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By P. E. Fitzgerald, Dana G. Hefley

An apparatus has been developed which permits selective acidizing of producing formations and determination of the relative permeability of a formation by fluid injection. This apparatus, known as the "Electric Pilot," is an electrical fluid-interface locator, the electrical circuit of which is completed when the elec-tcodes in the well are in contact with a conductive fluid, but is not completed when immersed in a nonconductive fluid. Results are given for a number of typical acidizing applications in which the interface locator was used to control the acid. Description of the method used in making a permeability survey and the data obtained are also included. Introduction Early in the development of the acidizing industry it was recognized that one of the most important problems to be solved in the chemical treatment of any well was the determination of what part of the exposed section in the well should be treated and the selection of the technique that would insure treatment of the desired section. One of the first techniques adopted for assisting in proper placement of the acid, which is still widely used, is the method of confining the acid to the producing section by means of a column of oil, which is known as the Carr1 method of treatment, named for its inventor. In the Carr method it is not possible to selectively acidize a specific horizon in a multiple pay zone, so many improvements and modifications of the basic Carr technique were devised to accomplish this result. In order to overcome the possibility of the acid entering an undesirable section at the bottom of the well, organic gel plugs2 were introduced into the bottom of the well, which served to halt the entrance of the treating solution into these zones.3 These chemical gels later liquefied because of bacterial action and were removed from the well with the produced fluid. In fields where a gas cap existed, as in the Goldsmith field of Ector County, Texas) it was imperative that a treating technique be evolved that would confine the acid to the oil-producing zone below the gas cap. By so doing the oil-productive capacity of the wells could be improved without greatly increasing the gas production and this would lower the gas-oil ratio of the well. ~h, technique employed4 to achieve this effect utilized two pumps, one for pumping the chemicals down the tubing, the other to simultaneously force oil down the annular space to confine the acid to the oil pay, thus preventing the chemicals from entering the upper gas-bearing zones. Experience has indicated that gas wells and certain types of oil wells respond better to ''stage treating.'' This technique utilizes the introduction of a certain volume of acid and then allows the well to ''clean up99 before introduction of the next and usually successively larger stages. Where such methods are employed steps must be taken to keep a disproportionate share of the acid from entering the most permeable and previously treated Zones. A special tool

Jan 1, 1944

By R. DiBella, H. Biloni, G. F. Bolling

A study of the detailed relationship between solidification substructure and microsegregation in dilute tin alloys has been continued. New observations reveal that depressions form at the solid-liquid interface not only as an initial form of segregation but throughout the range of increasing constitutional supercooling. In order to show the importance of this node formation it proves convenient to make two simplifications. Although substructure changes continuously as constitutional- supercooling increases,&apos; the following discrete stages may be used for discussion: 1) the planar solid-liquid interface; 2) ordered nodes, or depressions at the interface;&apos; 3) two-dimensional or elongated cells;3 4) regular or hexagonal cells;4 5) distorted cells, or hexagonal cells with branches;4 6) dendrites. It is also convenient to ignore observations made near grain boundaries which interact with the cellular substructure.2-4 And, it should be clearly pointed out that all singular depressions at the solid-liquid interface will be called nodes. Heretofore, the term "node" has been used without clear justification to describe both the truly isolated depression and the junction of cell walls appearing in a later stage of segregation. This usage is continued because it seems proved by the observations. Standard systematic growth of tin crystals was undertaken over a broad range of constitutional supercooling using various added solutes. Except for one or two chance observations, this research failed to reveal any appreciable range of growth conditions over which a disordered array of isolated nodes exists. Even though &apos;some finite range of random instability must exist, it is now concluded that stage one passes very rapidly to stage two. Next, after confirming that stage two passes to stage three by the elongation of isolated nodes: a reexamina-tion of stages three, four, and five followed. Standard metallography showed that pockets of higher solute concentration (for ko < 1) became more numerous in cell walls the more severe the growth conditions. These high-concentration regions must arise from depressions; however, in stage three their segregation is not distinguishable from the segregation of the nodes which join cell walls together. It seems, therefore, that the presence of nodes is causal in the formation of new cell walls, and that the mechanism by which stage three passes to stage four is initiated by nodes. If a similar reasoning is followed, the separation of stage four from stage five appears to be just a convenience that has arisen from the decanted interface observations made in the past. The present observations again show that more severe growth conditions relate directly to an increase in the number of nodes in the hexagonal cell walls. These nodes apparently serve as the origin for lines of segregation extending within the body of a cell, and can thus be assumed to represent the earliest form of branching,* as shown here in Fig. 1. The examination of stage six involved decanted-interface structures as in Fig. 2, which are similar to those considered by Rutter and Chalmers,5 Plaskett and winegard,6 and Hellawell and Herbert,7 and where distinct protrusions are each surrounded by a depressed boundary. The corresponding microsegregation behind the interface, but not far enough behind to allow a smearing of the segregation because of diffusion,4 is shown in Fig. 3. Both the shape of the decanted interface and the segregation pattern behind it

Jan 1, 1968

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&apos; 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&apos; 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 Paul Pietrokowsky

THE formation of intermediate phases in the solid state reaction of titanium with silicon, germanium. and tin (of subgroup 4B in the periodic table) was the subject of a recent paper.&apos; Further investigation of the system Ti-Sn revealed the presence of a new compound on the titanium-rich side of this phase diagram. Metallographic evidence indicated that this new phase was situated very close to 75 atomic pct Ti. The present work is concerned with the crystal structure of the intermediate phase Ti3Sn. Iodide-process titanium metal, furnished by the New Jersey Zinc Co., was used in this investigation. The metallic tin was received in powder form from Charles Hardy Inc., New York; its purity was 99.80 pct. The titanium rod was machined into small cups 1 cm in diam and about 1.5 cm in height. The tin powder was compacted, melted, and then placed in the titanium cups and alloyed by electric arc melting in a helium atmosphere. The alloys, weighing approximately 8 g, were sealed in evacuated quartz tubes and homogenized at 1030°C for 5 days. This isothermal heat treatment was terminated by a water quench from the soaking temperature. Filings of the alloyed pellets were sealed in evacuated quartz bulbs and quenched from 1030°C into liquid argon. A 14.32 cm Debye Scherrer X-ray camera was used for the powder diffraction study. The copper radiation was filtered. X-ray diffraction data for the compound Ti3Sn are given in Table I. The data were indexed on the basis of a hexagonal lattice. Good agreement between observed and calculated values of the square of the reciprocal interplanar spacings was obtained with the following expression: (1/d)2 = 0.03810 (h2 + hk + k2) + 0.04410 (l2) Unit cell parameters were calculated by the method of least squares from the reflections (20.3), (22.2), (40.1), and (42.1); ao = 5.916 & 0.004A, co = 4.764 ± 0.004A, and co/ao = 0.805. The relatively small size of the unit cell allowed the unambiguous indexing of most of the reflections from planes of large spacing. An inspection of the assigned indices (Table I) reveals the absence of (hk.l) reflections when 1 2n. A systematic absence of this type leads to the space group C 6/mmc or one of its subgroups. Assuming, for a first approximation, a linear increase in the density of titanium with the addition of tin, it follows that there are two stoichiometric molecules of Ti3Sn per unit cell. The density calculated from X-ray measurements is 5.194 g cm-&apos;. At this point it became clear that Ti3Sn might be isomorphous with Mg3Cd. The 6 Ti and 2 Sn atoms were placed in the following positions of space group D4 6h, C 6/mmc: 6Tiin (h): X 2X 1/4; 22;; 1/4;Xx 1/4;x2x3/4; 2x x 3/4; x x 4; with x = 516 2 Sn in (c): 1/3 2/3 1/4; 2/3 1/3 3/4.

Jan 1, 1953

By Louis E. Toth, Alan W. Searcy

A modification of Le Claire&apos;s microscopic model for self-diffusion is developed in a form suitable for prediction of activation energies for diffusion in disordered substitutional solutions as well as in pure metals Bonding is considered as a localized interaction, and the energy of bonding between atoms of different types is taken as the arithmetic mean of the energies in the pure elements. The activation energies for vacancy formation and migration in substitutional alloys are shown to depend on the empirical constants developed for self-diffusion when the equations are adjusted for the mole fractions of the two elements. The differences in activation energies between alloys and pure metals are calculated and compared with the experimental differences. MaNY different correlations have been proposed for use in predicting activation energies for self-diffusion or diffusion in dilute alloys. Usually theories for self-diffusion cannot be applied to alloys nor can theories for dilute alloys be satisfactorily adapted to self-diffusion. We present here a correlation scheme which can approximate activation energies for diffusion, vacancy formation, and atom migration in substitutional-alloy systems of any concentration. The activation energy for self-diffusion QD has been correlated to the melting temperature Tm,1, 2 the sublimation energy L,,l the heat of fusion Lf,3 crystal structure, and valence.4 Working with mechanical parameters Le claire5 proposed that the activation energy for vacancy migration Qm could be related to appropriate shear moduli. He also proposed that the activation energy for vacancy formation 62, is proportional to Ls. THEORY We consider that Le Claire&apos;s expression for 4, is satisfactory. But an alternate expression for Qm in terms of the bulk modulus is just as satisfactory from a theoretical point of view for the prediction of the energy of vacancy migration in pure metals and can more easily be used for alloys. In order for Qm to be a minimum, not only the moving atom but also adjacent and nearby atoms must undergo distortions. These distortions are neither isotropic as is implied by a correlation with the bulk modulus nor unidirectional as implied by a correlation with a shear modulus, but are complex and multidirectional. A complete analysis in terms of the bulk modulus and all the shear moduli is not yet available. In a first approximation in which only one parameter is used, there is no obvious theoretical reason to prefer the shear modulus over the bulk modulus. The bulk modulus is a much more convenient parameter for use in predicting Qm. Shear moduli are known for less than half of the metallic elements while bulk moduli are usually available. Furthermore, because of the directional dependence of shear moduli, their estimation for alloys appears inherently more difficult than is the estimation of bulk moduli. We assume that the bulk modulus Bs reflects an average value of the shear moduli such that the strain energy at the point of maximum distortion of the lattice during vacancy migration can be expressed as

Jan 1, 1964

By R. G. Vardiman, M. R. Achter

THERE has been interest recently in the conditions under which dislocation pipe diffusion may be observed. In order to extend the measurements to temperatures below Tm/2, where pipe diffusion becomes more important, a chemical sectioning technique was developed for silver single crystals which makes possible the removal of layers of 100A or less. The procedure is briefly as follows. Silver single crystals of 99.995 pct purity were cut in the form of discs t by 4 in., electropolished, and electropolated with Ag110 to about 1000A thickness. The thickness was determined by calibrating the activity with the weight of heavier platings, up to 10,000A. Both diffused and undiffused samples were sectioned in a two-step process. Reaction with a solution of iodine in alcohol formed a thin, even layer of AgI, which was then dissolved in a KCN solution. The reaction rate of the iodine solution varied slightly over a period of time, so that the thickness of the stripped layers, while quite even and regular for a given specimen, ranged from 65 to l00W for different specimens. This variation was checked by using a thickly plated standard with each run. Layer thickness was determined from undiffused samples by the point where the layer activity drops to half the maximum. This maximum intensity also provides, with appropriate corrections, the initial concentration per layer co. Because of the small penetration distances, it is necessary to use the exact solution of Fick&apos;s law for a source of finite thickness.&apos; For a plating of thick- where c is the concentration at depth x. flj the error function, D the apparent diffusion coefficient, and t the time. The diffusion coefficient was obtained from the concentration-penetration data by extrapolating to x = 0 where c/co = erf h/2(Dt)1/2 Enough points were taken to impart confidence in the accuracy of the intersection, generally about ten layers. Four temperatures were used as in Table I. For best accuracy, t and h were chosen to give values of the parameter (Dt)1/2/h between 1.0 and 1.7. A typical concentration-penetration curve is shown in Fig. 1. The diffusion coefficients calculated from Eq. [I] are plotted in Fig. 2. For comparison, the high-temperature data of Tomizuka and sonder 2 which go down to 630°C are plotted as the solid line 2(a) from their expression D = 0.40 exp (-44,090/RT). Also for comparison, the lowest temperature point of Hoffman and Tumbull3 is plotted. It is apparent that our data diverge appreciably from the high-temperature extrapolation by 373°C. A better straight line fit for the low-temperature portion is obtained by subtracting the extrapolated volume diffusion coefficient from the apparent. or measured coefficient, and plotting the difference, curve (h) of

Jan 1, 1970

By F. Brons, W. C. Miller

Pressure information for use in material-balance calculations is obtained, where possible, from pressure build-up surveys in shut-in wells. Using proper extrapolation methods, static pressures are obtained which, by averaging, give the field static pressure. Often, particularly in fields with a large number of wells, only spot pressure readings are available. A graphical method is presented here which enables the determination of the corrections which must be applied to the spot readings to give an estinzate of the static pressure. Although the static pressures thus obtained are not so reliable as those from build-up surveys, they are more nearly correct than the spot readings themselves for use in material-balance calculations. INTRODUCTION The average static pressure in a bounded reservoir is determined from a number of individual-well pressure measurements. Where pressure build-up curves are available, extrapolation methods such as described in Ref. 3 may be used to determine the static pressure in the drainage area of each individual well. The possibility of using pressure build-up curves presupposes that each well being surveyed is closed in during a certain period and that, during this time, a pressure recorder is left suspended in the hole. For surveys in fields with a large number of wells, this is usually not feasible for economic and other reasons. Either a large number of pressure recorders would have to be used simultaneously or, using a limited number of recorders, the time interval needed to complete a field-wide survey would be too long. The data obtained for this incomplete coverage are insufficient to permit reliable averaging of the few calculated static pressures over the entire reservoir. In many such cases another type of pressure information is available, i.e., spot pressure readings. During this type of pressure survey all wells are closed-in simultaneously and, after a reasonable shut-in time (e.g., three days), pressure readings are taken by running the recorder in and out of each successive well. These surveys, which are less expensive, are often taken at regular intervals, say once or twice a year. In fact, such surveys are required by the state regulatory bodies in many portions of the united States. These spot readings are normally lower than the static (fully built-up) pressure due to the relatively short shut-in time. No direct means of extrapolating such a reading to the static pressure is available because no pressure build-up record is obtainable. Consequently, these data are inferior to pressure build-up information as a basis for estimating the stabilized reservoir pressure in the drainage area of a specific well. For the common case where abundant spot readings but only a few pressure build-up surveys are available, our studies suggest that it may be possible to design a program which will combine the two types of information and provide an estimate of the average reservoir pressure that is more reliable than that obtainable solely from either set of data. in time) gives a point marked p. The actual static pressure at the time the well was shut-in is marked by p.. The illustration shows that, even if a build-up curve is available and can be extrapolated, a correction

By Hans Strack

Electroluminescence of GaAs p-n junctions fabricated by simultaneous diffusion of sulfur and iron was investigated at 77°K. A narrow emission peak with a half width of about 4 kT in the energy range between 1.14 and 1.155 eu was attributed to iron. Other transition elements exhibited light emission in the vicinity of the iron peak, namely nickel between 1.15 and 1.16 ev and cobalt between 1.16 and 1.17 ev. The efficiency of the doping with iron depended on the amoz~nt of arsenic present. A weight ratio of arsenic to iron of 4:l was sufficient to observe the emission lines associated with transition elements. The presence of oxygen reduces the intensity of the light emission. In addition to the levels associated with transition elements, levels at 1.05 and 1.28 ev, probably due to lattice defects, are observed except in diodes fabricated in solution-grown GaAs. THE near band edge emission of GaAsp-n junctions has been studied extensively in the past.&apos; GaAs devices utilizing spontaneous and stimulated near band edge emission are of considerable practical importance. Typical junctions are fabricated by diffusion of a heavily doped p region into degenerate n-type GaAs. Much less work has been done on investigating the radiative recombination via deep levels in lightly doped p-type material. This area is of interest in understanding the performance of GaAs n-p-n transistors. GaAs transistors show remarkable improvement in high-frequency performance and current-gain stability at high temperatures, when iron is added to sulfur during the emitter diffusion process. The present work was initiated to investigate deep-level electroluminescence of iron-doped GaAs p-n junctions fabricated on vapor-phase epitaxial GaAs and on solution-grown GaAs. For comparison several diodes doped with cobalt and nickel were studied. Iron, cobalt, and nickel have an electron configuration of the type

Jan 1, 1968

By E. N. Skinner, Arthur Philliops

During the course of an experimental program concerned with the hydrogen embrittlement of copper containing oxygen in concentrations within the solubility limits it became necessary to make a critical appraisal of the literature dealing with the solubility relationships of oxygen and solid copper. The latest determinations, and perhaps the only data obtained on "spectroscopically" pure copper, are those of Rhines and Mathewson&apos; who reported that the solid solubility increases from 0.007 per cent oxygen at 600°C. to about 0.01; per cent at 1500ºC. Hanson, Marryat and Ford2 had previously placed the solubility limit at less than 0.009 per cent oxygen at 1000ºC. and Allen and Street3 had suggested, on the basis of an unpublished research by T. Hemitt, not over 0.005 per cent oxygen at 500°C. In the introductory stages of the investigation indirect evidence accumulated to suggest that the solubility limits were significantly lower than those previously reported. For this reason it was deemed essential to clarify this point before proceeding with a program intended to establish a quantitative relationship between hydrogen embrittlement and oxygen concentrations positively known to be within the solid solution range. Furthermore, the increasing production and the highly selective applications of the commercial "oxygen-free" coppers inevitably direct attention to the practical necessity for exact knowledge regarding the effects of mini-tie concentrations of the elements ordinarily found in the high-purity coppers now available. Of these elements oxygen occupies a unique position, not only by virtue of its specific effects on copper but more particularly in view of its important reactive tendencies toward the other impurities with which it is associated. Rhines and Mathewson considered several methods for measuring the solubility of oxygen and finally adopted the simple plan of saturating the specimens, obtained from redeposited cathode copper, by heating at the desired temperature in air. After the removal of surface oxide by mechanical and chemical means, the oxygen content was determined in the underlying metal. In general, this process of saturation, with a few modifications, was followed by the present writers. Although the procedure is direct and has obvious advantages, its effectiveness, unfortunately, is reduced by an excessive scaling of the copper, particularly at the higher temperatures. After saturation treatments above 900°C. the writers found that the specimens, necessarily rather thin in the original condition, consisted largely of scale and yielded too little metal for a satisfactory analytical sample. Furthermore, great difficulty was experienced in effecting complete removal of the scale. Needless to say, it is necessary to exercise extraordinary care in the preparation of the surface of the analytical sample in order to eliminate submicro-scopic fragments of cuprous oxide which ordinarily are lodged in the crevasses and

Jan 1, 1941

By R. P. Thomas

Secondary fertilizer minerals are the mineral materials used to supply directly and indirectly the secondary and trace plant food nutrient needs of a fertilizer. Since few soils contain sufficient availability of all plant nutrients for their proper growth, man has prepared mixtures of plant food materials to correct these nutrient deficiencies. These mixtures or fertilizers, when added correctly to a soil, make it possible for abundant and economic crop growth. Many kinds of materials are used as sources of these needed nutrients. They come from natural and synthetic materials and minerals including many beneficiated byproduct compounds. A fertilizer consists largely of carriers of one or more of the three major plant foods, namely nitrogen (N), phosphorus-phosphorus pentoxide (P2O5) and potassium-potash (K2O). Many other nutrients are just as essential for plant growth as the three major plant foods. In fact, the efficient use of fertilizers today depends upon an adequate supply of all these other nutrients. Since these additional materials are usually removed from the soil by plants and supplied in fertilizer in less quantities than the major nutrients, they are called secondary and minor nutrients. In the early days these special nutrients were contained as impurities in the primary nutrient carriers. Today, fertilizers are made primarily from concentrated and synthetic materials which carry very few of these other essential nutrients. Consequently, many secondary and trace nutrient carriers, as salts, byproduct compounds and even minerals have to be added to fertilizers. Secondary Nutrient Carriers The secondary plant foods in fertilizer are next to the major nutrients in abundance. They are calcium, magnesium, sulfur, chlorine, silicon and sodium. Although many of these elements are added to a fertilizer as part of the major nutrient carriers, they are also added in special carriers. The large tonnage of these secondary nutrient carriers used in fertilizers represents only a small percentage of the total production of these materials. A fertilizer producer thinks in terms of materials which supply nutrients instead of minerals. Therefore, these materials will be discussed by elements. CALCIUM Soils need calcium to supply the nutrient needs of plants and maintain the desired physical and biological conditions in the soil. The available calcium is usually 40 to 80 pct of the exchangeable bases. (These bases are ones which can be displaced by other cations and determined quantitatively. They are then expressed as milliequivalents per hundred grams of soil-me.) Direct applications of lime materials such as burnt, ground or hydrated limes are the important sources of calcium for the soil. Most crops, especially legumes, have a high requirement for calcium. The average farmer does not use enough lime to maintain the proper level of available calcium. Hence, it is necessary for many fertilizers to contain soluble calcium materials for efficient use of the major nutrients. The following major nutrient carriers supply some calcium: calcium nitrate, ammonium nitrate mixtures and cyanamid, and many of the phosphates. Both synthetic and natural gypsum are used in fertilizer production. Some crops such as peanuts require a large amount of soluble calcium. Gypsum is the important supplier of this soluble calcium. It is not applied with the fertilizer

Jan 1, 1960

By E. A. Nesbitt

The important permanent-magnet alloys 15 years ago contained carbon and depended upon it for their permanent-magnet properties. In recent years great advances have been made in a number of new alloys substantially free of carbon. These include Remalloy,&apos; an alloy of iron, cobalt, and molybdenum, the various iron-nickel-aluminum alloys of the Mishima2 type, and the more recent Alnico V3 in which the best properties are developed by heat-treating in a magnetic field. The Mishima and the Alnico types of alloys are very brittle and after casting must be ground to size. This article describes a permanent-magnet material4 that can be machined as cast, and when handled with some care can be rolled to thin sheet and drawn to fine wire. Optimum magnetic properties are developed by a simple heat-treatment, and at this time the ductility of the alloy disappears. If the cast alloy is heat-treated without cold-working the mag netic energy product is about 1.0 X 106. This material is called Vicalloy I (pronounced vicalloy, V for vanadium, I for iron, and C for cobalt). When the alloy is first hot-worked and then considerably reduced in area by cold-swaging, drawing or grooved rolling, it is found that after heat-treatment the magnetic energy product measured in the direction of previous extension can be increased to 2.0 to 3.5 X 106. These higher values have been obtained only after reductions in area of 75 to 95 per cent, and since the material hardens considerably during working, the reduction ordinarily can be accomplished only in fine wires, although larger sizes can be reduced by the use of powerful machinery. When the material has been cold-worked in such a manner as to improve its energy product substantially, it is called Vicalloy 11. Commercial use of Vicalloy has been made in the recording of speech. Tape 0.002 by 0.050 in. has been found superior in quality to all others tried, and is now used in the Western Electric Mirrorphone 5 In a variety of forms Vicalloy I or I1 is useful in many laboratory instruments, and in experiments in which the sizes and shapes required cannot be obtained with the other more brittle permanent-magnet materials. In 1936, during a study of other age-hardening magnetic systems, it occurred to the author that some of the iron-cobalt-vanadium alloys might be suitable for permanent magnets. The proportions of iron, cobalt, and vanadium were varied and a range of alloys of particular interest was found, as shown by the indicated area in Fig. I. The limits of this range of composition are 30 to 52 per cent iron, 36 to 62 per cent cobalt, and 4 to 16 per cent vanadium. The compositions indicated by points outside this area were also tested. Preparation and Properties OF Vicalloy I The alloys were usually cast in graphite molds into bars 3/4 in. in diameter and

Jan 1, 1946

By D. K. Crampton, H. l. Burghoff, J. T. Stacy

THE effect of cold-working upon electrical conductivity of copper and of copper alloys appears not to be generally known in detail Although several papers on the subject have been presented, showing variable effects according to alloy composition, it is often assumed that the 2 to 3 per cent lowering of the conductivity of ordinary tough-pitch copper by severe cold-working is typical for copper alloys Because of this situation it was decided to carry out the present work upon several types of copper, copper-zinc alloys over the commercial range of brasses, other binary alloys, and numerous age-hardening alloys in the quenched, and quenched and aged conditions The large number of alloys investigated made it impossible to study every one in the detail it may have merited Inasmuch as several interesting points that could not be satisfactorily explained came to light, further work is contemplated by the authors It is usually considered that the normal effect of cold-work on ductile metals and unordered alloys is to decrease conductivity slightly In alloys that are in the ordered state, as annealed or otherwise heat-treated, cold-working tends to disorder the structure, resulting in very marked lowering of conductivity The random state of atomic arrangement produces lower conductivity than the ordered state for the same composition 1 PREVIOUS WORK previous work in the authors&apos; laboratory has shown the electrical conductivity of several copper alloys to be decreased by greater amounts than might have been expected, in view of the general knowledge on the subject, when cold-worked Guillet and Ballay2 investigated the influence of cold-work upon the resistivity of several metals and alloys, including copper and some copper alloys The increase of resistivity due to severe working was less than 4 per cent for all pure metals tested, while the increases for the alloys were generally higher In the copper-zinc alloys, they found that the increase of resistance due to drawing increased with zinc content, and reported a 21 7 per cent increase of resistance for an alloy containing 67 9 per cent Cu as severely worked Masima and Sachs3 studied the change in electrical resistance of three brass crystals when stretched in the tensile test, obtaining increases in resistance of the order of 3 per cent for 30 to 40 per cent reduction of area of the specimens The resistance decreased again when the cold-worked crystals were subsequently annealed Bardenheuer and Schmidt4 found that the conductivity of copper was decreased by 3 to 4 per cent when reduced 50 per cent by working The conductivity of 72-28

Jan 1, 1941

By P. A. Tucker, C. R. Hudgens, D. E. Etter, D. L. Roesch, D. B. Martin

The equilibrium phase diagram of the Pu-Cd system is presented based on data obtained by differential thermal analysis, metallography, and electron-microprobe X-ray analysis. Liquidus temperatures range from 320° to 934°C. The system contains one congruently melting compound, PuCd, (945°C), and three incongruently melting compounds, PuCd, (800°C), PuCd, (730°C), and PuCd11 (410°C). A liquid-miscibility gap extends from 2 to 60 at. pet Cd with the monotectic reaction isotherm at 910°C. INTEREST in the potential use of plutonium alloys as reactor-fuel materials has prompted investigation of the phase equilibria in plutonium binary systems. A cursory investigation of the phase equilibria in the Pu-Cd binary system was conducted by differential thermal analysis (DTA), metallography, and electron-microprobe X-ray analysis (EMX). Extensive solid solubility of cadmium in both e and 6 plutonium was predicted1 based on atomic radii and electronegativities. Liquid immiscibility between these two elements was also predicted based on Mott&apos;s extension of Hildebrand&apos;s method. In the only previous investigation of the Pu-Cd system,2 two intermetallic compounds, PuCd11 (incon-gruent melting point 406°C) and PuCd8, were identified. EXPERIMENTAL The plutonium metal used in this work had a total impurity content of 500 ppm; the major impurities were: carbon (215 pprn), silicon (75 ppm), iron (60 ppm), nickel (40 ppm), and aluminum (25 ppm). The cadmium was reagent grade with a purity of 99.99 pet. The DTA technique for the study of plutonium alloys was previously described in detail.3 The alloys to be studied were prepared in tantalum DTA specimen capsules which were sealed by inert-gas welding. The alloys were homogenized in the liquid state in these sealed capsules which prevented the loss of cadmium by vaporization. Only the thermal arrests in the DTA heating curves were used to define the transformation temperatures of the system since supercooling affected many of the results during cooling. After the alloys were analyzed by DTA, the same alloys were used for the metallographic studies. Metallographic examinations were conducted in the manner described for plutonium alloys., No reaction was detected between the alloys and the tantalum capsules. Alloys for EMX analysis were placed in metallographic mounts together with specimens of unalloyed plutonium and cadmium which served as standards. The samples were highly polished but unetched. No protective coatings were applied to the surfaces of these radioactive specimens. Such coatings are detrimental to the excitation conditions and have been found to be unnecessary for the control of radioactive contamination. RESULTS The results of the DTA studies are presented in Table I. The phase diagram, constructed from these data plus the metallographic and EMX results, is presented in Fig. 1. The congruently melting compound, PuCd2, was identified by the occurrence of a maximum melting point (945°C) at 33.3 at. pet Pu-66.7 at. pet Cd and by the presence of a single phase in this composition.

Jan 1, 1965

By J. E. Gruzleski, O. Knacke, M. J. Meixner

The evolution of CO from small specimens of solidifying steel was investigated using a thermobalance technique. Gas evolution begins in the temperature range between 1400" to .1450°C. This behavior is independent of the initial carbon content and the cooling rate. At a constant temperature above 1220°C, the rate of gas evolution is temperature independent. Out-gassing of the specimen is thought to proceed through small channels formed by the coalescence of bubbles between dendrites. LIQUID metals have a higher solubility for gas than the solid. During freezing, these gases form bubbles which may either escape or remain trapped in the solid. Recent work1 on the evolution of oxygen from solidifying silver showed that the gas is not liberated until a large fraction of the melt has solidified, and that the gas is evolved in an almost explosive manner. Because of the commercial importance of CO evolution in solidifying steel, a similar investigation was undertaken to study the mechanism of gas liberation in steel. EXPERIMENTAL The thermogravimetric method of Knacke and eixner1 to follow gas evolution by weight changes was employed. Weight differences of 0.1 mg could be reproducibly measured on specimens weighing 2.5 g. These specimens were taken from alloys with varying carbon contents from <0.01 to 0.11 wt pct and <0.01 wt pct of each of silicon, manganese, and aluminum. Specimens contained in 8 mm ID magnesium alumi-nate crucibles were heated to 1550°C under 1 atm of very pure (99.995 pct) CO with a tungsten resistance furnace. The specimen temperature was measured with a Pt-Pt/Rh thermocouple located directly beside the crucible. It is felt that the temperature thus measured was within 5" to 10°C of the specimen temperature since on fusion the weight of the specimen increased due to uptake of CO, and this weight increase was always observed to begin within the temperature range of 1530" to 1540°C. Even after 3 hr there was a small weight increase with time indicating that the molten specimen was not completely saturated with CO. Therefore, complete saturation was not attempted, and all specimens were simply held for 3 hr at 1550°C before cooling. Two types of cooling experiments were performed. One consisted of continuous cooling at linear rates from 5°C to 20°C per min down to 1020°C. The second type of experiment involved continuous cooling at 10°C per min to a predetermined temperature, and then holding the specimen at this temperature for a certain time. During all of these experiments, the sample weight was recorded as a function of time and temperature. OBSERVATIONS Continuous Cooling Experiments. No gas evolution was detected above 1450°C. The initial weight decrease always occurred between 1400" and 1450°C with the average at 1430°C. With further cooling, gas evolution continued to about 1150°C. Between this temperature and 1020°C no further outgassing was observed. This behavior did not seem to depend on the initial carbon content nor on the cooling rate in the range investigated. Typical patterns of gas evolution are shown in Figs. 1 and 2 for different initial carbon levels and cooling rates. The total amount of gas liberated during solidification varied with the rate of cooling. The total weight change on continuous cooling at a rate of 10°C per min

Jan 1, 1970

By M. King Hubbert

THE growth of human knowledge is an evolutionary process. His-torically our separate sciences came into existence as people became interested in various apparently unrelated domains of phenomena, and in this manner we acquired the sciences of physics, chemistry, astronomy, biology and geology. As various of these sciences became established, cognizance of them came to be taken by the universities and in this manner there arose the traditional departments of physics, astronomy, chemistry, biology and geology of our American universities. As there was no particular rationality in the boundaries separating the various sciences, in the university departments the jurisdiction of each has assumed quite arbitrary limits. In the domain of earth phenomena the first science to grow up was that of geology, which arose originally from the activities of the collectors of rocks, minerals and fossils. Thus geology evolved as a descriptive science dealing with directly observable terrestrial phenomena for which elementary rational explanations were offered. The traditional treat-ment of phenomena by the science of geology has rarely been with more than an elementary regard for the fact that these phenomena were also phenomena of physics and chemistry. Since the latter part of the nineteenth century, a new approach to terrestrial phenomena has been emerging and becoming of so great a significance that it can no longer be ignored. This approach has been made by people trained primarily in the sciences of physics and chemistry, who have investigated terrestrial phenomena as constituting phenomena of, their respective sciences. In this manner we have acquired the so-called "borderland sciences" of geophysics, the physics of the earth, and of geochemistry, the chemistry of the earth. Neither of these fields is new, having arisen chiefly at the hands of European investigators during the latter part of the nineteenth century. The European uni-versities have long since given official recognition at least to geophysics, by the establishment of departments or institutes of geophysics, which are on a par with ,the university departments of the other sciences.

Jan 1, 1938

By R. A. Generes, H. C. H. Darley

Laboratory tests showed that at elevated temperatures a reaction takes place between all metal hydroxides and clay muds, which results in a thickening or solidifying of the mud, the extent of which depends on the nature of the ingredients. Calcium hydroxide gave the strongest solidification whereas barium hydroxide only caused a mild thickening, indicating that the use of barium hydroxide muds instead of lime muds would be a good way of preventing high-temperature solidification. It was found possible to prepare barium mud in the laboratory with caustic soda and a thinner in the same manner as lime muds, and these barium muds had the same or better toleration of high solids content, resistance to salt contamination, and low gel strengths as the corresponding lime muds. Three field trials have been made with barium mud. The principal difficulty encountered was in determining the correct proportions of the tourly treatments required to maintain low gel strengths. A satisfactory systern was finally developed, and low gels were maintained throughout the third test. The wells on which the trials were made were not carried deep enough to test the resistance to solidification adequately, but oven tests at 350°F were made periodically and no tendency to solidification was noted except immediately after severe cernent contamination had introduced excessive amounts of calcium into the system. Although barium hydroxide costs considerably more than lime, the total mud costs were as low, and on the last well significantly lower, than the average cost of lime mud wells drilled in the vicinity. INTRODUCTION The advantages of repressing dispersion and hydra-tion of clay cuttings carried in the mud, particularly when drilling through thick clay formations, are well recognized. This repression is generally achieved by the use of lime, and lime muds have in consequence the desirable characteristics of high toleration of solids, low thixotropy, and good resistance to contamination. They have, however, the disadvantage of high-temperature solidification. This phenomenon has been described in detail by Gray et al, who have shown that it is the result of a chemical reaction between the hydroxides and the clay minerals. The work described in this paper was undertaken to find a substitute for lime which would not cause this solidification. LABORATORY EXPERlMENTS The principal positive requirement for a substitute for lime is that it should repress the hydration and dispersion of clay. It is well known that monovalent cations promote hydration while polyvalent cations repress it. Therefore, a few representative polyvalent salts and hydroxides were tested to determine whether they could be used as substitutes for lime. Their efficiency at repressing hydration and dispersion was measured by means of the clay-volume test. It has been shown elsewhere&apos; that this test is a good measure of degree of dispersion of clay in suspension and that hydration accompanies and correlates with dispersion, so that measuring one measures the other. The test is made by centrifuging a 1:100 mixture of mud and 1-N NaCl and observing the volume of sediment—the greater the volume, the greater the dispersion. The tendency to caux solidification was measured by heating the muds in pressure vessels for 16 hours at 150°F and 370°F. An approximate quantitative

Jan 1, 1957

By R. G. Patterson

The usual procedure in determining the magnetic susceptibilities of rocks and formations has been to take samples in the field and measure their volume susceptibilities in the laboratory, using one of numerous methods available. In none of these methods is the measuring instrument suited for field use. Usually the sample is pulverized; sometimes it is machined to a desired sue and shape, and in one method1 a cast of the sample is made and the susceptibility of the rock compared with that of a material of known susceptibility of the same size and shape, made from the cast of the original sample. Some writers assert that the difference in susceptibility of a rock sample in powdered and solid forms is negligible, and while doubtless this is true in many cases there are others in which the difference becomes appreciable. Further, the susceptibility of a small specimen may differ from that of the rock from which it is taken, owing to the stresses produced by the hammering or other forces used to obtain the sample and shape it for testing. Wilson2 found that an individual specimen of granite had about the same susceptibility in the solid as in the powdered form, but that pieces from different parts of the rock varied as much as 750 per cent because of unequal distribution of magnetite. The most accurate value of susceptibility would, obviously, be obtained from averag- ing a number of tests on the undisturbed rock instead of from one or two samples. No such procedures have been published, to the writer&apos;s knowledge. It is the purpose of this paper to describe a method by which susceptibilities of rocks may be determined in place by means of a portable instrument. Method The principle involved in this new method is that there is a change in inductance of a coil due to the presence in its magnetic field of a paramagnetic or dia-magnetic medium. In this case, however, the windings of the coil do not enclose any part of the rock under test. Instead, the coil is circular, being small in cross section as compared to its radius, and consists of several hundred turns of fine wire. It is placed flat on the rock of which the susceptibility is to be measured. Thus only part of the magnetic field from the coil penetrates the rock under test. The relation between the change in field strength or inductance of the coil and the susceptibility of the medium will be developed later. To measure the change in the inductance of the coil due to the presence of a magnetic material an alternating-current inductance bridge was chosen. Description of Apparatus Of many alternating-current bridge methods applicable,3 the one shown in Fig. 1 (Owen&apos;s bridge&apos;) was adopted for its simplicity and sensitivity. In Fig. I, the test coil is indicated by PlL1. It is connected to the bridge by about

Jan 1, 1946

By Whitman E. Brown, Louis J. Erck

L. A. ROE*—This paper is one of great value to the iron ore industry. The Humphreys spiral is a relatively new tool and gives promise of being quite useful in solving certain problems of iron ore beneficiation. Spirals have been tested on a martite ore at the Benson mine of Jones and Laughlin Steel Corp. in northern New York State. Our New York ore is considerably different, physically and mineralogically, than the one mentioned in this paper, and contains only 25 pct iron. This ore can be processed on spirals to give a concentrate containing 62 pct iron with an 85 pct recovery. On our particular ore we found operating difficulties when the spiral feed was coarser than 14 mesh. These were chiefly due to excessive "build-up" of locked middlings in the spiral circuit. In extreme cases these middling particles would accumulate to such an extent that the plant had to be shut down and the spiral surge tanks cleaned out. It is interesting to note that there exists a close relationship between the results of tabling a given iron ore and concentration of this same ore on Humphreys spirals. The size range of the ore must, of course, be within those limits acceptable to spiral concentration. Comparative tests on several of our mar-tite ores showed tabling results to be the same as spiral results. The authors make no mention of the use of a tailing stream splitter (now available from the spiral manufacturer) which is a useful tool in studying iron losses in the tailings stream. 011 our particular martite ore we found a considerable accumulation of fine-sized iron ore particles in the outside portion of the tailings stream. This fraction may be amenable to further treatment. E. H. ROSE*—The authors have concluded an interesting piece of work and this paper is an excellent factual account of a rapid and somewhat unusual transi-;ion in practice in the plant described. Perhaps it was modesty on their part which caused them so casually to limit to one sentence the fact that "several other methods of concentration on the fine ores representative of the Hill Trumbull group . . . failed to produce consistently an acceptable grade and recovery of finished product." The fact is that they were confronted by a difficult mineral-dressing problem and they are to be congratulated on their courage and persistence in staying with it until a satisfactory solution was evolved. A visitor to the plant might have been mildly astonished, as I was, to see one type of concentrator handling that part of the load early in the 1947 season, its experimental replacement by another a little later, and then in 1948 to see that both types had simply disappeared and their place taken by the spirals which were operating as placidly as though they had been there all the time. In working out economic methods of beneficiating Alabama red ore, most of which development is still ahead of us, it is likely that we also will pass through a period of successive disappointments, for we too have a problem where it is next to impossible either to "guess &apos;end right in the first place," or, because full-scale operating cost is such an important factor, to lay the ultimate answer on the line in advance by means of laboratory experimentation. Iron ore being what it is instead of what it used to be, it is encouraging to have the example the authors have given us today that a tough nut that will not crack on the first blow or the second is apt to do so on the third or fourth.

Jan 1, 1950

By A. G. Lyle, J. D. Runkle, G. A. Gillies

THE evaluation of data obtained by selective flotation from even a simple ore is a very difficult process, and when the ore tested is complex the process becomes extremely difficult and cumbersome. The authors, in the course of an investigation into the selective behavior of various flotation reagents on nonmetallic minerals§ were confronted with an aggravated form of this difficulty, owing to the large mass of data that had accumulated over a period of years. They finally devised a method whereby the results of the various flotation tests could be correlated and interpreted by means of graphs representing recoveries and rejections of the component minerals in the ore. This method of graphical analysis proved so useful in nonmetallic flotation that it was afterwards applied to sulphide flotation, where it yielded equally satisfactory results. Since this method of analysis leads to very definite conclusions as to the effect of changes in reagents and flotation procedure, it is felt that a wider application of the method might assist the industry by reducing the amount of test work required, and possibly increase the accuracy of the final analysis. GRAPHS In Fig. I, four curves are plotted on the same graph with cumulative percentages as ordinates and cumulative weights as abscissas. In this instance the four curves are named, respectively: the barite-recovery curve, the limestone-rejection curve, the silica-rejection curve, and the summation curve. In these tests barite was the mineral concentrated, therefore a barite concentrate was produced. Definitions Before explaining the curves in detail it might be advisable to define several new terms, such as "percentage rejection," "summation index," and "summation curve," as well as the word "test," which has been used in a special sense. A "test" will include all the operations performed upon a batch of ore from the time it is placed in the rod mill until the last product has been assayed. Thus a test may be a comparatively simple procedure producing only one concentrate and a tailing, or it may be a very complicated procedure producing five or more concentrates of a specific mineral as well as a tailing. The number of concentrates produced will depend entirely upon whether the collector was added to the pulp in the flotation cell in one lot or was added in five or more portions. Percentage Rejection.-The ability of a selective flotation collector to reject an undesired mineral is just as important as its ability to collect the desired mineral. The percentage rejection curves shown on the graphs give this factor due consideration and its value is calculated as follows: Suppose a concentrate contains 5 per cent of an undesired mineral. This indicates

Jan 1, 1942

By Albert R. Ledoux

I AM indebted to The Kaolin Co. of West Cornwall, Conn., and particularly to its engineer, Mr. M. Wanner, for permission to make public, through the Transactions of the American Institute of Mining Engineers, the interesting results of his experiments, having in view the winning of kaolin from deep deposits without shaft-sinking or removing of the overburden. So far as I am aware, nothing like it has been accomplished heretofore, although it reminds one of the methods successfully employed in Louisiana for the winning of sulphur from deep beds by the sinking of pipes one within another, injecting superheated steam under pressure through one pipe, the heat of the steam liquefying the sulphur and the pressure forcing it up through the other pipe to bins at the surface. The kaolin-deposit at Nest Cornwall is an alteration in situ-that is, it is not sedimentary. A series of clay-veins dipping about 500 from the vertical, lie between a foot-wall of limonite and a hanging-wall of gneiss and hornblende schist. The clay-veins alternate with veins or seams of more or less broken quartz, and unaltered feldspar. The deposit, which occurs at a point about 600 ft. above the Housatonic river, was opened five years ago, and about 5,000 tons of a superior grade of washed kaolin has been extracted from open pits and sold. It soon became evident that this node of extracting the product would prove unremunerative, by reason of the dip of the vein and the intercalary strata and lenses of -quartz, and a more satisfactory method of working the deposit was sought. It is well understood, that, in the preparation of all clays for market, especially residuary kaolin, the most important as well as the most difficult step is the washing of the crude product. The difficulties increase with the percentage of foreign matter, especially quartz and mica, contained in the product, hence a sys-

May 1, 1906