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By R. A. Meussner, C. T. Fujii

Chromium solution in wustite depresses the oxygen activity in a nonideal manner and expands the lattice slightly. Gravimetric measurements of the equilibrium compositions of wustite containing 0.00 to 1.38 wt pct Cr define the oxygen potential (CO2-CO atm) and the limits of the phase field at 1000°C. These data extrapolate to a maximum solubility of 2 wt pct Cr. The lattice parameter data, room-temperature measurements of quenched samples, differ significantly from those in the literature. Both pure and chromium wus-tites contract at uniform and equal rates as the oxygen content (metal deficit) increases. The a. US metal deficit relationships are straight lines showing none of the curvature previously reported. At constant metal deficit, the a. expands by 0.002? on alloying with 0.4 to 0.5 wt pct Cr but is insensitive to further chromium additions: a small expansion rather than a marked contraction. These results require a modification of the accepted alloying mechanism. IN the high-temperature oxidation of Fe-Cr alloys in Ha-H,and CO2-CO atmospheres the vapor transfer of oxygen from the continuous wustite outer scale to the porous inner scale/alloy interface sustains the high oxidation rates.1"3 The driving force for this transport is the difference in the oxygen activity of the outer wustite and that at the inner scale/alloy interface. In pure CO2, as well as in CO2-CO atmospheres, carburization of the alloy accompanies this oxidation. Current efforts to evaluate the parameters controlling this carburization have shown that the process is not simple; i.e., the carbon concentration in the alloy initially increases rapidly, reaches a maximum, and then decreases slowly as the oxidation time is extended. This is the same pattern reported by McCoy for the more complex oxidation-carburization of stainless steels and an Fe-Cr alloy in CO2 at lower temperatures.4 These changes in the carburization process occur while the overall oxidation rate and the lattice parameters of the scale layers remain constant. If this invariance of the lattice parameter is assumed to indicate a constant scale composition and thus a constant oxygen potential, the carburization results are not easily explained. Electron microprobe traces across the thickness of these outer scales, however, have revealed distinct chromium gradients penetrating 10 to 50 µ from the inner surface where the chromium concentrations were estimated at a few tenths percent. The variation of the chromium cmcentration on the inner surface of the scale, and the resulting change of the oxygen activity, during the oxidation process is considered to be important in defining the carburization process. Thus, to gain an understanding of the complex oxidation-carburization proc- ess, it was necessary to measure the properties of wustite containing known amounts of chromium (chromium wustite). Although the general features of the Fe-Cr-0 equilibrium diagram between 900° and 1300°C have been fairly well established by Richards and white: Wood-house and White,6 Seybolt,7 and Katsura and Muan,8 there have been no detailed studies of the limits of the chromium wustite phase field or the properties of these alloyed wustites. The recent results of a limited study of chromium wustite by Levin and wagner9 indicate that more than 0.67 wt pct Cr is soluble in wustite above 850°C and that this alloying is accompanied by a substantial lattice contraction. This change in the lattice parameter was not evident in the X-ray diffraction patterns of wustite layers from the oxidation experiments;1,3 the lines were sharp even though a chromium gradient existed in the scale. The present paper describes gravimetric equilibrium experiments which delineate the boundaries of the chromium wustite single-phase field at 1000°C and define the changes in the oxygen activity and the lattice parameter of wustite as functions of chromium and oxygen contents. The lattice parameter data of chromium wustite obtained from these equilibrium and special quenching experiments differ considerably from those reported.9 Those for pure wustite show significant differences from the widely accepted data of Jette and Foote.10 Since the causes of these differences are not easily assignable, and since the literature contains many sets of data on wustite which if not in conflict are at best not in harmony, the experimental procedures are discussed in the present paper. EXPERIMENTAL Oxide Preparation. The specimens used in these studies were porous pellets compacted from high-purity (Fe,Cr)2O3 or Fe2O3 powders. These powders were prepared from electrolytic chromium (99.8 pct purity) and electrolytic iron purified by consumable-electrode, vacuum arc-melting processing (299.9 pct purity).11 The oxides were produced by standard analytical procedures: solution of the metals in acids (HC1, then HNO3 added), coprecipitation of the hydroxides (NHaOH), and filtering and washing these precipitates. Initial dehydration of the coprecipitated hydroxides was done in a porcelain evaporating dish heated by a Meker-type burner, final dehydration by firing in a recrystallized alumina crucible at 1000" to 1050°C for 20 hr in an electrically heated furnace. Spectrographic analysis detected the following impurities: silicon, 0.01 pct or less; aluminum, 0.001 pct to trace; manganese and copper, 0.0001 pct to none. Each of these levels is at least one order of magnitude lower than in commercially available CP grade ferric and chromic oxides. Fluorescence analy-

Jan 1, 1969

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of the gaseous, topo-chemical reduction of porous hematite spheres. Gas-solid reduction is permitted at each of three advancing interfaces and is controlled by a complex series-parallel sequence of chemical and transport steps. Despite the fact that transport resistances are significant to the advance of each interface, little deviation from linear advance is predicted for the first 98 pct of reduction. Calculations to predict the movement of magnetite /wustite interface by a solid-state diffusion mechanism have been incorporated into the earlier dense-pellet model.' The porous-pellet model is found to give a better description than the dense-pellet one for McKewan's measurements2 of interface movements in dense polycrystalline hematite reduced in hydrogen-water vapor mixtures. THIS paper reports a continuation of work"3" directed toward the better understanding of gas-solid reactions and the development of mathematical models that may be helpful in the design or control of ore-reduction processes. Laboratory studies of the reduction of single oxide samples in tube furnaces normally employ an abundant excess of pure reducing gas. Reduction may appear to be adequately described by a model assuming gas-solid reaction solely at the iron/wustite interface.''' However, when iron ore is reduced in either a fixed bed or an efficiently operated counter-current column, there are portions of the bed where the partially spent gas is no longer capable of reducing wustite to iron. Nevertheless, the formation of the intermediate reaction products, wustite or magnetite, can and does continue. In order to account for this aspect of the reduction of beds of particles, three semiempirical mathematical models were devised.' One of these was for the limiting case of completely dense particles, and two alternatives were provided for porous particles. For purposes of the analysis, a dense pellet was defined as one in which the wustite and magnetite layers were impervious to the reducing gas when the atmosphere was capable of forming iron. In a porous pellet, the intermediate product layers were assumed to be sufficiently permeable to allow reducing gas to penetrate beyond the iron/wustite interface to form wustite and magnetite by removal of oxygen as a gaseous product rather than by a solid-state redfiction mechanism. Further progress required a better understanding of the reaction of the individual particles with the gas stream. A comprehensive mathematical treatment was developed' to describe the continually changing interplay of transport and reaction steps

Jan 1, 1967

By Adrien Berton

FOR nearly a century, the Corocoro deposit has been renowned among geologists from the fact that it shares with the Lake Superior deposits of the United States the distinction of being the only important copper districts where native copper is worked commercially. The Corocoro district, named after the city of Corocoro, the capital of the Province of Pacajes (Department of La Paz, Bolivia) is situated towards the western edge of the Bolivian high plateau, at an altitude of a little over 13,000 ft. The most interesting part of the district is that immediately surrounding the city of Corocoro, at a distance, by railway, of 65 miles from La Paz and 210 miles to the Chilean port of Arica on the Pacific Coast. The climate of the region is that of the semi-desert, dry and relatively cold, with big differences of temperature between day and night. The rainy season begins in December and ends in March. The cupriferous lodes of Corocoro have not attracted as much interest as the silver mines of Potosi but they have been known for a long time. In the precolonial period the Indians were using the charquis, or natural native copper sheets, to make small brass objects, and the beautiful pale green brochantite of the outcrops as a source of green pigments. During the colonial period, the oxidized ores of the outcrops were worked for copper, which was used by the mint at Potosi for making currency. The native copper ores were neglected because the Spanish miners were at a loss how to concentrate and smelt them. About 1830, work by rudimentary processes, which were improved little by little, was begun on the native copper ores. The total production of native copper in the following hundred years amounted to 100,000 tons. This native copper, which was remarkably pure, was much appreciated on the European markets before the introduction of electrolytic copper. It was useful for making special ornamental brass or bronze and the granular concentrates of native copper, called barrilla, containing 80 to 85 per cent copper were suitable for making copper sulfate by direct oxidation and subsequent leaching with sulfuric acid.

Jan 1, 1936

By G. H. Matheson, J. M. W. Mackenzie

The flotation rate of coal has been studied using a continuous laboratory flotation cell and a multiple exposure photographic technique. The effects of particle size, reagent additions and cell turbulence on the flotation rate of coal have been investigated. The results have been analyzed in terms of current theories of particle bubble encounter and adhesion. The rupture forces which occur during particle bubble encounter have been shown to have an important effect on the flotation rate of coarse coal particles. The flotation of coal is a time dependent process, and in order to obtain a complete understanding of the operation it is necessary to determine the kinetics of the process. In coal flotation, the flotation rate and the associated values of cell productivity in terms of tons per kilowatt-hour and tons per cubic foot of cell volume are of greater importance than in most other mineral flotation operations. The reasons for this are associated with the low unit value of coal and the relatively high cost of coal flotation compared with other coal cleaning processes. An important aspect of coal flotation kinetics is the design of coal flotation cells. The cells used in many coal cleaning operations are often replicas of those used for the treatment of sulfide ores and are not necessarily suitable for the treatment of coal washing pulps, which usually contain a higher percentage of coarse and floatable material than the sulfide pulps for which the cells were designed. This disadvantage of many coal flotation cells has been recognized by Russian engineers who, by the addition of baffles to their subaeration coal flotation cells have increased the cell capacity by 100%. Investigation of the variables which influence flotation kinetics and cell productivity are, therefore, important to the coal industry where flotation is the only accepted method of cleaning the fine (-1/2mm) coal. The kinetics of the flotation process have been investigated in detail by Schumann10 who developed a continuous flotation cell which permitted the study of flotation under steady state conditions. This technique has been used by Gaudin et a1.,6 Brown and Smith and recently by Jowett and Savfi.7 The latter authors have developed a refined mathematical treatment for interpreting the results of continuous laboratory tests. Attempts have also been made to study flotation kinetics using conventional batch testing techniques. The experimental difficulties, however, and the problems of determining the order of the flotation rate process have made this technique of dubious value. A summary of the proposed rate equations for batch testing and the difficulties associated with this technique is given by Brown and Smith. 2 The experimental techniques described above are concerned with the rate of production of froth product. However, several authors, notably Sutherland, 11 Bogdanov1 and Philippoff, 9 have analyzed flotation

Jan 1, 1963

By John Birkinbine

A specimen of brown hematite, taken from an iron-ore mine near Anniston, Alabama, exhibits a metallic streak or thread running throngh it. This specimen having been sent to me, I have no personal knowledge of its occurrence; but Mr. Albert E. Noble

Jan 1, 1895

By J. Szekely, V. Stanek

Heat and gas flow interactions in nonisothermal packed beds were examined in the paper. A study was made of the response of the system to a step or pulse change in the inlet gas temperature, with a fixed value of the overall pressure drop across the bed. Under these conditions the heat flow and fluid flow transients are coupled because the convective heat transfer rate is alfected by the mass flow rate of the gas which, in turn, for a fixed pressure drop will depend on the temperature profile in the system. The Problem was stated in terms of differential equations, which were integrated numerically. The parameters used in the computation were so chosen to reflect the operation of the stack region of blast furnaces and sinterbeds. The computed results showed that the pressure drop-flou1 relationships and the rate of progress of the temperature fronts (waves) were strongly interrelated and were also markedly affected by variations in particle size and in void fraction. MANY metallurgical processes involve the contact of solid particles with a gas stream in a packed bed arrangement under nonisothermal conditions. Examples are shaft furnaces, regenerators, pebble heaters, and the sinter process. Although the heat and mass transfer aspects of packed bed processing have been extensively studied, the associated flow phenomena and in particular the effects of nonisothermality on the flow, have received little attention to date. :In fact, most of the previous workers considered the flow rate of the carrier gas time invariant and independent of the heat or mass transfer processSzekely and carr2 have shown that the pressure drop-flow relationships in nonisothermal packed beds may be strongly affected by the temperature profile within the system. These authors have devised a method for relating the pressure drop to flow for a given temperature profile. thus providing an extension of the Ergun equation to steady nonisothermal systems. Finally, in a recent paper willmot3 examined the response of regenerators to externally imposed changes in the gas flow rate. Both these investigations were somewhat specialized since, in general, neither the temperature distribution nor the gas flow rate may be regarded as truly independent variables, thus the heat transfer and the fluid flow problems have to be solved simultaneously. The work reported here is divided into two parts: in Part 1 the general formulation is given and a detailed discussion is presented of fixed bed systems. Part is devoted to systems in which a gas and particulate solids are contacted in a counter flow arrangement. FORMULATION Consider a nonisothermal fixed packed bed, extending from through which a gas is flowing. The problem is to develop a relationship between pressure drop and gas flow (with the gas flow being the dependent variable) and to evaluate the rate at which a change in the gas temperature, imposed at the inlet, travels through the system. Let us consider an infinitesimal section of the bed and establish differential heat, mass, and mechanical energy balances over this region. In addition, relationships are needed describing the temperature dependence of gas density (equation of state) and the temperature dependence of viscosity. These may be written as: where c, and are constants. It is noted that in this formulation we neglected any temperature gradients within the solid particles, thus assuming these to be either sufficiently small or of sufficiently high thermal conductivity to meet this condition. The justification and consequences of this assumption will be mentioned in the discussion.

Jan 1, 1970

By Richard Akerman

At the International Sessions of the Iron and Steel Institute of Great Britain, the American Institute of Mining Engineers and the Verein Deutscher EisenhUttenleute, held in Allegheny City, Pa., in October, 1890, Sir James Kitson, then President of the Iron and Steel Institute, presented an account by Sir Henry Bessemer of the origin of the process which bears his name.? The paper graplhically told how, after the first successes immediately following the first reports given at Cheltenham of the new process, there rapidly succceded such obstacles and difficulties in its practical application, that the whole matter was nearly abandoned in 1858. Suddenly, however, the situation changed, so that at length it became possible

Jan 1, 1894

By H. F. Bishop, F. A. Brandt, W. S. Pellini

The solidification mechanism of experimental steel ingots (7x7x20 in.) was studied by thermal analysis. It was determined that solidification proceeds in wave-like fashion at rates which are determined by the carbon level, superheat, and mold thickness. The thermal cycles of the mold walls were related to the course of solidification. ESPITE marked advances in the field of solid state transformation, metallurgical research has contributed comparatively little exact quantitative data on the mechanism of solidification of metals. There is, therefore, a great need for such data in the various metallurgical industries. The mechanics of solidification of ingots have been investigated in the past primarily by studies of the rate of skin formation as indicated by bleeding or "pour out" tests. The "pour out" method, however, is a tool which gives only approximate information. In the case of alloys with wide solidification ranges, such as irons and certain nonferrous alloys, the method will not work at all; in the case of alloys of intermediate solidification ranges, such as commercial steels, the information may be misleading. Thus, the general adoption of this method has resulted in divergent conclusions regarding the solidification process. Chipman and Fondersmith1 by means of bleeding tests have shown that the linear growth of a solidifying ingot wall follows a parabola of the general form, D = K C, with the start of solidification delayed until superheat is exhausted, as indicated by the constant C. These tests were carried only to a wall thickness of about 5 in. using an ingot of approximately 17x39 in. in cross-section; hence the latter stages of solidification were not studied. Matuschka2-3 indicated that linear solidification of ingots is rapid at first, then slow, but toward the end of solidification the rate becomes extremely rapid again. Spretnak's4 bleeding studies indicated that, wall growth is expressed more rigorously by two parabolas, and that their point of intersection corresponds to a change of solidification mode from columnar to equiaxed. Spretnak also showed that the K values of the first parabola are always the same regardless of superheat. Nelson bled ingots of square cross-section and found that linear wall growth is initially rapid but decreases continually until the end of solidification. He also concluded that rate of solidification in ingots of square cross-section increases 2.15 pct for every 10 pct increase in cross-sectional area of the mold. The mold ratios considered (ratio of cross-sectional area of the mold to cross-sectional area of the ingot) were all less than 2 to 1. The subject of solidification has also been treated mathematically in many cases, but because of the lack of accurate thermal constants and the simplifying assumptions required, as their authors generally acknowledge, they represent only approaches to the actual conditions of ingot solidification. A third method of studying solidification is the electrical analogue method promulgated by Pasch-kis6-7 and by Jackson and coworkers.8 This method treats solidification as a heat transfer problem with the solidification cycle synthesized on an electrical circuit. Paschkis in his treatment of solidification considered the fact, which was generally ignored, that solidification of steel is not simply the growth of a plane solid wall but a more complex process occurring over a temperature range as indicated by the constitution diagram. Undoubtedly, the anomalous results obtained by bleeding tests arise from the inability to measure quantitatively this mushy condition. The shape of Paschkis' solidification curves are more nearly in accord with those of Matuschka, in that they indicate rapid linear solidification at the beginning and end of solidification with intermediate solidification occurring at a slower rate. Paschkis indicates a definite lengthening of solidification time with increasing superheat. Thermal analysis is a direct method providing exact information for all types of metals regardless of solidification range and was thus adopted in the present program to follow the entire course of solidification from the surface to the centerline of the ingots. The method has the added advantage of being adaptable to following the thermal cycle of the ingot mold during the course of solidification. Test Methods The ingots studied were of square cross-section, 20 in. long, tapered from 71/4 in. at the top to 63/4 in. at the bottom, and fed with a hot top 7 in. in diam and 12 in. high. The molds were uniform in wall

Jan 1, 1953

By K. C. Strebig, C. W. Schultz, A. A. Selim

The effect of some organic additives in diamond drilling of quartzite was investigated in the laboratory. The drill was designed to measure the rate of penetration, the thrust, and the torque and to record each as a function of the distance drilled. A statistical plan was followed throughout the investigation and an equation representing the bit performance was derived from the mathematical theory of reliability. The drilling torque was found to increase with the use of additives while the sliding coefficient of friction and the wear coefficient decreased. The energy per unit volume consumed was found to increase with the use of additives. A hypothesis explaining the effects achieved with the additives is given. INTRODUCTION For some time researchers have attempted to increase drilling efficiency by adding certain agents to the flushing medium. Much of this interest is the result of the observations of Rehbinder, Shreiner and Zhigach1 They postulated that "...in processes for the mechanical destruction of solids, a region of increased crack formation is created in the deformed layers adjoining that surface of destruction, forming the predestmction zone. The surrounding medium (for example, a liquid) which wets a given solid will penetrate the embryo microcracks of the predestruc-tion zone. Increasing the molecular affinity of this liquid for the surface of the solid considerably facilitates the deformation and destruction by softening the solid in the zone of increased crack formation. In this manner, the hardness or strength of the deformed body is decreased by the influence of the penetration of the liquid into the predestraction zone." This is known as the "Rehbinder effect". Rehbinder's work has prompted many investigators to examine the effect of additives on the mechanical destruction of rocks. Engelmann, Terichow and Selim reported that the maximum penetration of the rock by a diamond point in a solution environment was at the isoelectric point of the solution.* Robinson reported that his results did not appear to support the theory of Rehbinder.3 Joris and .McLaren suggested that additives with surface tension lower than water will be more efficient in cooling the diamonds.4 Their effectiveness in removing the fine cuttings from the face of the bit will also improve the efficiency of the system. They reported an improvement in impregnated bit life and penetration rates with the use of soluble oil additives. In contrast, Long and Agnew, drilling with surface set bits, reported that lubricating agents increase bit temperature and wear.5 A significant change was reported6 in the mechanical properties of rock with polar additives. It was concluded that this change in the mechanical properties of the rock in the presence of the additive is due to the rock hydrophilic properties. Ethylene glycol, glycerine and anionic detergent were selected for this investigation because their surface tension is lower than that of water. The surface tension of these additives for the concentrations studied was 42 to 75 percent of the surface tension of water. A low surface tension additive would wet the surface of the diamonds more easily and hence would be more effective in cooling the diamonds. Another characteristic of these low surface tension additives is their effectiveness in removing the cuttings and preventing the flocculation of the formed particles in the drilling process. This article summarizes the results of an investigation performed at the laboratories of USBM, Twin Cities Mining Research Center. The objective of the investigation was to study the over-all effects of some organic additives on the performance of diamond impregnated bits in atmospheric drilling conditions only and not in downhole pressured conditions.

Jan 1, 1970

By C. R. Van Hise

[Concluding Contribution of Prof. Van Hise to the Discussion of his Paper, and Others on the Same General Subject, presented at the Washington Meeting, February, 1900 (see Trans., xxx., 27, 177, 323, 424, 5 S); also of the contributions of Vogt, De Launay, Beck, Lindgren, hemp, Rickard, Bain, Keyes, Collins and Adams, presented at the Richmond Meeting, February, 1901, and printed in the present volume.] IN June, 1900, shortly after my paper was published in the Transactions, I made a briefer statement* before the Western Society of Engineers covering the same `round, which, in certain respects, is somewhat of an improvement. For instance, instead of using the terms descending and ascending with reference to the waters resulting in the two concentrations, my modified statement is as follows " The first concentration of many ore-deposits is the work of a relatively deep water-circulation, while the reconcentration is the result of reactions upon an earlier concentration through the agency of a relatively shallow water-circulation. Commonly the deep water circulation is lacking in free oxygen, and contains reducing agents, and the shallow water contains free oxygen. The deep water is therefore a reducing, and the shallow water an oxidizing agent."† Of the papers upon ore-deposits which, in vol. xxx. of the Transactions, follow my own, or which were presented at the Richmond meeting, a considerable number are wholly confirmatory of the conclusions which I have presented. Among these are the Washington paper of Emmons upon the Secondary Enrichment of Ore-Deposits‡ and his discussion at Richmond of other papers,§ that of Weed upon the Enrichment of Gold and Silver Veins,[ ]the discussion of Emmons', and at Richmond of Weed's paper by Collinst and Prof. De Launay,† the paper of Lindgren on Metasomatic Processes in Fissure Veins,¶ that of-Rickard upon the Formation of Bonanzas in the Upper Portions of Gold Veins,** and the remarks of Bain upon the Mississippi Valley lead- and zinc-deposits.†† It is therefore un-

Jan 1, 1902

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10'a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann' in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5'6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1'-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1' ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968

By D. D. Pollock, D. I. Finch

Relationships between the compositions of specially prepared manganin-type alloys and some of their electrical properties have been established. Empirical equations, based upon the electronic configurations of the alloying elements, are given which describe the resistivity, temperature coefficient, peak temperature, and thermoelectric power of Cu-Mn-Ni-Fe alloys at approximately room temperature. Calculations based upon these relationships are correlated with experimental data. SECURING suitable alloys for the construction of stable resistors, for use in precise electrical measuring devices, has been important ever since the art of electrical measurement was begun. German silver, Pt-Ag, and Platinoid are examples of some of the alloys in early use. These early alloys were un- satisfactory for one or more of the following reasons: l—insufficient stability of electrical properties with time, 2—poor reproducibility of electrical characteristics from melt to melt, 3—excessive temperature coefficients of resistance, and 4—excessive cost. Weston introduced the Cu-Mn-Fe and Cu-Mn-Ni-Fe alloys of the type now generally known as manganins. His patents are believed to represent the first disclosure of any alloy with a negative temperature coefficient of resistance. After this work, the German company, Isabellenhutte, in conjunction with Feussner and St. Lindeck, produced alloys of

Jan 1, 1957

By J. A. Roberson, Robert A. Rapp

From the observation of platinum wire marker movement in the oxidation of columbium at high lemperatures and low oxygen pressures, predonzinant cation diffusion in CbO, has been demonstrated. The Cu,0 molecule was used as an oxidizing species to study the nature of the porous scale and the location of the reduction site in the oxidation of colum-bium. The Cb205 scale contains microporosity and forms by alternate ionic diffusional growth and fracture. The oxidation of columbium at high temperatures and very low po, results in a relatively compact and protective Cb205 layer. THE observation of marker movements during oxidation is one means for the identification of the mobile ionic species in an oxide lattice. Previous marker experiments in the oxidation of columbium have all resulted in the markers being found on the outside surface of the Cbz05 scale. The Cr203 powder markers of Klopp et a1.,' the gold film marker of Kofstad and ~jijllesdal,' and the platinum wire marker of Cathcart et a1 .3 were found at the oxide/gas interface for oxidation temperatures ranging from 450" to 120O0C. However, in all experiments relatively high oxygen pressures were used. As discussed by Mrowec, even the interpretation of marker experiments in simple scales containing only one compound is not without ambiguities. In brief, it can be said that a marker may be found almost anywhere in the scale layer if the metal oxidizes by cation diffusion through the scale; the position of the marker depends upon morphological happenings in the scale. When considering marker movement in a polyphase scale one must proceed with extreme caution. For example, in the past (and present) work markers have never been found at the columbium-scale interface, and one might infer that the oxygen ion is mobile in CbO and CbO,. However, only trace quantities of CbO and CbOz have been present on any of the specimens, so no firm statement is justified on this basis. Despite previous experimental work, considerable doubt still exists concerning the role of the oxides CbO and CbOz in the oxidation of columbium. The identification of the mobile ionic species in CbO and CbOz from the observation of platinum wire markers was one goal of the present investigation . The linear kinetics of columbium oxidation at high temperatures (T - 1000°C) suggests that the Cbz05 scales which form on columbium are porous. From mercury absorption measurements on a Cbz05 scale formed at 500"C, Aylmore et al.' reported a minimum volume fraction of connected voids equal to 0.15. While these scales often appear to be quite porous when viewed in metallographic cross section, they are so brittle that metallographic preparation is likely to exaggerate any porosity originally present. In this investigation, porosity developed during the oxidation of pure columbium and present at the high temperature was detected by oxidizing specimens in sealed evacuated capsules containing large compacts of mixed copper and CuzO powders. wooda has demonstrated that the CuzO, or (CuzO),, molecule is volatile and that oxygen is transferred by the CuzO molecule from a Cu/CuzO mixture to materials having a greater affinity for oxygen. For each molecule of CuzO that is reduced at a sink for oxygen, two atoms of copper are deposited. Quantitatively, essentially all of the oxidation carried out by a Cu-Cu20 compact results from a displacement reaction involving the CuzO molecule. When a metal which oxidizes to form a porous scale is exposed to the CuzO vapor, the CUZO molecules are reduced in the pores leaving a deposit of metallic copper to mark the site of the reduction. This technique has the rather unique advantage that any copper-coated pores found in the scale are unambiguously related to the reduction site in the growth of the scale under consideration. Pores or cracks which form in a msition*- external to the reduction site or which occur as a result of cooling or handling of the specimen will not exhibit the copper deposit. EXPERIMENTAL PROCEDURE Marker experiments were made on columbium metal, and on pellets of CbO which had been pressed and sintered. Platinum wire markers (0.001 and

Jan 1, 1968

By J. W. Lacey, F. H. Brinkman, J. E. Faris

This paper presents an analysis of the high-pressure, gas-driven LPG-slug process, based on fluid flow tests in areal models. Two types of tests were made. One series was made in low-pressure models which permitted observation of fluid movement. Three completely misci-ble analog fluids were used. A second series of tests was made in high-pressure models using methane, propane and a light refined oil saturated with methane at room temperature and 1,550 psig. Under the test conditions of room temperature and a pressure level of 1,550 psig, the phase diagram for the fluids used is similar to those for many of the field systems where the process is considered for use. A method for using these laboratory data to calculate field performance of the process is outlined. As a result of this work, it is concluded that small banks of LPG (5 per cent HV or less) are not effective in increasing oil recovery in horizontal reservoirs. Znstead, where small banks are used, the driving gas quickly penetrates the LPG bank because of fingering and channeling; and from this point on, the process behaves essentially as an immiscible gas-injection project. The validity of this conclusion was substantiated by: (1) laboratory studies of the effect of rate, model size and mobility ratio on miscible displacement in areal models; and (2) calculation of field recovery, which compared closely with actual field recovery. INTRODUCTION Field applications and pilot tests of the gas-driven, LPG-bank, oil-recovery process are on the increase. Most of these tests are employing small banks (2% to 5 per cent hydrocarbon volume) of LPG, which is miscible with both the driving gas and the oil in place, in an effort to attain an effective yet economical miscible displacement of oil by gas. The expectation of miscible displacement with small banks is based on the concepts that: (1) lengths of solvent-oil mixed zones, measured during miscible displacements in long slim cores, are representative of those that will occur in the field; and (2) areal sweep efficiencies5 measured in electrolytic model studies are applicable to miscible displacement in reservoirs. Our experimental evidence indicates that the mixed-zone lengths and sweep efficiencies mentioned are not applicable to miscible displacement in reservoirs. In this paper we present an evaluation of the gas-driven, LPG-bank oil-recovery process based on fluid flow experiments in areal models. These results are used to predict the performance of a field pilot test of this process, and the results are compared with the actual test results. THE EFFECTIVENESS OF LPG BANKS The effectiveness of LPG banks of various sizes in accomplishing miscible displacement of oil by gas was determined by displacement tests in a model representing one-quarter of a confined five-spot pattern. The model, 12 X 12 X 1/4 in. in size, was packed uniformly with glass beads. It was operated at a pressure of 1,550 psig and at room temperature; the fluids used were methane, propane and refined oil saturated with methane at 1,550 psig. The saturated oil had a viscosity of 1.2 cp at room temperature. The results of these tests are shown in Fig. 1, where recovery is plotted as a function of the volume of fluid injected for: (1) an immiscible-gas drive with an oil-to-gas viscosity ratio of 85; (2) three sizes of LPG banks; and (3) two completely miscible displacements with mobility ratios of 85:1 and 10:1. (The miscible displacement data plotted are the averages of several tests.) The results show that a 2½ per cent bank of LPG does not increase oil recovery over that obtained by immiscible-gas drive. The 7 and 17 per cent banks are, respectively, about 30 and 50 per cent effective (with reference to the M = 85 miscible-displacement curve) in increasing oil recovery at the point where 2½ hydrocarbon volumes (HV) of fluid have been injected. The percentage effectiveness of the banks at a given volume of fluid injected is defined as Recovery by Bank — Recovery by Gas Drive Recovery by Miscible Recovery by Flooding Gas Drive We conclude from these results that banks of LPG smaller than about 5 per cent HV in an individual stratum will cause from little to no increase in oil recovery. This finding was substantiated by work in low-pressure models, which permitted visual observation of fluid movements. In these tests, three completely miscible fluids having the same viscosity ratios as those used in

By D. B. Rushmore, K. A. Pauly

Of primary importance in mine-installations is the hoist, which has a very direct bearing on the successful operation of a mine. Conditions vary greatly with different mines, and especially in different localities. Such factors as depth, incline, the number of levels, permissible or desirable speeds, conditions of ore, etc., are always more or less special in each case. Veins of ore are never exactly duplicated, and the nature of the ground through which shafts are sunk may considerably modify permissible values. As mining-laws are made by the different States, they necessarily vary somewhat, and, even when not fully observed, they introduce factors which qualify the conditions of hoisting men and ore. The amount of timbering required is often of importance as relating to hoisting-conditions. Methods of loading ore affect the time required, as also does the question of the use of cars or skips. Safety-precautions must be very carefully considered, and the number of men in each mine, the number of compartments, and often the method of removing water from the mine, must have careful consideration. While a general discussion of the subject of hoisting is possible, most cases are entirely special, and can be considered only in connection with the peculiar conditions pertaining to that particular installation. The cost of installation of the hoisting-plant may be an appreciable amount, while the cost of raising the ore may be but a small part of the total operating-charge. In many cases, however, the output of the mine is limited by the capacity or the hoist, and the latter thus becomes of the first importance.

Jan 1, 1911

By T. R. Scott

The acid pressure leaching of zinc-lead flotation concentrates from the McArthur River deposit, Northern Territory, Australia, has been studied in a three-stage, continuous, co-current system, using titanium reactors of 6 gal capacity. The starting pulp contained 2.7 lb solids per gal of synthetic spent electrolyte and the final liquors contained 120-125 gpl Zn. Parameters investigated included temperature (95-120°C), oxygen pressure (30-100 psi), acid addition (80-130% of theoretical), and leaching time (35-65 min per stage). Technical factors studied included mixing and pumping of feed, agitation, settling and washing and control mechanisms. The chemistry of liquor impurities, of scale formation in autoclaves and of lead jarosites in residues was studied in some detail. Results indicated that 90-93% zinc recovery could be obtained with a "low- acid" process, using 113°C and 70 psig with oxygen as the favored operating conditions. Residues contained 16-18% elemental sulphur and 15% lead, together with unreacted pyrite and gangue minerals. Pelletizing of residues was impracticable, and alternative suggestions for the recovery of lead, sulphur and silver are discussed. Preliminary estimates for plant and operating costs are given and enable some comparison to be made with conventional procedures.

Jan 1, 1973

By G. R. M. Del Giudice

A survey of the flotation literature of the past 10 years indicates an increasing use of the microscope as a tool for investigation. Thus, the metallurgical microscope has been used by Tucker and Head;' Taggart, Taylor and Ince;2 Ince,3 and del Giudice4 to examine mineral surfaces that had been subjected to the action of various flotation reagents and to the action of slime pulps. It has also been used by Gaudin, Groh and Henderson;5 Martin;6 Morrow and Griswold;7 and others to examine bakelite briquets of mill products. The microscope with transmitted light, both with bright-field and dark-field illuminations, has been used by Taggart, Taylor and Knoll8 and by Ince9 to observe Brownian motrement and flocculation in flotation pulps. The use of the microscope at low-power magnifications with incident illumination for the examination of mill products has been known for years.10 Finally, del Giudice11 has used a relatively new type of illumination, the Ultropak, for the examinntion of slime-coatings.

Jan 1, 1935

By Chas Dobbel

THE Chief Consolidated properties are situated in the Tintic mining district of Utah, being included in Juab and Utah Counties, about 70 miles south of Salt Lake City. The drilling referred to in this paper has been carried on in the Chief Consolidated No. 1 mine, the Gemini mine, and the Eureka Hill mine at Eureka, the Grand Central mine, above Mammoth, and the Apex Standard mine just south of Dividend. The occurrence of ore through the district is typically in lenses on bedding or breaks, and in connecting pipes, without accurate geometrical trend so that the ratio between the total length of development in drifts and crosscuts to the square feet of ore exposed is very high. A section of one of the western channels (Fig. 1) through the Tintic district, shows, roughly, the irregularities calling for excessive development work, so typical of the Tintic mines. This irregular trend of the ore constantly calls for excessive cutting up of the whole area for offshoots and the connecting links always present.. In the planning of prospecting and development, no regular system may be laid out without overlooking some orebodies or segments of orebodies. It was with these facts in mind that Cecil Fitch, the general manager of the Chief Consolidated Mining Co., decided that some method of drilling was the more feasible way of successfully cutting up and bringing about the discovery of ore believed to exist; yet this drilling had to compete with a great. margin of cost over crosscutting, as a crosscut in the Tintic district, even though barren, brings out geologic facts that, in many cases, are worth the price of the working itself. Diamond drills met with the success that might be expected in a district that has a reputation for the wear and loss of diamonds; after 6 or 8 months, this method was discarded on account of the high costs. Simultaneously, a small churn drill outfit was set up underground but a few shifts proved its inapplicability. At the same time, the ordinary hammer drill was usd to drive prospect holes with jointed steel.

Jan 9, 1925

The members of the Institute will recall the account given in the March Bulletin of the inauguration exercises of the Engineering Foundation which was inhibited by an initial gift of $200,000 by Mr. Ambrose Swasey, to be administered by the United Engineering Society as trustees. The Engineering Foundation Board is now constituted as follows: GANG DUNN, Chairman, EDWARD D. ADAMS, Vice-Chairman FREDERICK R. HUTTON, Secretary, JOSEPH STRUTHERS, Treasurer, American Society of Civil Engineers. J. WALDO SMITH, CHARLES WARREN HUNT.

Jan 12, 1915

By Stephen Krickovic

AS it is commonly understood in the bituminous coal mining industry, pillaring means removal, as completely as is practical, of all pillars formed in the development of headings and rooms on first mining. The degree to which this can be accomplished, termed percent of recovery, is of course dependent generally upon the physical conditions of the bottom and the overburden, the system of min-

Jan 1, 1956