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By R. D. Pehlke, J. V. Gluck

AS a portion of a general study of liquid-metal thermodynamics, high-temperature galvanic cells were used to study the effect of added dilute solutes on the activity of zinc in dilute solution with molten bismuth in the range 450° to 650°C. 1,2 The cells were of the type The experimental procedures have been described previously.1 In the course of studies conducted in the bismuth-rich corner of the systems Bi-Zn-Au and Bi-Zn-Cu, marked discontinuities were observed in the electromotive force-temperature relations for a number of the experimental compositions. Above the discontinuity temperatures, the relations, which were linear, exhibited slopes similar to the binary alloy of the same mole fraction zinc, as shown in Figs. I and 2. Below the discontinuity temperatures, the slopes were markedly different, but the relations remained linear. In general, as the amount of the third eletnent was increased, the slope of the lower portion of the relations tended to become less positive. The slopes of electromotive force-temperature relations reflect the entropy of mixing of zinc and, therefore, the occurrence of a discontinuity marks the transition between two different equilibrium situations involving the solution of zinc. A number of other investigators3-5 have used such observations to determine liquidus boundaries in binary alloys. Since the upper portions of the ternary electromotive force-temperature relations of this study had the same slopes as the binary alloys, the discontinuities are interpreted as marking the transition between the single-phase liquid region and the underlying two- and three-phase regions. Reference to the Zn-Bi equilibrium diagram6 confirms that the binary alloys were single-phase liquids at the experimental temperatures. Fig. I shows the electromotive force-temperature relations for the alloys containing Bi-Zn-Au and Fig. 2 shows similar relations for the Bi-Zn-Cu alloys. In the lower portion of each figure, the temperature of the discontinuity is plotted vs the mole fraction of the added solute at the various levels of zinc concentra- tion. Cross-plots from these curves at constant temperature permitted the construction of the partial liquidus surface isotherms shown in Figs. 3 and 4.

Jan 1, 1967

By K. J. Gill, P. Chiotti

Thermal, metallographic, and vapor pressure data were obtained to establish the phase diagram for the thorium-zinc system. Four compounds corresponding to the stoichiometric formulas Th2Zn, ThZn2, ThZn4, and Th2Zn17 were observed. The melting points of these compounds under constrained vapor conditions were found to be 1055°, 1105°, 1095°, and 1015°C respectively. Four eutectics exist in this system with the following eutectic temperatures and thorium contents in wt pct: 1040°C, 89 Th; 945°C, 79 Th; 1045°C, 55 Th; and 995°C, 35 Th. The standard free energy, enthalpy, and entropy of formation for the compounds were determined from zinc vapor pressure data. ALTHOUGH the thorium-zinc system has been of technical importance in the commercial production of thorium and more recently of interest to some proposed pyrometallurgical separations processes for reactor fuels or blanket materials no detailed investigation of this system has been made in the past. Some previous work has been reviewed by Hanssen.1 The existence of four compounds, Th2Zn17, ThZn4, ThZn2, and Th2Zn has been established and their crystal structures have been studied by X-ray diffraction techniques.2-4 Smirnov et al.,5 determined the solubility of thorium in zinc and investigated the two-phase region between Th2Zn17 and zinc. They calculated some of the thermodynamic properties for these alloys from emf measurements on the cells Th/ThCl4(fused)/Cl2, C and Th2Zn17(s)+ Zn (l)/ThCl4(fused)/Cl2, C. The possibility of reaction between the anode materials and fused thorium tetrachloride to produce a lower valent thorium salt would have to be resolved in order to evaluate the results obtained. The purpose of the present investigation is to establish the phase diagram for the thorium-zinc system and to determine the standard free energy, enthalpy, and entropy of formation for the compounds formed. MATERIALS AND EXPERIMENTAL PROCEDURES The metals employed in the preparation of alloys were Bunker Hill slab zinc, 99.99 pct pure and Ames Lalboratory thorium. The major impurities in the thorium in parts per million were oxygen—1250, carbon—350, iron—100, nitrogen-75, and silicon—70. The metals in the form of several small massive pieces, total weight about 30 g, were cleaned with acid, washed with water and acetone, and dried just prior to their use for alloy preparation. Tantalum containers were found to be suitable for all the alloys studied and were used throughout this investigation. The metals were sealed inside of small 1-in.-diam tantalum crucibles by welding on preformed tantalum covers. A small thermocouple well made from 1/8-in.-diam tantalum tubing was welded in the bottom of each crucible. These crucibles were enclosed in

Jan 1, 1962

By Albert Sauveur

It is delightful to read a technical paper like that of J. E. Johnson, The Effect of High Carbon on the Quality of Charcoal-Iron, presented in October, 1912, at the Cleveland meeting of the American Institute of Mining Engineers.' The clear, simple, and straightforward manner in which he describes his experiments and results makes you feel as if you had been, so to speak, at his elbow during the course of his investigations, while his method of procedure is so rational that you can fairly anticipate each step in the logical sequence of the tests performed. The following notes suggested by Mr. Johnson's paper are presented here in the hope that they may help, if only a mite, towards the final solution of a problem of considerable scientific and industrial importance. Physical Properties of Cast-Iron us. Its Ultimate Composition. Mr. Johnson writes that " an investigation along the lines of consumption showed that different irons have different characters totally independent of their analyses," and he declares that " the presence or absence of these elements [meaning carbon, phosphorus, silicon, and manganese] alone will not account for all, scarcely for a half, of the facts which have long been known." He further tells us that some foundries have " proved, by the most irrefutable tests, that they could take a certain iron of a given analysis and produce certain results," while with " another iron of the same analysis they could not produce these results at all." I feel confident that every experienced and thinking metallurgist will readily believe Mr. Johnson's statements and will share his views in regard to the hopelessness of inferring the

Jan 1, 1914

By William B. Hughes

The rubber-sleeve core barrel was developed to improve core recovery from unconsolidated sands, where it is most difficult to obtain cores with conventional barrels. The use of a rubber-sleeve core retainer, together with other departures from clsual design, has required a considerable amount of testing to prove its op-erability. Tests run in shallow experimental holes and in drilling wells in the U. S. and Vemzuela have, to a large extent, proved the operation of the barrel. Internal mechanism troubles, such as sandbinding of the sleeve, have been largely overcome. Cores have been recovered from completely unconsolidated sands where conventional coring has almost been abandoned because of poor recovery. In addition to retaining the core until brought to the surface, the barrel gives a "packaged-ar-cut" core, which is coilverzient for handling and transportatiorz. In the initial work, drag blade cutters, roller cutters, and tungsten carbide insert cutters were usrd for cutting unconsolidated sands. Further bit head development is presently being conducted using diamond heads in unconsolidated sands where shaler, hard sands, and limestones are encountered in adjacent formations. Thir work should render the barrel capable of cratting and recovering most types of formations, possibly including broken and frac- tured fornlations. This development is being carried on in cooperation with a diamond bit manufacturer. INTRODUCTIO N For many years the oil industry has needed greater recovery of cores from unconsolidated formations. Conventional equipment has been used to core unconsolidated sands with little success. Specifically, a core barrel was needed which would recover unconsolidated sands in a condition that would give useful reservoir information. DEVELOPMENT OF 'THE RUBBER-SLEEVE CORE BARREL Basic Requirements of Unconsolidated Sand Corino The basic need was defined as a core barrel that would obtain a continuous unconsolidated core with sand grains in place as deposited in the formation. A preliminary survey of coring equipment and search of the literature pointed out the weaknesses of conventional core barrels. Laboratory tests using unconsolidated sand in a metal tube simulated actual sand movement into the core barrel during conventional coring. In conventional barrels the core sometimes crumbles and bridges, or fails under compressive column action, becomes oversize, and wedges against the walls of the inner barrel. The core barrel requirements established by the surveys and preliminary tests are as follows. 1. The core should be held to- gether as it is cut so it cannot crumble and bridge against the walls of the coring tool, care being taken not to permit damage from fluid circulation. 2. The core should be continuously supported as it is cut so it will not have to support itself in compression. 3. The core should be packaged in the barrel to retain an undisturbed condition during the trip out of the well. The packaging should be such that the core can be removed from the barrel and shipped to the core analysis laboratory without physical disturbance or alteration of fluid content by exposure to the atmosphere. Operation of the Rubber-Sleeve Core Barrel The rubber-sleeve core barrel (Fig. 1) meets the basic requirements for the recovery of unconsolidated sands.

By E. F. Johnson, V. O. Naumann, D. P. Bossler

A method is presented for calculating individual gas and oil or water and oil relative permeabilities from data obtained during a gas drive or a waterflood experiment performed on a linear porous body. The method has been tested and found both rapid and reliable for normal-sized core samples. INTRODUCTION Individual oil and gas or oil and water relative permeabilities are required for a number of reservoir engineering applications. Chief among these is the evaluation of oil displacement under conditions where gravitational effects are significant, such as a water drive or crestal gas injection in a steeply dipping oil reservoir. Numerous proposed methods of obtaining relative permeability data on reservoir core samples have been too tedious and time consuming for practical use, or have yielded questionable and sometimes inconsistent results. A method has been developed by which the individual relative permeability curves can be calculated from data collected during a displacement test. The method is based on sound theoretical considerations. Using this method, with a properly designed experimental procedure, relative permeability curves can be obtained using core samples of normal size (i.e., 2 to 3 in. in length and 1 to 2 in. in diameter) within a few days after receipt of the core. In a recent publication D. A. Efros1 describes an approach to the calculation of individual relative permeabilities that is based on the same theoretical considerations. We believe the approach described in the present paper is more adaptable to practical application than the method implied by Efros. In addition, comparisons with independently determined relative permeabilities are furnished to substantiate the reliability of the new method. DERIVATION Previously the theory of Buckley and Leverett as extended by Welge2 as been used to calculate the ratio of relative permeabilities. In the derivation which follows, this theory is further extended to permit calculation of the individual relative permeabilities. The theory assumes two conditions which must be achieved before the method is applicable. They are that the flow velocity be high enough to achieve what has been termed stabilized displacement,3 and that the flow velocity is constant at all cross sections of the linear porous body. In stabilized displacement the flowing pressure gradient is high compared with the capillary pressure difference between the flowing phases. The high pressure drop insures that the portion of the core in which capillary effects predominate will be compressed to a negligibly small fraction of the total pore space. The assumption of constant flow velocity at all

By Charles E. Wait

IT is said by some that the occurrence of a deposit of sulphide of antimony in Southwestern Arkansas has been known for fifteen or twenty years. Whether or not such is the case I am not prepared to say, but I am not able to find any record of such a discovery, or any analysis of antimony ore obtained from that section, published at so early a period. The present discoveries, that seem to be attracting some attention, date back to the winter of 1873-74. At that time a vein of ore was found by Mr. Robert Wolf, in honor of whom the vein was named, and still is called, "the Wolf lode." At the time of the discovery the ore was unknown to the prospector, and its composition was not thoroughly understood in that locality until samples were sent to several analytical chemists, who pronounced it sulphide of antimony-stibnite. Since the discovery of this ore there have been three mines opened, and a number of interesting minerals of the antimonial series have been found. I have had an unusually good opportunity to collect specimens from these mines; and it is owing to the constant inquiry concerning the character of these ores that I have collected for publication the results of quite a number of analyses, sufficient I trust to clearly point out their composition. This is one of the few localities in the United States where antimony ore is found in workable quantities; I say workable quantities, because two different shipments of ore have been made to English reduction works, and in both cases excellent returns were made. The discovery of these deposits will, it is hoped, give rise to a prosperous and remunerative industry at no distant day, and when fully developed they may yield ore in sufficient quantity to supply the regulus for the home demand, thus adding wealth not only to those interested, but also to the State of Arkansas. The three mines are situated in the northern part of Sevier County, and may be reached by the St. Louis, Iron Mountain and Southern Railway to Fulton, thence by wagon-road to Columbus, Nashville, Centre Point, and to the mines. During most seasons of the year the

Jan 1, 1880

By W. R. Hibbard

Evidence is presented which confirms previous findings that models of solution strengthening depending solely on lattice parameter changes are incomplete. Direct evidence for the Suzuki interaction of chemical effects was obtained from alloys with constant lattice parameter, for which solution strengthening was nearly independent of temperature from 300° to 20°K. SOLUTION hardening principles have been reviewed recently by Parker and Hazlett.' In addition, the interactions of dislocations and solute atoms were reviewed by Cottrell.' It is not proposed to review this information again here, but to refer only to those details which are pertinent to the developments which have occurred since these papers were published. Literature Survey To set the stage, it has been known for some time that solid solutions are stronger than the pure parent metals, and that the strength increases with increasing amounts of alloying element. One of the most extensive earlier investigations was that of Lacy and Gensamer,3 who reported that the solid solution strengthening of iron is a power function of the composition, that the relative strengthening is a function of the solubility limit, and that the rate of strain hardening is a function of the amount of solution hardening. Thus, the slope of the plastic portion of the stress-strain curve increases with increasing yield strength. An approach to the development of principles resulted from work by Gulyeav,4 who reported that the strengthening effect of solid solution alloys is periodic in character when plotted as a function of the atomic number of the solute. A more quantitative approach was to relate the amount of solution hardening to the lattice parameter of a solid solution. This was done quite early by Norbury,5 and later by Brick, Martin, and Angier,6 Frye and Hume-Rothery,7 and French and Hibbard. This relationship is only approximate in character. The next development was to relate the amount of solution hardening to lattice stress, as proposed by Frye and co-workers.9 They calculated what they called ionic overlap from the lattice parameter changes represented as a change in volume, using Bridgman's hydrostatic compression equation. The resulting correlation was somewhat improved as compared to the simple correlation with lattice parameter. The next step was carried out by Dorn, Pietrow-sky, and Tietz,10 who suggested an effect of valence differences in addition to the effect of lattice parameter. Their proposed parameter shows flow stress as a single valued function of the concentration and a relationship involving these two atomic variables. In addition, they contributed new data on the temperature dependence of solution hardening which indicated that it was a strong function of temperature for aluminum alloys. Allen, Schofield, and Tate11 carried the valency effect even further by reporting data indicating that with a given solvent element the stress-strain curve is a function of electron density, entirely neglecting the size factor, which varied by a factor of two. This evidence led to a quantum mechanical calculation by Cottrell, Hunter, and Nabarro,12 based on the formation of a dipole around an edge disloca-

Jan 1, 1959

By K. T. Aust

The occurrence of annealing twins in high-purity aluminum resulted in the formation of grain boundaries having orientation relationships which correspond to a high density of coincidence sites. The results provide support for the coincidence site model and indicate that large-angle coincidence boundaries have lower free energies than large-angle noncoincidence boundaries. Observations are presented concerning the coherent structure of twin interfaces in aluminum and the importance of inter-facial energy in preferred orientation. RECENT experiments1 have shown that when an annealing twin is formed during grain boundary migration in zone-refined lead, a large-angle random boundary is replaced at the growth front by a large-angle coincidence site boundary. The coincidence site orientation relationships obtained by twinning were of the type considered by Kronberg and Wilson,2 Frank,3 and Dunn.4 On the basis of the theory of annealing twins advanced by Fullman and Fisher,5 these observations indicate that the energy of a coincidence site boundary is less than the energy of a random boundary by an amount which exceeds the energy of the coherent twin boundary. This energy difference between the coincidence and random boundaries must be at least about 5 pct since the ratio of twin boundary energy to grain boundary energy in zone-refined lead is 0.05 * .014.6 Fullman7 has found that the twin boundary energy in aluminum is about 21 i 5 pct that of a large-angle grain boundary. A twin boundary energy as large as this would be expected to exclude the formation of many coincidence site grain boundaries, especially those which have a relatively low density of coin- cidence sites. Therefore, if the coincidence site model is a useful interpretation of certain large-angle boundaries, then it would be predicted that only coincidence boundaries which separate adjacent crystals with a relatively high density of coincidence sites may be obtained as a result of twinning in aluminum. The present experiments provided a means of testing this prediction since annealing twins occurred during the growth of recrystallized grains into striated, melt-grown single crystals of zone-refined aluminum. EXPERJMENTAL PROCEDURE A striated single crystal of zone-refined aluminum, about 1 cm sq and 37 cm in length, was obtained during zone melting of aluminum of 99.996 wt pct starting purity in a graphite boat under helium atmosphere.8 A molten zone of 2 to 3 cm in length, which was maintained by induction heating. was passed along the length of the bar for eleven passes at a rate of 0.9 mm per min. An additional final pass was given at a rate of 0.2 mm per min. The center portion of the zone-melted bar was characterized by an electrical resistivity ratio between room temperature and 4.2° K of 8000 to 9000. Single crystals of 1 to 2 cm in length were removed from the center section of the zone-refined bar and electrolytic ally polished in a 2:l solution of methyl alcohol and concentrated nitric acid. The specimens were then chemically polished in Alcoa R-5 solution. X-ray analysis of the single crystals indicated the presence of striations or lineage substructure having misorientations as high as 2 deg. New, recrystallized grains were introduced into each striated crystal by the technique of artificial nucleation and growth, previously described.9 During the growth of the recrystallized grains at 300' to 600°C in argon, it was sometimes found that a

Jan 1, 1962

By E. H. Herron, J. H. Perry

Mathematical simulation of reservoir behavior may be used to help understand reservoir processes and to predict reservoir behavior, thereby leading to the most economically desirable form of exploitation. In addition, simulation can be used as a tool for reservoir description to learn more about the physical nature of the reservoir and the mode of primary recovery. This use is essential in most reservoir studies and represents one of the more significant applications of simulation. Prediction of reservoir behavior provides information concerning displacement efficiency, optimum well locations, and the comparison of alternative producing processes. Since oil, water and gas all commonly occur in many reservoirs, a simulation that takes into account the simultaneous flow of three immiscible phases is a prerequisite for obtaining such information. Furthermore, a simulation that describes this flow in two dimensions provides the capability of evaluating combination gas- and water-drive reservoirs with either an areal or a cross-sectional description. Many reservoir problems require such a simulation. The objective of the research described here was to develop a mathematical model and associated computer program for accurate, efficient, and economical prediction of the reservoir flow of three phases in two-dimensional geometry. Several authors have discussed multidimensional reservoir simulation of two phases.l-3 Gottfried et al.' presented an analy- sis of three-phase simulation in one dimension. Fagin and Stewart" and Garrett6 have discussed the simulation of three-phase flow in two dimensions, but their solution techniques were different from the method discussed in this paper. In particular, previous models and computer programs have usually involved either fewer capabilities or inefficient and less rigorous descriptions resulting in limited applicability. In the following sections, we present a description of the model, an evaluation of the method, and the application to reservoir problems. Additional and supporting material is presented in the Appendix. The Three-Phase Model General Description The three-phase model consists of the mathematical description of the flow of oil, water and gas in a reservoir. Conceptually this description considers flow in all three space dimensions, but in the subject simulator it is assumed that no flow occurs in the third dimension. The model includes the effects on reservoir behavior of fluid and rock compressibility, viscosity, gravity, capillary pressure, relative permeability and gas solubility. Within the two-dimensional restriction, the reservoir considered may be completely heterogeneous and anisotropic. The differential equations governing multiphase, multidimensional flow in a reservoir are too complex to be solved analytically, so they are approximated by a system of finite difference equations and solved

Jan 1, 1970

By K. Reinhardt

THE idea of burning blast-furnace gases directly in gas-engines, instead of under steam-boilers, as had previously been done, was first put into practice barely ten years ago, almost simultaneously in Great Britain, Germany and Belgium. The pioneers of this movement made their first experiments with small engines. After these experiments had given satisfactory results, and it had been shown that the thermal value of the poor blast-furnace gases, in spite of defective scrubbing, could with safety be directly transformed into mechanical work in the gas-engine, there very soon arose a considerable demand for gas-engines of large power, similar to the large steam-engines employed in metallurgical works. In face of these sudden requirements, the gas-engine builders were placed in a difficult position; for up to that time the gas-motor was considered as suitable for small engines only, and it was generally believed that the limit of size bad been attained with 100 to 150 effective h.p. in a single cylinder. Manufacturers of gas-motors, however, did not underrate the advantages offered by this new field for their manufactures, and it so happened that in Germany the Berlin-Anhaltische Maschinenbau-Gesellschaft, of Dessau, was the first to undertake the construction of a 600-h.p. two-cycle gas-engine, with two cyl¬inders of the Oechelhäuser-Junkers type, for the Hoerder Mining & Smelting Company. The engine was started in 1898, and, with a few improvements and alterations, is still working satisfactorily. This engine worked with astonishingly high of efficiency, considering the period. The builders were therefore

Nov 1, 1906

By S. M. M. Safvi, A. Jowett

Small-scale continuous flotation tests are described in which the influence of 1) pulp density and 2) feed rate on the rate of flotation are investigated. The results provide further evidence of first-order kinetics for flotation and indicate that tests at different feed rates provide a particularly simple method of determining rate constants. Flotation kinetics are discussed in general terms. Over a period of many years numerous research workers have studied the rate of recovery of valuable materials from flotation pulps with a view to deter-mining the mechanism of the froth flotation process. Froth flo ation is fundamentally a collision process involviug at some stage collision and then mutual attachment between air bubbles and mineral particles. It is possible to draw analogies therefore between the flotation process involving mainly macroscopic particles and the ordinary processes of chemical reaction kinetics involving collisions between atoms, molecules and ions. By adopting this analogy we may postulate a general equation representing the kinetics of the flotation process: -dC/dt =K.CC ,Aa (1) The rate constant, K, will be a complex function involving reagent concentrations, particle and bubble sizes, induction times and no doubt flotation cell design. However, these are factors which can be kept constant in any series of experiments, permitting investigation of the exponents a and c, which determine the order of the reaction occurring in flotation. The various research investigations carried out so far have all aimed at evaluating a and c and in the majority of cases only since the concentration of air has usually been kept constant in a series of tests, so that a relationship of the following type has been investigated: -dC/dt = K1 Cc (2) The techniques of both batch testing and continuous testing have been used to investigate this relationship. The technique of continuous testing, in which steady-state conditions are established, permits direct investigation of the above equation. In the case of batch testing, C is decreasing continuously

Jan 1, 1961

By D. Turnbull, H. N. Treaftis

Precipitation of tin from Pb-Sn alloys (lead-rich) occurs by the nucleation and growth of hemispherical cells which consist of tin lomelloe interspersed in the depleted solid solution. Nucleation and growth of these cells and the tin interlamellar spacing at various compositions and temperatures have been investigated. The interlamellar spacing increases approximately as the reciprocal of the logarithm of the supersaturation ratio. For constant initial tin concentration the concentration of cell nuclei increases with decreasing temperature to a limiting temperature-independent value. The kinetic results support the view that the cell growth rote is governed by the diffusion of tin along the cell boundary. In the main, the results confirm the authors' earlier deductions, drawn from resistometric and calorimetric data, about the precipitation mechonism. IT has been shown1, 2 that tin (ß) precipitates from lead-rich (a) PbSn solutions by the nucleation and growth of cells (cellular or discontinuous precipitation). These cells consist of tin lamellae, with a spacing 1, interspersed in a depleted a solution. Reorientation of a also accompanies cell growth. The kinetics of cellular precipitation of tin from lead have been measured by resistometric2, 3 and ca1orimetric1, 3 techniques. The time-transformation isotherms (t equals time; x, volume fraction of specimen transformed) of the initial rapid precipitation, which drains about 60 pet of the tin from solution, have been described by a kinetic law having the form x = 1 —exp (—bt n) [I] where n usually has the value 3.0. It was shown" that this law and the other kinetic facts can be explained satisfactorily if it is assumed that the cells grow at a constant rate and that all the cells nucleate in a time negligible in comparison with the period of cell growth before impingement. Thus, for hemispherical cells b = (2/3)pNG3 [21 where G is the rate of cell growth in cm per sec, and N is the number of cell nuclei per unit volume. The rapid rate of cell growth at low temperatures can be accounted for"' if it is assumed that the dissolved tin drains to the lamellae edges by diffusion along the sweeping cell boundary rather than by diffusion through the a crystal (volume diffusion). For cell growth governed by cell boundary diffusion it was shown, approximately G=2(X° - X° / X° ) DBA / l2 where A equals the thickness of the cell boundary; D R, the coefficient of diffusion of tin atoms within the boundary; and X° and X, are the atom fractions of tin in the supersaturated and saturated solutions, respectively. Zener8 had already shown that, where

Jan 1, 1959

By V. N. Cox, C. H. Grant

Both the underwater method and the rock cratering method contribute useful information in evaluating and comparing new explosive compositions. Results indicate that metallized explosive systems which contain no high explosives can be formulated to offer more energy and to do potentially more work than other slurry explosive systems. Commercial field trials are presently being conducted with a metallized explosive that does not contain any high explosive. Although there have been only a few commercial blasts to date, the results are encouraging. The Dow Chemical Co. has been engaged in explosives research since 1953. The incentive for this research was based on the desire to find additional markets and uses for magnesium metal of which DOW is a heavy producer. The thermodynamic calculations for explosives incorporating light metals indicate energies approximately twice that of nonmetallized explosives currently being used. Early in 1960, additional patent rights were acquired from independent inventors and a development station at Virginia, Minn., was set up to conduct a commercial testing and market evaluation program with this new product. The actual manufacturing of the explosive was to take place in the boreholes. Due to the complexities involved in controlling the manufacture of the explosive in the borehole, performance was sometimes in doubt. Furthermore, experience indicated that the metallized explosive systems could not be evaluated by the standard laboratory methods then being used, and it was necessary for us to look for more suitable research methods. Tests were conducted on several known methods for explosive evaluation. The most promising were the Navy underwater method for energy evaluation and a modified Livingston crater method intended to compare explosive performance in rock. After shooting over 2000 charges of 8 to 60 lb under water and in taconites and granites with many types of explosives, a metallized explosive was developed which is now being manufactured at a pilot plant in Virginia, Minn. and is being evaluated commercially. UNDERWATER METHOD An underwater method of evaluating explosives has a number of advantages. A permanent site can be established and operated indefinitely. A large number of charges may be fired in a short length of time. The medium in which the explosive is shot is exactly the same for successive shots. Data are recorded electronically minimizing human judgment. A disadvantage of the underwater method is the lack of confinement provided by the water medium. Many explosive compositions require a greater degree of confinement to develop good energy release. Although the relative significance of the two components of energy release that are usually measured, the shock energy and the bubble energy, and their relationship to breaking rock are not clearly understood, the underwater method is a valuable research tool for screening explosive compositions and gaining an insight into the manner in which explosives release their energy. Fig. 1 shows schematically the underwater apparatus. The piezoelectric gages are calibrated tourmaline crystals which convert the shock wave to an electrical impulse which is transmitted to an oscilloscope and recorded on Polaroid film. The shock traces are picked up by scopes 1 and 2. Scope 1 is timed to pick up the full trace whereas scope 2 is timed to cover the first increment of the shock trace expanded, and therefore allows full inspection of the propagation and peak pressures. Scope 3 records the bubble trace. When the explosion occurs, a bubble of gaseous detonation products is formed. The outward momentum of the water keeps expanding the bubble even after

Jan 1, 1963

By D. R. Parrish, F. F. Craig

In some respects, forward combustion (alias: fie-flooding, underground combustion, in-situ combustion, dry combustion) is an efficient oil recovery method. For example, its displacement efficiency (as much as 95 percent in reservoirs with high porosity and high oil saturation) is good. In its use of heat, however, forward combustion is grossly inefficient. Most of the heat generated during forward combustion is wasted. About one-fifth of the heat is picked up by the incoming air and re-used (regenerated); the remainder is left behind the combustion zone and ultimately is lost. Compressed air is expensive, and heat generated from compressed air via underground combustion is too valuable to be thrown away. Improvement is needed. Since the early 1950's, improvements in forward combustion by addition of water injection have been discussed, particularly in the patent literature, with increasing frequency.'-'' These concepts are based on the fact that relatively inexpensive water can be used to pick up much of the heat that is ordinarily wasted during forward combustion, and transport it forward to a more useful place, thereby reducing the amount of air required to move a heat front through the reservoir. Several approaches have been proposed. Merriam and Squires1 taught that a combustible (fuel) gas should be injected along with the air and water. This, however, would give at least a tendency toward reverse combustion instead of forward combustion, and would reduce the velocity of the heat bank, defeating the primary purpose of the water injection. Pelzer2 described primarily a batchwise method of forward combustion and water flooding. He advocated burning part way through a reservoir with forward combustion, then switching from air to water injection alone to push the heat toward the producing wells. Though possible, this method has serious disadvantages, the major one being that, by the time water injection is started, much of the heat has been irretrievably lost to the overlying and underlying formations. We have described what is considered a practical Combination Of Forward Combustion And Water-flooding (COFCAW).3,4 Air and water are injected simultaneously (or alternately) after a small heat bank has been formed by forward combustion. Some of the injected fluid fills up the region behind the heat bank; the rest enters the heat bank. Upon encountering heated rock, the water is converted into steam, which then flows ahead of the combustion zone and displaces much of the oil in place. Only enough air is injected to provide heat for vaporization of the water and to compensate for reservoir heat losses. Since the size of the heat bank is minimized, heat losses also are minimized. Because of more efficient oil displacement ahead of the combustion zone, fuel consumption is reduced. Too, unlike a forward combustion zone that cannot move until all fuel at a point has been consumed, COFCAW leaves some

Jan 1, 1970

By W. D. Johnston, T. P. Thayer

THE minerals that collectively are known as chromite form an isomorphous series of the general formula (Mg,Fe) 0. (Cr,Al,Fe) 203. So wide is the range in chemical composition in this group that chrome ore consisting entirely of the mineral chromite may range from less than 30 pct to more than 60 pct Cr203. The most comprehensive published data on the chemical com- position of chromite are by Stevens,62 who made complete analyses of 52 samples of chromite concentrate from many localities in North, Cen- [ ] tral, and South America. These samples were mechanically purified to remove associated silicates and might be regarded as the cleanest chromite that could be obtained by any mechanical milling process. Fig 1 shows the predominant zone of isomorphism, within the triangular prism of composition defined by the mineralogical end members of the series, wherein his analyzed samples fell.

Jan 1, 1949

By L. D. Keller

The application of hydraulic concentration to large scale operations has been effectively accomplished by the use of the SiphonSizer. Operation has been simple, automatic and essentially trouble free. The use of the primary desliming SiphonSizer on magnetic taconites has shown an improvement in grade of concentrate and an increase in recovery over conventional hydroseparators. Magnetic concentrates have been further deslimed and upgraded in SiphonSizers by floating a coarse middling product away from the heavier concentrate. The application of the Siphon-sizer to closed circuit grinding has met with only partial success to date. Hydraulic concentration of minerals has been practiced for a good many years. Until recently, however, the practice has been limited to equipment using a multiplicity of small pockets and relatively low tonnages and flows. The adaptation of the SiphonSizer to the concentration and classification of magnetite has changed this concept. Some fifty commercial units varying in size from a 16-ft diam circular unit to a 25x100-ft rectangular unit are currently in operation on magnetic taconites. Additional units up to 38 ft diam are under construction. Depending upon the application in the flowsheet, upgrading varies from 0.75% to 14% Fe in a single stage. To those not familiar with taconite processing, the importance of the struggle to remove economically as much silica as possible may not be fully appreciated. Perhaps some figures pertaining to transportation costs will underscore this important process. If the silica content of the concentrate from a 10,000,000 ton per year plant could be reduced by I%, a savings in boat freight, at $2.00 per ton, would amount to $200,000 annually! THE SlPHONSlZER The SiphonSizer, as illustrated in Figs. lA, 1B and 2, is a hydraulic classifier in which the hydraulic water is distributed uniformly across the bottom of the vessel by means of a system of headers (1 and 2), jet pipes (3), and nozzles (4). The depth of the teeter bed is automatically maintained by the siphon-float assembly. The feed is introduced through a feed well (5) and separated into two fractions by the effects of rising water and the density of the teetered bed. The magnetite fraction is discharged by the siphon (12) while the fine slime and light middling overflow a peripheral weir (9) to the overflow launder (6). The bed depth is controlled automatically by float valves (7), which are responsive to changes in the height of clear water supported in the superelevation tubes (8) by the density of the teetered bed. On top of the float (7) is a needle valve (10) which permits

Jan 1, 1963

By J. Gurland

A method of measuring the degree of contact between grains of 1 phase in multiphase alloys is derived. It is shown that the number and the areas of contacts between grains can be determined by metallographic analysis. Relations between the area of contact, the dihedral angle, and the mean free path of spherical grains are developed. It is often desirable to interpret the mechanical behavior of alloys in terms of structural features observed under the microscope. A quantitative description of microstructures of multi-phase alloys requires consideration of geometrical and topological factors such as the amount, size, and shape of grains and the continuity of the constituent phases. The number and dimensions of grains may be metallographically determined by applying the methods described by Smith and Guttman1 and by Fullman2 in their papers on the measurement of particle size and internal boundaries in opaque bodies. The present work intends to show that the same methods can be used to evaluate some of the parameters of phase continuity; namely, contiguity, number of contacts, and areas of contact of grains of 1 phase. Application of these concepts may be found in such problems as the calculation of electrical conductivity of 2-phase alloys, or the evaluation of the length of fracture path through grains of a brittle phase more or less dispersed in a matrix. I. DEFINITION The following definitions and derivations are based on 2-phase alloys, of which the units of the microstructure are grains. Contiguity is defined as the average fraction of surface area shared by 1 grain of a phase with all neighboring grains of the same phase. In a 2-phase alloy of constituents A and B, the contiguity of phase B is given by: where Cb is the contiguity of phase B aBß is the average area of contact between a grain of phase B and adjacent grains of phase B, aAB is the average area of contact between a grain of phase B and adjacent grains of phase A. The contiguity is a measure of the average degree of contact between grains of phase B in the 2-phase mixture. The ratio varies from 0 to 1 as the distribution of phase B changes from a completely dispersed to a fully agglomerated structure. Smith and Guttman1 have shown that the relative areas of 2 kinds of interfaces in a volume are directly proportional to the number of interfaces of each type intersected by a random line. The lines can be drawn on metallographically prepared surfaces as long as these are random sections through the sample. The contiguity ratio of phase B then becomes: Cb = 2NBB/NAB + 2N BB [2] where: NBB is the number of interfaces between grains of phase B intersected per unit length of random line. Nab is the number of interfaces between grains of phase B and grains of phase A intersected per unit length of random line. The factor 2 arises in Eq. [2] because each interface B-B is associated with 2 grains of B-phase, whereas the interface A-B involves only 1 grain of B-phase. The calculations of contiguity do not require any assumption as to volume fraction, particle size, or particle shape. Fullman2 gives an expression for the determination of the mean free path between particles. The mean free path PB between grains of phase A, i.e., through grains or agglomerates of phase B, may be found from the relationship: PB =2fB/NAB [3] where fB is the volume fraction of phase B. The calculation of the mean free path is independent of grain shape and grain size distribution. The calculation of the number of contacts and of contact area requires assumptions of grain shape, grain size, and contact shape. In the case of uni-

Jan 1, 1959

Jan 1, 1966

By E. B. Johnson

Cleveland-Cliffs lron Co., which operates Marquette lron Mining Co.'s Republic mine, conducted a test whereby 35,000 tons of self-fluxed pellets were produced in the grate-kiln system from specular hematite flotation concentrates. A brief description of the pelletizing plant is presented along with pertinent operating details. Date is included which compare operating conditions and the chemical and physical properties of the green and fired pellets for the self-fluxing pelletizing test with the normal acid pelletizing operation. The success of self-fluxed sinter in enhancing the operation of the blast furnace during the past few years has reasonably led to the assumption that the use of self-fluxed pellets might result in even greater furnace efficiencies. A great share of development work in agglomeration has been directed towards techniques related to the production of self-fluxed pellets, but only a limited tonnage of self-fluxed pellets had been produced on a commercial scale until this past year when The Cleveland-Cliffs Iron Co. produced 35,000 tons of such pellets by the grate kiln system at the Republic mine during the period May 21-June 5, 1962. REPUBLIC'S GRATE-KILN PLANT The grate-kiln pelletizing process consists of four stages, namely: feed or balling circuit, traveling grate, rotary kiln and annular cooler (Fig. 1). The balling section is conventional and utilizes four 9x30-ft balling drums in closed circuit with 5x14-ft vibrating screens having 3/8-in. rod decks. The traveling grate is 12 ft wide by 126 ft long and has 14 windboxes — six in the drying section and eight in the preheat section. The rotary kiln is 15 ft ID shell and 114 ft long. The annular cooler is 40 ft in diameter and has 12 windboxes. The cooler is divided into two zones by a moveable curtain wall. The high temperature air from the first zone is used as secondary combustion air in the kiln. Normally the only heat supplied is through the burning of No. 6 oil in the single kiln burner. Hot gases pass counter to the pellet flow through the system. The exit gases from the kiln pass down draft through the preheat section through cyclones and are drawn through the drying bed prior to exiting via the stack. The temperatures are normally held within the following ranges: Kiln 2400-2445 °F Preheat 1850-1950°F Drying 480-520°F Exit gas 200°F Pellets 120°F The design capacity of the Republic mine grate-kiln system was 2500 Itpd. Sustained production in excess of 35% over design capacity has been achieved. No screening of the cooler product is practiced. PELLETIZING TEST CONDITIONS When a decision was made to proceed with a test at the Republic mine pelletizing plant to produce 35,000 tons of self-fluxed pellets, several potential failure factors had to be carefully considered. Research work on a batch and pilot plant scale indicated that the grate-kiln system at Republic would require some major changes in order to obtain optimum conditions. In many cases compromises were agreed upon as major equipment changes and revisions were not feasible. The pelletizing conditions which laboratory development tests revealed were required in order to insure successful production of self-fluxed pellets were: 1) Good mixing of limestone and concentrate and proper moisture control; 2) Higher gas flow rates in the preheat section than are normally used; 3) Higher preheat temperatures than normal; 4) Maximum kiln temperature 2350°F. There was just cause for concern about balling problems that might occur. Approximately 10% of dry pulverized limestone was to be added to the specular hematite concentrate just ahead of the Pekay mixers on the belt feeding the balling drum. Large scale

Jan 1, 1963

By Sir Robert Hadfield

SINCE the writer has been intimately connected with the development of manganese steel for many years, some remarks upon the early work with regard to the rolling and forging of this material might he of interest, and particularly as to the question of rails of special quality and of superior wearing qualities. In a paper on Iron Alloys, with Special Deference to Manganese Steel, read before this Institute at the International Engineering Congress in Chicago in 1893,1 the writer mentioned that, about 20 years ago, his firm in Sheffield produced railroad material, such as tires and axles, of forged and rolled manganese steel, thus showing that this product could be manipulated and worked up into the various required forms. The tires illustrated in the paper referred to above formed a particularly difficult class of work to produce in a special steel, but no special obstacles were met with Although there was no difficulty at that time in making and producing manganese steel in various forms, forged, rolled or pressed; nevertheless, on account of its higher expense, sufficient encouragement

Jan 2, 1914