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By P. S. Rudman

Laves phases, AB2, are considered as Izerrzisub-stitutional solutions m1hich are defined by a one-for-truo replacement scheme. Atomic-size tnisfit is considered in terms of deviations of the ratio 2V°b/V°A from unity, where v° = atomic volume. A simple elastic model has been used to calculated deviations from "Vegard&apos;s law of atomic vol-umes". Comparison has been made between calculated and observed atomic-volume deviations fov 222 Laves phases. Agreement is generally very good although there ave some few exceptions which appear to be excusable in terms of electronic changes that ore beyond the scope of the present model. We can consider the formation of a binary sub-stitutional solution A-B from an A solvent as one-for-one replacements of A atoms by B atoms. As the atomic-size ratio deviates from unity, the solution becomes thermodynamically less stable and hence more restricted because of atomic-misfit strain energy. In accordance with our previously presented conclusion1 that the atomic volume, v, is in general the most appropriate measure of atomic size, the ideal size ratio for a binary sub-stitutional solution is vg/vA = 1. The Laves phases have been described by Berry and Raynor2 in terms of various stacking sequences of hexagonal layers of B atoms for the three structures MgZn2(C14), MgCu2(C15), and MgNi2(C36). To form the Laves phase of ideal composition AB, we start with complete hexagonal layers of B atoms in the appropriate stacking sequence and we remove, according to an appropriate scheme for each structure, two out of every four B atoms and replace the two removed atoms by one A atom. We thus might expect to find that the ideal size ratio for the Laves phases is 2v/B/ VA= 1. From this point of view, then, we call Laves phases hemi-substitutional solutions since we employ one-for-two replacements. By analogy with substitutional solutions we can expect for Laves phases that as the ratio 2VB/Va deviates from unity the phase occurrence will be more restricted. Laves3 has plotted the distribution of Laves phases as a function of the radius ratio, ?A/rB, and found that, while the distribution extended from 1.05 < rA/B < 1.50, the

Jan 1, 1965

By David Reger

LITTLE new oil was found in West Virginia, during 1923, but there were important discoveries of gas. Most of the large oil producers have contented themselves with pumping old wells or in drilling only enough new wells in defined territory to maintain a fairly constant production, the attitude being that no, profit is made in producing high-grade oil at a low price and that an eventual loss is sustained by draining the reserves of a limited commodity that, at some more favorable time, will be of much value. The representative of one large company said: "We have done nothing but pump old wells during 1923 and we have made no plans for 1924." Careful attention to producing wells has been the rule, there having been few abandonments; the belief is prevalent that small wells will eventually become profitable under more favorable marketing conditions. In natural gas, the opposite point of view prevails. Because of the vast capabilities of the state for producing gas, its output being ahead of all others, great systems of transportation and distribution into the markets of four adjoining states have been built and a demand has been created that no present, or apparently potential, production can satisfy. This demand has become so great that large distributing companies not only discourage new applications for service but advise old customers to install coal furnaces for auxiliary fuel; some have requested public-service commissions to grant higher &apos;rates against large industrial consumers than those allowed for domestic heating. The response to this known market has been a rapid increase in price, both at the well mouth and at the door of the ultimate consumer, and the industry has become so stable that the only uncertainty, or hazard, appears to be the question of the presence of gas in fair quantity in a given territory under consideration. Several oil companies have now forsaken their policy of selling gas, wells outright when drilled and ;have organized gas departments to drill for gas and to dispose of the daily output by meter to distributing corporations. With such companies and with other producers whose interest is chiefly gas, the year has been busy and profitable. Some new territory of apparently large value has been proved and deeper producing sands in old fields have been tapped.

Jan 3, 1924

By T. L. Joseph

Sulfur balances calculated from operating data covering thirty-five blast furnaces indicate that approximately 92 per cent. of the total sulfur charged enters with the coke, 7 per cent. with the ore, and 1 per cent. with the stone.. Most of the sulfur is carried from the furnace by means of the slag, the total amount eliminated being the product of the slag volume and the percentage of sulfur it contains. Additional sulfur in the charge must be eliminated either by increasing the percentage of sulfur in the slag or the quantity of slag. From relations found between slag volume and coke consumption and sulfur in the coke and slag volume, curves have been prepared showing the relative value of blast-furnace coke as its sulfur varies from 1 per cent. CHARCOAL was the predominant blast-furnace fuel until 1838, when it was found, by the operation of a 2-ton experimental furnace, that anthracite could also be used. This information was a stimulus to the iron industry, particularly in eastern Pennsylvania where anthracite was available at low cost. The production of anthracite pig iron increased steadily and, in 1855, its tonnage exceeded that of charcoal iron. Of the 680 furnaces in operation in 1874, the 226 using anthracite produced nearly one-half the total tonnage. In 1869, the production of coke furnaces exceeded that of charcoal furnaces and, in 1875, coke surpassed anthracite as a metallurgical fuel. In 1907, the output of anthracite pig dropped well below a million tons and its present significance is largely historical. In recent years, the production of coke has gone hand in hand with the production of pig iron and it has gradually attained the position it now occupies as a universal blast-furnace fuel. Charcoal, however, has great merit as a blast-furnace fuel chiefly because of its freedom from ash and sulfur. The harmful effect of the latter and the necessity of keeping the percentage of this element in pig iron at a minimum are well recognized. Other contaminating elements can be reduced to specified limits in the steelmaking process, but the control of sulfur belongs essentially to the blast furnace. The purpose of this paper is to point out the distribution of this impurity in blast-furnace

Jan 9, 1924

By Robert L. Dean, Michael Hoch, Samuel M. Wolosin, Chung K. Hwu

The general shape of the 1450°C isotherm of the Ti-TiO-ZrO2-Zr region was evaluated from the surrounding binary phase diagrams and from thermo-dynamic data on the metal-oxygen binaries. The phase boundaries were accurately determined using X-ray and metallographic techniques. At 1450°C the system shows a large bcc ß field, which extends from the two metal-oxygen binary systems as a Gaussian error function, and is stable up to 30 at. pct 0 when Ti and Zr are present in equal amounts. At higher O Concentrations, the ß field is in equilibrium with t-ZrO . The following four regions, with three solid phases, are present: two a ß t-ZrO,, a TW t-ZrO,, and TiO t-ZrO2 c-ZrO2. On cooling the ß phase transforms into the a phase, going through the w transition phase. The isotherm at 1500°C for the region TiO-TiO,-ZrO, was obtained by using X-ray diffraction. At 1500°C a large c-ZrOz region is present as well as a large two-phase field, Ti0 c-ZrO,. The following regions, with three solid phases in equilibrium, were found These regions are relatively small. The solidus and liquidus relationships were determined by observing samples suspended in a tungsten crucible by means of a fine tungsten wire and heated in vacuum. Eleven univariant points were found. C-ZrO, decomposes through a peritectic reaction into liquid t-ZrO2. The activities of Ti and TiO in the TiO t-ZrOz and in the two a ß t-ZrO regions were measured using the Knudsen effusion method. In the a TiO t-ZrO, region the activities of Ti and Ti are the same, as in the a — Ti TiO binary. In the two a t-ZrO, regions, the Ti activity is high and the Ti0 activity very low, although all phases present contain at least 30 at. pct 0. This indicates a short-range order in the solid phases, Zr atoms being preferentially surrounded by 0. 1 HE system Ti-Zr-0 is of interest because of the wide ranges of solid solubility exhibited by the boundary systems; as titanium and zirconium both belong to the same group of the periodic table, large single-phase regions should occur within the system, with a great variation of properties (as the composition changes within the single-phase region). Furthermore, the possibility of modifying ZrO, to make it a more usable refractory by the addition of other metals makes this system also of interest. Because of the high affinity of titanium and zirconium for oxygen, the oxygen partial pressure is very low at all compositions; thus, there exists a ternary metal-metal-oxygen system in which the oxygen pressure is not an important variable, so long as it is low enough. When a sample is heated in vacuum to a temperature high enough for vaporization to occur, the vapor phase will consist of metal and metal-oxide gas, the oxygen concentration being very low. The phase relationships in the surrounding binary systems have already been reported in the literature; therefore, the study of the ternary diagram

Jan 1, 1962

By Roland de Wit

Conclusions reached in a paper by weertmanl are amplified in a mathematical and graphical way. It is shown that in a stressed crystal a straight dis-location may be in a position of unstable equilibrium with respect to helix development, and how a small perturbation may start the dislocation off on its helical path. Helix development occurs by diffision; bulk diffusion is necessary for development from a screw, but core diffision is sufficient for development from an edge dislocation. For a mixed dislocation helix development can take place by core diffusion if the helix also climbs; a diffusion reversal takes place when the slope of the helix equals the slope of the Burgers vector. The work done on a crystal by the external forces is graphically shown to be consistent with the direction of motion of the dislocation in helix development. Finally a detailed mechanism for tangle formation from helices is presented. In the course of helix development a glide situation may be reached where a segment of each helix loop lies in a slip plane in which it can expand by glide. Thus is it visualized how a helix can deteriorate into a tangle. A paper by weertmanl proposes dislocation-tangle formation by a helical dislocation mechanism. The present paper amplifies Weertman&apos;s arguments in a mathematical and graphical way and presents some further ramifications of the proposed model. The importance of dislocation tangles is discussed in Weertman&apos;s paper and the references cited therein. The mechanism of their formation is not yet understood. Weertman proposes that in cold-worked crystals conditions exist suitable for the conversion of straight dislocations into helices and subsequently into tangles. Helix formation occurs by a diffusion process and Weertman proposes that at low temperatures only core diffusion is important. The present paper necessarily repeats some of Weertman&apos;s work. Since the mathematical development and notation used are slightly different from his, this was thought necessary for clarity. GEOMETRY OF THE HELIX weertman2 has shown that the equilibrium form of any dislocation line is a helix if it is assumed that the energy per unit length (line tension) of the dis- location is constant. For the special case that no external forces act on the dislocation, the helix reduces to a straight line. We shall assume in this paper that the dislocation has a helical form even when it is not in equilibrium. The parametric equation of a helix is, see Fig. l: where a is the radius of the cylinder tangent to the helix, and 270 the pitch of the helix. The pitch is related to v, the number of turns per unit length (along the axis) by the relation: When a = 0 Eq. [I] gives a straight line in the z direction. The growth of a straight dislocation into a helix is now described mathematically by letting a vary from zero to its final value. The tangent to the helix is given by where is the path length along the helix. This gives the direction of t and since its magnitude is unity we must have So that dcp/ds = (a2 +p2)-"&apos;. The curvature of the helix is given by where n = -(cos + sin) is a unit vector normal to the helix. Note that the vectors k and n always point toward the axis of the helix, Fig. 1. FORCE ON THE HELIX The external force which makes the straight dis-

Jan 1, 1963

By Raymond L. Orr

Calorimetric measurements have been made of the heats of solution of gold axd indium in a number of liquid tin-rich alloys at a temperature of 705°K. Relative partial molar enthalpies of gold were determined as a function of dilute solute concentrations in the binary Au-Sn system and in the ternary Ag-Au-Sn and Au-In-Sn systems. Relative partial molar enthalpies of indium were determined for dilute solute concentrations in the In-Sn, Ag-In-Sn, and Au-In-Sn systems. Through application of the interaction coefficient concept introduced by Wagner and more recently extended by Lupis and Elliott, ualues have been obtained for the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. The results are inte@reted in terms of solute atom distributions through comparisons with the predictions of dilute solution models. INTEREST in the thermodynamic behavior of dilute liquid alloys stems from two primary sources. From a practical viewpoint, it is often of importance to know or to be able to predict the effect that one solute will have on the thermodynamic properties of the other solutes in a multicomponent system. Studies of dilute solutions may also be rewarding from the theoretical point of view. Some of the difficulties arising from the more complex interactions possible in concentrated solutions are avoided, leading to easier interpretations in terms of solutibn models and bonding energies. For example, in a binary alloy the limiting values of the partial molar properties of the solute represent the case for which each solute atom is completely surrounded by atoms of the solvent, and no other interactions are possible. Solute - solute interactions in dilute solutions are conveniently treated by the interaction coefficient concept of ~agner.&apos; Using a Taylor series expansion for the logarithm of the activity coefficient, In yi, of a component, i, in a solution consisting of dilute solutes with atomic fractions xi, xj, xk, and so forth, in a solvent, s, and neglecting the second- and higher-order terms, Wagner obtained the expression: Where Wheyz is the limiting value of yi in the pure solvent, s. The interaction coefficients, e:, e:, and so forth, are defined by: Since yi is related to the excess partial molar Gibbs energy of component i by GfS = RT In yi, E: is re- ferred to as the "Gibbs energy interaction coefficient". Lupis and Elliott~ extended Wagner&apos;s treatment to the relative partial molar enthalpy, aHi, and the excess partial molar entropy, qS. They defined the enthalpy interaction coefficient as: and the excess entropy interaction coefficient as: leading to expressions similar to Eq. [I]: The three interaction coefficients are related by? The self-interaction coefficients, E:,qf,and at, represent the effects of interactions between atoms of component i in solvent s; €3, q{, and 03 represent the effects of interactions between i and j atoms in solvent s; and so forth. From the Maxwell-type relationships between partial molar quantities, it may be shown1&apos;2 that e{ = ej, r}\ =tj), and ai - crj. Experimental determination of the interaction coefficients requires extremely precise measurements of the appropriate properties as functions of solute concentrations in very dilute regions. Few such data exist for intermetallic alloys, even for binary systems, because of experimental difficulties. This is especially true with respect to enthalpy data for dilute alloys. Examination of the compilation of data for binary alloys by Hultgren, Orr, Anderson, and ~elle~~ reveals that determination of limiting values of &fii(Xi =0) often requires extrapolations to infinite dilution from xi = 0.05 to 0.10. Direct measurements of the enthalpy interaction coefficient, qi, for multicomponent systems are virtually nonexistent. This quantity is of course subject to direct calorimetric measurement, but its determination must be limited to cases where high experimental precision is possible. The heats of solution of gold and indium in liquid tin can be measured with relatively high precision, which makes determinations of 73 involving these metals as the measured solutes experimentally attractive. This paper presents the results of such determinations of the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. MODELS FOR DILUTE-SOLUTION BEHAVIOR Random-Solution Behavior. In the quasi-chemical treatment of solutions, only nearest-neighbor bonds are considered, and a composition independent value

Jan 1, 1967

By Bruce W. Gonser, Robert I. Jaffee

Recent work by the authors1 established the constitutional diagram of the gold-germanium system. Of particular interest in the simple euctectiferous system was the eutectic alloy at 12 per cent Ge, which melted at the very low temperature of 356°C and had an unusually fine eutectic structure. It was of interest to investigate the effect of third components on the melting point, microstructure, and strength of this alloy, and in this work the effect of copper is discussed rather completely, with less complete data on the effects of silver, platinum, nickel, and zinc. No reference in the literature has been found on ternary systems with gold-germanium. Materials and Alloying -4s in the work on the binary system, gold-germanium, the germanium used in this investigation was the cyanide-reduced, 99.9 per cent product, produced by the Eagle-Picher Co. Fine gold sheet from Handy and Harmon, pure platinum sheet from the American Platinum Works, copper magnet wire from Anaconda, nickel wire assaying 99.6 per cent Ni. and electrolytic zinc were used for alloying. To make the alloys, charges of the pure metals were put in a graphite crucible and melted in an atmosphere of pure hydrogen. The temperature was brought up to about I050 C, and the metal allowed to freeze in the crucible. Except with alloys containing zinc, melting losses were consistently less than a few milligrams. When zinc was a component, weight losses up to half the weight of the zinc present were incurred, and the alloy compositions were calculated by assuming the entire weight loss to be that of zinc. In all other cases the composition of the alloys could safely be taken as that of the charge. The ingots, as solidified, were segregated, the heavier primary phases being at the bottom and sides of the ingots and the lighter primary phases at the top, but by sectioning the entire ingot vertically for microscopic examination, this factor could be evaluated. Ingots for microscopic examination weighed one gram, and those for thermal analysis weighed three grams. Thermal Analysis In this work, the eutectic line composition and thermal arrests were desired, and, after microscopic exploration had established the position of the eutectic line at a given percentage of the third component, a thermal analysis was run at that composition. The method of thermal analysis used in the work on the binary Au-Ge system,&apos; a method particularly well suited for a small quantity of material, was used in this work. Clearly defined arrests were obtained, although with some alloys containing platinum

Jan 1, 1946

By Robert I. Jaffee, Bruce W. Gonser

Recent work by the authors1 established the constitutional diagram of the gold-germanium system. Of particular interest in the simple euctectiferous system was the eutectic alloy at 12 per cent Ge, which melted at the very low temperature of 356°C and had an unusually fine eutectic structure. It was of interest to investigate the effect of third components on the melting point, microstructure, and strength of this alloy, and in this work the effect of copper is discussed rather completely, with less complete data on the effects of silver, platinum, nickel, and zinc. No reference in the literature has been found on ternary systems with gold-germanium. Materials and Alloying -4s in the work on the binary system, gold-germanium, the germanium used in this investigation was the cyanide-reduced, 99.9 per cent product, produced by the Eagle-Picher Co. Fine gold sheet from Handy and Harmon, pure platinum sheet from the American Platinum Works, copper magnet wire from Anaconda, nickel wire assaying 99.6 per cent Ni. and electrolytic zinc were used for alloying. To make the alloys, charges of the pure metals were put in a graphite crucible and melted in an atmosphere of pure hydrogen. The temperature was brought up to about I050 C, and the metal allowed to freeze in the crucible. Except with alloys containing zinc, melting losses were consistently less than a few milligrams. When zinc was a component, weight losses up to half the weight of the zinc present were incurred, and the alloy compositions were calculated by assuming the entire weight loss to be that of zinc. In all other cases the composition of the alloys could safely be taken as that of the charge. The ingots, as solidified, were segregated, the heavier primary phases being at the bottom and sides of the ingots and the lighter primary phases at the top, but by sectioning the entire ingot vertically for microscopic examination, this factor could be evaluated. Ingots for microscopic examination weighed one gram, and those for thermal analysis weighed three grams. Thermal Analysis In this work, the eutectic line composition and thermal arrests were desired, and, after microscopic exploration had established the position of the eutectic line at a given percentage of the third component, a thermal analysis was run at that composition. The method of thermal analysis used in the work on the binary Au-Ge system,&apos; a method particularly well suited for a small quantity of material, was used in this work. Clearly defined arrests were obtained, although with some alloys containing platinum

Jan 1, 1946

By M. Metzger, T. A. Read

The strengthening effects of hydroxide and synthetic plastic films in the creep of cadmium crystals were studied. The results were broadly consistent with the naive mechanical model. The dislocation-film reactions and the significance of the macroscopic stresses associated with certain films are discussed in the paper. ALTHOUGH a number of studies have been made of the strengthening of metal single crystals produced by surface films usually less than Ir in thickness, the mechanisms underlying this phenomenon are still not well established. Roscoe&apos; first noted the critical shear stress and the stress-strain curve of cadmium-crystal wires to be raised markedly by the presence of oxide films. Subsequent investigators2-&apos; have confirmed the effect for several metals and films including a number of plated poly-crystalline metal films. Harper and Cottrel1" with a thin film on zinc presumed to have formed as a result of etching and washing treatments) did not detect a strengthening at a rate of extension of 10 &apos; sec-&apos; although at lo-&apos; sec-&apos; the film raised the flow stress by 7 pct at 0.0005 extension and by 22 pct at 0.01. The marked strengthening at moderate strains thus appeared to be the result of a dynamical effect dependent on the rate and amount of plastic flow. Other observations&apos;. " are consistent with this view. The large effects of films on the tensile creep rate of single crystals were demonstrated when the observation of Andrade and Randall," that the creep rate of cadmium crystals increased on immersion in aaueous solutions of certain cadmium salts. was shown&apos; * to hold only when a film was present initially and was explained by the attack of the solution on the film and the removal of its strengthening effect. Changes in the creep rate interpretable in terms of the removal or formation of various films have been observed by other investigators.3,8,10,31 Certain other experiments have been reported in which surface films or liquid environments have affected the plastic behavior of metals, but these are not within the scope of the present work which deals with the effect of solid films on single-crystal slip. Possible Mechanisms—The film does not significantly reduce the load on the crystal in the elastic range (the elastic moduli of film and crystal are not too greatly different and the area of the film is so small that its share of the load is negligible) so that the initial operation of internal Frank-Read sources is not affected. However, as Fisher" has pointed out, a source terminating on the crystal surface requires only half the critical stress for activation as an internal source of the same length and a relatively strong film (even a very thin one) would pin the free ends of the surface sources so that, if surface sources are responsible for plastic flow in a clean crystal. such a film would increase by roughly a factor of 2 the stress necessary for generation of dislocation loops at a given rate. The other general possibility is that the film resists the passage to the crystal surface of internally generated dislocations. If the film is adherent and if the specimen is to exhibit slip of the same general character as a film-free specimen, the film must deform or fail in shear at the active slip planes. The naive mechanical model, where shear-stress relaxation across the active slip plane in the metal transfers load to the film until it deforms and slip can

Jan 1, 1959

By Attilio Ligasacchi

The production of magnetite in copper smelting has been the subject of wide investigation in the past.1-9 It is accepted that most of the magnetite is produced in the converters and returned to the re-verberatory furnace with the converter slag. Part of this magnetite is circulated back to the converters in the matte. As a result, if proper fluxing practice is not followed, and temperatures in the converting process are not strictly controlled, an undesirable circulating load of magnetite may occur. This might ultimately lead to saturation in the reverberatory bath with consequent settling of the magnetite at the furnace bottom. This paper contains the cumulative results of a series of investigations on the formation and control of magnetite presently being conducted by the metallurgical department of the Chino Mines Division of Kennecott Copper Corp. THE METHOD USED FOR THE DETERMINATION OF MAGNETITE AND OTHER MAGNETIC MATERIALS Conventional wet chemical magnetite analyses are neither reproducible nor theoretically sound. These analyses are sensitive to time, temperature, and heating rate-all factors which tend to decrease their accuracy and reproducibility. To overcome the unreliability of the above method, H. W. Mossman1 developed an inductance bridge magnetite "meter" which completely replaces the wet chemical analysis with the advantage of quicker and reproducible results. Fig. 1 is a schematic diagram of the meter in use in the Chino metallurgical laboratory. When a pulverized specimen with magnetic properties is placed in coil A of the inductance bridge circuit, the permeability of the core is increased, causing a voltage drop across the coil. The unbalance is amplified to operate the balancing motor which adjusts the movable iron core in coils C and D to bring the bridge back to balance. An indicator arm connected to the movable iron core indicates directly the percent, or weight, of the magnetic material in the specimen. Coil B acts as a reference coil and a zero adjustment. The meter is standardized with a set of various amounts of -100 mesh pure magnetite crystals (99.8 pet Fe3O4) thoroughly mixed in a test tube with -100 mesh quartz sand. These mixtures are combined with inert transoptic powder and heated to 140° to 160°C (melting point of the powder) and subsequently cooled to room temperature, solidifying the whole mixture, in this manner eliminating any possible preferential orientation of the magnetite grains. In order to determine the effect of the particle size" of the magnetite and other magnetic materials on the meter determinations, five size fractions were obtained by wet screening of the 99.8 pet pure magnetite and several reverberatory matte and slag samples. The following size fractions were investigated: -80 + 100; -100 + 150; -150 + 180; -200 + 250; -250 + 300 and -100 mesh. The deviation of the meter readings for the various sizes of each sample never exceeded ±0.3 pet. This deviation is considered well within the accuracy needed for common smelter operation procedures. Further investigation proved also that grinding slag and matte samples in our laboratory disc grinder normally produced a powder constituted of 95 pet -200 + 300 mesh. For practical purposes a - 100 mesh size was used as standard for our studies. It was also found that for rapid determinations tamping of the sample in the test tube was sufficient and gave comparable results with those samples solidified with transoptic powder. For the purpose of this study we define the magnetite content in copper smelter slags and matte as the equilibrium amount of crystalline Fe3O4 existent in the specimen at a given reference temperature, excluding any secondary magnetite precipitated in the specimen during nonequilibrium conditions. MAGNETITE DETERMINATION IN SLAGS Since it is impossible to ascertain the status of equilibrium of a conventional slag sample, due to

Jan 1, 1965

By Ulf S. Landergren

Diffusion coefficients and marker movements have been determined in brass using welded couples. Three different concentration ranges were employed at 750°C, while a fourth concentration range was measured at 500°, 600°, 700°, and 800°C. Marker displacements toward and porosity development in the high zinc side of the couple were observed in all cases. The results were interpreted as favoring a vacancy diffusion mechanism. IN the large amount of diffusion literature which has accumulated during the past half century, very few experimental data have been presented on body-centered-cubic metallic phases. The impressive combination of experimental and theoretical studies which has given the vacancy mechanism a fairly secure position as the preferred mechanism for most face-centered-cubic metals has no counterpart for body-centered-cubic phases, although the theoretical picture seems to be in a better state than the experimental work. The attempts to select diffusion mechanisms by the theoretical calculation of the activation energy for the various conceivable unit diffusion processes and the energy of formation of the type of lattice defect required have been based on models of two kinds. The first kind utilizes potential functions fitted for certain properties of pure crystalline copper; the second kind is fitted for sodium. The latter is an example of an open metal in which the metallic ion is small compared with interatomic distance,&apos; while the former is characteristic of the larger class of metals in which the ions have diameters about as large as the interatomic distance. brass should resemble copper in this fundamental property. It should be evident that results on the mechanism of diffusion obtained for one of these classes need not necessarily apply to the other. Huntington and Seitz, using a model of the copper type, showed that the activation energies to be expected for interstitial migration or a two-atom direct interchange were much higher than that for vacancy diffusion. Zener pointed out that a four-atom ring rotation would involve an activation energy considerably lower than the two unlikely mechanisms although still higher than the vacancy mechanism in the face-centered-cubic structure. Furthermore, he argued, the four-atom rotation would be relatively easier in a body-centered-cubic lattice and might be competitive with the vacancy mechanism. Paneth showed that a body-centered-cubic crystal-like sodium could form interstitial defects of special type, called a crowdion, by crowding an extra atom into < 111 > directions where the defects would affect a line of about eight atoms. The defect was constrained to move along the defining line. Unlike the face-centered-cubic case, therefore, the theoretical calculations for the body-centered-cubic mechanism do not provide a very clear-cut answer, and the absence of adequate experimental studies is the more serious. This investigation was undertaken for the purpose of obtaining useful information on diffusion in body-centered-cubic phases. brass was chosen for several reasons: 1—the phase field is sufficiently wide at high temperatures to permit the use of diffusion couples with adequate concentration ranges for satisfactory chemical analysis, 2-—thermodynamic activity data are available for the calculation of mobilities from diffusion coefficients, 3—the phase is as close to the theoretical model of the copper -type on which the calculations have been done as any body-centered-cubic metallic phase is likely to be. Measurements of the movements (if found) of inert markers during the diffusion process would indicate that a vacancy or Or mechanism played a major role in diffusion in brass. If no marker movement should be found, a ring mechanism would be indicated but not assured. Experimental Procedure The alloys used in these experiments, listed in Table I with analyses, were supplied by the Naval Research Laboratory. They were from ingots of 3x3 in. cross-section, heated to 760°C, reduced under a

Jan 1, 1957

By George R. Elliott

Methods are presented for measuring and comparing "degree" of water drive, and for observing the control that rate of withdrawal exerts over decline of reservoir pressure. Degree of water drive is studied from pressure-production curves of 10 reservoirs; the method used to present these comparatively is to convert cumulative oil production from barrels to percentage of ultimate. Degree of water drive is also represented by a "water-encroachment factor," representing barrels of water influx per pound-month per acre-foot of oil reservoir. Pressure-production curves for the water-drive reservoirs after a period of declining pressure show a diminishing angle of slope, in some cases to the point where pressure ceases to decline or where it even increases; the shapes of these curves are in marked contrast to the dissolved-gas type of curve, which shows a general trend toward zero pressure at ultimate oil recovery. Yearly rate of oil production in percentage of ultimate oil recovery is correlated with pressure decline. The correct rate of production of oil with its associated gas and water sustains pressure in reservoirs having a high water-encroachment factor. For reservoirs having a low water-encroachment factor, it is necessary to inject the produced water and even inject large volumes of water from an outside source. The discussion of the actual reservoirs is preceded by a general review and is followed by a substantial bibliography. It is now generally accepted that water drive is capable of yielding 60 to 80 per cent of the original oil in place in most reservoirs, as compared with 20 to 40 per cent for dissolved-gas drive. There is no need to question the importance of controlling a reservoir in order to take advantage of such an efficient mechanism. What is a water-drive reservoir? Oil reservoirs usually combine two or more of the four basic mechanisms: dissolved-gas drive, gas-cap drive, water drive, gravity drainage. A water-drive reservoir is one in which water advances to take the place of the oil and gas produced. When the oil withdrawal rate is sufficiently low, the water will tend to maintain pressure. The maximum effectiveness is attained when the water follows the oil withdrawal so closely that little or no decline in pressure occurs. Oil in its underground reservoir is associated with water. This water is significant in the production of the oil according to the source of supply and the permeability of the surrounding formation. As oil is produced and the pressure is lowered, water can move in to replace the oil. With adequate supply and sufficient permeability, actual movement takes place on an extensive scale. The first movement of water takes place by expansion of the water and its associated fluids. While this expansion is of little importance in some fields, in others it is sufficient to supply all of the energy required for the production of oil. When a pressure differential has been established

Jan 1, 1946

By George R. Elliott

Methods are presented for measuring and comparing "degree" of water drive, and for observing the control that rate of withdrawal exerts over decline of reservoir pressure. Degree of water drive is studied from pressure-production curves of 10 reservoirs; the method used to present these comparatively is to convert cumulative oil production from barrels to percentage of ultimate. Degree of water drive is also represented by a "water-encroachment factor," representing barrels of water influx per pound-month per acre-foot of oil reservoir. Pressure-production curves for the water-drive reservoirs after a period of declining pressure show a diminishing angle of slope, in some cases to the point where pressure ceases to decline or where it even increases; the shapes of these curves are in marked contrast to the dissolved-gas type of curve, which shows a general trend toward zero pressure at ultimate oil recovery. Yearly rate of oil production in percentage of ultimate oil recovery is correlated with pressure decline. The correct rate of production of oil with its associated gas and water sustains pressure in reservoirs having a high water-encroachment factor. For reservoirs having a low water-encroachment factor, it is necessary to inject the produced water and even inject large volumes of water from an outside source. The discussion of the actual reservoirs is preceded by a general review and is followed by a substantial bibliography. It is now generally accepted that water drive is capable of yielding 60 to 80 per cent of the original oil in place in most reservoirs, as compared with 20 to 40 per cent for dissolved-gas drive. There is no need to question the importance of controlling a reservoir in order to take advantage of such an efficient mechanism. What is a water-drive reservoir? Oil reservoirs usually combine two or more of the four basic mechanisms: dissolved-gas drive, gas-cap drive, water drive, gravity drainage. A water-drive reservoir is one in which water advances to take the place of the oil and gas produced. When the oil withdrawal rate is sufficiently low, the water will tend to maintain pressure. The maximum effectiveness is attained when the water follows the oil withdrawal so closely that little or no decline in pressure occurs. Oil in its underground reservoir is associated with water. This water is significant in the production of the oil according to the source of supply and the permeability of the surrounding formation. As oil is produced and the pressure is lowered, water can move in to replace the oil. With adequate supply and sufficient permeability, actual movement takes place on an extensive scale. The first movement of water takes place by expansion of the water and its associated fluids. While this expansion is of little importance in some fields, in others it is sufficient to supply all of the energy required for the production of oil. When a pressure differential has been established

Jan 1, 1946

By William K. Antle

The successful application of ther mo compression lead bonding to semicondtctor or thin-film electronic devices depends on the establishment of the associated parameters. The quality of a thermocompression bond is primarily related to the process temperature and bonding force. A technique using the coelyicient of friction is presented that both reduces the time necessary for determining optimum parameter values and increases the accuracy of the results. Modern theories of the friction process are used to develop mathernatical expressions for shear and tensile bond strengths in terms of friction measurements. A further application of the pararneter-deterlnination technique concerns the measurement of surface contamination that may affect thermocompression bonding. In spite of the extensive use of thermocompression bonding, adequate methods for determining the bonding parameters have not been utilized. The quality of the weld depends on the temperature, force, and time used. There is a definite value or range of values for each parameter which assures an optimum weld. The process now generally used to obtain these values is to make several weld samples at each parametric setting, determine the mean pull strength, and relate the maximum consistent strength to optimum weld conditions. This could involve a very large number of test samples if a thorough search of each parameter were made. Experience and prior knowledge can reduce this number somewhat by limiting the investigation to a range known to contain the correct value, but the time and effort involved are still objectionable. The problems associated with thermocompression bonding of interconnecting leads to semiconductor or thin-film devices can be alleviated by the application of a new technique for establishing the process parameters. Obtaining the correct temperature, force, and duration to assure an optimum bond is accomplished by a simple measurement of the coefficient of friction. This approach increases the accuracy of parameter determination and greatly reduces the time necessary to complete the process. The approach made can be better understood by analyzing the principles of adhesion and friction on which thermocompression bonding depends. When two flat polished surfaces are placed together, the area of actual contact is much less than the apparent area determined by the over-all dimensions of the surface. This is because the microscopic surface is covered with projections which prevent uniform contact. Careful measurements of the electrical resistance across the contacting surfaces indicate the actual area may only be 1100,000 of the apparent area.&apos; Because the actual contact area is small, extremely high pressure results from moderate force. This will produce deformation and plastic flow at contact points of the microscopic projections. The process will terminate in the creation of a large number of minute welds formed at extreme pressure and cold-worked to strong, hard bonds. Load removal will generally result in fracture of most of these microbonds because of the residual elastic stresses, unless the materials are soft. Friction between metals is due to the formation and

Jan 1, 1967

By H. S. Price, R. L. Reed, J. E. Warren

The behavior of the reverse-combustion process in a linear adiabatic system is theoretically investigated by means of an idealized physical model. T his model is described by a pair of non-linear equations involving heat and mass transfer which are coupled by a concentration-dependent reaction-rate function of the Ar-rhenius type. The differential equations governing the quasi steady-state temperature and concentration distributions are approximately solved by using either physical or mathematical simplifications. It is shown that the reverse -combustion process can be mechanistically described by simple physical models whose behavior equations can be solved formally. It is further demonstrated that the derived reverse-combustion equations can be solved numerically within the error limits for the experimental data. The theoretically predicted peak temperature-flux-velocity relationship exhibits reasonable agreement with experimental data obtained from Athabasca tar sand. The principal contribution of this work lies in its usefulness as a starting point for developing a more comprehensive theory. A description of the vaporization-coking process must be obtained; then, the theory must be extended to three dimensions to include geometrical effects and heat losses. INTRODUCTION In another paper,&apos;" he physical processes visualized as occurring during reverse combustion have been described. In this paper, the extent to which an elementary theory can account for experimental observations is determined. Theoretical results that can be used to estimate some of the behavior characteristics of importance to this process are also presented. Since it is not possible to include all the features of the combustion mechanism of which we are currently aware, the mathematical formulation refers to the highly idealized system developed herein. This simplified physical model is based on the simultaneous transfer of mass and heat accompanied by a chemical reaction: it is described mathematically by a pair of coupled, nonlinear differential equations. Similar sets of equations have been studied extensively in the field of flame propagation; an excellent review of these investigations has been published by Evans.1 FORMULATION OF THE PROBLEM It will be recalled that the experiments are performed with a thin-walled cylindrical tube that is uniformly packed with sand and oil. The system is maintained substantially adiabatic by means of heat supplied externally in such a way that the radial temperature gradient in any plane normal to the axis of the tube approaches zero. Initially, the tube is at ambient temperature, except at one end where it is rapidly heated to a predetermined temperature. When the prescribed temperature is achieved, air is caused to flow into the cold end of the tube. As the oxygen in the air stream contacts the hot oil, a localized exothermic reaction takes place. The generated heat is conducted and convected away from the reaction zone so that definite temperature and concentration profiles are rapidly established and move uniformly in a direction opposite to that of the air flow (Fig. 1). As a consequence of this mode of oxidation, all of the oxygen in the air is consumed; then, the remaining nitrogen and the gaseous combustion products sweep out all vaporized hydrocarbons and leave an immobile hydrocarbon-coke on the sand.

By John V. Morgan

Although the Lansing-Kansas City groups One one of the more important producing horizons of Central Kansas, exploitation has been hindered by inability to consistently identify and correlate the various productive intervals. A study of gamma ray-neutron logs and core data indicates that definite zones exist which are related to production and which may be generally correlated over an appreciable portion of Central Kansas. A suggested system of zoning and nomenclature is developed and illustrated, along with examples of its specific application in overall evaluation and in development of zonal production characteristics. General adoption of the suggested system should aid appreciably in the future development of commercial Lansing-Kansas City production in Central Kansas. It is probable that similar systems might be developed for other regions where production is obtained from various uncorrelated and unnamed zones in thick pay intervals. GENERALIZED GEOLOGY OF CENTRAL KANSAS The most important large subsurface feature in Central Kansas regarding oil production is the Barton Arch, which is part of the Central Kansas uplift. The Barton Arch is a buried ridge of Pre-Cambrian granite running northwest-southeast, near which the majority of Central Kansas oil fields have been found. To the northeast of this arch, the granite dips sharply into the Salina Basin and similar basin areas to the west and south are termed the Hugoton Embayment and Anadarko Basin, respectively. This report deals Primarily with the region of the Central Kansas Uplift and its southwestern flank. Fig. 1 indicates the general location of subsurface structural features along with the oil and gas fields of central Kansas. Above basal granite lies the Cambro-Ordovician Arbuckle Dolomite which is the principal oil producing zone in Central Kansas. This formation, as well as those higher in the section, reflects the general underlying granite structure; however, the Arbuckle top is an erosional surface and most oil producing structures are probably topographic hills. Formations above the Arbuckle in ascending order may include those of the Ordovician, Silurian, Devonian, Mississippian, Pennsylvanian, and Permian periods as well as certain recent sediments. As the Barton Arch is approached, those formations below the Pennsylvanian and above the Arbuckle tend to pinch out until Pennsylvanian rocks, which include the Lansing-Kansas City groups, rest directly upon the Arbuckle. The Arbuckle itself is also completely eroded away at points on the Arch, but is up to 600 ft thick only 20 to 30 miles down dip. Formations of the Pennsylvanian system vary considerably in thickness but probably average about 1,000 ft as an overall total. The more commonly known oil productive zones are the Tarkio, Topeka, Toronto (Dodge), Lansing-Kansas City and Marmaton. Of these, the Lansing-Kansas City, which varies from about 200 ft to 400 ft in thickness, is the most important, since its areal frequency of oil production is exceeded only by that of the Arbuckle. Most Pennsylvanian rocks in Central Kansas were deposited in shallow seas which alternately covered, then retreated from the land. This resulted in recurring cycles of thin beds which cover relatively large areas. Small surface deformations during the period of deposition also caused variations in the type material deposited and its thickness. The local structures of Pennsylvanian time probahlv influenced the accumulation of

Jan 1, 1952

By Leon McCulloch

WIIen clean iron and metallic zinc dust, protected from the air, arc heated below the melting point of zinc, the iron takes on a coating that has excellent protective value. This coating is a brittle alloy of zinc and iron, and the process is called sherardizing. Although the zinc particlcs are covered with oxide and cannot touch the iron, an extremcly small amount of the zinc vaporizes and the vapor, reaching the iron, alloys with it. Other zinc then vaporizes to replace that which has been removed from the atmosphere. This process continues indefinitely at a decreasing rate, for the coating already formed permits zinc to diffuse through it to combine with the iron beneath. In this way, the coating grows outward from the surface of the iron, as the bark grows from a tree. The method of growth was clcarly seen while sherardizing small cubes of cast iron, at about 450" C., in a srnall glass-stoppcrcd bottle enclosed in a rotating drum. The dust contained about 3 per cent. iron, which prevented caking, and coatings % in. thick were grown in a few hours. After a heavy layer had been formed, the cubes mere again treated for a shorter time. The layer last formed was seen to lie next to the iron, instead of at the outer surface, showing that the growth was from the surface of the iron outward. The coatings split at the edges and corners, leaving the iron exposed there. Flakes of graphite from the iron were lifted upward and embedded in the coatings. The composition of sherardized coatings varies from the outer surface inward, as would be expected from the mode of growth. That is, the iron content increases slowly at first, then more rapidly as the iron is approached. At the surface the least amount of iron possible is 6 per cent., as the experiments described below have shown. A study was made of the effect of iron in zinc dust on the proccss and on the resulting coatings. Glass bulbs, holding the small pieces to be sherardized, together with enough zinc dust to make them two-thirds full, were heated in a small, rotating electrically heated and controlled furnacc. The bulbs had 6-in. (15 cm.) necks, of 96-in. (9.Fj mm.) tubing, plugged

Jan 1, 1923

By T. T. Read

A SHORT time ago, one of the large steel companies courteously furnished the author with detailed records of the operations of a considerable number of iron blast furnaces over a period of two months. These will be made the basis of a subsequent study, but in beginning this study one of -the first points requiring consideration was the probable error of the records, for what otherwise might be regarded as significant differences of performance under different conditions were perhaps really due to errors of observation, or failure to observe and record variations. If it is assumed, in blast-furnace records and calculations, that known quantities or factors are constant, when as a matter of fact they are variable, the effects of these variations may erroneously be ascribed to some other cause. This is quite clearly expressed in the following quotation from E. Buckingham:1 Theory always operates on an ideally simplified picture of reality because real phenomena are unmanageably complicated. The results obtained are not exactly true for any, real phenomenon, though they may be for an ideal one; and the approxi¬mation with which a theoretical equation, however obtained, represents the actual facts, always depends on the approximation in essentials between the ideal picture and its real prototype. The purpose of dimensional reasoning is to find out how some quantity which is involved in the phenomenon under consideration is related to certain others; or to find the relation connecting two or more quantities which vary, or may vary, simulta-neously during the course of the phenomenon. Since we know that we must have a complete equation to start with, we begin by thinking the matter over, to see whether the quantities we have in mind are the only ones involved. Usually it is evident that they are not; so we next make a list of all the quantities we can think of which might under any circumstances be important. Upon considering this list, which is often a long one, it is usually evident that under the actual circumstances a number of these quantities may safely be ignored; so we cross them off the list and thus pass from our most general conception of the phenomenon to an ideal simpler one, in which these quantities are not involved at all.

Jan 3, 1925

By F. M. Lewis, J. F. Myers

The crushing of ore, as defined by Taggart, is "usually a stage process, utilizing . . . machines especially suitable for the reduction of particular sizes. . . . down to a final stage, employed for the reduction of the finest sizes. ... In contradistinction, comminution to 20-mesh or finer is called grinding. There is a twilight zone in which the product is 6, 10, or 14-mesh limiting size which is either crushing or grinding. ..." Since the data in this paper pertain to a rod-mill operation, comminuting a particular ore size of ¾ in. to a final stage, coarser than 20-mesh, the rod mill is designated as a "fine crusher machine" in this paper. The published literature discloses a wealth of data regarding a rod mill as a fine-grinding machine but relatively little as a fine-crushing operation. Typical of the latter operation is: (I) a description by F. J. Tuck2 in which a fine-crushing rod mill replaced crushing rolls and (2) a description by the present authors3 in which a fine-crushing rod mill was installed instead of a collventional fine-crushing machine. The experience of the authors is that a definite distinction must he made between the rod mill functioning as a fine crusher and as a fine-grinding machine. As a fine crushing machine it prepares relatively large amounts of ore for a subsequent fine grinding operation; as a grinding machine, it grinds relatively small amounts of ore to some predetermined finished product. Pulp Movement and Action in Mill In considering the work performed by a fine-crushing rod mill, it seems important to understand just what takes place within the mill. We were inspired to study this matter by a paper by E. W. Davis,4 which indicated that definite water classification of ore particles took place in a ball mill. However, in thinking of the rod-mill action from this point of view, we were confronted with the fact that our rod-mill discharge product showed no evidence of action by water classification. The Tennessee Copper Co. ore is relatively high in sulphides, and the gangue rock and the sulphides are of about the same hardness. In the presence of any action by classification, the coarser sizes are definitely very lean in sulphide minerals.

Jan 1, 1947

By Leon McCulloch

WIIen clean iron and metallic zinc dust, protected from the air, arc heated below the melting point of zinc, the iron takes on a coating that has excellent protective value. This coating is a brittle alloy of zinc and iron, and the process is called sherardizing. Although the zinc particlcs are covered with oxide and cannot touch the iron, an extremcly small amount of the zinc vaporizes and the vapor, reaching the iron, alloys with it. Other zinc then vaporizes to replace that which has been removed from the atmosphere. This process continues indefinitely at a decreasing rate, for the coating already formed permits zinc to diffuse through it to combine with the iron beneath. In this way, the coating grows outward from the surface of the iron, as the bark grows from a tree. The method of growth was clcarly seen while sherardizing small cubes of cast iron, at about 450" C., in a srnall glass-stoppcrcd bottle enclosed in a rotating drum. The dust contained about 3 per cent. iron, which prevented caking, and coatings % in. thick were grown in a few hours. After a heavy layer had been formed, the cubes mere again treated for a shorter time. The layer last formed was seen to lie next to the iron, instead of at the outer surface, showing that the growth was from the surface of the iron outward. The coatings split at the edges and corners, leaving the iron exposed there. Flakes of graphite from the iron were lifted upward and embedded in the coatings. The composition of sherardized coatings varies from the outer surface inward, as would be expected from the mode of growth. That is, the iron content increases slowly at first, then more rapidly as the iron is approached. At the surface the least amount of iron possible is 6 per cent., as the experiments described below have shown. A study was made of the effect of iron in zinc dust on the proccss and on the resulting coatings. Glass bulbs, holding the small pieces to be sherardized, together with enough zinc dust to make them two-thirds full, were heated in a small, rotating electrically heated and controlled furnacc. The bulbs had 6-in. (15 cm.) necks, of 96-in. (9.Fj mm.) tubing, plugged

Jan 1, 1923