last two decades the synthesis of ferromagnetic oxides has been the object of extensive research, but commercial production has been started only within the last ten years. Along with more fundamental studies, there remains the never- ending task of developing ways to realize the optimum characteristics of materials in large-scale production. Ordinarily, to produce a ferrite material it is necessary for the constituent oxides to be mixed intimately, pressed, and then fired at temperatures above 1000°C. Ferrite Synthesis: Formation of a basic ferrite by solid state reaction from Fe,O, and a monoxide such as NiO, under normal atmospheric conditions, is governed by a progressive diffusion of cations between adjacent particles of the constituents. Firing temperature, furnace atmosphere, and cooling can vary the magnetic properties, however. If, for example, a dioxide, a sesquioxide, or an oxide of the Me0 type is substituted for the monoxide, the reaction mechanism becomes more complex and extremely dependent on atmospheric conditions and firing cycles. For this reason reproduction often

Jan 1, 1958

By S. L. Couling, G. W. Pearsall

MOTT and Hainesl have summarized the available techniques for the examination of aluminum and some anisotropic metals under polarized light. Many of these techniques are rather complicated and cumbersome. This note presents a simplified procedure for using polarized light to obtain information about the crystallographic orientation of any particular grain in a magnesium alloy. Since other hexagonal metals are more anisotropic than magnesium, similar methods might well be applied to them. Ernst and Laves2 produced a double-refracting layer on magnesium alloy specimens by SuCCeSSiVe etches in solutions of perchloric acid in alcohol, magnesium perchlorate in perchloric acid and alcohol, and calcium and magnesium carbonates in water. They examined their specimens under polarized light and were able to determine the direction of the hexagonal axis in any particular grain from a measurement of the extinction behavior of that grain. The disadvantages of their technique were the complexity of the etching procedure and the explosive hazard of the perchloric acid-alcohol solutions. Results equivalent to those of Ernst and Laves were obtained in this investigation after etching specimens for 6 to 8 sec in an acetic picral solution containing 100 parts 6 pct picral, 10 parts distilled water and. 5 parts acetic acid. A. similar etch has been used by George3 in earlier metallographic

Jan 1, 1958

By R. A. Wyman

KYANITE schists in the Sudbury area have been generally described by Haw,1 who has also given particular information on preliminary treatment of three large samples from Dryden township, Ontario.2 Kyanite, garnet, biotite, quartz, and feldspar comprise the main ingredients of this ore. Kyanite is the valuable mineral. About 5 ½ tons of -35 +200 mesh product, made by dry rod milling, screening, and separation on the Exolon magnetic separator, were available for treatment by flotation. Magnetic separation had effectively reduced garnet and biotite so that flotation feed consisted essentially of kyanite, quartz, and feldspar, the kyanite content averaging 32 pct and representing about 86 pct of the kyanite in the original ore.

Jan 1, 1958

By H. L. Washburn, G. L. Judy

DURING recent years thermal drying of fine coal has increased at a tremendous rate, but very little discussion of the several excellent units has found its way into print. This is particularly true for operating and maintenance costs, and the operator who is faced with his first fine coal drying installation must depend chiefly on hearsay when trying to determine what his drying costs will be. This article presents the maintenance and operating costs for the seven drying units now installed in preparation plants of Pittsburgh Consolidation Coal Co. and lists other cost information that should be obtained before any particular drying unit is selected. Plant Description: The fine coal drying section of Plant A consists of four Flash driers operating on two furnaces equipped with spreader stokers. Plant B has one Flash drier operating (together with a screen-type coarse coal drier) on one furnace equipped with a spreader stoker. Plant C has two Cascade-type driers operating on a single furnace with a spreader stoker. Plant Costs: Tables I, 11, and III present the cost of operating these units as reported by the individ- ual plants. As can be seen, the labor rates vary, depending on the amount of overtime paid and the time interval the cost figures cover. There is considerable variation in thermal units used and in the value given to the thermal units at the particular mine. There is some difference in power costs at a given location and, finally, the power costs of conveyors leading to the drying plants were included in some cases. Maintenance supply costs are simply a tabulation of the cost of all supplies used on the driers, furnaces, and stokers. Depreciation is not included, and the tables omit items such as supervision, plant cleanup, oiling, general maintenance, taxes, and insurance. These tables in themselves do not offer a true comparison of costs. This information must be reduced to some common basis. But what is this common basis to be? A mine operator must calculate his overall mine and preparation plant costs in terms of tons of clean coal sold. Unit costs on pieces of equipment within a given plant are correctly calculated on the same basis. However, when unit costs are compared between one plant and another, some thought must be given to unit design. This reasoning is similar to the old argument concerning i solid bowl vs basket-type centrifuges—the units themselves are not directly comparable without their supporting equipment. So it is with thermal driers. Except in rare cases of low entering moisture i content, driers are sized on the basis of water that must be evaporated, while the wear each unit gets de-

Jan 1, 1958

By E. S. Greiner

STUDY of the plasticity of germanium or other semiconductor crystals affords unusual opportunities to extend our knowledge of deformation mechanisms. Crystals are available having extraordinary perfection and very high purity. They deform by slip on the systems {111} <110>,1-3 as do crystals of the simple face-centered-cubic structure. Dislocations generated in them during slip are easily revealed in the form of etch pits on either (111) or (100) surfaces.4,5 This fact alone makes possible more detailed studies of mechanisms than is usually the case with metals but, even further, the effect of deformation on their electrical conductivity is very large compared with metals. This comes about not only because the mobility of the charge carriers is reduced, as in deformed metals, but also because the number of these carriers is greatly altered. This latter effect seems closely related to the formation of both line and point imperfections during deformation and thus provides a needed tool for the study of the kinds and distributions of these imperfections. Other investigators have deformed germanium at elevated temperatures by bending,1, 6-8 compres-sion,6, 0,10 tension,2,3,6,11,12 torsion,23 and indentation." Wang and Alexander" have also reported successful indentation at room temperature. Dislocation etch pits consequent to deformation have been observed and studied.7,8,10,18,14,20 The experiments to be de- scribed here include principally the compression and the subsequent annealing of germanium with concomitant studies of etch pits, microstructures, and electrical properties. Both single crystals and heavily twinned specimens were used. Some indentation studies are included. Experimental Methods Plastic compression was effected in the apparatus shown schematically in Fig. 1. It consists of two tantalum platens contained in a helium atmosphere and so arranged that pressure can be applied by a hydraulic press. The specimen between the platens is heated by the surrounding furnace. The specimen is usually a small crystal cube about 0.30 in. on an edge. A control specimen is always inserted so, that it is subject to the same thermal cycle as the one being deformed. This serves to detect any impurity contamination that might accompany the thermal treatment. For high temperature work, where such impurity contamination often occurs, the specimens were first plated with gold whenever subsequent electrical properties were to be determined. This method" is effective in preventing significant contamination of germanium up to temperatures at least as high as 750°C, as evidenced by the constancy of the electrical conductivities of control specimens subjected to the same heat treatments. The total range of temperature used for deformation was from 375°C, the lowest at which significant flow was observed, up to 900°C. Microscopic examination was made after mechanical and chemical polishing and etching. Dislocation pits were revealed with CP-4 etchant by the tech-

Jan 1, 1958

By P. W. Ramsey, D. P. Kedzie

INCREASING demand for improved strength-weight ratios made on aircraft structures has resulted in a gradual increase in the tensile strength requirements for steels used in such applications. As the cyclic loads often are more critical than static loads, and the fatigue properties are generally the design criteria, the question arises as to whether an improvement in fatigue properties accompanies the increased tensile strength. The present investigation was undertaken to determine the relationship between fatigue and tensile properties for an aircraft quality steel in the 155 to 280 ksi (1000 psi) tensile strength range, using the Prot method of fatigue testing. Procedure and Results After preliminary work to establish proper heat treating procedures for this heat of aircraft quality electric furnace steel (a Ni-Cr-Mo-V steel," AMS- Prot Fatigue Testing Method—The determination of the endurance limit by the conventional Wohler method can be time-consuming and easily require 20 specimens when statistical variance is to be established. This is also true when endurance limit loads are determined on actual parts or subassem-blies, and the desirability of a reliable accelerated method has been evident for some time. The primary advantage of the Prot method of fatigue testing is in reducing the number of specimens and the time required for each test. Unlike the Wohler method, every Prot specimen tested con- tributes to the determination of the endurance limit, and the authors have been able to duplicate Wohler results obtained with 20 specimens with only half the specimens and a fourth of the total cycles. This new technique for defining the endurance limit was proposed in 1948&apos; by Marcel Prot and consists of progressively increasing cyclic stress until fatigue failure occurs. By varying the load rate, a, a useful relationship is found to exist with failure stress, so that for steel the failure stress appears to

Jan 1, 1958

By W. D. Robertson, R. E. Reed-Hill

DEFORMATION of magnesium crystals in a direction parallel to the basal plane has a special significance as a result of the preferred orientation characteristic of cold worked and recrystallized polycrystalline magnesium sheet and extruded rod in which the basal plane tends to lie in or near the plane of the sheet or the axis of a rod. The principal objective of the present study is a determination of the modes of plastic deformation in magnesium single crystals in this orientation. Evidence for nonbasal slip in magnesium has been presented by a number of authors. Schmid and Was-serman&apos; indicated that pyramidal slip on {1011} < 1120> or {1012} <1120> could occur above 225°C. Bakarian and Mathewson2 stablished that the slip system {1011} <1120> operates at high temperatures and that 225°C was a lower limit for pyramidal slip. The latter authors also showed that the critical resolved shear stress for {1011} slip was 400 g per sq mm at 330°C, while that for basal slip was 66 g per sq mm at the same temperature. Thus, at 330°C basal slip should be expected for all orientations except those in which the stress axis lies almost in the basal plane. More recently Burke and Hibbard3 oserved pyramidal slip at 25°C, when the stress axis was 6" to the basal plane and 14" to a <1120> slip direction. The critical resolved shear stress for pyramidal slip was 52 g per sq mm, which is only slightly greater than their value for basal slip (46 g per sq mm). Chadhuri, Chang, and Grant4 have observed non-basal slip in creep tests with polycrystalline specimens in the temperature range 250" to 350°C. The observed slip bands, which were extremely irregular in appearance, can be explained in terms of cooperative slip on {1011} and (1010) planes which have a common slip direction. Prismatic (1070) slip in polycrystalline magnesium was observed by Hauser, Landon, and Dorn.5 It was found to occur at low temperatures (78" and 195°K) and it was accompanied by cross slip in which the cooperating plane was the basal plane. Since prismatic slip occurred only at regions of high stress concentrations, the critical resolved shear stress could not be determined. Experimental Procedure The present work was performed on crystal specimens which were all cut from the same large single crystal. The original cylindrical crystal, 0.5 x 7 in., was grown in a Bridgman type furnace in which the temperature gradient was moved past the stationary crystal in the manner described by Jillson6 and Burke.&apos; High purity magnesium was furnished by the Dow Chemical Co. with the following spectro-graphic analysis in weight percent: 0.003 pct Al, <0.01 pct Ca, 0,002 pct Cu, <0.001 pct Fe, 0.008 pct Mn, <0.001 pct Ni, <0.002 pct Pb, <0.01 pct Si, <0.001 pct Sn, and <0.01 pct Zn. The large crystal was cut into four cylindrical pieces about 1.5 in. long. A flat surface parallel to the basal plane was made by hand grinding with lubricated metallographic paper on one side of each cylinder. In order to prevent bending in subsequent cutting operations, the crystals were supported by

Jan 1, 1958

By Jr. F. M. Perkins.

Capillary forces play a controlling role in water-drive displacement processes both in laboratory experiments and in actual reservoirs, but their quantitative importance may be quite different in the two cases. Because of the importance of conducting laboratory experiments which are representative of field conditions, it is necessary to understand exactly the role of capillary forces in the displacement process. Though a number of experimental investigations related to this subject are contained in the literature, there appears to be a lack of information pertaining to unsteady-state experiments in water-wet media. This experimental study was conducted to obtain additional laboratory data to clarify further the role of capillary forces in both the macroscopic and microscopic flow of oil and water in porous materials. THEORETICAL CONSlDERATlONS The capillary pressure is defined as the difference in pressure between a continuous oil phase and a continuous water phase in a porous material.&apos; The magnitude of this pressure difference depends on the interfacial curvature and the interfacial tension. The interfacial curvature is determined by the geometry of the pore spaces, the wettability of the rock surfaces, and the quantity of cach phase present. Capillary forces are involved in a water-drive displacement process in that they exert a controlling influence on the microscopic fluid distribution which in turn is reflected in the saturation or macroscopic flow behavior. Microscopic Fluid Distribution Because of the microscopic nature of the displacement of oil by water, it is necessary to consider the flow and the fluid distribution in individual pores. On this microscopic scale the capillary Forces, which act over a distance of one or two sand grain diameters, control the distribution of oil and water under static equilibrium conditions. When an external force is applied to the fluids, such as in a water-injection experiment, the applied forces tend to distort the oil-water interfaces. However, in most fine-grained, water-wet sands, the applied pressure difference across one or two grain diameters is usually several orders of magnitude less than the capillary pressure difference. These con-siderations lead to the theory&apos; that even during flow the capillary forces continue to control the microscopic distribution of oil and water within the pores of a porous material for all practical reservoir and laboratory flow rates. This concept of capillary forces controlling the microscopic distribution of fluids has been substantially verified by other investigators3-7 who have found a lack of dependence of relative permeability and residual oil saturation on rate of fluid injection. Macroscopic Distribution The microscopic influence of capillary forces cannot be observed easily and only the effect on the macroscopic or average saturation can be detected. The saturation, of course, is really the point of interest. During a water flood, large differences in saturation at the flood front cause large capillary pressure gradients. This, in turn, causes water to advance ahead of the flood front thereby reducing the capillary pressure gradient in this region. The result is that in homogeneous porous media capillary pressure gradients tend to cause a diffuse displacement front. At low rates in laboratory columns, the front may extend over the entire column length. When the advancing water first reaches the outflow face of a core, the water, which is the wetting phase, cannot be produced because the pressure in the water just inside the core is lower than the pressure in the oil-filled space around the outflow face. This difference in pressure is equal to the capillary pressure for the water saturation existing at the outflow face. Water, therefore, accumulates at the outflow end of the core which causes a reduction in the capillary pressure. Because the capillary pressure does not vanish except at the residual oil saturation,7,8,9 water will not be produced until the residual oil saturation exists at the outflow face. This entire effect,"&apos; which is called the "boundary effect", results in a region of relatively high water saturation near the outflow face. At low rates of injection in a short column, this region of high water saturation may extend over a considerable portion of the column. The influence of capillary forces on the macroscopic flow of oil and water have been described by Leverett.10 For unidirectional, viscous flow in the absence of gravity segregation, the expression in dimensionless form for the fraction of water in the flowing stream, f, is

Jan 1, 1958

By R. A. Swalin

IN this paper, the results of an investigation concerning the diffusion of three elements, magnesium, silicon, and molybdenum, in nickel are presented. The work represents a continuation of a diffusion program relating to solute diffusion in nickel. The program has the dual aim of obtaining useful diffusion data and of yielding insight into the factors governing solute diffusion in close-packed metals. The first paper of this series has been published earlier? In both investigations, in agreement with recent results from other laboratories, the activation energies for solute diffusion were found to be close but not identical to that of self-diffusion in the pure solvent in question. In order to obtain valid diffusion data, certain experimental pitfalls recognized only in recent years had to be avoided. Chief among these were the necessity for minimizing short-circuiting diffusion paths such as grain boundaries and the necessity for using low solute concentration gradients. In this series of investigations the following precautions were taken in an attempt to minimize such errors. 1) Samples with large grain sizes, 0.5 to 10 mm, were prepared. 2) The diffusion coefficients were measured at relatively high temperatures, since imperfections such as dislocations play a less important role at such temperatures than at lower temperatures. 3) Alloys containing less than 1 atomic pct were chosen for study. Experimental Work Materials—A diffusion couple technique was employed in the experimental investigation. Briefly, this technique consisted of the following. A diffusion couple was fabricated by placing a flat face of a cylindrically shaped alloy disk against a similar face of a pure nickel disk, and a bond was formed at an intermediate temperature under pressure. The diffusion couple thus fabricated was subjected to a diffusion anneal at higher temperatures for a measured period of time and then sectioned perpendicular to the direction of diffusion. After analyzing the sections for solute concentration the diffusion coefficient was determined from a probability, plot of concentration vs distance from the diffusion interface. Vacuum melted Mond nickel was used in the experimental program. The chemical analysis of this nickel is listed in Table I. Alloys used were prepared

Jan 1, 1958

By A. J. de Witte

It has been observed that upon invasion of a sand containing oil or gas and connate water by mud filtrate the hydrocarbons are more rapidly flushed by the filtrate than is the connate water.&apos; In time, it appears that the following displacement pattern emerges: oil (or gas) is being swept ahead by connate water which, in turn, is pushed by invading fluid. Eventually the connate water may have "banked up" sufficiently to form a zone of appreciable thickness leading the invading front. In the extreme case, Fig. 1 shows how the situation will develop.&apos; Immediately adjacent to the borehole (radius r) there is a zone, the invaded zone proper, where the connate water has been flushed out completely and which contains only residual oil or gas and mud filtrate. This zone (extending out to a radius ri) grades more or less abruptly into the next (thickness A), which contains only residual hydrocarbon and connate water. Beyond it, again more or less sharply bounded, extends the virgin formation with the original interstitial water saturation Sw. The various saturations are indicated in Fig. 1. The three zones generally will be marked by resistivity contrasts owing to their different fluid contents. As the connate water is usually more saline than the invading fluid, the second zone having a high connate water saturation forms a concentric cylindrical ring or annulus of low resistivity R, around the borehole.&apos;,&apos; It will be referred to as the "low zone." Fig. 1 shows schematically the resistivity profile. It is clear that the phenomenon of a low zone could not occur in invaded water sands. The presence of a low zone, therefore, would be a qualitative indication of a hydrocarbon-bearing formation. Granted that the phenomenon is real, if it were pronounced enough to be detected, one might thereby have a means of locating oil or gas in the ground. This is the aim of the "displacement logging" method.&apos; In any case, the presence of a low resistivity zone will affect the reading of electric logs. Using conventional log interpretation techniques, one must be aware of this and, if necessary, correct for it. Whether correction or detection should be the goal will depend primarily on the magnitude of the effect. The type of log which is likely to be affected most is the induction log. The current pattern of an induction log is concentric with the borehole. Any concentric ring of low resistivity, therefore, will tend to become crowded by current lines. This zone of maximum current density will obscure the relative contributions to the current conduction by other portions of a bed making, for instance, the contribution of the virgin formation less significant and thus detracting from the value or the induction log as an R, reading device. The present note is intended to ascertain the maximum possible effect of a low zone in the extreme case portrayed by Fig. 1 on three commercially available types of induction logs, sc., 5 FF 27, 5 FF 40 and 3 F 60. Type 5 FF 27 or 5 PF 40 is currently run in conjunction with a 16 in. normal and SP log. This combination is gradually replacing the regular electric survey (two normals and one lateral) as a standard log in many areas. On the basis of the scheme of Fig. 1 (sharp boundaries between successive zones), the thickness of the low zone may be computed for various amounts of infiltration measured by the ratio of invaded zone diameter to hole diameter D,/d. Referring to Fig. 1, we can set up a material balance for the water displaced from the invaded zone proper and the water present in the low zone. The volume of connate water displaced from invaded zone upon flushing by mud filtrate is: V1 = e p (r2 - r2) ? Sw . where c = bed thickness ? = porosity Su, = original connate water satu-ration. The volume of water finally accu-mulated in the low zone is: Vz = e p [(r1 -?)2 - r2 4] ? Sw . where SW1 = 1 — Sor = "water" saturation in the invaded and low zones both. The volume of water originally present in the low zone is:

Jan 1, 1958

By Robert Bakish

VARIOUS aspects of structure-sensitive corrosion of single crystals and polycrystalline aggregates of Cu,Au have been presented in papers by the author, in association with W. D. Robertson. Prompted by some observations in the course of these studies, a new approach to the problem was undertaken. Results of these new experiments are reported here. Thin slices, less than 2 mm thick, were prepared from single crystals 3.5 mm in diam grown by the Bridgman technique. The crystals were homogen- ized for 300 hr at 850°C. Crystals with no deformation, crystals deformed in tension to the yield point, and crystals deformed 20 pct in excess of the yield point were used. Crystals of several different orientations were studied. Slices were immersed for one month in 2 pct aqueous solution of FeCl3 and, subsequent to this immersion, were subjected to bending. Immersion and bending were carried out at room temperature. The size and geometry of the crystals did not permit accurate data on the loads involved. A most unexpected result was obtained in the process of bending these slices of Cu3Au crystals normal to the (110) plane. Completely brittle be-

Jan 1, 1958

By G. W. P. Rengstorff, L. E. Olds

PREVIOUS research has shown that cast molyb-denum has good ductility at room temperature if the metal is sufficiently pure. In practice, however, it is very difficult to reduce the impurity content of molybdenum to a few parts per million—the maximum content of impurities allowable to obtain reasonable ductility in coarse-grained molybdenum. Also, subsequent fabrication may reintroduce enough impurity to damage ductility greatly, unless extreme precautions are taken to protect the metal during working. The major impurities which embrittle molybdenum are oxygen, nitrogen and, to a lesser degree, carbon. It is reasonable to assume that the harmful effects of such impurities might be neutralized by small amounts of alloying additions. The desired alloying elements would be those which might fonn stable metal oxides or nitrides that would not be harmful to ductility, or thosewhich might increase the tolerance of molybdenum for oxygen and nitro-

Jan 1, 1958

By Kichizo Niwa

A LTHOUGH studies on the roasting of ferrous A sulfide have been carried out by several investigators, some disagreements still remain among those results. Schwab and Philinis1 have measured the rate of oxidation by a precise thermobalance and have concluded that the rate is controlled by diffu-

Jan 1, 1958

By E. T. Wessel

UNEXPECTED brittle failures of metals in practical applications are a serious problem to many industries and to the nation as a whole. Considerable effort has been devoted to studies of the brittle behavior in metals. However, the major portion of this effort has been directed at developing techniques and apparatus for the purposes of determining the susceptibility of metals to brittle failure and of making various types of observations of the phenomena. Relatively minor effort has been made to understand the basic mechanisms involved in initiating brittle failures. A more complete understanding of the nature and mechanism of the brittle failure problem would be very helpful in efforts directed toward predicting and avoiding brittle failure and toward the development of suitable materials and designs that are not susceptible to a brittle behavior. The intent of the present investigation is to acquire this basic understanding. The pronounced transition from a ductile-to-brittle behavior is most prevalent in metals having the body-centered-cubic lattice structure, primarily be- cause metals of this structure exhibit a strong dependence of yield strength upon temperature and the rate of straining. The generally recognized qualitative concept of the ductile-to-brittle transition is that brittle (cleavage) failure occurs when the yield strength exceeds the cleavage fracture strength. This condition can apparently be achieved by decreasing temperature or increasing strain rate. Likewise, a normally ductile metal can be made to fracture in an apparently brittle manner by the introduction of triaxial stresses (notches) where the ratio of normal to shear stresses can be increased to such an extent that the normal stress exceeds the fracture strength before the critical shear stress for plastic flow is achieved. Neither of these concepts require any prior plastic deformation or explain why the observed fracture strengths are so much less than the theoretical cohesive strength. The results of several investigations of the ductile-to-brittle transition in body-centered-cubic metals illustrate rather conclusively that measurable amounts of nonelastic deformation do precede cleavage fracture, even at extremely low temperatures. These studies suggested that the early stages of plastic flow, particularly abrupt yielding, and their relationship to brittle fracture should be examined

Jan 1, 1958

By L. J. Klinkenberg

It is pointed out that the current concept of pore size distribution is not unequivocally defined and that different methods aiming at a determination of such a distribution therefore do not lead to the same results. A pore size distribution should not be based on the idea that a core should, under all circumstances, behave as a bundle of straight non-interconnected capillaries of the same pore size distribution. This is illustrated by calculations and experiments on the displacement of miscible liquids. INTRODUCTION The introduction of the concept of pore size distribution has been an attempt to characterize the intricate geometry of the flow channels in porous media. As pores in a porous medium are interconnected it is impossible to describe exactly what is meant by a "pore" and, therefore, the term pore size distribution requires further amplification. In the visual method for the determination of pore size distribution "the pore" is considered to be the hole between the grains as observed on thin sections or on a polished surface of the rock under a microscope. In all other presently known methods,1,2 a displacement process is studied and it is ascertained what as- semblaae of straight cylindrical capillaries would show the same behavior. The distribution of the capillary diameters of this assemblage is said to represent the size distribution of the pores of the actual porous medium. From the foregoing it is already apparent that it is useless to try to decide which process or which method of investigation leads to a "correct" pore size distribution. To illustrate this further a displacement process in which a fluid is displaced by another miscible with it will be discussed and the results will be interpreted in terms of a pore size distribution. DISPLACEMENT EXPERIMENTS WITH MISCIBLE LIQUIDS OF NEARLY IDENTICAL VISCOSITY AND DENSITY Interpretation in the Form of a Pore Size Distribution If distilled water is displaced from a homogeneous unconsolidated sand pack by, for instance, a dilute solution of NaCI, the breakthrough recovery i.e., the amount of distilled water produced at the moment the first trace of NaCl can be detected in the effluent water, is between 95 and 100 per cent of the pore volume of the pack. This result can be understood by following in imagination the course of one particle of the liquid. Imagine a length, ?l, at the end of which a liquid particle has an independent chance of a renewed choice of pores of different diameters. In other words, the particle has a choice of traveling time, at, for any length ?l; instead

Jan 1, 1958

By Harold R. Bradford

EXPANSION initiated during and after the war has placed industrial plants in new areas and increased reduction and manufacturing facilities in communities already established. With added expansion interest has grown in possible area contamination from waste products. Evolved flue waste contains many chemical contaminants that may or may not cause concern; however, atmospheric pollution has always been a problem to industrial communities. For some time effects attributed to small quantities of compounds of fluorine in various waste gases have been studied by industrial, medical, agricultural, and associated interests.1&apos;2 Aside from an article by Churchill, Rowley, and Martin in 1948," little has been published on the subject of fluorine in coal except by foreign investigators. The first indication of fluorine compounds in coal was noted in England in 1934 by R. Lessing,4,5 who found that the presence of fluorine in Midland and West County coals was definitely established by etching of glass and by severe corrosion of porcelain fillings in a gas works scrubber. Etching of glass in a direct contact annealing kiln initiated research, and in 1944 four papers were published by H. E. Crossley,6-9 giving results of investigations of fluorine in coal of England by the Fuel Research Board, Department of Scientific and Industrial Research. These investigations studied methods of determining fluorine, the quantities present in various coal deposits, the geographical distribution of fluorine in British coals, occurrence of fluorine in minerals associated with coal, amounts of fluorine compared to other constituents of coal, the nature of fluorine compounds, and industrial significance of fluorine in coal. It was shown that British coals contain from 5 to 200 ppm of fluorine, which is probably present as fluorapatite [Ca10F2(PO4)6], often written as [3Ca3P2O8.CaF2]. The fluorapatite is intimately associated with shale in some coals and can often be separated from these coals along with the shales. H. E. Crossley8 also reported no correlation between the amounts of chlorine, sulfur, or ash and the amount of fluorine in different coals. He found, however, a relationship between the content of fluorine and phosporus in many British coals. Thus it should be possible to anticipate likely fluorine-rich coals from existing data giving phosphorus content. Behavior of the fluorine compounds of coal was compared with that of 12 fluoride-phosphate minerals in sink-float separations and solvent ex-

Jan 1, 1958