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By E. T. Turkdogan, Klaus Schwerdtfeger

OelSEN and Maetz1 detected some 20 years ago the existence of a miscibility gap in iron oxide-CaO-P2O5 slags melted in iron crucibles at about 1400°C. Because of the importance of this system for the dephos-phorization of steel in the basic Bessemer process, equilibria between liquid iron and selected iron oxide-CaO-P2Q slags have been measured since by numerous investigators.2-5 When in equilibrium with metallic iron, the iron oxide of the slag is present mainly as FeO. In connection with oxygen-blowing steelmaking processes, it is useful to know the phase relations in the slag system at higher oxygen pressure, when major parts of the iron oxide are present as Fe2O3. This problem was investigated by Turkdogan and Bills7 by equilibrating the oxide mixtures contained in platinum crucibles with CO2-CO mixtures at 1550°C. It was found that increasing the Fe2O3 content decreases the composition range of the miscibility gap strongly so that the miscibility gap has almost disappeared at pco2/pco = 75. This result was refuted by the careful work of Olette et a1.,''' who equilibrated their slags with controlled Ha-H2-Ar gas mixtures. Their equilibrium measurements, at 1600°C and at oxygen pressures of 5 x 10"* and 10"5 atm, showed that the oxidation state of the iron has almost no influence on the formation of the miscibility gap. The present experiments were undertaken to check the previous results of Turkdogan and Bills. The experiments were performed at 1625°C in the strongly oxidizing atmosphere of air (PO2 = 0.20 atm) for which no experimental data are available. About 10 g of slag were melted in platinum crucibles and held at constant temperature for 1 hr. After equilibration, the crucible was rapidly pulled out of the furnace and cooled in air. The platinum crucible was removed from the sample. The two slag layers were carefully separated with a small diamond disc, and the surface of the top layer, which may have changed its oxidation state during cooling, was removed. The slags were crushed and analyzed chemically for CaO, P2O5, Fe2+, and Fetotal. The starting mixtures were prepared by sintering the desired amounts of reagent-grade 2CaO . P2O5 - H2O, CaCO3, and Fe2O3. Sintering and subsequent crushing were done three times to ensure homogenization. Molybdenum wire resistance heating was used. The furnace was provided with a recrystallized alumina reaction tube which was left open to air at the top. The temperature was controlled electronically. The reported temperature was measured with a Pt/Pt-10 pct Rh thermocouple and is estimated to be accurate within +5°C. The composition of the equilibrated melts is given in Table I. For the graphical illustration of these quaternary slags the type of projection suggested by Trömel and Fritze10 was used. In this representation, Fig. 1, the composition point of a mixture within the tetrahedron Fe2O3-CaO-P2O5-FeO is projected into the Fe2O3-CaO-P2O5, triangle (triangle I) so that the direction of projection is parallel to the side FeO-Fe2O3, and into the triangle Fe2O3-P2O,-Fe0 (triangle 11) so that the direction of projection is parallel to the side CaO-P2O5, of the tetrahedron. The projected point has the coordinates wt pct CaO, wt pct P205, and wt pct (FeO + Fe2O3) in triangle I and wt pct FeO, wt pct Fe2O3, and wt pct (CaO + PzO5) in triangle 11. Both triangles are turned into the same plane around the Fe203-P20, side of the tetrahedron. An illustration of the projection of a quaternary point in the present system is shown in Fig. 1. The advantage of this type of projection is that all four components for an equilibrium curve can be read directly from the diagram. The present results are shown graphically in Fig. 2. The curves depicting the miscibility gap are dashed in parts where no experimental points were obtained. The composition range covered by the miscibility gap

Jan 1, 1968

By R. W. Shoenberger, J. A. Grina, R. J. VanPelt

The many alternatives open to coke plant operators for improving overall coke quality and strength are discussed in this paper. Programs undertaken by US Steel research and coal operations during the previous ten years to improve coke strength are described. New techniques in use, or being considered for future use, are also discussed.

Jan 1, 1982

By G. Derge, Ling Yang, G. M. Pound

The specific conductance and its temperature dependence were measured over the entire composition range of the molten Cu2S-CuCI system. At a typical temperature of 1200°C, 10 rnol pet of the ionically conducting CuCl reduced the specific conductance from about 77 ohm-lcm-l for pure Cu2S to about 32 ohm -1cm -1, and 50 mol pet CuCl reduced the conductance to that for pure CuCI—about 5 ohm 1cm1. The nature of electrical conduction in molten Cu2S, FeS, CuCI, and mixtures was studied by measuring the current efficiency of electrolysis at about 1100°C. The Cu2S, FeS, and mattes were found to conduct exclusively by electrons, but addition of 1 5 wt pet CUS to Cu2S produces a small amount of electrolysis. Addition of CuCl to Cu2S suppresses electronic conduction, and ionic conduction reaches almost 100 pet at a CuCl concentration of about 50 mol pet. These facts are interpreted in terms of electron energy level diagrams by analogy to the situation in solids. RESULTS of electrical conductivity studies on molten Cu-FeS mattes as a function of composition and temperature have been reported.' The specific conductances ranged from about 100 ohm-' cm-' for pure Cu2S to 1500 ohm-' cm-1 for pure FeS. This is in sharp contrast with the low specific conductance of molten ionic salts for which the transfer of electricity is by migration of ions in the field. In general, these ionically conducting molten salts, such as NaC1, KC1, CuC1, etc., have a specific conductance of the order of magnitude of 5 ohm-' cm-'. It was concluded on the basis of this evidence that molten FeS and Cu,S exhibit electronic conduction. Pure molten FeS has a small negative temperature coefficient of specific conductance, resembling metallic conduction, while pure molten Cu2S has a small positive temperature coefficient, resembling semi-conduction. The molten Cu2S-FeS mattes follow a roughly additive rule of mixtures, both with respect to specific conductance and temperature coefficient. Savelsberg2 has studied the electrolysis of molten Cu2S and Cu2S + FeS. He concluded that while molten Cu2S is an electronic conductor, there is some ionic conduction in molten Cu2S + FeS3 owing to the formation of the molecular compound 2Cu2S.FeS and its dissociation into Cu1 and FeS2-1 ions. The present work does not verify his results. Chipman, Inouye, and Tomlinson" have studied the specific conductance of molten FeO and report a high specific conductance, about 200 ohm-1 cm-1 of the same order of magnitude as that found for molten mattes, and a positive temperature coefficient. They interpret these results in terms of p-type semiconduction in the ionic liquid by analogy to the situation in solid FeO.1 imnad and Derne' detected appreciable ionization in molten FeO by means of electrolytic cell efficiency measurements. In order to verify the conclusion that electrical conduction in molten Cu2S and mattes is electronic, and to gain further insight into the structure of molten sulfides, the following investigations were carried out in the present work: 1) The specific conductance, s of the molten system Cu2S-CuC1 was measured as a function of temperature over the entire composition range. As discussed later, molten CuCl is an ionic substance. It was thought that if molten Cu2S were simply ionic in nature, addition of small amounts of CuCl might not have a catastrophic effect in lowering the high conductance of the Cu2S. On the other hand, if much electronic conduction occurs, addition of the ionic CuCl should have a large effect in destroying the electronic conduction. 2) The electrolytic cell efficiency of the following molten systems was measured at about 1100°C in specially designed cells: Cu3; Cu2S + FeS, 50:50 by wt; FeS; Cu2S + CuS, 15 wt pet; Cu2S + CuC1, 5.9 to 46.4 mol pet; and CuC1. This gives a direct measure of the fraction of current carried by ions in these melts. Further, the cell efficiency, extrapolated to zero ionic current, is given by cell efficiency = (s leasile + s elexstronic). [1] s lucile for molten CulS would be expected to be no greater than that for molten CuC1, whose s lonle is about 5 ohm-' cm-1, as will be seen in the following. u,.,,.,.,.......for molten Cu,S is of the order of 100 ohm-' cm-'.' Thus, a large increase in cell efficiency from 0 to values of 10 to 100 pet upon addition of CuCl to Cu2S would indicate destruction of the electronic conductance. Conductance Measurements Experimental Procedure—The apparatus and experimental method were the same as those described in detail in connection with the study of electrical conduction in molten Cu,S-FeS mattes.' A four terminal conductivity cell and an ac poten-

Jan 1, 1957

By C. W. Sherman, N. J. Grant

The correlation of the high temperature chemical properties of slag-metal systems with some easily measured property of either slag or metal at room temperature has been the goal of both process metallurgists and melting operators for many years. There are several rapid methods for estimating various constituents in steel in addition to the conventional chemical methods which are quite fast, but these do not reveal the nature of the slag as a refining agent, which is of primary interest to the steelmaker. Furthermore, there are several methods for examining slag, the three principal ones being slag pancake, petrographic examination, and the previously mentioned chemical analysis. The main objection to the last two is the lime required to make a satisfactory estimate of the mineralogical or chemical components. The objection to the first is the inadequacy of the information obtained. A new technique has been developed by Philbrook, Jolly and Henry1 whereby the properties of slags are evaluated from an aqueous solution leached from a finely divided sample of slag. It is known that the pH or hydrogen ion concentration (of saturated solutions that have dissolved certain basic oxides, notably calcium oxide) will indicate a pronounced basicity. Philbrook, Jolly and Henry devised the pH measurement technique in order to supply open hearth operators with a fast, reasonably accurate method of estimating slag basicity. They offered the method as an empirical observation and made no claims as to its theoretical justification. The results were presented as an experi-metally observed relationship which applied over an important range of basic open hearth slags. They found that, in plotting the measured pH against the basicity, the best relationship existed between the pH and the log of the simple V ratio, CaO/SiO2. Extensive investigation also showed that there were several variables in the experimental technique that influenced the results and necessitated following a standard procedure to obtain reproducible pH readings. These variables were: 1. Particle size of the slag powder used. 2. Weight of sample used per given volume of water. 3. Time of shaking and standing allowed before the pH was measured. 4. Exclusion of free access of atmospheric carbon dioxide to the suspension. 5. Temperature of the extract at the time the pH was measured. In subsequent investigations of the pH method by Tenenbaum and Brown2 and by Smith, Monaghan and Hay3 the general conclusions of Philbrook's work were reaffirmed. It was the object of the present investigation to extend the technique to a point where it could be used to evaluate slags of all types. Experimental Results PARTICLE SIZK OF SLAG POWDER A large sample of commercial blast furnace slag of intermediate basicity (V-ratio 1.15) was selected for the study. The slag had been put through a jaw crusher until all of it passed through a 20 mesh screen. Five fractions of this crushed material were separated, -20 to +40, -40 to +60, -60 to +100, -100 to +200, and -200 mesh. A representative sample of 0.5 g was removed from each fraction and the pH determined using the method of Philbrook. Check pH analyses on the sample fractions varied due to the different amounts of shaking. To eliminate this variable, a mechanical shaker was employed. In order to know the exact time of contact between the slag and water, it was found necessary to filter the extract at the end of the shaking period. Using the mechanical shaker and a filtering apparatus, similar runs were made on the five fractions for contact times of 5, 10, 20, and 40 min. Random checks gave reproducible results within 0.02 pH. The data are plotted in Fig 1. It can be seen from the plot that each slag fraction is hydrolyzed to an extent that is roughly proportional to the surface area exposed to the water. The (—100 to +200) mesh material changed very little in pH after 10 min. shaking time. The curves are symmetrical and lie in proper relation to one another. The —200 mesh curve appears to be somewhat flatter than the others, but this can be attributed to the portion of very fine material that is not present in the other fractions. The closeness of the (-100 to +200) mesh curve to the —200 mesh curve and the fact that a —100 mesh sample would contain amounts of slag down to 1 or 2 microns in diam were considered sufficient reasons for selecting a —100 mesh sample as representative of the whole sample of slag for the purposes of this investigation.

Jan 1, 1950

By M. H. Childs, K. E. Merklin

Blast furnace feed specifications are being revolutionized because of the large increase in iron pellet production from low-grade ores of the Lake Superior region. Recent laboratory findings aimed at a better understanding of factors influencing the physical quality of pellets produced from taconite concentrates are reviewed. Tests for determining better product quality, the effects of additives, and production factors are discussed. The current revolution in specifications for blast furnace feed is typified to a great extent by the recent tremendous growth in iron ore pellet production from low grade ores of the Lake Superior region. Indeed, pellets are responsible, at least in part, for many of the stringent new requirements that are being placed on the suppliers of furnace raw materials. As the tonnage of pellets going to the steel mills increases, more and more attention is being turned to the detailed characteristics that make this product an ideal blast furnace feed. Control of quality in pellets is similar to that of any other product. A basic understanding of the factors that are encountered in their production, from the crude ore through to the finished product, is required, along with careful process supervision and frequent quality checks. Normally, chemical grade is not a problem. This usually can be controlled within the desired specifications by minor operating variations in the con- centrator. While future changes in requirements may result in the need for self-fluxing pellets1 or other chemical changes, today's quality demands center primarily around the physical characteristics of the pellets. It is in this area that many of the recent laboratory studies have proven helpful to the operating plants. A better understanding of the physical factors involved in pelletizing has provided the basis for a continuing program of quality improvement. Tigerschiold and Ilmoni2 and Cooke with various associates are responsible for the development of much of the basic understanding of the pelletiz-ing process. These earlier findings have served as a most useful background for this work. LABORATORY PROCEDURES Magnetite concentrates produced from eastern Mesabi Range magnetic taconites were used for all of the work reported herein. The sizing and chemical analysis of a random sample are shown in Table t Additives usually are mixed with the concentrates in taconite plants before pelletizing to improve the strength characteristics of the unfired balls. Ben-tonite, soda ash, and coal are in common use. The bentonite used in these studies was of the Wyoming sodium type; the soda ash was a standard commercia1 brand. Anthrafines were used where coal was called for. The procedure for making batches of balls at the Hibbing Laboratory is as follows: In an especially designed mulling equipment 2800 g of dry ore are mixed for 10 min with the desired additives. Water is added and mixing continued for 1 1/2 min. The charge is removed from the muller and put through a mechanical shredder to break down any lumps that may have formed. sixty previously formed seed balls are placed in the balling drum, which is in fact a 6 x 16-in. diam airplane tire turning at 53 Wm. Two thousand grams of the shredded concentrate and additive mix are fed by hand into the tire at a con-

Jan 1, 1961

By A. A. Collins

OF widespread interest to all lead metallurgists is a dross smelting process that will consistently give mattes and speiss of low lead and high copper contents. It is a problem that has intrigued operators through the years. In the past few years, with increased amounts of copper and overcrowded metallurgical furnaces, it has been almost imperative to evolve some method. Experience at El Paso has shown that high copper-to-lead ratios can be consistently attained by use of the new soda process. † Older Methods Three older methods, i.e., 1. Dross plus siliceous ore and limestone. 2. Dross plus one fourth blast-furnace speiss and siliceous ore, 3. Dross plus sulphides and siliceous ore and scrap iron, do not give consistent results and the products are higher in lead and lower in copper than those produced with the soda process. Any radical changes in the blast-furnace drosses will throw any of these older methods into a tailspin. For almost ten years, El Paso used the third method, with varying results. It was noted that as the arsenic and anti- mony contents of the dross increased, the speiss and matte steadily increased in lead and decreased in copper. A dross containing four parts of copper to one part of arsenic was considered to be ideal. At times this balance of copper to arsenic was almost impossible to obtain, especially when handling copper Cottrell dusts, which vary so greatly in copper and arsenic. Custom smelters like El Paso, handling a great variety of dusts, concentrates and ores, are apt to have anywhere from I to 15 pct copper on charge, with a variable in arsenic of from 0.5 to 2 pct. With such conditions, and drosses varying from 12 to 40 pct copper, an operator using the older dross reverberatory practices would find it just about impossible to control the reverberatory operations and to produce a good product low in lead and high in copper. These conditions prevailed at El Paso from the year 1940 to the present. In May 1942 it was decided to experiment with the soda process. The Soda Process After considerable work the soda method was finally evolved to the present state. It has never failed to produce a good product even under the most adverse conditions. It might be well to remember that many men of thought in the smelting industry have at one time or other sugge~ted the removal of all copper, arsenic and antimony from the lead blast-furnace charge as an aid to better metallurgy.

Jan 1, 1949

By A. A. Collins

OF widespread interest to all lead metal¬lurgists is a dross smelting process that will consistently give mattes and speiss of low lead and high copper contents. It is -a problem that has intrigued operators through the years. In the past few years, with increased amounts of copper and overcrowded metallurgical furnaces, it has been almost imperative to evolve some method. Experience at El Paso has shown that high copper-to-lead ratios can be consistently attained by use of the new soda process.* OLDER METHODS Three older methods; i.e., I. Dross plus siliceous ore and limestone, 2. Dross plus one fourth blast-furnace speiss and siliceous ore, 3. Dross plus sulphides and siliceous ore and scrap iron, do not give consistent results and the products are higher in lead and lower in copper than those produced with the soda process. Any radical changes in the blast-furnace drosses will throw any of these older methods into a tailspin. For almost ten years, El Paso used the third method, with varying results. It was noted that as the arsenic and antimony contents of the dross increased, the speiss and matte steadily increased in lead and decreased in copper. A dross containing four parts of copper to one part of arsenic was considered to be ideal. At times this balance of copper to arsenic was almost impossible to obtain, especially when handling copper Cottrell dusts, which vary so greatly in copper and arsenic. Custom smelters like El Paso, handling a great variety of dusts, concentrates and ores, are apt to have anywhere from 1 to 15 pct copper on charge, with a variable in arsenic of from 0.5 to 2 pct. With such conditions, and drosses varying from 12 to 40 pct copper, an operator using the older dross reverberatory practices would find it just about im¬possible to control the reverberatory operations and to produce a good product low in lead and high in copper. These conditions prevailed at El Paso from the year 1940 to the present. In May 1942 it, was decided to experiment with the soda process. THE SODA PROCESS After considerable work the soda method was finally evolved to the present state. It has never failed to produce a good product even under the most adverse conditions. It might be well to remember that many men of thought in the smelting industry have at one time or other suggested the removal of all copper, arsenic and antimony from the lead blast-furnace charge as an aid to better metallurgy.

Jan 1, 1947

By EVERETTE DE GOLYER

USE of geophysical methods in the search for new pools and as an aid in the development of known pools and prospects reached a new all-time peak for the oil industry in 1933. The outlook for 1934 is for work to continue at an even greater rate. The area of greatest activity, as in previous years, was in the Gulf coastal plain of Texas and Louisiana, particularly through a belt of territory some 20 to 30 miles wide parallel to the coast line and some 80 miles inland from it-the so-called "Jackson play" or "Conroe trend." This area was surveyed in an attempt to find additional pools of a type similar to Conroe, a pool not discovered directly as a result of geophysical surveys but one which was indicated by refraction surveys before it was drilled and one which was accurately outlined as to structure by reflection surveys shortly after the completion of the first few wells. Surveys were made over this belt, extending from Texas, across Louisiana and into Mississippi and Alabama, chiefly by the reflection method and torsion balance, and to some extent by pendulum and magnetic methods.

Jan 1, 1934

By J. H. Palm

Experiments have shown12 that the formula -S = St - (St - Se')e ne [1] expresses very well the relation between the true stress S and the true form monotonic deformation of plastic metals in single tension and compression (Fig 1). St (asymptotic or final stress), Se' (threshold stress) and ne (characteristic or specific strain) are constants, the significance of which immediately follows from Fig 1. Only at the initial stages of deformation the experimental curve runs below the theoretical curve. This may be due, at least partly, to the uneven stress distribution caused by the anisotropy of the crystals. It is now obvious that a similar formula H = Ht- (Ht- He)e ne' [2] might be valid for the relation between the hardness and the strain. The hardness can be only a function of the strain and must therefore be independent on the hydrostatic tension present in the neck during straining. Hence, if Eq 2 is correct it will also represent the relation between hardness and strain in the middle section of the neck, the strain of which is generally assumed to be almost or fully homogeneous. For aluminum, copper, and several copper alloys it is indeed observed that Eq 2 agrees very well with the experimental Vickers hardness-strain relation from zero strain on up to the strain at fracture. Moreover nc' is, for several metals fairly equal to nc- Hence H = C1 + C2S [3] C1 and C2 are constants during uniform uniaxial tension. Eq 3 was also obtained for copper by Voce.3 According to Hencky's theory4 the ratio of the Brinell or Vickers hardness and the yieldstress (expressed in kg per mm2) of a non-strainhardening metal is approximately equal to 2.8. If Eq 1, 2 and 3 are correct the ratio Ht/S, must accordingly be the same for all plastic metals and be equal to 2.8. It is now experimentally established that this ratio varies between 2.7 and 3.1 with a mean value of 2.9. Taking into account that Ht and especially St can be obtained only by extrapolation from the range of rather low strains, the agreement with the theory is very satisfactory. References 1. J. H. Palm: Appl. Sci. Res. Al (1948) 198. 2. E. Voce: Jnl. Inst. of Met. (1948) 74, II, 537. 3. E. Voce: Metal Treatment (1948) 15, 53. 4. H. Hencky: Zlsch. f. angew. Math. and Mech. (1923) 3, 241.

Jan 1, 1950

By G. N. Goldberg, Robert A. Rapp

The steady-state kinetics and microstructures of simultaneous internal oxidation and external scale formation were investigated for the oxidation of Cb-Zr and Ch-Zr-Re alloys in pure oxygen at 1000°C. For each binary alloy, a constant rate of scale formation was observed at steady state; the internal oxidatton zone reached a steady-state, time-independent thickness. The dependence of the scaling rate on zirconium content exhibited a maximum at a low zirconium colttent; more concentrated alloys oxidized at a slower rate than pure columbium. This composition dependence of the scaling rate may be partially attributed to the effect of the internal oxidation process as an intenla1 sink for oxygen, with the formation of voluminous, and relatively impermeable ZrO2 precipitates. However, the morphologies of the ZrO2 internal oxide precipitates also affected the scaling rate. The internal oxide precipitates were distributed uniformly in the external scale. The steady-state thicknesses of the internal oxidation zones were not in agreement with those predicted theoretically from an idealized simple model. However, in this particular alloy systen1 the ideal model is not satisfied experitmentally. For ternary Cb- Zr - Re alloys with Nr10e = 0.02 or 0.05, the steady-state thicknesses of the internal oxidation zones were less than those for the corresponding binary Cb-Zr alloys. For ternary alloys with NRe(0) - 0.05, a more adherent and much less porous external scale was formed, and a reduction in the kinetics of scale formation was observed. A number of authors'-7 have reported linear oxidation kinetics for the reaction of pure columbium at 1000°C in air or in oxygen of about 1 atm pressure. A thin and tightly adherent oxide layer is found at the metal/oxide interface beneath a porous external layer of scale. Although the suboxides CbO and CbO2 represent thermodynamically stable phases at 100O°C, generally only Cb2O5* is identified as a reaction product in quenched specimens. Studies at 1000°C at lower oxygen pressures8,10 (Po2 - 10-4 Torr) show that both CbO and CbO2 do form and that CbO2 is a protective oxide. The growth of CbO2 results in parabolic kinetics until Cb2O5 is nucleated and grows. Apparently because of the large volume change associated with its formation, Cb2O5 is porous and does not serve as a diffusion barrier; linear kinetics prevail after the surface is covered with Cb2o5. On the basis of these observations, several authors5,9,10 have suggested that the linear oxidation of pure columbium at 1000°C in air or oxygen of 1 atm is limited by a Loriers-type mechanism,11 whereby the total rate or reaction is controlled by ionic diffusion through a thin layer of CbO2 which is maintained at a constant thickness throughout the linear oxidation. However, the concept of a Loriers model for a three-phase CbOlCbO2 Cb2O5 scale, with the only oxygen activity gradient across the NbO2 phase, is not self-consistent. Further, the suboxides CbO and CbO2 were not observed in the high-temperature X-ray diffraction study of columbium oxidation by Goldschmidt.8 From investigations in which the large PO2, dependence of the linear scaling rate was demonstrated, the importance of an oxygen adsorption or dissolution step has been suggested.4,5,7,10,12 Thus the mechanism for the linear oxidation of pure columbium remains quite controversial. Since further insight into the oxidation mechanism of pure columbium is not provided by this investigation, the authors wish to emphasize at the outset that their experimental results are not interpreted in terms of a particular rate controlling step for the oxidation of pure columbium. Previous investigations13-18 of the oxidation of Cb-Zr solid-solution alloys in air or oxygen at 1000°C suggest a remarkable dependence upon zirconium content. For an alloy of bulk zirconium mole fraction, N2r(0) equal to 0.05 or 0.10, the oxygen uptake is reported to be as high as four times greater than that for pure columbium;13,14 for alloys with NZr(0) 0.05 or 0.10 the oxygen uptake is reported to decrease with increasing NZr(0); to a minimum uptake of about one quarter that for pure columbium at NZr(0): = 0.50.13-15Since zirconium forms a more stable oxide (ZrO2) than the lowest columbium oxide (CbO), and since columbium exhibits a high solubility19,20 and diffusivity21,23 for oxygen, the internal oxidation of the zirconium component to ZrO2 is expected at a reaction front ahead of the advancing metal/scale interface. The external scale is then formed at the metal/scale interface by the inward migration of oxygen through the scale, probably through a series combination of molecular and ionic diffusion. Internal oxidation in conjunction with external scale formation has been investigated by Maak24 for the oxidation of dilute Cu-Be alloys in pure oxygen at 850°C. For cu-Be and many other binary alloys,24-27 very small, essentially uniaxial internal oxide particles are formed in the most dilute compositions; for somewhat more concentrated alloys. the internal oxide particles precipitate as platelets or needles. From pertinent solutions to the diffusion equation, Maak28

Jan 1, 1967

By B. Trenary, D. D. McNaughton, C. D. Baer

High capacity off-highway haulage trucks equipped with electric wheel drives have been available for commercial applications since 1963 and, although still interesting to study, cannot be considered as a "new" type of equipment any longer. However, the electric wheel drive components which played a key role in the development of these trucks has indirectly led to another new trucking development-the gas turbine engine for off -highway vehicles. Although most of the production models of the electric-wheel haulage trucks are equipped with 700 hp engines (the largest production engine commonly available), the electric drive components of the motorized wheel were designed to transmit more than 700 hp. To utilize this added potential, 1000-hp class diesel engines are in the process of being developed, but progress has been much slower than expected. The delay has caused some engineering thoughts to concentrate on the adaptation of the 1000-hp gas turbine engines, originally designed for aircraft applications, for use in haulage trucks. The question in most minds centered around the ability of such an engine to withstand the tough usage expected of it in an open pit.

Jan 5, 1967

By Carl F. Floe, John Chipman

THE system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or C02 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modem metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100° to 1500°C., and pressures from about 20 mm. of mercury to somewhat above atmospheric. REVIEW OF PREVIOUS WORK The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as 02, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: [2M -}-G2 = 2MGK =G) IYf X[I]] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: [MG = Ki Pa,[2]] Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: [6Cu + S02 = Cu2S + 2Cu20[3] K Cu2S X (Cu20)2(Cu)e(Psm)[4]] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: [K1 =or Vdo,= K2/PBO [5] PsO]

Jan 1, 1941

Organization Place 1917 National Association of Stationary Engineers .... Evansville, Ind. Sept. 10-15 National Safety Council New York City. Sept. 10-15 National Exposition of Safety and Sanitation.... New York City. Sept. 10-15 American Iron, Steel & Electrical Engineers Philadelphia, Pa. Sept. 10-14 American Association of Port Authorities Cleveland, Ohio. Sept. 11-14 American Institute of Metals Boston, Mass. - Sept. 24-29 American Foundrymen's Association Boston, Mass. Sept. 24-29 Chemical Industries, Third National Exhibition.. New York City. Sept. 24-29 American Electrochemical Society Pittsburgh, Pa. Oct. 3-6

Jan 9, 1917

By WILFRED SYKES

IT is with particular pleasure that I welcome the members of the Open-hearth Conference of the I American Institute of Mining and Metallurgical Engineers to this meeting, as I feel this is one of the most useful activities of the Institute in the field of ferrous metallurgy. For the information of our other members I might say the Open-hearth Conference was organized by Mr. Reynders when he was president, and is made up of open-hearth superintendents and metallurgists. All the plants are invited to send representatives, and practically all do, with the exception of the U. S. Steel Corporation. It meets twice a year to discuss various problems in connection with the manufacture of steel, and its minutes are published for the benefit of those attending, the expense being defrayed by the participating companies. This conference, .1 believe, should be a model for activities in the other branches of the work covered by this Institute. It works, not by reading formal papers, which we all know is not a very satisfactory method to bring out the experience of others, but rather by a round-table method of discussion. The spirit of the meetings is such that each member feels perfectly free to state his experience, and he gets as much as he gives. A series of topics for, discussion is brought to the attention of the chairman and after one is exhausted the next point is taken up. In this way there is a real interchange of ideas and experiences which cannot fail l to be of the greatest benefit to those attending. That these meetings are beneficial is evidenced by the "continued growing attendance and lively discussions at these half-yearly meetings.

Jan 1, 1930

Albin, B. R. Billings, Mont. '28 Amster, Nathan L 25 Broad St., New York, N. Y. '28 Bache, Jules S 42 Broadway, New York, N. Y. '28 Barrett, C. P 5338 Harper Ave., Chicago, Ill. '28 Baum, Frank G., Cons. Hydro-Electric Engr Cassel, Shasta Co., Cal. '28 Bayless, William S Russ Bldg., San Francisco, Cal. '28 Bean, Louis H., V.P., Dwight P Robinson & Co., Inc. 125 E. 46th St., New York, N. Y. '28 Beatty, Ross J 1105 First National Bank Bldg., Chicago, Ill. '28 Benwell, Oswald F 110 Gilpin St., Denver, Colo. '28 Beymer, Albert S., V P., Keystone National Bank Pittsburgh, Pa. '28 Blumenthal, Hugo 44 Pine St., New York, N. Y. '28 Boettcher, Charles Ideal Cement Bldg., Denver, Colo. '28 Bowlus, Thomas H Iola, Kans. '28 Brown, Colvin B. .. Chamber of Commerce, Washington, D. C. '28 Burt, Maxwell Struthers Southern Pines, N. C. '28

Jan 1, 1923

By H. H. Pentz

This paper gives the derivation of a practical formula for the calculation of slopes in seismic reflection prospecting. The derived formula is an approximation and can be used where the slope of the reflecting horizon is less than 250 ft. per 1000 and the depth to the reflecting horizon is greater than 2500 ft. The slope of sediments in oil regions is generally considerably less than 250 ft. per 1000. This is particularly true of the Gulf Coast, with the exception of the salt domes, which usually have the sediments at a greater slope than 260 ft. per 1000. Derivation In Fig. 1, o represents the image of the shot point a. Then the length of the path acb is equal to ob and ae'd is equal to od. In the triangle aob, p is equal to ob, x is equal to , and c is equal to ao. The angle u is the apparent dip of the reflecting horizon. Angle oab is equal to (90" - u). The quantity m is the slope of a line tangent to the curve, defined by equation 1, at the point (p, x). The quantity m' is the slope of the line tangent to the curve at the point (p', 2').

Jan 1, 1940

By H. H. Pentz

This paper gives the derivation of a practical formula for the calculation of slopes in seismic reflection prospecting. The derived formula is an approximation and can be used where the slope of the reflecting horizon is less than 250 ft. per 1000 and the depth to the reflecting horizon is greater than 2500 ft. The slope of sediments in oil regions is generally considerably less than 250 ft. per 1000. This is particularly true of the Gulf Coast, with the exception of the salt domes, which usually have the sediments at a greater slope than 260 ft. per 1000. Derivation In Fig. 1, o represents the image of the shot point a. Then the length of the path acb is equal to ob and ae'd is equal to od. In the triangle aob, p is equal to ob, x is equal to , and c is equal to ao. The angle u is the apparent dip of the reflecting horizon. Angle oab is equal to (90" - u). The quantity m is the slope of a line tangent to the curve, defined by equation 1, at the point (p, x). The quantity m' is the slope of the line tangent to the curve at the point (p', 2').

Jan 1, 1940

By P. T. Carter, A. B. Murad, H. B. Bell

The distribution of manganese and oxygen between molten iron and FeO-MnO-SiO2 slags not saturated with SiO2 has been determined and used to calculate activities of MnO and SiO2 in MnO-SiO2 slags. These were found to be intermediate between the corresponding activities in FeO-SiO2 and CaO-SiO2 slags. THE equilibrium constant for the reaction between molten iron containing manganese and slags containing FeO and MnO, namely: FeO(slag) + Mn = MnO (slag) + Fe(1iquid) is most conveniently represented by: (MnO) Kmn== (FeOHMn] [Fe] is omitted, since for dilute solutions of manganese in iron, afe is approximately constant. When activities are used for (MnO), (FeO) and [Mn], Kmn is a true equilibrium constant and will apply to all types of slags, but when weight percentages are used, the values obtained for Kmn for different slags vary considerably. The equilibrium between iron containing manganese and relatively pure FeO-MnO slags has been investigated by several workers;1-4 the most recent investigation reported is that of Chipman, Gero, and Winkler.4 Their results, corresponding to slags containing up to 4 pct SiO2, were represented by the equation: 6440 log KMn = +2.95 In this case both slag and metal may be assumed to be ideal solutions, therefore the values of Kmn so derived represent the true constant for the manganese reaction. As the molecular weights of MnO and FeO are almost equal, weight concentration of these oxides may also be used in the above expression. Acidic oxides such as SiO2 and P2O5 affect the activities of FeO and MnO differently, so that when total concentrations by weight of FeO and MnO are used in the above expression for Kmn the values obtained are no longer constant. These will be denoted by K'mn. Körber and Oelsen5 investigated the manganese reaction using silica-saturated iron-manganese-silicate slags and found: 7940 logK'mn =3.172 This corresponds to Kmn values much higher than those obtained for pure oxide slags. The results of Körber and Oelsen, and Chipman, Gero, and Winkler are summarized in Table I. In the present investigation it was decided to study the manganese reaction using iron-manganese-silicate slags not saturated with silica, and which fell mainly between the orthosilicate join 2FeO . SiO2 - 2MnO.SiO2 and the FeO-MnO side of the ternary system FeO-MnO-SiO2. It has been shown" that the phases present in solidified slags of this part of the diagram are (FeO, MnO) and (2Fe0.Si02, 2Mn0-SiO,) solid solutions. Such an investigation would be of interest in deoxidation and also gives information on activities in liquid slags. This equilibrium has not as yet been investigated successfully. Hilty and Crafts7 attempted to examine this reaction in a rotating crucible furnace, but were unable to obtain suitable slag samples. In the present investigation one series of experiments was carried out in a rotating crucible furnace, because the success of Taylor and Chipman8 with such a furnace in their study of oxygen distribution between molten iron and (CaO, MgO) — FeO-Si0, slags suggested that it would minimize contamination of the slag by the crucible material. A second series was carried out using a wire-wound resistance furnace. Rotating Crucible Furnace Experiments In all cases the metallic charge consisted of 800 to 1000 g Armco iron containing 0.02 pct C, 0.03 pct Mn, and traces of Si. Manganese and silicon additions consisted of electrolytic manganese (99.9 pct)

Jan 1, 1953

By John C. Smock

THE question of the proper valuation of mines of iron ore was suggested to me by the difficulties experienced in getting answers for the United States Census Office, while I was engaged in the work of collecting the statistics of mines in New Jersey and New York The answers to the questions relating to values of real estate of mine properties varied so greatly that it was necessary to revise them according to some general principles of valuation. Generally the returns of mine proprietors Seemed to be too low. There were, however, examples of what would be termed excessive valuation. The Subject appeared to be of practical importance, and led to the paper here presented. The following table of selected mine statistics is given, prefacing the discussion of the principles of valuation. It is in part made up of census returns and partly of data obtained directly from mine owners and managers. The mines which were Selected for the Several groups and mining districts include nearly all of those from Which the more full and carefully filled returns were received, and are also representative of their respective districts. Hence the averages obtained from them become good types of these groups or districts. The mines of New Jersey appear in Six groups, each containing from three to eleven mines, or, in all, thirty-four mines. The magnetic iron ores of New York are in four well-marked groups, and there are twenty-six mines in them. Then follow the red hematite mines of St. Lawrence and Jefferson counties; and, lastly, the brown hematite groups of Dutchess and Columbia counties, and those of the adjacent parts of Connecticut and Massachusetts. The whole number of mines represented by the table is eighty-eight, of which twenty-eight are hematite mines. The first column gives the value of the real estate; the second that of the plant; the third is the sum of these two, or the capital invested. Then follow the number of men employed, the amount of wages paid during the census year, and the value of materials used in mining and preparing the ores for market.* The seventh column gives the total expendi- * The value of materials is somewhat uncertain in many cases, as royalties are included under this head. Likewise, under wages, the cost of explosives and light is often included. Hence it is impossible to draw the line sharply between these items of expenditure.

Jan 1, 1882

By A. Grant Elliot, H. W. Lavendel

qualitative picture has been developed to describe the oxidation behavior of TaSi2-coated tantalum and CbSi2-coated columbium. These systems have a significantly lower inherent oxidation resistance than MoSi2-coated molybdenum does. This stems primarily from the fact that Ta2O5 and Cb2O5 are nearly as stable thermodynamically as SiO2, whereas MoO2 or Moos are not. Further, diffusion of silicon in the Ta- and Cb-Si system is considerably slower than in the Mo-Si system. These ,factors prohibit the mechanism of selective oxidation of- silicon which accounts for the oxidation resistance 01- MoSi2-coated molybdenum. The silicide can be stabilized by adding suitable Modifiers which increase the thermodynamic stability of the silicate formed during oxidation. Modifiers, such as aluminum, can be inroduced into solid solution in the coating. in controlled amounts through proper selection of the source in the pack cementation process of coating fov~rzatiorz. Addition of aluminum to TaSi2, coatings on tantalum was effective in moderately increasing the oxidation resistance. EXTENSIVE experimental work and analysis have established the nature of the oxidation behavior exhibited by MoSi2- and MoSi2 -coated molybdenum-base alloys, and defined the conditions for maximum protection against oxidation of the substrate.'-* The oxidation resistance of MoSi2 in the temperature-pressure range of 1100°C-PO2 > 10-5 atm to 1900°C— PO2 > 10-1 atm is due to the formation at the surface of a continuous film of SiO2 which results from selective oxidation of silicon. Under the prevailing kinetic conditions, this film is stable toward the molybdenum silicide with which it comes in contact. Initially molybdenum oxidizes also, but it forms volatile species. SiO2, however, nucleates and grows as a condensed phase. Once a continuous film of SiO2 has formed, the oxidation rate falls to that observed for the oxidation of pure silicon indicative of diffusion through the oxide film as the rate-controlling mechanism. This oxidation behavior is of course highly dependent upon temperature and oxygen pressure. Bartlett and Gage13 and Bartlett, McCamont, and Gagelb define precisely this dependence in terms of the oxygen partial pressures and silicon diffusivities required to support a stable SiO2 film. At low temperatures (near 500°C—the "pest" region) silicon diffuses too slowly to be selectively oxidized. Hence, molybdenum and silicon oxidize readily in proportion to their stoi- chiometry. At high temperatures and low pressure, SiOz dissociates to form volatile SiO(g), and a protective film cannot be maintained. Application of the MoSiz/Mo system is limited to temperatures below 1900oC, the eutectic between MoSi, and MO5Si3.5 The oxidation behavior of MoSi2-coated molybdenum is essentially the same as that outlined above with the exception that the MoSi2 is not in equilibrium with the molybdenum substrate. At the temperatures under consideration silicon will diffuse rapidly into the molybdenum eventually converting the coating to MosSi3.4 The rate constant for subsequent decomposition of Mo5Si3 into Mo3Si plus silicon, and/or the diffusivity of silicon through Mo3Si then becomes low enough to allow active oxidation of both molybdenum and silicon with subsequent degradation of the specimen. A stable silica film can be formed but at temperatures and/or oxygen partial pressures higher than those required with MoSi2 present as a source of si1icon.l, 4 Because of the similarity between the silicides of molybdenum and those of columbium and tantalum one would expect similar oxidation behavior for coatings in the respective systems. This is not entirely the case, however, as shown by the experimental results reported herein. Regarding tantalum and columbium disilicide coatings on tantalum and columbium substrates, respectively, the oxygen arriving at the surface of the coating partitions itself nearly equally between the metal and the silicon, and a two-phase oxide layer (Me2O5 plus SiO2) is always formed. The diffusion of silicon in the tantalum and columbium silicides is relatively slow, compared to that in the molybdenum silicides, which further enhances this equipartitioning of oxygen. Thickening of the coating during service by inward diffusion of silicon into the substrate is correspondingly slow, and the effective thickness of the coating at the roots of cracks and defects is only slightly changed providing high probability for premature coating failure. Furthermore, the SiO2 glass that is generated is not thermodynamically stable with respect to the coating. The metal silicide tends to reduce the SiO2 liberating either free silicon or SiO. The situation can be improved by suitably modifying the coating such that the stability of the protective glass which is generated during service is increased. Thus, selective oxidation of silicon and the modifying agent will occur, and the silicide coating will not tend to reduce the oxide layer. Modifying agents can be introduced into the coating by the pack cementation process. Using sources containing the modifier at controlled chemical potentials allows control of the coating composition. Partially substituting aluminum for silicon in TaSi2 coatings by forming a Ta(Si,Al)2 solid solution was effective in moderately increasing the oxidation protection.

Jan 1, 1968