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By R. H. Ernst, H. R. Ogden, D. J. Maykuth

AT present, no theories exist which allow prediction of the effect of alloying additions on the thermoelectric properties of metals. Nevertheless, Battelle and others1 have observed that, at high temperatures, the peak thermal electromotive-force output (relative to a platinum standard) occurs with metals in Group VI of the Periodic Chart. The authors suspected that this peak was associated with the fact that maximum electronic bond stability is achieved with these metals which have six bonding electrons per atom. On the basis of current electron-concentration theory for transition metals and alloys:' it was surmised that the addition of valency electrons to metals of Groups IV and V (accomplished by the addition of metals from Groups VI, VII, or VIII) should progressively increase the thermoelectric-power output of the resulting alloys until an alloy composition is reached at which the number of valency electrons per atom is six. A further increase in the ratio of valency electrons per atom should then decrease the thermoelectric power. In contrast, the addition of bonding electrons to Group VI, VII, or VIII metals should decrease their thermoelectric power since the electron per atom

Jan 1, 1965

Discussion of the paper of Frederic P. Dewey, presented at the Cleveland Meeting, October, 1912, and printed in Bulletin -No. 70, October, 1912, pp. 1075 to 1101. EDWARD KELLER, Perth Amboy, N. J. (communication to the Secretary *) :-Mr. Dewey, in his paper, offers a liberal addition of new data to those already to be found in the technical literature on this subject. However, now as before, the work issuing from the U. S. mints and assay-offices conveys the impression that systematic sampling in those institutions is more or less a secondary consideration, the chief attention being given to the principle of producing approximately homogeneous bars; recourse being taken to remelting or refining the bullion. This practice has been definitely rejected in the realm of copper-bullion sampling, for the reason that in such operations there are always unaccounted losses. Does not the same objection hold true for gold-bullions; although, perhaps,in a lesser degree ? Differences of opinion would seem justified on the following statements made by Mr. Dewey: 1. "Only two classes of alloys can form homogeneous bars-those that are solid solutions, and the eutectics."

Jan 3, 1913

By F. A. Emmerton

I have used for about two years, in the laboratory of the Joliet Steel Company, a rapid method for the determination of phosphorus in iron, steel, and ores, which possesses one or two features sufficiently novel to warrant description. In general, it is the method described by Mr. Benjamin B. Wright (Transactions, vol. x., p. 197), involving the precipitation of the phosphorus by means of molybdate solution, and its estimation in the yellow precipitate by reduction of the molybdic acid, and titration of the resulting oxide with a standardized permanganate solution, according to the principles laid down by Werncke (Fres, Zeit., vol. xiv., p. 1). In the use of this method, I had difficulty at first in obtaining a yellow precipitate of reasonably uniform composition. It is a well-known fact that, to secure this result, the conditions of precipitation must not vary. The principal condition is temperature; and acidity, concentration, proportion of nitrates and chlorides, and time, are important elements. I am aware that uniformity in these conditions has been obtained to a reasonable extent by many chemists,. so that they are enabled to use with success, methods based on the

Jan 1, 1887

By J. A. Bailey, J. H. Tundermann

The dihedral angles of the solid-liquid interfaces were measured at various temperatures above the solidus and the interfacial energies calculated when small additions of copper, indium, lithium, magnesium, antimony, and silicon were made to an aluminum alloy containing 3 pct Sn. When the results were compared with those of the Al-Sn alloy some differences were found which could be interpreted in terms of the ability of the added element to enter into solution or form intermetallic compounds with the aluminum and tin. It was shown that in some cases considerable changes in the shape of intergvanular liquid films can be brought about by comparatively small compositional changes in the alloy. DURING the melting or solidification of an alloy a temperature range is usually found where the presence of a liquid phase may be detected at the grain boundaries of a solid. It is believed that the presence of this liquid phase is responsible for hot tearing in castings and welds and hot shortness in the working of some alloys at elevated temperatures. Rosenberg, Flemings, and Taylor1 in a study of the solidification of aluminum castings have indicated the importance of intergranular liquid films and shown that their shape and distribution at the end of solidification effect the hot tearing characteristics of the material. The shape of such intergranular liquid films are determined largely by the ratio between the solid-liquid interfacial energy (yLS) and the grain boundary energy (ySS). A measure of this ratio (yLS/ySS , relative interfacial energy) is the dihedral angle 8. The dihedral angle 0 is related to the relative interfacial energy by the following expression: Rogerson and Borland 2 have also suggested that the shape of the intergranular liquid is an important factor in determining the susceptibility of a material to hot shortness. They showed that on a comparative basis materials having the lowest dihedral angles at a given temperature gave the greatest severity of cracking. They stated that liquid in the form of globules should be less harmful than liquid in the form of extensive films as more intergranular cohesion should be possible. Rogerson and Borlland 2 also showed that the susceptibility of an A1-Sn alloy to hot cracking can be reduced by small additions of cad- mium. It was found that the cadmium gave an increase in the dihedral angle at all temperatures. Ikeuye and smith3 investigated changes in the dihedral angle and relative interfacial energy with temperature for a number of ternary alloys formed when small additions of bismuth, cadmium, copper, lead, and zinc were made to an A1-Sn alloy. They found that in most instances changes in the dihedral angle were caused by compositional changes in the liquid phase; as the composition of the liquid approached that of the solid the dihedral angle decreased. They noted that the addition of a third element which was soluble in both the liquid and solid phases at a given temperature may decrease the dihedral angle (e.g., the addition of copper or zinc) but otherwise the ternary alloys formed exhibited dihedral angles between those of the A1-Sn binary alloy and those of the binary alloy of aluminum with the added element. Dwarakadasa and Krishnan4 investigated the changes in dihedral angle and relative interfacial energy with temperature when small additions of magnesium, iron, silicon, manganese, sulfur, cobalt, and silver were made to a copper alloy containing 3 pct Bi. They found that in all cases the added elements gave an increase in the dihedral angle and relative interfacial energy when compared with the values obtained for the simple binary alloy at the same temperature. It was noted that an increase in temperature gave a decrease in dihedral angle and relative interfacial energy in each of the ternary alloys studied. Similar results have been obtained by Ramachandran and Krishnan5 for the addition of small quantities of lead. This paper describes the application of dihedral angle measurement to the determination of the shapes of liquid phases at various temperatures above the solidus when small additions of copper, indium, magnesium, lithium, antimony, and silicon are made to an aluminum alloy containing nominally 3 pct Sn. An attempt is made to correlate the measurements with the relative solubility of the added elements in tin and aluminum. The work was undertaken to provide more data concerning the effects of temperature and composition on the shape of liquid films above the solidus. EXPERIMENTAL PROCEDURE In the present work ternary aluminum alloys containing nominally 3 pct Sn and small additions of high-purity copper, indium, lithium, magnesium, antimony, and silicon were made. The alloys were melted in a graphite crucible under an inert atmosphere of argon and cast into ingots 6 in. long by 0.5 in. diam. The ingots were then cut into rods 1.5 in. long, given a 50 pct cold reduction, and machined into test pieces 0.5 in. long by 0.5 in, diam for heat treatment. The alloy samples were annealed at the various test temperatures between the liquidus and solidus for approxi-

Jan 1, 1967

By George S. Ansell, John B. Hudson, Stephen A. Koffler

The permeability of hydrogen through the a phase of palladium has been measured by a low pressure permeation technique under conditions such that bulk diffusion was the rate-controlling process. The observed permeability is described by the equation: J = 1.80 x 1O-3 P½exp(-3745)/RT) cc(stp)/sec/cm2/en over a range of hydrogen pressure, P, from 2.9 x 10-5 m Hg to 5.0 x 10-3 cm Hg, and over a temperature range, T, from 300" to 709°K. The fact that the permeability shows a square root dependence on pressure and a reciprocal dependence on thickness was taken as evidence that bulk diffusion, rather than surface reactions, was the rate-controlling process. The permeability data were used in conjunction with the solubility data of Salmon et al., to determine the diffusivity of hydrogen through palludium as: D = 4.94 x 10-3 exp(-5745/RT) cm2/sec There was no influence of sub structural defects observed over the temperature range employed. From the permeability data obtained, coupled with grain size measurements, it was concluded that the ratio of grain boundary diffusivity to bulk diffusivity was less than 105 over the range of temperature investigated. THE diffusive mass transport of hydrogen in the a phase of palladium has been studied previously by numerous investigators.' In spite of the large amount of attention this system has received, there is not good agreement between the results obtained in different investigations.' This is due in part to the fact that the mass transport was surface-limited during some of these studies, rather than being diffusion-controlled3-5 The reason for the disagreement in other cases is not clear. These studies made use of such techniques as rate of absorption from solutions6 and gases,' electrochemical potential,8 time lag,' and permeation10,11 to determine the mass transport behavior. Of these, the gas permeability technique is the only method which allows an easy test to determine if diffusion is the rate-controlling mechanism, thus eliminating the uncertainty regarding the limiting transport processes inherent in the other techniques. The two most recent permeability studies are those of Toda10 and Davis." Toda determined the permeability of hydrogen in the a phase of palladium over the temperature range from 170" to 290°C, and over the pressure range from 36 to 630 mm Hg utilizing a steady-state gas-permeability technique. Toda's result was: J = 1.41 x 10-3 P½ exp(-3220/RT) where J = specific permeability in cc(stp)/sec/cm2/cm, P½ = square root of the inlet pressure in (cm Hg)½, R = Universal gas constant, and T = temperature in deg Kelvin. Davis11 also employed a steady-state gas-permeability technique over the temperature range from 200" to 700°C and over the pressure range from 0.02 to 760 mm Hg. His result for the permeability of hydrogen in the a phase of palladium was: J = 3.15 x 10-3 P½ exp(-A440/RT) In the range of overlapping temperature for these two investigations, the values of the specific permeability calculated from the above two equations differ by a factor of about 1.8. In the present investigation, the permeation of hydrogen in the a phase of palladium was determined over a wide temperature range, 27" to 436oC, and over the pressure range from 2.9 x 10-5 to 5.0 x 10-3 cm Hg. This temperature range overlaps that of the previous investigations of Toda and Davis, but also covers the lower temperature range which has never before been investigated. The lower pressure range used here avoided the interaction between the dissolved hydrogen atoms observed at higher hydrogen concentrations.' MATERIALS The as-received palladium specimens were cold rolled from a casting and were supplied as 5.08 cm discs of 0.508 and 0.762 mm thickness. According to J. Bishop and Company specifications, the composition of the discs was 99.95 pct Pd, the balance being Cu, Ag, Au, and Ir. In order to obtain samples of varying grain size, the as-received discs were then heat treated. Sample 1 was treated for eight minutes in a nitrogen atmosphere at 810°C and then air-cooled. Sample D was heated first to 550°C in helium. The helium atmosphere was then immediately replaced by hydrogen and the temperature was slowly raised to 1220°C and held for 22 hr. The sample was then cooled to 550°C where the hydrogen was replaced by helium and the disc was further furnace-cooled to room temperature. Sample H was given the same heat treatment, only with hydrogen substituted for helium below 550°C. The reason that hydrogen was not used throughout the entire annealing cycle for samples D and H was to prevent the distortion encountered by low-temperature cycling in hydrogen observed by Darling." After these heat treatments were completed, the

Jan 1, 1970

By J. W. Spretnak, D. A. Chatfield, G. W. Powell, J. R. Eifert

In nzost cases, the driving force for a lattice transformation is produced by supercooling below the equilibriunz transformation temperature. The interfnce reaction in isothermally annealed, multiphase diffusion couples may involve a luttice transformation which also requires a driving force. Direct experinzental evidence has been obtained for the existence of the driring force in the form of a supersaturated phase at the aocc)-0@cc) interface in Cu:Cu-12.5 ult pct A1 couples; the super saturation is equivalent to an excess free energy of approximately 3 cal per mol at 905. A tentatiue interpretation of the dynanzic situation a1 the interface based on the free energy-composition diagram is proposed. THE presently accepted theory of diffusion in multiphase couples1 states that there will be a phase layer in the diffusion zone for every region which has three degrees of freedom and which is crossed by the diffusion path in the equilibrium phase diagram. For binary systems, this restriction excludes all but single-phase fields and, for ternary systems, only one- and two-phase fields are included. In addition, Rhines"~ as well as other investigators3 6 have reported that the compositions of the various phases adjacent to the interfaces are, for all practical purposes, the compositions given by the intersections of the diffusion path with the solubility limits of the single-phase fields of the equilibrium phase diagram. Some studies of the rate of thickening of these intermediate diffusion layers indicate that the thickness of the layer changes para-bolically with time, or: where x is the position of the interface relative to an origin xo, t is the diffusion time, and k is a temperature-dependent factor. crank7 shows mathematically that, if the compositions at an interface are independent of time and the motion of the interface is controlled by the diffusion of the elements to and from the interface, then the segments of the concentration penetration curve for a semi-infinite step-function couple will be described by an equation of the form: hence, Eq. [l] follows from Eq. (21 if the interface compositions are fixed and if the motion of the interface is diffusion-controlled. Although the concept of local equilibrium being attained at interfaces has assumed a prominent role in the theory of diffusion in multiphase couples, experimental evidence and theoretical discussions which challenge the general validity of this concept have been reported in the literature. arkeen' has stated that strict obedience to the conditions set by the equilibrium phase diagram cannot be expected in any system in which diffusion is occurring because diffusion takes place only in the presence of an activity gradient. Darken also noted that it is usually assumed that equilibrium is attained locally at the interface although the system as a whole is not at equilibrium, the implication being that the transformation at the interface is rapid in comparison with the rate of supply of the elements by diffusion. ISirkaldy3 indicates agreement with Darken in that he believes the concept of local equilibrium is at best an approximation because the motion of the phase boundary requires that there be a free-energy difference and, hence, a departure from the equilibrium composition at the interface. Seebold and Birks9 have stated that diffusion couples cannot be in true equilibrium, but the results obtained are often in good agreement with the phase diagram. The initial deviation from equilibrium in a diffusion couple will be quite large because alloys of significantly different compositions are usually joined together. Kirkaldy feels that the transition time for the attainment of constant interface compositions (essentially the equilibrium values) will be small, although in some cases finite. Castleman and sieglelo observed such transition times in multiphase A1-Ni couples, but at low annealing temperatures these times were quite long. Similarly, ~asing" found departures, which persisted for more than 20 hr, at phase interfaces in Au-Ni and Fe-Mo diffusion couples. Braun and Powell's12 measurements of the solubility limits of the intermediate phases in the Au-In system as determined by microprobe analysis of diffusion couples do not agree with the limits reported by Hiscocks and Hume-Rothery13 who used equilibrated samples. Finally, Borovskii and ~archukova'~ have stated that the determination of the solubility limits of phase diagrams using high-resolution micro-analyzer measurements at the interfaces of multiphase couples is not an accurate technique because of deviations from the equilibrium compositions at a moving interface; diffusion couples may be used to map out the phase boundaries in the equilibrium diagram, but the final determination of the solubility iimits should be made with equilibrated samples. The purpose of this work was to investigate the conditions prevailing at an interface in a multiphase diffusion couple and to compare the interface compositions with those associated with true thermodynamic equilibrium between the two phases. Microanalyzer techniques were used to measure interface compositions in two-phase Cu-A1 diffusion couples annealed at 80@, 905", and 1000°C for various times.

Jan 1, 1969

By Jack L. Taylor

Single crystals of tungsten grown from powder -metallurgy swaged rod by high-temperative annealing were deformed in tetzsion at temperatures from 2500 to 5000 OF. Orientation of specittzen tensile axis, strained ratrix, and defortnation bands was determined optically by reflections from {110} etch pits. Slip traces meve analyzed and slip directiorz determined. Results indicate that {110}(111) , {112){111}. and {123}{111} type slip occur in tungsten over the terpe,atuve rutge investigated. Slip is orientation-dependent occuvring on tCuzt cowzbitzation oj slip plane and direction which has the highest critical resolved shear stvess. Overshooting appears to be a general occurrence between 2500' and 5000°F. Dejornatiotz bands show rotation in a directiorz opposite to the yotation of tire tensile axis. DEFORMATION in bcc metals has been reviewed by Maddin and Chen,' Keh and eissman,' and most recently by Nabarro, Basinski, and olt. From these reviews it is apparent that some disagreement exists concerning the crystallography of plastic deformation in bcc metals. There is evidence of noncrystallo-graphic slip, the crystal slipping on or near a noncrys-tallographic plane in the (111) zone for which the resolved shear stress is greatest. There is also evidence to indicate that crystallographic slip occurs in the planes of the same zone. On the other hand, there is agreement that the close-packed direction ( 111) is the slip direction in bcc metals. Further, in pure bcc metals4 and alloys the operative crystallographic slip systems are strongly dependent on temperature. Both crystallographic and noncrystallographic slip have been reportede8 in tungsten, a group VIA bcc metal. The number of slip families which operate in the case of crystallographic slip, however, has been in question. The earliest study by oucher' of single-crystal tungsten tested at temperatures of 1800 to 5000°F led to the conclusion that only {112)( 111) type slip operated. Raymond and eumann recently reached the same conclusion studying deformation by rolling of plasma-flame single crystals at 1800°F; however, only [loo] and [110] orientations were studied. Work at high temperatures by Leber and Pughs on tungsten and Chen and Maddin9 on molybdenum suggests that conjugate slip on nonparallel (110) planes may account for the slip on (112) and (123) planes found by others working with bcc metals. The present paper presents evidence of three families or modes of slip in tungsten in the temperature EXPERIMENTAL PROCEDURE Material. Standard microtensile specimens, 0.160 in. diam by 0.640 in. gage length, were ground from commercial powder-metallurgy swaged tungsten rod, type MK. Specimens were heated for 10 min at 5150°F or 6 hr at 5400°F in vacuum of 1 x 105 Torr or less to produce single crystals. At the lower temperature an average of two out of seven specimens heated in a group developed single crystals throughout the specimen length as shown in Fig. 1, the rest remaining wholly poly crystalline. At the higher temperature, three or four out of seven specimens became single crystal. Other than to note that Laue X-ray photographs generally showed sharp, well-defined spots, no attempt was made to assess crystal perfection or measure dislocation density. Two tungsten single crystals grown from the melt by the plasma-arc process were also used for this study.

Jan 1, 1967

By C. K. Eilerts, J. D. Ham

Laboratory research has been conducted to evaluate the characteristic effects of condensate saturation on the mobility of gas in typical reservoir rocks. A pump with two pistons provided phases in equilibrium at controlled flow rates and constant liquid-vapor volume ratios. Core samples were tested in a holder that permitted sealing steady-state phases in the pore spaces under flow test pressures for weighing with sufficient precision to give an accurate measure of the attained saturations. Parameters of the study were pressure, apparent velocity, flowing liquid-vapor volume ratio, fluid composition, core material and length-to-diameter ratio. Tests were conducted at 515 and 1,515 psia to determine the effect of pressure on the mobility-saturation relationship. Influence of the apparent velocities 0.30, 0.15 and 0.07 cm/sec and of five liquid-vapor volume ratios from 0.0001 to 0.01 was determined at 515 psia The principal fluid system was nitrogen and and separator liquid from a Gulf Coast condensate, but the effect of a condensate of different viscosity was also determined. The significance of a possible concentration of liquid near the outlet end of the test cores was investigated. Core materials included a consolidated sandstone and a low-permeability limestone. Relative mobility and liquid-vapor volume ratio relationships are concluded to be dependent on pressure, saturation and, to a lesser extent, on velocity. For each porous medium and fluid there is a minimum saturation essential to two-phase flow, and high velocities of flow have only limited effect on saturations in this range. INTRODUCTION It is now recognized that knowledge of the availability of a reservoir gas — the period that gas may be recovered from a reservoir at a given rate — is as important as the estimate of gas in place. When reservoir conditions are such that pressure decline owing to production will result in retrograde condensation, liquid saturation can increase in the structure around the production well in a way that may restrict flow capacity, and hence future availability. l Based on a numerical solution of transient radial flow of single-phase gas-condensate fluids, 2 a program for computing the accumulation of condensate in a reservoir and the effect of this condensate on deliverability has been developed. During this development a need evolved for data that described the influence of pressure, velocity of flow and condensed liquid on mobility as recovery progressed. This paper presents the results of experimental investigation to obtain insight into the mobility relationship at reservoir pressures of gas-condensate fluids. A core holder for flow tests at reservoir pressure was developed to weigh the core and its fluid contents under pressure to determine saturation. A specially constructed pump was used to drive a two-phase fluid through the core until a steady state prevailed. The core was used as a differential device, and properties measured were intensive rather than extensive. APPARATUS Fig. 1 shows a schematic representation of the major pieces of equipment used in the mobility determination. The weighable core holder is connected to a two-piston, constant-displacement pump. Attainment of steady-state flow is indicated by stability of the flow differential read from the high-pressure manometer. WEIGHABLE CORE HOLDER An important part of the data needed was the mobility-saturation relationship. This required that mobilities and saturations be measured at pressures, flow velocities and liquid-vapor volume ratios characteristic of condensate reservoirs.

By J. W. Axelson, J. N. S. Kwong, J. T. Adams, E. L. Pire, J. F. Johnson

CRUSHING has always been a major operation in the chemical and metallurgical industries, yet little is known about the theory of crushing, and today, the design of crushers is still based almost entirely on empirical knowledge and accumulated practical experience. In view of the increasing national need for the economic working of poorer grades of ores, the lack of a fundamental understanding of this unit operation hardly presents a satisfactory situation. Basic investigations of crushing have been concerned mainly with three phases of the problem, 1—the mechanism of the fracture process itself, 2— the particle size distribution of the crushed product, and 3—the relationship between the energy input and the amount of new surface produced. Probably adequate information on these phases will be required for a comprehensive understanding of the process of crushing. A bibliography covering these phases will be given as well as a review of the work done in recent years at the University of Minnesota on the relationship between the energy input for crushing and the amount of new surface produced. Fracture of Solids This phase of the crushing problem is the most fundamental because it is concerned with the actual mechanism of fracture. The main problems in a study of the fracture process are concerned with the questions of why and how fracture occurs and why there is such a discrepancy between the actual and theoretical energies needed in a fracture process. In considering the how of fracture, Poncelet40 carried Out experiments On the crushing of glass under compression. Actual photographs were taken of the glass plates in various stages of fracture-From these experiments Poncelet was able to postulate a probable mechanism of fracture. Probably because of the quantitative nature of the problem, considerable effort has been expended to find an explanation for the low tensile strength of materials and the conversely high energy for crushing. Tensile strengths are often only 1/500 of the theoretical while the energy for crushing is usually at least 500 times the theoretical. A review of the work to explain the low strength of glass is given by Weyl,52 in which the work of Griffith," Joffe,32 and Powell and Preston " are discussed. In a recent paper Seitz46 holds that the presence of flaws and fissures, as originally expounded by Griffith, is the most probable reason for the low strength of metals. Since a mass of data has been accumulated on the fracture strength of materials, several investigators have attempted to correlate this data in the form of an equation. Glathart and Preston," Taylor,40 Ponce-let,40 Machlin and Norwich," and Frederickson and Eyring,20 have all considered this problem, and the final relationship has always been that the stress for fracture is proportional to the logarithm of time. Murgatroyd30 arrived at a very similar relationship by a different method. The study of the fracture process has used many methods. Among some of these are the thermody-namic approach used by Furth21 which was based on the work of BornxL and later used by Saibel,43 and the statistical method applied by Fisher and Hollo-mon.10 In recent years metallurgists have concerned themselves with the problem of brittle .fracture as opposed to the usual plastic failure of metals. The great amount of interest shown is reflected by the number of contributors to the recent symposium on the fracture of metals.' Repeated failures of welded ships during World War II have accelerated these Studies.31,50,34 The shifting of thought from an emphasis on the

Jan 1, 1952

By P. Hazebroek, M. Prats, E. E. Allen

Well locations in water floods frequently do not coincide with the ideal well locations associated with the flood pattern which is used. A question of importance is. "How much oil is lost because of this?". This is the problem treated in this paper. It is assumed that each pattern in a five-spot flood has the proper number of production and injection wells but that the wells may be off-pattern. The distance by which a well is off-patern is given in terms of the pattern spacing, defined as the length of one side of a five-spot. The influence of off-pattern wells on the performance of a five-spot flood has been investigated mathematically for unit mobility ratio. All production and injection rates are assumed to remain equal. The loss in recovery resulting from pattern irregularitie: has been calculated at a cumulative water injection corresponding to a 98 per cent water-cut in a regular five-spot. Displacing a single production or injection well by about one-third the pattern distance reduces the total field recovery by 4.4/N per cent of the recovery obtainable with regular spacing, where N is the number of five-spots in the flood (assumed large). When off-pattern wells are separated by at least one regular five-spot and are displaced by less than one-third the pattern distance, the total loss in recovery in a large-scale flood is, at most, 1 per cent of the recovery obtainable from that field with a regular five-spot pattern. However, much higher losses may occur if the off-pattern wells are not separated by a regular five-spot, if the rates are imbalanced, or if the mobility of the injected water is higher than that of the crude. Although the loss in oil recovery due to pattern irregularity often may be low, the off-pattern case will always require injection of more water to reach the same final water-cut. The volume of water injected per unit volume of oil displaced has been calculated for each five-spot adjacent to a five-spot containing a single 08-pattern well. The cumulative water injection at the time of 98 per cent water-cut may be increased by as much as 37 per cent when a production well is displaced one-third the pattern distance toward an injection well. The existence of differences between actual subsurface locations and the idealized well patterns used in secondary recovery operations is well recognized. However, the methods commonly used for predicting waterflood behavior ignore such differences, even when subsurface locations are known. The reason for this is simple. The idealized well patterns are highly symmetrical and, as such, the production history of the pattern (and even of the field) can be determined from that of a few production wells—usually from only one. Consideration of the many irregular well spacings found in a specific field would entail a large amount of work, and then the results would be applicable only to that specific field. In an attempt to provide an answer to the more general problem, this paper considers a water flood having an idealized well pattern, except for one well which is not at its regular location. When several off-pattern wells are present, their contributions are assumed to be additive unless the off-pattern wells are close to each other. Only four positions of the off-center well (at x, y. of Fig. 1) are considered in this paper. These are shown

INTRODUCTION Trade financing is a particularly important component of short-term financing for a minerals company since errors, extra costs, or payment delays/defaults can easily wipe out the profit margin on a particular shipment or can cause problems when arranging purchases of e.g. reagents. It is required to make any minerals operation function and does not have to be cross-border to require proper management. Sources of working capital are as follows: 1. Extended credit terms from suppliers 2. Inventory loans from banks, finance companies 3. Accounts receivable financing or factoring 4. Credit lines or overdraft facilities from banks. TRADE CREDITS These are provided under the familiar terms "net 10 days" or payment due by the "10th day of the following month." Thirty days for payment is usual but longer periods can be negotiated with regular suppliers. Shipment may be made on open account with specified periods for settlement. In the mining industry, a custom smelter gains trade credit by paying for concentrates three months after the month of shipment. INVENTORY LOANS Various forms of inventory finance are provided via "floor-plan" or warehouse financing. A set percentage, usually 60%-80%, of a good-quality, readily saleable inventory item (e.g. bullion, concentrates, ingots) will be provided by a bank or finance company which will usually have security over these products and has a right to inspect the goods from time to time. Legal security will he achieved by warehouse receipts, floating liens, chattel mortgages, trust receipts, or through collateral management service companies. The latter certify control over stock or distribution outlets and often carry insurance against fraud. Costs range around 1.5% - 2.0% p.a. or more plus some fees to cover out-of-pockets or other costs. ACCOUNTS RECEIVABLES Accounts receivable financing is based on the company's generation of satisfactory receivables which are continuously assigned to a bank or finance company ("factoring"). Because of the risks in being able to collect receivables, such as payments to a smelter for its blister copper shipments to a refinery, this form of financing costs as much as 3% - 5% of the debt amount purchased plus an additional charge for processing paperwork. Receivables can be purchased with or without recourse and on a notification or non-notification basis to the client's customer to, respectively, pay the invoice directly to the bank or not. LETTERS OF CREDIT Letters of Credit ("L/C's") are a common feature of international trade finance whereby a bank, at the request of the buyer, issues a written undertaking to an exporter to pay a specified sum of money within a set time on presentation of previously specified documents. This undertaking means that the exporter is no longer relying on the credit standing and integrity of the foreign importer. A dispute about shipment does not otherwise affect the obligation to pay upon presentation of a "clean" set of documents. These documents include the hill of lading and other documentation, often on standard "form" bases. There are a number of conventions and techniques in L/C's such as irrevocable/revocable L/C's, time L/C's, confirmation/advising L/C's and transferable L/C's. These are tools to adjust for the varying risks that the importer will not pay. Other routes where one is comfortable with an importer include documentary sight hills (D/P hill), documentary term bills (D/A bill), and, of course, open account.

Jan 1, 1985

By Edward Wisser

THE Pachuca silver district, situated about 100 kilometers northeast of Mexico City (Fig. 1), covers roughly the southeastern half of the Sierra de Pachuca. The latter is a mountain range with northwest trend, and forms a part of the northeastern rim of the topographic basin known FIG. 1.-LOCATION OF PACHUCA DISTRICT AND OTHER MINING CAMPS. as the Valley of Mexico. The length of the Sierra proper is about 50 km., its greatest width about 9 km., and it rises to a maximum of 600 meters above the general level of the basin floor. The Pachuca district consists of two contiguous subdistricts, the Pachuca area and the Real del Monte area. The center of the Real del

Jan 1, 1936

[Abrahamson, Guy C., (5'43) 1st Lt., A.C., 0-880861, Base Weather Sta., Fairfeld-Suisun AAB, Suisun, Calif. Adam, Howard Wilbur, (S'46) 45 Eaton Ave., Woburn, Mass. Aguilar, Ruperto G., (S'43) Texas College of Mines, El Paso, Texas. Ainge, Ronald Farra, (S'43) Otago University, Dunedin, New Zealand. Albala, Américo, (S'44) Casilla 4106, Santiago, Chile. Albrecht, Theodore J„ (S'42) Pfc., Co. F, Syme Hall, Rm. 1, SCU 3421, ASTP, N. C. State College, Raleigh, N. C. Aldridge, E. E., Jr., (S'39) Box 58, Eagle Pass, Texas. Alfred, Robert M., (S'40) 25 South St., Brighton, Mass. Allan, Douglas H. W., (S'40) 460 Main St., E., Hamilton. Ont.. Canada.]

Jan 1, 1946

By John J. Elango

Strain gage load cells, the most widely used type of nonmechanical weight sensor, are capable of taking measurements between 0.45-4.5 million kg (1-1 million lb) with an accuracy of 0.05%. They are available in a wide range of standard capacities, configurations, and accuracies, and special load cells may be custom-manufactured to meet unusual requirements. Typical applications include automated batch processing, process monitoring and control, mixing of powders and liquids, weighing coal or other materials in silos, and in large platform systems that weigh trucks and railcars. Because the strain gage load cell produces an electrical signal proportional to the applied load, it readily interfaces with readouts, keyboards, computer terminals, and alarm systems.

Jan 6, 1979

By W. L. McMorris, Shiou-Chuan Sun

The Convertol process was first described in Ger- many by Muschenborn1 in 1952. In the U. S. Fraser2 reported this new process in 1953, and Brisse and McMorris-resented the results of a Convertol pilot plant at the Alpheus preparation plant in Gary, W. Va., illustrating the mechanics of the process by a series of sketches. The purpose of the present investigation was threefold: 1) to determine the relative effectiveness of various oils and hydrocarbons for recovering coal by the Convertol process, 2) to ascertain the behavior of coal pulps in this process under various operational conditions, and 3) to compare Convertol with flotation in the recovery of fine coals.

Jan 11, 1959

By G. R. St. Pierre, A. Ghosh

In the Si-C-0 system at temperatures of interest in process metallurgy there are four stable condensed phases—silicon, carbon, silica, and silicon carbide (Sic). Silicon melts at 1683oK1 and shows negligible solubility for carbon and oxygen at 1700°K. However, silicon dissolves approximately 1.5 at. pct C at 2500oK.2 Carbon in the form of graphite remains pure and dissolves negligible amount of silicon.' Silica (crysto-balite) melts at 2001°K' and is essentially a stoichio-metric compound. Silicon carbide is a solid and shows negligible deviation from stoichiometry up to approximately 2800oK.2 Besides the condensed phases there is a gas phase

Jan 1, 1970

AARONS, J. BOYD, Major. AGNEW, FRANK VANS. ALLEN, HERMAN H., Private, D Co., 8th Reserve -Engineers. AMBLER, HARRY A., Second Training Camp, Ft. Sheridan, Ill. BAINS, THOMAS M., JR., Major, Engineer Officers' Reserve Corps. BANKS, H. R., Lieutenant, Canadian Engineers, B. E. F. BARBOUR, PERCY E., Deputy Supt. (Captain), New York State Troopers; Captain, 22c1 Regiment, N. Y. N. G. BARLING, H. B., 1st Lieutenant, Engineer Officers' Reserve Corps. BARRETT, LESLIE P., Lieutenant, A. E. F., France. (Unattached.) BENSEL, J. A., Major, Engineers' Reserve Corps. BIGELOW, BRAXTON, Royal Engineers, B. E. F. BLOOMFIELD, E. C., Lieutenant. BORROW, F. K. BOWLES, MARTIN F., 2d Lieutenant of Infantry, Camp Funston, Kans.

Jan 10, 1917

By Paul A. Farrar, Sanford Adler

The Tz-Zr system was reinvestigated using both metallographic and X-ray diffraction techniques. It mas found that titanium and zirconium are soluble in all proportions in both the a and 0 phases. The minimum in the transformation was found at 50 at. pct and 535°C. THE Ti-Zr system has previously been the subject of several investigations.1-6 A study by Hayes et al.5 using magnesium-reduced titanium and zirconium melted in graphite crucibles indicated that the system was a continuous series of solid solutions in both a and 0 phases with a minimum at approximately 545°C and 65 pct* Zr. These conclusions were substantiated by the work of Duwez4 as well as by the limited data of Craighead et al.,3 Fast,2 and deBoer.1 However, a more recent investigation of the titanium-rich region by Ence and Margolin6 indicated that the solubility of zirconium in a, titanium at 500°C is approximately 22 pct with the a + 0 field extending to approximately 47 pct Zr. Therefore in order to resolve this discrepancy the following investigation was initiated. EXPERIMENTAL PROCEDURES The alloys used in this investigation were prepared as 20- to 30-g buttons by nonconsumable electrode melting in a helium atmosphere. The starting materials were Bureau of Mines titanium BHN 71 and Foot Mineral iodide crystal bar zirconium. The titanium was premelted before the alloys were prepared to avoid excessive weight losses in the final melting. The compositions of the alloys prepared were as follows: Ti-12.0, 22.2, 29.0, 39.6, 50.0, 58.0, 72.4, 83.5. and 90.8 pct Zr. Prior to heat treatment the alloys were cold-worked 10 to 20 pct, stopping at the first signs of cracking. Specimens for heat treatment were wrapped in molybdenum sheet and annealed in argon-filled quartz capsules for the following times and temperatures: 750°C-40 days, 675°C-61 days, 600°C—109 days, 575°C-112 days, 550°C-112 days, 525°C—127 days, and 450°C —153 days. Quenching was accomplished by breaking the capsules in an iced-brine solution. The standard techniques used for polishing the specimens involved belt grinding, grinding on emery paper, polishing electrolytically, and etching with Remington "A" etch7 or "R" etch 8 Debye-Scherrer X-ray powder photograms were obtained for a number of samples using a 114.6-mm camera and CuK, radiation. Exposure times were from 19 to 23 hr. The powder samples were obtained by filing to 270 mesh size. After filing the samples were wrapped in molybdenum foil capsuled in quartz and reannealed at the temperature of original heat treatments; following the heat treatment the samples were quenched into iced brine without breaking the capsules. RESULTS AND CONCLUSIONS On the basis of the microstructural examinations of the heat-treated samples and of the X-ray diffraction data, the Ti-Zr system shown in Fig. 1 was constructed. The data indicate that a, and 0 titanium form a complete series of solid solutions with a, and ß zirconium. The minimum was found to occur at 65 pct (50 at. pct) Zr and 535°C, in excellent agreement with the earlier investigations,1-5 see Fig. 2. Typical microstructures are shown in Figs. 3 to 7. Figs. 3, 4, and 5 show the 22.2, 39.6, and 50.0 pct Zr alloys after heat treatment at 675°C for 61 days with the 22.2 pct Zr showing equiaxed a, and the 39.6 pct Zr alloy a + transformed ß, while the 50 pct Zr alloy shows only transformed B. Figs. 6 and 7 show the 29.0 and 39.6 pct Zr alloys after heat treatment for 109 days at 600°C. The 29 pct Zr alloy has an equiaxed a structure while the 39.6 pct alloy has a partially recrystallized a+ß structure. X-ray diffraction data obtained from the 50 pct Zr alloys after heat treatment at 525° and 450°C as well as from the as-cold-rolled material showed only those lineos which couid be indexed a: a titanium, good agreement with the previously published values. 2,4,5,9 Chemical analysis* of the 50 pct Zr alloy

Jan 1, 1967

By R. C. Buehl, M. B. Royer

High manganese slags of low phosphorus and iron content are produced by air oxidation of high phosphorus spiegeleisen in a basic-lined converter. Control of phosphorus and iron within specification limits for ferromanganese ore feed is obtained by a unique cyclic operating procedure. Various types of slags, or synthetic manganese ore, can be made. AN affiliated paper' describes the production of high phosphorus spiegeleisen containing 14 to 23 pct Mn and up to 4 pct P in an experimental blast furnace from open-hearth slag or manganiferous iron ore. This phosphorus content is too high for use of the spiegel in normal steel-production operations. Consequently, a preferential separation must be effected whereby the manganese is concentrated in a product that is usable in industrial operations. The preferential separation methods being investigated for this phase of the work are confined to pyrometal-lurgical processes for ready incorporation into steel-plant operations. It is fortunate that manganese is more actively oxidizable than iron or phosphorus, and therein lies a preferential separation method for isolating manganese from these two elements. Silicon is more strongly oxidizable than manganese, and its oxidation precedes, or occurs simultaneously, with manganese. Therefore, manganese and silicon are separable into a high manganese oxide slag phase while the phosphorus and iron remain in the molten metallic state. Complete separation of these elements represents an ideal condition which is not generally attainable in actual operations. This pyro-metallurgical method for separating manganese from phosphorus and iron by preferential oxidation was investigated by blowing 500 lb of metal in a basic-lined vessel to obtain preliminary information on the effectiveness of the procedure. Certain conditions of attainment in the separation process are desirable in any method for removing manganese from high phosphorus spiegeleisen, such as: 1—High recovery of manganese in the oxidation product; 2—the product to be of equal or better quality than ferromanganese-grade ore—48 pct Mn minimum, less than 10 pct SiO2, and Mn-P ratio of 300:1; and 3—attainment of the enumerated objectives in a product amenable to industrial handling, such as a slag of high manganese content that will flow from the processing vessel and of sufficient fluidity for ready separation of metallic granules that may have become mixed with the manganese slag phase. Previous Work Recovery of manganese from low grade ores and industrial byproduct slags by smelting to spiegeleisen, with subsequent oxidation to synthetic ferro-manganese-feed ores, has been a subject for periodic investigation during the past four or five decades in the United States and Germany. Joseph' and associates of the Bureau of Mines North Central Experiment Station, Minneapolis, Minn., smelted manganiferous iron ores of the Cuyuna range, Minn., to spiegeleisen and subsequently tried air and ore oxidation procedures for concentrating the manganese into synthetic ferrograde manganese ore. Joseph's results on the operation of a side-blown basic-lined converter for air oxidation of manganese from molten spiegeleisen were so discouraging that the procedure was abandoned after 11 blowing tests. Much slag was thrown from the converter vessel; phosphorus content was four to five times the maximum allowable for ferro ore; and a manganese-iron ratio of only 2 or 3:1 was obtained in the slag instead of the required 8:1. Oxidation of manganese from spiegeleisen with about 0.5 pct P, by adding iron ore to molten spiegel in an experimental open-hearth furnace, proved moderately successful in Joseph's experiments. The main drawback to the operation was the necessity for over-oreing for effective oxidation of the manganese with consequent too high iron oxide residual in the slag. Furthermore, the phosphorus content was proportional to the iron concentration and therefore much too high, so that several hours of reduction by a carbonaceous material were required to adjust the iron and phosphorus to the desired content of high grade ferro feed. A troublesome feature of the slag product of the spiegel oxidation process was its lack of fluidity if the silica content was less than 10 pct, the concentration considered desirable for the synthetic ore. Approximately twice the desired concentration of silica was required to impart enough fluidity for transfer from the vessel by pouring. The acute shortage of manganese in Germany

Jan 1, 1953

By R. L. McCarron, G. R. Belton

The diffusivities of oxygen and sulfur in liquid iron have heen determined hy a capillary technique in which the surface concentrations of the solutes were established by means of appropriate H2/H2 and H2S/H, gas mixtures. Total diffusate and concentration profile results are shown to be in good accord, yielding for- 1560 and Supporting results at 1660°C are also presented. The conditions necessary to avoid gas transport control in this type of experiment are discussed. IN spite of their importance in understanding the kinetics and mechanisms of refining reactions, the dif-fusivities of oxygen and sulfur in liquid iron are not well established. Accordingly, as a first step in studies of rates of solute absorption from the gas phase into liquid iron, new measurements of these diffusivities have been made and are presented in this paper. The only published results for the diffusion of sulfur in pure liquid iron are those of Kawai.' He used a diffusion couple technique in which two cylindrical specimens, one containing sulfur and the other with negligible sulfur concentration, were joined together and held in a refractory capillary. After an experiment, the sample was quenched and the concentration distribution of the solute determined. Kawai recognized that significant changes in solute distribution occurred during melting and freezing and he attempted to correct the concentration profiles for these effects to give a sulfur diffusivity of 4.6 x 10-6 sq cm per sec at 1560°C. The method of correction, however, was not rigorous and the uncertainty in this result cannot be easily assessed. Koslov et a1.2 have reported the diffusivity of oxygen in iron as 7.8 x 10"3 sq cm per sec at 1660°C. This value appears to be unreasonably high but, unfortunately, details of their experiments are not available. Shurygin and Kryuk have used the rotating disc method for a study of oxygen diffusion in liquid iron. In their experiments a silica disc was rotated in liquid iron containing oxygen, and the rate of formation of liquid iron silicate was determined by measuring the decrease in weight of the disc. On the assumption that the rate of dissolution was controlled by the diffusion of oxygen in the iron, the diffusion coefficient was computed to be 5.2 x sq cm per sec at 1550°C. However, the Levich equation, which was used to interpret the rate data, was originally de- rived for the case of mass transfer between a solid disc and a single-phase liquid. The hydrodynamic and diffusion boundary layers in the iron stirred by a disc, via coupling of the silicate melt, may be appreciably different from those predicted by Levich's equations. Recently, Novokhatskiy and Ershov, using an identical experimental method to that of Shurygin and Kryuk, obtained a diffusivity for oxygen in liquid iron of 1.22 x 104 sq cm per sec at 1550°C: no reasons were offered for the disagreement. Schwerdtfeger5 has also recently studied the diffusivity of oxygen in liquid iron. He reacted shallow melts of liquid iron, 0.5 to 1.0 cm deep and contained in high-purity alumina crucibles, with appropriate H20-HZ-He mixtures. The total sample was analyzed, without sectioning, to obtain the average concentration of diffusate. A value at 1610°C of D = 12(3) x 10-5 sq cm per sec was obtained from the results of twenty experiments.= Oxygen profile measurements, which were carried out in three additional experiments using long capillaries and the semiinfinite boundary conditions, indicated a diffusivity about half that computed from the shallow bath experiments. Possible sources of error in Schwerdtfeger's study will be discussed later in this paper. EXPERIMENTAL TECHNIQUE The essential arrangement of the diffusion cell is shown in Fig. 1. The liquid iron was contained in an alumina capillary, 3 to 4 mm diam and 3 to 9 cm long, which was supported by a hollow alumina pedestal and this whole assembly was held within a movable alumina reaction tube. This tube, which was about 7 mm in bore

Jan 1, 1970