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By C. J. Ramsburg

THE construction and operation of by-product coke-oven plants in America are essential to strong national defense and of the greatest importance to many widely diversified undertakings as well as to safety and health. CARBONIZATION PROCESS Coal used under a boiler or in a locomotive is consumed by combustion. Coal used in a by-product oven is distilled or carbonized, meaning that heat is applied to the coal, out of contact with air, causing a distillation that removes the volatile matter in the coal in the form of gas and vapor, leaving coke as a final product. From the gas and vapor distilled from the coal, many valuable substances can be secured, known as by-products. Hence the name "by-product oven." The simplest example of this principle can be shown by means of an ordinary clay pipe. If powdered coal is placed in the bowl of the pipe, the opening of the bowl is plugged with clay, and the bowl placed in a flame, the bowl will become hot, transferring the heat through the wall of the bowl to the coal within. When this coal attains a temperature of about 950°F., gas will begin to pour out of the pipe stem, and this gas may be lighted. A black liquid also will exude from the stem of the pipe. This is tar mixed with certain other products. What remains in the bowl after distillation is coke. A coke oven corresponds to the bowl of the pipe. A modern oven of the latest type is a refractory brick chamber approximately 42 ft. long and 14 ft. high, averaging 18 in. in width. The oven is filled with coal through closable charging holes in the oven top. Each end of the oven consists entirely of a self-sealing door, the removal of which permits the finished coke to be discharged by means of a power-operated pusher machine. The ovens are built in batteries, and the heating is effected by gas burned in vertical flues in the oven walls, each set of flues heating the walls of two adjacent ovens. Such ovens carbonize a charge of approximately 18 tons of coal in 18 hr., or have a daily throughput of 24 tons per oven, producing about I 7 tons of coke. In times of need, the output may be increased by raising the temperature of flues, thus shortening the coking time. There is one great essential difference in principle between distillation in a clay pipe and in a coke oven. In the 18-in. oven, the distillation proceeds from two parallel walls held at a high temperature (over 2000°F.) and instead of all the coal being heated at once, the distillation is a progressive one creeping inward. The average travel of this heating is 1/2 in. per hour from each vertical wall, and as the volatile products are formed progressively they must push away from the interior toward the wall through the previously formed hot coke, then up the walls and over the top of the coal charge, finally escaping through the outlet pipe. This results in a cracking of the components into many different and valuable substances not formed when the carbonizing temperature is low.

Jan 1, 1942

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain' and magnesia.' Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann'" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By Thomas Fraser, David R. Mitchell

THE primary purpose of the loading plant is to transfer the finished product from the preparation machines to the railroad car, truck, or barge in which it is to go to market. Secondary purposes of the loading plant are: to prevent excessive degradation of sizes during loading, to reduce segregation as much as possible, and to prevent excessive quantities of very good or off-grade coal from entering any one car. Nonuniformity of consignments is one of the chief sources of complaints by consumers and coal merchants. A properly designed loading plant will do much to reduce complaints and insure uniformity, not only from shipment to shipment but also in each individual consignment along the length of the car and in cross section. DEGRADATION IN STORAGE, LOADING AND SHIPMENT The object in loading is not only to handle the coal without breakage and segregation, but also to produce a well-trimmed load that will ride to its destination without spillage o~ breakage en route. The small sizes present in a car-of prepared coal as received by the purchaser consist of: missed small sizes not screened out in the preparation plant, breakage during loading, and breakage caused by handling en route. For domestic sizes of anthracite shipped from the Pennsylvania anthracite field to Atlantic coast cities, the dealers' loss because of breakage in loading and shipment amounts to from 2 to 5 per cent and for anthracite shipped to Middle West cities, the loss is 8 to 9 per cent. This difference is in part because dealers in the Middle West rescreen their coal more thoroughly than is usual in the East. One dealer handling Illinois No. 6 coal shipped from southern Illinois mines to Chicago reports an average size loss of 10 per cent when lump coal is unloaded with a fork. This runs as low as 5 per cent for carefully loaded coal and as high as 15 per cent for carelessly loaded coal. An Ohio dealer estimates the degradation in loading and shipment of West Virginia coals consigned to Ohio cities as follows: Pocahontas lump

Jan 1, 1950

By Nicholas J. Grant, Ulf Kalling, John Chipman

THE operation of a blast furnace is dependent to an important extent upon the sulphur content of materials charged and the desired limit of sulphur in the product. It has long been known that the blast furnace is the most efficient tool for desulphurization in common use and that this efficiency is associated with the strongly reducing conditions of the hearth and is enhanced by increased basicity and fluidity of the slag. The chemical reactions of desulphurization may be studied from the viewpoint of the ratio of the process or of the final equilibrium conditions. Both kinds of studies contribute to an understanding of the process and both are included here. A simple measure of the desulphurization power of a slag is given by the ratio: Pct sulphur in slag (Pet S) Pct sulphur in metal [Pct S] This ratio was used by Holbrook and Joseph',' to measure relative desulphurizing powers under controlled laboratory conditions. It was also used by Hatch and Chipman3 as a measure of the equilibrium distribution. For the latter purpose it would be preferable to employ thermodynamic activities rather than percentages, but until very recently this has been impossible for lack of data. Now, thanks to the work of Morris and Williams and Morris and Buehl," the effects of carbon and silicon upon the activity of sulphur in the metal are known. The confirmation of this work and its extension to include the effects of other elements by Sherman and Chipman and by Rosenqvist and Cox' make it possible to calculate the activity of sulphur in pig iron of any composition. Hence it is now possible to use data on the equilibrium distribution of sulphur to find its activity in the liquid slag and to approach an ultimate solution of the thermodynamic aspects of the problem. The rate of transfer of sulphur from metal to slag is the problem of major industrial importance and indeed the principal need for equilibrium data has been as a necessary adjunct to the kinetic studies. The rate of approach to equilibrium under laboratory conditions seems slow compared to the requirements of industrial practice, and it is clear that further laboratory studies of rates are needed. In the research reported below, the items which were investigated were the following: I—The role of mechanical stirring on the approach to equilibrium. 2—The role of MgO in desulphurization as compared to CaO. 3—The role of MnO in desulphurization. 4— The limiting reactions which constitute the slow steps in desulphurization. Experimental Procedure The experimental set-up and procedure previously described by Hatch and Chipman" were essentially followed with several small modifications. The graphite crucible containing the slag and metal charge was altered to provide considerably more active stirring and mixing of the slag and metal in the carbon monoxide atmosphere. For this purpose the crucible was machined to provide two deep cylindrical wells which were interconnected at top and bottom as shown in Fig. 1. A graphite screw with a flat thread and of shallow pitch (4 threads per in.) spinning at 600 to 800 rpm was used to lift the slag and metal over the partition between the two wells and throw them over into the second well, where the metal settled through the slag into the reservoir at the bottom. It was possible to see actual particles of slag and metal being thrown over the partition. In this respect, the stirring was more vigorous than used in the work of Hatch and Chipman. A charge of 400 g of wash metal was first melted, and 20 g of FeS was then added to yield a bath containing 1.65 pct S. Immediately 400 g of slag (as pure mixed oxides) was added and fused. The slag was generally fused in 1 hr * 10 min. Within 30 to 45 min after melting, the temperature was adjusted to 1525"C, and the first slag and metal samples were taken. The slag was picked up on the end of a cold Armco iron rod, whereas the metal was sucked into a silica tube. The wash metal composition was (in percent): 4.29 C; 0.022 S; 0.021 P; 0.38 Si. The slags used were of four fixed starting compositions covering a wide range of acid-base ratios shown in Table I. Deliberate variations in MgO were made in these slags to check the role of MgO in blast-furnace desulphurization. Changes due to additions and reactions were followed by analysis of samples. Additions of Mn and MnO were made to most of the heats to note the role of Mn and MnO on desulphurization. Three heats (62 through 64) were made in an open pot induction crucible (graphite) using a

Jan 1, 1952

Report of the Secretary GENTLEMEN Herewith are transmitted reports from the Treasurer and of the principal standing committees of the Institute. To these special reports members are referred for details as to the year's work. Despite the unfavorable business conditions obtaining throughout the year, the Institute was able to carry on its various activities without curtailment and without drawing on the surplus accumulated through previous years. In fact, small additions were made to the Life Membership and various other funds. It is highly desirable that such additions should continue to be made, especially to the Life Membership fund, for reasons reported last year. At present, money must be used from current receipts in order to enable the Institute to fulfill its obligations to those who on joining the organization commuted their dues by a single payment. In addition, with the passage of years the number increases of those who have paid dues forty years or more and who, by reason of age or disability, are unable longer to practise their profession. These men have supported the Institute through their active professional life and it would be a pity to lose them as members through resignation or for failure to keep up their dues. In accordance with the By-laws the Board has authority to advance such members, on application, to the Honor Roll of Senior Members and to relieve them from further payment of dues. It has been the policy of the Board to do this liberally, but to keep up this, as well as to meet other obligations, it is necessary for money to be provided. It has been estimated by the Treasurer that nearly $50,000 additional should be placed in the Life Membership fund as soon as possible to meet these obligations without using current income and to that end it is necessary, not only to avoid running behind currently but to earn, if possible, some surplus each year. The small amount transferred to the Life Membership fund from surplus this year was, as a matter of fact, made possible by certain members paying personally bills that were properly chargeable to the Treasury. Such generosity is common among those active in Institute work and probably no year would have closed with a surplus except for it.

Jan 1, 1929

By John A. Putnam, Morrough P. O’Brien

DATA on the physical and thermodynamic properties of hydrocarbons have been made available in recent years but the formal method of applying these data to flow in porous media appears not to have been fully developed. By making usual thermodynamic assumptions and employing existing data on permeability to two-phase flow, Darcy's law may be applied to obtain the flow characteristics for representative combinations of flowing medium and geometry. The numerical examples presented herein are based on hydrocarbons for which complete physical and thermodynamic data are available under equilibrium conditions. INTRODUCTION Thermodynamic data are obtained in the laboratory under equilibrium conditions and their application requires the assumption that equilibrium also exists during flow. This assumption is at least usual in engineering analyses, though not easily justified in many instances, and will be followed here. In regard to hydrocarbons, laboratory experience in determining the pressure-volume-temperature relationships indicates that gas-liquid mixtures must often be stirred vigorously for periods of 15 to 20 min. before reaching equilibrium. On the other hand, boiling and condensation are known to occur on solid surfaces and the large surface exposed to the flowing substance by a porous medium may bring about rapid approach to equilibrium. For the purpose of providing at least a guide to experimentation and a standard for later comparison with experimental results, it will be assumed that the phases present in cross sections perpendicular to the direction of flow are in thermodynamic equilibrium. Another assumption usually made in the solution of problems of flow in porous media is that the fluid remains at a constant temperature; i.e., isothermal flow. This assumption is arrived at by considering the porous medium and surroundings to be an infinite heat source and the rate of heat flow to be infinite at a boiling front. Its validity depends in large measure upon the character of flow, the number of components, and the physical and thermodynamic properties of the fluid. However, the assumption of isothermal flow represents a limiting case. The other limit can be represented by the assumption that the fluid is thermally isolated; i.e., irreversible adiabatic. The thermodynamic process characterizing the actual flow of a given fluid system probably lies somewhere between these two limiting cases and might be thought of as a flow system in which the confining walls are maintained at a constant temperature. For isothermal flow the solid material of the porous media is considered as the infinite heat source capable, without loss in temperature, of giving up heat to the fluid as the latter tends to cool by expansion. For the thermally isolated system, the solid material is considered to give up no heat to the fluid. In the intermediate case the impervious walls confining the porous media are at constant temperature from which heat is transferred along various paths, solid and fluid, throughout the porous media. It would appear that an actual petroleum-

Jan 1, 1941

By Joseph Hartshorne

The attention which this process has attracted, especially in Europe, has led me to believe that members of the Institute would be interested in a report of the progress which has been made in the year and a half that has elapsed since my paper on the subject was read at the Colorado Meeting of this Institute. As already described in that paper (Duns., xxvi., 380), this process is a modificatioii of the open-hearth steel manufacture, whether acid or basic, collsistillg essentially in the division of the charge between two furnaces, one of which is charged about two hours earlier than the other, and tapped into the other after the charge in the latter has become fluid, the slag of the first bath being removed from it during the transfer. This description still remains true as far as it goes, but further experience has demonstrated that circumstances will very materially modify the relation of the two furnaces to each other, and the character of the work done in each of them. The function of the primary furnace has become more clearly and entirely that of doing the rough work of desiliconiziug and dephosphorizing, while that of the second or finishing-furnace has become almost entirely that of decarburizing and finighing the heat. To indicate these developments and their results is the object of this paper. In order to avoid needless repetition, I shall try to accomplish part of this object by giving a short resume' of what has been published elsewhere on this subject since my former paper was read. This will at least enable those interested to study the matter for themselves from original sources. Since that time the following papers have been read and published: " The Bertrand-Thiel Process of Making Steel," by Percy C. Gilchrist (Cleveland Institution of Engineers, Session of 1896-

Jan 1, 1899

By P. E. Rider, K. A. Gschneidner, O. D. McMasters

The solid solubilities for thirteen rare-earth metals in gold were determined by using the X-ray parametric method. Solubilities ranged from 0.1 at. pct for lanthanum in gold up to 8.8 at. pct for scandium in gold. The solubilities from lanthanum to gadolinium were very small and essentially constant, but a sharp increase occurred from gadolinium to scandium. The large solubilities for the heavy rare-earth metals were not expected because of the large size and electrochemical differences between rare-earth atoms and the gold atom. Contributions from first- and second-order elasticity theory plus an electronic contribution were found to reasonably account for a more favorable size factor. Electron transfer from the rare-earth metal to the gold Is thought to occur such that the resultant rare-earth and gold electronegativities are favorable for solid-solution formation. It was also found that this mutual adjustment of size and electronegutivity does not occur if the pure-metal size factors are greater than a critical value of 25 pet. The eutectic temperatures for ten systems were determined and these remained fairly constant at approximately 809 "C for the lighter lanthanide metal-gold systems until the Er-Au system was reached, at which Point the eutectic temperature successively increased reaching a maximum of 1040°C in the Sc-Au system. This rise was correlated to the size factor becoming more favorable for solid-solution formation at erbium. The valence state of ytterbium was found to change from two in the pure metal to three when ytterbium is dissolved in the gold matrix. RECENT results1 reported concerning the solubility of holmium in copper, silver, and gold, showed that the solubility of holmium in gold was quite large, 4.0 at. pct, compared with 1.6 in silver and 0.02 in copper. The small solubilities of holmium in silver and copper are quite reasonable in view of the large size difference (22.2 and 38.2 pct, respectively), large electronegativity difference (0.59 for both systems), and possible unfavorable valency factor (assuming one for silver and copper and three for holmium). The large solubility in gold, however, is unexpected because these same factors are also unfavorable for holmium and gold (22.5 pct size difference and 0.69 electronegativity difference), and because the light rare-earth metals, lanthanum, cerium, and praseodymium, have negligible solid solubilities in gold.2 In view of this unexpected behavior, it was felt that a study of the solid solubilities of most of the rare-earth metals in gold would be desirable to better understand the factors involved in the formation of solid solutions. Of the rare-earth metals added to gold in this study, only ytterbium is divalent in the pure metallic state (the other rare-earth metals are all trivalent) and many of its physical properties (such as the metallic radius, electronegativity, and so forth) are much different from those of the normal trivalent rare-earth metals.' The properties of ytterbium are such that one would expect solid-solution formation to be less favorable for ytterbium in gold than for any of the normal trivalent rare-earth metals. But chemically ytterbium is known to possess a stable trivalent state, and it is quite possible that ytterbium may alloy as a trivalent metal under certain conditions rather than as a divalent metal. Because of the dual valency nature and because so little is known about the alloying behavior of ytterbium, the gold-rich ytterbium-gold alloys are of special interest. EXPERIMENTAL PROCEDURE Materials. The gold used in this investigation had a purity of 99.99 pct with respect to nongaseous impurities. In general the rare-earth metals were prepared by reduction of the corresponding fluoride by calcium metal.3 The impurity contents of the metals used in this study are given in Table I. Preparation of Alloys. Two- or 3-g alloy samples were prepared by arc melting. The samples, with the exception of some of the Er-Au alloys, had weight losses of 0.5 pct or less. All alloy concentrations noted in this paper are nominal compositions. After arc melting, the alloys were wrapped in tantalum foil, sealed off in quartz tubing under a partial atmosphere of argon, homogenized for approximately 200 hr at 780°C, and then quenched in cold water. X-Ray Methods. The X-ray parametric method was used in determining the solubility of the rare-earth metals in gold. filings were sealed in small tantalum tubes by welding under a helium atmosphere. The tantalum tubes were then sealed in quartz tubing under a partial argon atmosphere, and annealed for times ranging from 1/2 to 3 hr (the length of time was inversely proportional to the an-

Jan 1, 1965

By R. G. Ward, John Henderson. R. G. Hudson, G. Derge

Densities of melts of the iron oxide-silica system in contact with solid iron have been measured by the maximum hubble pressure method in the composition range O to 37 wt pct SiOz and the temperature range 1255 to 1410C. The constitution of the melts is discussed and it is postulated that the structure changes from a dislribution of iron ions in an oxygen ion network at pure "FeO" to a distribution. of iron ions in a network of silicate tetrahedra at the orthosilicate composition. JOHN HENDERSON, Junior Member AIME, was formerly with the Metals Research Loborotory, Carnegie Institute of Technology, Pittsburgh, Pa., on leave from Broken Hill Proprietary Co., Ltd., Research Division, Shortland, Australia. R. G. HUDSON, formerly with Metals Research Laboratory, is now with the John Jay Hopkins Loborotory for Pure and Applied Science, General Atomic Division, General Dynamics Corp., LaJolla, Calif. R. G. WARD, was formerly with the Department of Metal lurgical Engineering, Carnegie lnstitute of Technology, while on leave from the Department of Metallurgy, University of Sheffield, England. G. DERGE, Member AIME, is Jones and Laughlin Professor of Metallurgical Engineering, Carnegie lnstitute of Technology. Manuscript submitted January 19, 1961. ISD The system iron oxide-silica is an important one metallurgically because it forms the basis of several complex slag systems in use for industrial smelting and refining processes. In recent years considerable work has been done on liquids of this system but there are still many points of difference among workers using different experimental techniques and theoretical approaches. Phase equilibria/"3 activity,4-6 electrical conductivity,' current efficiency,' transference number,8 viscosity,9 surface tension,'' and density" measurements have all contributed to an understanding of the problem. Measurement of density is one procedure which is directly indicative of liquid structure since any deviation from ideality must be a result of structural interactions. Liquids of the iron oxide-silica system are of special interest because this is one of the few metal oxide-silica systems on which measurements can be carried out conveniently over the entire composition range from pure oxide to silica saturation. This includes the range of high basicity which has received relatively little attention in other systems. Although one investigation of density in this system has previously been undertaken," the results seem of sufficient importance to warrant the independent redeter-mination reported here.

Jan 1, 1962

By A. J. Carlson, G. M. Marincel, M. L. Hovland, J. H. Healy

Research personnel of Erie Mining Co., a pioneer taconite mining firm on the Mesabi Range, have invented a new method to make an effective 325 mesh separation at high tonnage rates over stationary screens. The company regards this development as historically significant in that it represents the first successful method to commercially screen large tonnages of ore at fine sizes. Erie, which is now completing an expansion program at its plant site near Hoyt Lakes, Minn., has incorporated this screening method as part of that expansion. When completed, the concentration plant will produce 10.3 million tons of iron concentrate, all of which will have been efficiently screened at 325 mesh.

Jan 4, 1967

By J. B. Cohen, B. W. Howlett, M. B. Bever

The partial molar heats of solution at infinite dilution in tin of aluminum at 300° and 350°C and of gallium, indium, and thallium at 240°, 300°, and 350°C have been measured by tin solution calori-metry. Aluminum, gallium, and thallium are endo-thermic on solution; indium is exothermic. Any temperature dependence of the heats of solution lies within the experimental scatter. Over the dilute ranges investigated, only aluminum has a measurable change in its heat of solution with composition. HEATS of solution of one element in another reflect the interaction between them. The investigation of partial molar heats of solution in dilute alloys is of particular interest as the properties of the solvent are altered to only a limited extent by the presence of the solute and also as the interaction between solute atoms is small. When the heats of solution of a related series of elements in a solvent are known, a systematic comparison may be made. In the investigation reported here, the partial molar heats of solution of the Group III elements aluminum, gallium, indium, and thallium in dilute solution in tin were measured. This work follows an investigation of the heats of solution in tin of the Group IB elements.' EXPERIMENTAL PROCEDURES Materials. Samples of gallium, indium, and thallium were obtained from Johnson, Mathey and Co., Ltd. Indium and thallium were supplied as wire, 1.6 mm in diam; gallium was in the form of irregular pieces. The supplier reported the following minimum purities: gallium—99.95 pct; indium—99.99 pct; thallium—99.99 pct. The aluminum, obtained from Alcoa Research Laboratories, was reported to be 99.995 pct pure. The tin was supplied by Baker and Co., Inc.; the reported analysis indicated a tin content of at least 99.96 pct with lead as principal impurity. Calorimeter. this description will cover only the essential features of the calorimeter with special attention to modifications made since an earlier description was published.' A Dewar flask containing the tin bath was held in a constant-temperature bath of a near-eutectic mixture of lithium, sodium, and potassium nitrates. This bath, which was stirred vigorously, was heated by a primary resistance winding in the container wall and by a secondary winding immersed in the salt. The voltage supplied to both windings was stabilized. The temperature of the salt bath was controlled by means of a platinum resistance thermometer in one arm of a Wheatstone bridge. The light from a mirror galvanometer in the bridge circuit fell on a photocell which controlled the current in a saturable reactor in series with the secondary winding. In this manner, the temperature of the salt bath was controlled to ±0.003°C and that of the tin bath to at least ±0.002°C. Each of these temperatures was measured by two iron-constantan thermocouples in series, coiled in a helix to minimize heat loss and immersed in the salt and tin baths in protective sheaths. The temperature of the laboratory was kept constant to ± 1°C during a run. Specimens were dropped into the tin bath from an addition arm held at O°C which was part of the cal-orimetric system. The system was evacuated to about 0.02 1 to minimize oxidation and to reduce transfer of heat. The bath was stirred by a glass stirrer introduced through a double Wilson seal. The samples were scraped clean before weighing, which was carried out as rapidly as possible. Each sample was immediately placed in the evacuated addition arm to minimize contamination. These precautions were especially necessary with aluminum. After the runs with gallium and thallium at all temperatures and with indium at 240° and 350°C (Series I) were completed and before the runs with indium at 300°C and aluminum at 300° and 350°C (Series 11) were begun the following changes were made. The shape of the Dewar flask was changed so as to result in a lower surface to volume ratio of the bath and at the same time the amount of tin was reduced from 500 to 400 g. The paddle type stirrer was replaced by a helical screw and the rate of stirring was increased to about 150 to 200 rpm.

Jan 1, 1962

By J. H. Hensley

The mine of the Miami Copper Co. is in the Miami district, Gila County, Ariz., approximately 7 miles west of Globe. In 1906, the General Development Co. secured the ground now owned by the Miami Copper Co., and about a year later discovered ore in a prospect shaft at a depth of 220 ft. The Miami Copper Co. was organized in 1907, the claims held by the General Development Co. were transferred to it, and an active development campaign was inaugurated. The railroad was extended from Globe to Miami in 1909, a concentrating plant was constructed, and the company began producing early in 1911. The unit size of mineral tract in the district is the standard lode claim 600 ft. in width by 1500 ft. in length. Ownerships of land are held in fee. The geology of the district has been described by F. L. Ransome.' The formations of local importance are: The pre-Cambrian Pinal schist, which consists mainly of metamorphosed sedimentary rocks and is commonly of a thinly laminated sericitic variety; the diabase, which is thought to have been intruded in late Paleozoic or early Mesozoic times; the Schultze granite and granite porphyry, considered early Tertiary; the dacite of late Tertiary time; and the Gila conglomerate of early Quaternary. General Items Influencing Mining Methods The bodies of disseminated ore in the district are flat lying masses of irregular outline and variable thickness. As a rule, these masses lack definite boundaries; the orebody follows a curve along one of the main ridges, approximately 5500 ft. in length with a maximum width of 1600 ft. The minerals occur as finely divided and uniformly disseminated chal-cocite in the Pinal schist and Schultze granite. The typical overburden or capping is a barren rusty brown, very friable, highly siliceous, leached schist, or granite-porphyry. The topography of the district is fairly rugged and irregular; the altitude ranges from 3400 ft. above sea level, at the town of Miami, to 3900 ft. on the hills above the Miami orebody. The climate is mild; the mean annual temperature is 63.°F.

Jan 1, 1925

By O. U. Bradley

THE methods of handling the oil output of the mid-continent fields are not unlike those practised in other oil fields of the United States, and it is not expected that this paper will present any entirely novel ideas. Some features of the practice of handling this oil may be of interest, however. WOODEN CAGING TANKS Practically all of the oil sold to pipe lines and other purchasing agencies throughout the Mid-continent field is gaged from wooden tanks. Steel gaging tanks are slowly coming into use, and are preferable in many ways-leakage and evaporation are reduced, and the strapping and recalculation of capacities are unnecessary. The wooden tanks are slightly coned to facilitate tightening the hoops. The-sizes in, common use are 250, 500, 800 and 1600 bbl. The number and the capacity of the gaging tanks upon any producing oil property depend upon its production, and the facilities for disposing of the output. The 1600-bbl. size was the most common in the Cushing field, particularly during the period of flush production. The tanks are distributed over the leased premises in groups of two, three, and four tanks each, and these are filled from flow tanks, or through direct pipe connections with the heads of the wells. Flow tanks are merely temporary reservoirs to facilitate the transfer of oil from the wells to the gaging tanks. They diminish fire risk,, and are considered indispensable on small producing properties where .water is pumped with the oil, as they permit the refuse and water to settle out before the production is run to the gaging tanks.

Jan 3, 1918

By B. F. Tillson

HAVING been asked to talk about recent devel-opments in mining equipment, I chose the sub-ject of small units of storage-battery locomo-tives which recently have been developed with the idea of motorizing transportation in the mines as far as possible, replacing the manual labor of hand-tramming. Metal mines are probably less advanced in this field than coal mines, where transportation of large ton-nages on any one level is quite common. Of course, metal mines, where large tonnages are handled on any one level, are as advanced as coal mines, and storage-battery locomotives for main haulages are used quite commonly in such metal mines, but the mines having levels at many intervals in the depth of the orebody, or a number of intermediate levels in which a consider-able amount of hand-tramming has to be done, and small metal mines in which the size of the orebody does not seem to warrant the initial capital expenditure for the driving of main haulage levels and installation of rock and ore chutes and raises for the delivery of the broken ore and rock to the cars have been at consider-able disadvantage in replacing manual labor by some mechanical means of transportation. Several years ago the field was canvassed among the manufacturers of electric-locomotive equipment and the conclusion was reached that the art had not been devel-oped to the advantage of metal miners who desire to replace small units of labor by locomotive equipment. The need for such small locomotives is all the more em-phasized by the development in the past few years of mechanical mucking-machines (loading equipment for filling the cars from muck piles on the level). Any me-chanical loader is a liability instead of an asset unless means are also provided for keeping the material away from the loading-machines. Therefore the transporta-tion system must be equal to the capacity of a loading-machine, otherwise the latter is idle such a large per-centage of its time as to prove an unprofitable invest-ment. So there is a need for portable, small haulage units to handle small mine cars in many metal mines, and, naturally, units are desired which can be so readily shifted from level to level as to facilitate their free use. Of course, in mines in which each level comes to the shaft it is not such a difficult problem, but many mines have a great many intermediate levels which must be approached through raises, timber slides or other small openings required to transfer ore and to get timber and other supplies to those levels.

Jan 5, 1927

By George S. Evans

CERTAIN American operators believe that desulphurizing in the ladle offers a means of increasing blast-furnace and open-hearth yields with the possibility of improvements in quality of the steel. In fact, several producers have experimented with practically all of the known desulphurizing agents, including both standard grades of the alkalies and special preparations that have been offered from time to time during the past several years. Some of these are regularly being used today in large-scale commercial operations, with good results. Also, it is the practice to treat off-sulphur casts in the blast-furnace ladle at a number of plants. It is not known, however, that anyone in the steel industry (American) has ever adequately equipped a plant for desulphurizing blast-furnace metal in an efficient manner as regular operating practice. The purpose of this paper is to illustrate the importance of correct equipment and proper handling for obtaining uniform and efficient results. As will be shown, at the temperature of molten iron the alkalies are instantly neutralized by any free slag present, dissipating their desulphurizing value. Entrained silicates are rapidly washed out of the metal bath by the highly basic soda slags and will be satisfied ahead of desulphurizing reactions with FeS. More or less of the reagent will always be used up through reactions with the refractory lining. Desulphurization will be limited to the action of the free alkali then remaining in the slag. Causes for the erratic results generally found with desulphurizing tests in blast-furnace transfer ladles would include, among other things, variations in the quantity of furnace slag coming down with the metal, and differences in the percentage of kish and entrained silicates in the different casts. As the alkalies instantly unite with any free slags or silicates present, these, with any kish coming off, both dilute the reagent and reduce the surface contact between the slag and metal, thereby retarding the desulphurizing reactions.

Jan 1, 1938

By R. G. Powell, R. Schuhmann, E. J. Michal

Liquidus surfaces in the ternary system FeO-Fe2O3-SiO2, were determined from 1250' to 1450°C by the procedure of equilibrating small samples in platinum crucibles, quenching, and microscopic examination. The experimental results were combined with previously published information to construct a ternary diagram for the system showing the entire temperature-composition range of stability of iron silicate slags. Metallurgical applications of the diagram, especially in copper smelting, are discussed briefly. IRON oxides are almost unique among the common oxide constituents of metallurgical slags in that the iron occurs in two different states of oxidation, ferrous and ferric. Moreover, in liquid slags the degree of oxidation of the iron is readily changed by reactions of the slags with oxidizing agents or reducing agents. This behavior of iron oxides in slags accounts, for example, for the effective transfer of large quantities of oxygen through slag layers in open hearth steelmaking. In this process, oxygen supplied by reactions at the gas-slag interface is dissolved in the slag with the oxidation of ferrous iron to ferric. Ferric oxide is transported across the slag layer by convection, and at the slag-metal interface the oxygen reacts with liquid metal while the ferric iron is reduced back to the ferrous state. Another group of processes in which variation in degree of oxidation of iron has great practical importance is in copper smelting. In matte smelting and converting, such large proportions of the iron are oxidized to the ferric state that problems are encountered in preventing or controlling the formation of solid magnetite. The ferrous-ferric relationship also affects the attack of iron oxides on high-SiO2 refractories, which appears to be most severe under reducing conditions for which ferrous iron predominates. Darken and Gurry' determined the chemical properties and phase equilibria of pure iron oxide slags. Their data show that iron oxide melts can have compositions ranging almost all the way from FeO to Fe2O3. The melts of lowest oxygen contents, which exist in equilibrium with metallic iron, approach ferrous oxide in composition but still have a small percentage of ferric oxide. The melts of highest oxygen contents, which have oxygen dissociation pressures of 1 atm, are above magnetite in oxygen content, with over two-thirds of the iron in the ferric state. The previously established phase diagrams for silicate slag systems all show FeO as the iron oxide component. However, Bowen and Schairer? who determined the FeO-SiO2 diagram and many of the other diagrams used by slag chemists, have been careful to point out that their systems always contained both ferrous and ferric iron. Thus, their data are for limiting mixtures with minimum contents of ferric iron, obtained by melting and equilibration in iron crucibles. Under these conditions, the Fe2O3 percentages found by analysis were small enough to justify simplification of the published phase diagrams by calculating the Fe2O3 to equivalent FeO and ignoring Fe2O3 as an additional component. On the basis of experimental measurements of melting points of iron oxides on silica in the presence of various gas mixtures, Darken3 worked out phase diagrams for the Fe-Si-0 system which show the important phase equilibria in terms of temperature and gas composition. This study clarified many aspects of the application of the phase rule to the FeO-Fe2Oa-SiO2 system and was an important basing

Jan 1, 1954

By R. D. Burlingame, T. L. Joseph, Gust Bitsianes

DESPITE almost fifty years of commercial practice, the sintering of iron ore has received little fundamental study. Much of the theoretical work1-'has dealt with the constitution of sinter produced under widely varying conditions. While these studies have broadened our knowledge of the changes that occur in the sintering zone and in the freshly formed sinter during the early stages of cooling, they provide little insight into the changes that precede the formation of sinter. These preliminary changes merit study as a part of the overall process. Hessle. working with beds of Swedish magnetite concentrates, was one of the first investigators to study the sintering process in its entirety. On the basis of temperatures observed at various levels of the bed during sintering, he postulated a number of distinct reaction zones to account for the chemical changes leading to the formation of sinter. A more direct method of attack is that of arresting the sintering zone after it has progressed part way through the bed. A study of a vertical cross section through such a quenched bed provides direct information on the changes taking place at various levels. This method was used by McBriar et al.' to show that several well-defined zones of chemical change existed within beds that were typical of British sintering practice. The same general method of attack was developed independently in the present investigation to study partially sintered beds typical of American practice. Experimental Sintering Equipment The sintering operation was carried out on an experimental scale with the equipment shown in Fig. 1. The refractory-walled sintering chamber A was 11 in. deep and averaged 9 in. in diameter. Air was introduced through a tapered flow section B, which contained the orifice C for accurate metering of the incoming air. This section was located directly above the square ignition housing D, which in turn rested upon the sintering chamber A. The bed was ignited with burner E. The required suction for the operation was furnished by a fan F, which had an air capacity of 500 cfm (stp). Hot exhaust gases from the sintering chamber were cleaned in the dustcatcher G before entering the exhaust fan. In the study of partially sintered beds, it was essential to find some technique for removing the entire charge from the sintering pot without disarranging the unsintered bottom portion. This problem was finally solved by sintering the charge in a removable basket, which snugly fitted the sintering chamber. This basket was constructed of two thicknesses of window screen and was lined with a 3/16-in. layer of asbestos paper. The bottom of the basket consisted of two thicknesses of wire screen, which were fastened to the basket wall. For high fuel mixtures, additional insulation was provided by a somewhat thicker layer of asbestos cement. Preparation of Partially Sintered Mixtures The moist feed was carefully placed in the sintering basket, to prevent segregation of the particles, which varied widely in size and composition. A thermocouple was placed in the center of the basket with the hot junction halfway down, and the mixture was evenly distributed around it. During ignition and throughout the sintering of the upper half of the bed, the hot junction temperature increased very little. When the sintering zone reached the halfway point, as indicated by the sudden increase in the hot junction temperature, the charge was quenched. During quenching the suction was turned off and the orifice was tightly stoppered to prevent further influx of air. At the same time, nitrogen was admitted to the sintering chamber through the orifice tap. As soon as the nitrogen had displaced the air and products of combustion, the charge was removed from the sintering pot for immediate dissection. It is impossible to preserve the exact zone structure of the bed at the instant that combustion is arrested unless the downward transmission of heat is also immediately stopped. Fortunately, heat transfer is very slow in beds containing a stationary fluid, especially if the particle size is small. It follows that the minimum quantity of nitrogen should be used to displace the air and that static conditions be established as soon as possible. A very steep temperature gradient across the combustion zone for some time after the quench was evidence of in-

Jan 1, 1957

By Michael Bradbury

INTRODUCTION A major change in financing exports in recent years has been the decreased importance of subsidized export credits, following the commitment of the OECD countries to eliminate the subsidy element. Subsidized export credit rates are now often more expensive than market rates as the financing for exporters has decreased in volume and importance. The forfait market, in recognition of this decreasing importance, provides a rapidly expanding source of nonrecource finance for exporters. The following is a step by step guide to what it is, how it works, its benefits and problems. WHAT IS FORFAITING? Forfaiting is not new. It has been used in Europe for about 25 years to provide export finance for both capital goods and commodities without recourse to the exporter. Although long the preserve of exporters in Germany, and more lately Italy, forfaiting is now used increasingly by exporters in Great Britain, the United States, Canada and Scandinavia. It is a fairly simple operation with easy straight-forward documentation. The transaction involves the purchase by the forfaiting bank of a bill of exchange or a series of bills without recourse to the exporter. These bills will have been drawn by the exporter, accepted by the importer, and will usually bear the unconditional guarantee of the importer's bank. They are normally drawn payable at intervals during the credit period agreed between importer and exporter and are purchased at a discount by the forfaiter. The exporter thus obtains his cash payment and the importer receives his credit period. The forfaiter collects the amount of the bills as they mature directly from the importer. Credit periods vary, depending upon the type of goods and the country and commercial risk of the importer. The period is generally between one and five years with six monthly maturities. The usual forfait currencies are US dollars. Deutschmarks and Swiss francs and others, such as sterling, French francs, and the Scandinavian currencies are being used more frequently. CHOOSING FORFAITING Most types of financing require the continued involvement of the exporter in the financial side of the transaction during the credit period. Forfaiting has certain comparative advantages. In particular, it is possible to forfait 100 percent of the risk without recourse to the exporter, unlike government sponsored export finance schemes, where some retention of the risk by the exporter is required. In addition, exports from country sources do not present problems and forfaiting can also cover trade within the EEC. Other benefits for the exporter are: (a) The exporter's balance sheet is improved; debts are turned into cash thus improving the liquidity of the company and enhancing its cash flow. And there are no contingent liabilities for bills of exchange. (b) If the sales contract is in a foreign currency forfaiting removes the risk to the exporter of adverse movements in foreign exchange during the credit period. (c) Fluctuations in interest rates during the credit period can be ignored since in forfaiting the transaction is usually done on fixed interest rate terms on a discount basis. (d) The political and transfer risks are taken by the forfaiter. (e) The commercial risk is taken by the forfaiter. (f) The costs of administration and collection etc. during the credit period are removed.

Jan 1, 1985

By B. G. Agnew

In evaluating fracture treatments, the need to answer such questions as "What zone or zones were actually treated?" and "What was the vertical extent of the treatment" is necessary, since determining effectiveness of the fracture treatwrent depends on knowledge of the reservoir portions stimulated and the vertical extent of the fracture system or systems. Injection of hot or cold fluids during fracturing operations will transfer heat to the surrounding formations and fracture faces mainly by heat conduction. Once injection ceases, temperature anomalies will develop opposite the zone fractured because the rate of temperature decay is less than that opposite zones heated or cooled by flow inside the wellbore or along the cement sheath. Thus, temperature surveys can he used to determine where fractures were generated outside the wellbore and to reasonahly estimate the vertical extent of the fractrires. This technique has been used successfully to evaluate over 344 fracture treatments at depths ranging from 1,500 to 15,700 ft. Examples of actual temperature surveys are presented to show how this method of fracture treatment evaluation can be used effectively and beneficially. INTRODUCTION Stimulation of producing or injection wells by fracturing is commonplace in the industry today. In evaluating these treatments, two basic questions which arise are "What zone or zones were actually stimulated?" and "What was the vertical extent of the treatment?". Knowledge of the reservoir portions stimulated and vertical extent of the fracture system or systems is vital to effect efficient and economical well completions and to assure maximum recovery from reservoirs. Not all fracture treatments are successful and many times the desired or anticipated results are not achieved. When this occurs, it is in most cases the engineer's job to determine why. The answer to this problem forms the primary basis for deciding whether to spend more money for development drilling and/or completion attempts or to forego additional expenditures to improve the particular zone. Also, knowledge of the reservoir portion actually stimulated is invaluable in planning future workovers. This is especially true in wells producing from reservoirs containing multiple porosity stringers or zones. For various reasons, all zones within a reservoir may not be perforated on initial completion with the thought of developing remaining zones through future workover operations. Because particular zones are perforated and fracturing fluid pumped down the wellbore, it cannot be assumed that all perforated zones are stimulated, and in turn drained. Occasionally, unperforated zones which are planned for future development are actually stimulated on initial completion. eliminating the need for future recompletion attempts or all zones perforated initially are not stimulated, thus requiring additional completion work to insure that these zones are adequately drained. In most cases, it is costly. if not impossible, to determine with assurance why a fracture treatment is unsuccessful after the job has been completed and the results tested. Further, unpredictable upper and lower fracture barriers. as well as possible borehole communications (cement channels), do not permit it to be taken for granted that the formation opposite the perforations is the only zone receiving the fracture treatment. Thus. evaluation of fracture treatments is necessary for efficient and prudent well completion practices and should be done simultaneously with the fracture job. Several methods have been used to locate fractured zones, all of which are based on detection of radioactive tracer materials added to either the fracturing fluid or the propping agent. These methods have been helpful in increasing knowledge of fracturing operations; however, they are seriously limited because of cost and inability to detect accurately radioactive tracer material more than a few inches away from the borehole. To develop a better diagnostic tool to pinpoint which zone or zones had actually been fractured, temperature surveys were run after fracturing with heated and cooled fluids. Significant temperature anomalies were found to exist opposite zones suspected of receiving the fracture treatment. From the analysis and examples to be shown, it can be seen that temperature surveys run in a stabilized wellbore several hours after a fracture treatment using hot or cold fluid will yield temperature anomalies which show the actual reservoir portion stimulated, the vertical extent of the fracture system or systems and a qualitative indication of the portion of fracture-fluid volume entering a given depth interval. The experience and illustrations used in this paper are based on evaluation of over 344 fracture treatments during the past three years using this diagnostic tool at depths ranging from 1.500 to 15,700 ft and fracture volumes ranging from 2.000 to 110.000 gal. Based on analyses of these temperature surveys, analyses of fracture gradients and evaluation of several open-hole packer impressions in the West Texas area,' vertical fracturing is the predominant mechanism and horizontal fractures occurred frequently, if at all.

Jan 1, 1967

By H. A. Jr. Koch, C. A. Hutchinson

Miscible phase displacement of oil from reservoirs has been emphasized in the past few years. The reason for this emphasis lies in the high oil recovery attainable by this process. Removal of capillary effects in the reservoir leads to recoveries approaching 100 per cent in the area contacted by the miscible phase. The miscible slug process is one means of obtaining a miscible displacement. Here a band or slug of I,PG is injected into the reservoir prior to gas injection. The idea is to maintain the band of LPG "wedged" between the gas and oil phases and thus achieve a miscible phase displacement. A second method lor achieving miscibility is through the injection of a gas which is not miscible with the reservoir fluid but which develops a zone of miscibility in [he reservoir through mass trans-ier with the reservoir oil.' This mass transfer results in either an enrichment of the lean injected gas by intermediates from the oil or an enrichment of the oil by intermediates from a rich injection gas or one that has been enriched on the surface by LPG addition. We are interested here in discussing the process in which miscibility is developed at the displacement front by the evaporation of interrnediatcs from the oil phase into the gas phase. This process "builds up" its own slug of miscible material at the displacement front and therefore does not require the injection of LPG to obtain miscibil-ily. Each process has its own area of applicability. Generally, the high pressure gas process is applicable only with reservoir fluids which con-!ain a high concentration of inter- mediates. If the high pressure gas process is technically feasible at pressures less than 4,500 psi, it is probably more desirable economically than the slug process. The slug process has broad applicability in the shallower reservoirs and with reservoir fluids which contain a relatively low concentration of LPG and natural gasoline constituents. This paper deals with some new concepts of the high pressure gas injection process where it is proposed that flue gas can be substituted for hydrocarbon gas without sacrificing our goal of miscibility. MECHANISM Introduction Considerable effort has been devoted to study of the mechanics ot the high pressure gas injection proc-one generalization result-ing from some of these studies was that the composition of the injected gas is relatively unimportant in establishing the miscibility pressure* for a given reservoir fluid. This generalization is correct for the composition range of gases typically encountered in the field. Two such gases are a gasoline plant tail gas containing 85 per cent methane and 15 per cent ethane, and a field separator gas containing 70 per cent methane and 30 per cent heavier components. The most important factor which sets the miscibility pressure in the operation is the reservoir fluid composition, particularly the concentration of LPG-natural gasoline constituents. The injected gas is the agent by which the LPG-natural gasoline constituents are concentrated at the displacing front to create a miscible displacement. Based on these results, it appeared feasible that some inexpensive gas, such as flue gas, might be substituted for hydrocarbon gas for use in the high pressure gas process. A re-examination of the phase relations of the high pressure gas injection process should clarify the principle behind using flue gas (essentially nitrogen) as an injection gas. Three Component Diagram The phase relations of the high pressure gas injection process have been illustrated by the use of the three component diagrams.'," In Fig. 1 we have arbitrarily represented the multi-component reservoir system by three components; methane, ethane through hexane, and heptanes plus. The solid curve ABC is the phase boundary curve. It represents the locus of compositions which have fixed saturation pressure at a fixed temperature; the lower branch AB shows bubble point compositions, the upper branch BC, the dew point compositions. Point B is the coniposition of the critical mixture at this temperature and pressure. The dashed lines (tie lines) connect vapor and liquid compositions which are in equilibrium. Let us consider Reservoir Fluid D which we wish to displace in 21 miscible manner by gas injection. Let us further restrict the discussion to the case where miscibility between an injection gas and the reservoir fluid at the displacement front is developed by gas enrichment in the reservoir. For this case, any gas whose composition lies between Points C and E on the right side of the three component diagram can be used to give a miscible displacement of Reservoir Fluid D. This is true because the more mobile injected gas moves faster than the displaced oil and is in continuous contact with virgin oil at the displacement front. This leads to a continuing enrichment 01' the gas at the displacement front by evaporation of the C, - C,