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By L. F. Marek, G. W. King, A. Bogrow

THE purpose of this paper is to present the data and some interpretation of the results of a laboratory study of the reduction of iron ore and the deposition of carbon from the reducing gas mixtures in such reductions. One major object of the study was to determine the effect of gas pressures on these chemical processes. Effort was made to approximate the conditions of temperature, gas composition, linear and mass gas velocities, pressure range, and extent of reduction prevailing in commercial blast furnaces. The results show that the reduction of Fe203 proceeds by two steps, largely consecutive under the conditions used herein: reduction of Fe203 to FeO, and reduction Of FeO to Fe. Unless the gas has a CO/CO2 ratio greater than 2.1 only the first step occurs under these conditions (850°C) but the following generalizations apply to either step or to the combination. The rate of reduction of relatively fine ore particles at any time is proportional to the mass rate of supply of CO (provided some of it is thermodynamically available) the rate therefore is proportional to the linear velocity at constant pressure, or to the pressure at constant linear velocity. Thus, the rate of reduction may be increased without increase in linear velocity f the reducing gas by increasing the mass velocity of the gas and increasing the pressure correspondingly to avoid any increase in the linear velocity. The rate "constants"-i.e., the efficiency of conversion of the "available" CO supplied-is not actually constant but decreases as the reduction proceeds, and is a function only of the state of the ore; i.e., of the amount of reduction already accomplished and hence of the amount of CO passed. The particle size Of ore used in nearly all the experiments was relatively small (8 to 14-mesh). The rate of reduction in run 16 with 3 to 8-mesh ore particles is within experimental error the same as with the finer ore. Although this would indicate an absence of effect due to particle size in this range of ore particles, it is desirable to have more data on other ore sizes and on ore of different densities before arriving at any generalizations on this point. Although it is possible to extend the analysis of these results to consideration of the more detailed kinetics and mechanism of iron oxide reduction, such extension is beyond the scope of the present paper. From the experiments on carbon deposition, it was evident that if carbon deposition is increased at all by the application of pressures up to 10 psi ga., such increase appears to be less than the experimental and analytical error. It appears safe to conclude that at top pressures on the order

Jan 1, 1947

By Avnulf Muan, Egil Aukrust

The activity-composition curve for cobalt oxide in (Co,Fe)304 solid solutions with spinel-type stmcture has been determined experimentally by studying the equilibrium between the spinel phase and a coexisting cobaltowüstite phase, "(Co,Fe)O", at 1200°C. A large negative deviation from ideal behavior prevails in the spinel at low cobalt oxide concentrations and a positive deviation at high cobalt oxide concentrations. The activity-composition curve for iron oxide in the solid solution is determined from the above curve by integvation of the Gibbs-Duhem equation along the join Co3O4,-Fe3O4. The standard free energy of formation of cobalt ferrite, CoFe2O4, from the oxide components CoO and Fe2O3 is calculated to be -8.2 kcal. ThERMODYNAMIC properties of (CO,Mn)3O4 solid solutions with spinel-type structure have been presented recently.' The present paper deals with similar relations in another spinel solid-solution phase, that represented by the system Co3O4-Fe3O4. The principles involved in measurements and calculations of thermodynamic properties for the system Co3O4-Fe3O4 are analogous to those used and discussed in detail in the work on (CO,Mn)3O4. A (CO,Fe)3O4 solid solution coexists in equilibrium with a (Co.Fe)Ot solid solution over a considerable Here acOo1.33 and aao are the activities of cobalt oxide in the spinel and the oxide solid solutions, respectively, pO2, is the oxygen pressure of equilibration, and pb, is the oxygen pressure at which CoO and CosO4 coexist in equilibrium in the binary system Co-O at the same temperature. The activity-com position curve for cobalt oxide in the (Co,Fe)O solid solution in contact with metal has been determined in a previous investigation by the present authors.' The system shows a small positive deviation from linear behavior. Because of the large defect concentration in wiistite and in (Co,Fe)O solid solutions, one cannot assume that the activity-composition relations in the oxide phase coexisting with a spinel phase at relatively high oxygen pressures are the same as those prevailing in the oxide solid solution coexisting with metal. However, a Gibbs-Duhem integration over the ternary Co-Fe-0 solution can be used to determine activities of cobalt and iron, and hence of CoO and FeO, from a knowledge of the oxygen potentials. Several papers have dealt with the subject of application of the Gibbs-Duhem equation to multi-component systems. 3-6 In the present case, it was

Jan 1, 1964

By R. M. Douthwaite, G. Birkbeck

The effect of grain size and specimen dimensions on the occurrence and magnitude of a yield point drop in pure iron has been examined. The tests were done at room temperature. The results indicate that gain size is the critical factor determining whether a yield drop occurs. The specimen diameter:gain size ratio does not influence the magnitude of the yield drop for the range of gain size and specimen diameters investigated. HUTCHINSON,' petchY2 and worthington3 have investigated the grain size dependence of the upper yield stress (uUYP) and the yield point drop, ouyp - aLYP, in Armco iron, mild steel, and Si-Fe, respectively. These authors used center-annealed wires to avoid stress concentration from specimen shoulders and to ensure uniformity of the applied stress. Coarsegrained specimens show no yield point drop; the yield point drop then increases as d-'I2 increases (where d is the grain diameter). These results can be understood in terms of Petch's analysis2 in which the magnitude of amp depends on the strain rate in the (limited) number of grains deforming plastically at the upper yield point. If N grains per unit volume are undergoing plastic deformation, the strain rate in the deforming grains is l/Nd3 times higher at the upper yield stress than when the whole specimen deforms homogeneously. If N is constant and independent of grain size at uUyp, then all the grains are deforming when ~d~ = 1, so there is no yield point drop. At finer grain sizes, the yield point drop is given by: where AU, is the friction stress increase corresponding to a tenfold strain rate increase. Christ, Smith, and Burton studied the upper yield point in 0.050-in.-diam wire specimens prepared from zone-refined iron. Each end of the 2; -in. specimens was soldered to a & -in. diam steel ball and the load applied through the two balls. There was a yield point drop in specimens with grain diameters less than 0.1 mm; no drop was observed in specimens of grain diameter greater than 0.1 mm that were free from veining substructure, but specimens of grain diameter 0.129 mm, annealed in the y range, showed an upper yield point. and this was associated with the presence of a veining substructure in these specimens. Christ et al. suggested the upper yield point occurs when more than a specific number of grains fill the specimen cross section so a multiplicity of slip is required to initiate plastic deformation. Table I summarizes the published data on the grain size at which the yield drop disappears. On the basis of this data the ratio of specimen diameter:grain diameter = 5 to 27 appears to be the critical value for the occurrence of a yield point drop. Thus, petch2 interprets the appearance and magnitude of the yield point drop in terms of the limited number of grains deforming plastically at uuyp, whereas Christ et a1. consider that the occurrence of the yield drop depends on the ratio specimen diame-ter:grain diameter. The published data cover a wide variety of materials so some variation between the results is to be expected, but the size range covered in the data of Table I is rather limited. In an attempt to discover whether the specimen diameter:grain size ratio or the grain diameter is critical in determining

Jan 1, 1969

By C. E. Shoenfelt

Jan 1, 1942

By C. E. Shoenfelt

Jan 1, 1942

By Richard Moldenke

So FAR as the quality of the product is concerned, the history of the production of pig iron for foundry purposes is one of constant retrogression. The steps in this deterioration began with cold-blast charcoal pig iron, then anthracite iron, coke iron; then gradually warm to hot-blast coke iron, with the charcoal furnaces also heating their blast to get greater tonnages, and finally the present day hot-blast coke irons with scrap additions to the ordinary burden that, according to one European report, have gone as high as 135 per cent. Parallel with this quality retrogression is the enormous increase in furnace tonnages from about 15 tons daily to over 1000 tons per day in exceptional instances of modern practice. The key to this situation is economic pressure. The effect is a growing differentiation between furnace production for gray iron and malleable foundries and for the production of commercial steel. As the foundry is often compelled to draw upon the pig irons made for steel purposes, for economic reasons, whereas the steel industry does not draw upon foundry pig irons proper, the situation is resolving itself into one of grave consequence for the life of the gray-iron castings industry, and hence the intensive present-day feeling in foundry circles for rigid specifications to govern the quality of pig irons sold for foundry use. In the discussion of a paper on the use of scrap in the blast furnace held recently in the Institute, a very pertinent remark was made by one of the participating furnacemen, who confessed that "the things found wrong by the foundryman with his iron were beyond his depth." It may be added that those things are also beyond the depth of most foundrymen who, however, know from their results that they are getting poorer castings today with many pig irons than they did with those same brands in former years. Under the former fracture buying, the foundryman at least could select the strongest metal, as judged by the sledge, from various brands of similar fracture and pig section, and his results proved the soundness of his conclusions. With the advent of iron analysis, and in spite of the growing uniformity of the metal through greater tonnage

Jan 2, 1927

Institute of Metals - Iron and Steel - Mineral Industry - Industrial Minerals Year ?Division - Petroleum Division ? Division - Coal Division - Education Division -Division 1918 W M CORSE 1919 1920 W. H BASSETT 1921 1922 W B PRICE RALPH ARNOLD 1923 E DEGOLYER 1924 G K ELLIOTT 1925 F JULIUS FOHS 1926 PAUL D MERICA 1927 JOHN M LOvEJOY 1928 S SKOWRONSKI A W AMBROSE RALPH H SWEETSER

Jan 1, 1952

By S. Norton

GEORGE C. FOOTS, Port Henry, N. Y. (written discussion).-The paper by Mr. Norton and Mr. LeFevre will bear the most careful consideration by all interested in the iron business, particularly in the East. There is much information contained therein which should be emphasized. The idea of handling iron-bearing rock in quantities comparable to the porphyry coppers does seem at first blush to be beyond the pale of commercial possibility. Yet, today in the Adirondack region 25 per cent.

Jan 4, 1917

By J. A. Kitchener, J. P. Anfruns

Measurements have been made of the rate of capture of single particles of strongly hydrophobic, surface-methylated, quartz, of sizes ranging from 12 to 40 µm diam., by single rising bubbles of diam. 0.5 to 1.1mm. The results agree closely with the theoretically calculated hydrodynamic collision rates, indicating that, in this system, every collision results in capture and retention of a particle.

Jan 1, 1976

Jan 1, 1888

By S. H. Williston

IT is not often that bore hole surveys can be checked by actual civil engineering methods. A recent Arizona survey was checked by normal surveying methods and the comparison of the results should be of value to both oil and mining men. During the summer of 1948 the Phelps-Dodge Corporation, at its Copper Queen property near Bisbee, Ariz., drilled a 1245 ft, 8 in. diam, churn drill- hole in a mineralized area and cased part of it, intending to use it to transfer mill tailings for stope fill. The hole, as frequently occurs, was not straight, and, in endeavoring to locate the bottom in- the underground workings, they found no evidence of the hole at the underground coordinates directly below the surface location. The noise of the drilling tools was reasonably clear, but the direction of sound was uncertain. Preliminary tests with available equipment were not successful in locating the bottom of the hole. Be- cause of the mineralized character of the area and the fact there was some casing in the hole, any magnetic method of well surveying would give results ' of doubtful value.

Jan 1, 1950

By W. M. McKewan

Magnetite pellets were reduced in flowing hydrogen at pressures up to 40 atm over a temperature range of 350° to 500°C. The rate of weight loss of oxygen per unit area of the reaction surface was found to be constant with time at each temperature and pressure. The reaction rate was found to be directly proportional to hydrogen pressure up to 1 atm and to approach a maximum rate at high pressures. The results can be explained by considering the reaction surface to be sparsely occupied by adsorbed hydrogen at low pressures and saturated at high pressures. PREVIOUS investigation1,2 have shown that the reduction of iron oxides in hydrogen is controlled at the reaction interface. Under fixed conditions of temperature, hydrogen pressure, and gas composition, the reduction rate is constant with time, per unit surface area of residual oxide, and is directly proportional to the hydrogen pressure up to one atmosphere. The reduction rate of a sphere of iron oxide can be described3 by the following equation which takes into account the changing reaction surface area: where ro and do are the initial radius and density of the sphere; t is time; R is the fractional reduction; and R, is the reduction rate constant with units mass per area per time. The quantityis actually the fractional thickness of the reduced layer in terms of fractional reduction R. It was found in a previous investigation2 of the reduction of magnetite pellets in H2-H,O-N, mixtures, that the reaction rate was directly proportional to the hydrogen partial pressure up to 1 atm at a constant ratio of water vapor to hydrogen. Water vapor poisoned the oxide surface by an oxidizing reaction and markedly slowed the reduction. The enthalpy of activation was found to be + 13,600 cal per mole. It was also found that the magnetite reduced to meta-stable wüstite before proceeding to iron metal. The following equation was derived from absolute reaction-rate theory4,8 to expfain the experimental data: where Ro is the reduction rate in mg cm-2 min-'; KO contains the conversion units; Ph2 and PH2O are the hydrogen and water vapor partial pressures in atmospheres; Ke is the equilibrium constant for the Fe,O,/FeO equilibrium; Kp is the equilibrium constant for the poisoning reaction of water vapor; L is the total number of active sites; k and h are Boltzmann's and Planck's constants; and AF is the free energy of activation. Tenenbaum zind Joseph5 studied the reduction of iron ore by hydrogen at pressures over 1 atm. They showed that increasing the hydrogen pressure materially increased the rate of reduction. This is in accordance with the work of Diepschlag,6 who found that the rate of reduction of iron ores by either carbon monoxide or hydrogen was much greater at higher pressures. He used pressures as high as 7 atm. In order to further understand the mechanism of the reduction of iron oxide by hydrogen it was decided to study the effect of increasing the hydrogen pressure on rebduction rates of magnetite pellets. EXPERIMENTAL PROCEDURE The dense magnetite pellets used in these experiments were made in the following manner. Reagent-grade ferric oxide was moistened with water and hand-rolled into spherical pellets. The pellets were heated slowly to 550°C in an atmosphere of 10 pct H2-90 pct CO, and held for 1 hr. They were then heated slowly to 1370°C in an atmosphere of 2 pct H2-98 pct CO, then cooled slowly in the same atmosphere. The sintered pellets were crystalline magnetite with an apparent density of about 4.9 gm per cm3. They were about 0.9 cm in diam. The porosity of the pellets, which was discontinuous in nature, was akrout 6 pct. The pellets were suspended from a quartz spring balance in a vertical tube furnace. The equipment is shown in Fig. 1. Essentially the furnace consists of a 12-in. OD stainless steel outer shell and a 3-in. ID inconel inner shell. The kanthal wound 22 in. long, 1 1/2, in. ID alumina reaction tube is inside the inconel inner shell. Prepurified hydrogen sweeps the reaction tube to remove the water vapor formed during the reaction. The hydrogen is static in the rest of the furnace. The sample is placed at the bottom of the furnace in a nickel wire mesh basket suspended by nickel wire from the quartz spring. The furnace is then sealed, evacuated, and refilled with argon several times to remove all traces of oxygen. It is then evacuated, filled with

Jan 1, 1962

By J. B. Goddard

Crystallization of ammonium paratungstate (APT) is frequently the last effective purification step in producing high-purity tungsten. However, crystallizer mother liquors are often several times higher in tungsten than predicted by the solubility of APT. The formation of heteropoly anions, particularly those containing phosphorus and silicon, is largely responsible. Solubility of tungsten in APT mother liquor can be linearly correlated with the concentration of these and other impurities. The problem can be overcome by direct treatment of the crystallizer feed solution with aluminum sulfate. By appropriate treatment, the aluminum hydroxide flocculates and is easily filtered, resulting in a purified low-aluminum crystallizer feed from which high APT yields can be attained.

Jan 1, 1985

E. B. WILSON, Scranton, Pa. (written 'discussion *).-Prof. Young's paper shows another application of electricity in solving problems in coal mining, and suggests that it may be possible to utilize the data he has collected in developing an electric firedamp detector. If electric lamps are to be adopted in gassy coal mines, the use of an electric firedamp detector becomes almost imperative, for safety lamps and electric lamps in the same mine are not always conducive to safety, and Liveings electric firedamp detector, is too cumbersome to meet with general approval. Three well understood facts are verified in a new way by Prof. Young's experiments: - 1. The temperature at which methane ignites. 2. The more inflammable gas present in an atmosphere, the hotter will be the flame, and the longer the cap in a safety lamp. 3. As the temperature at the source of ignition varies, the length of the gas-cap flame varies. Prof. H. B. Dixon collaborating with Mr. H. F. Coward, some years ago, made experiments on the ignition of various gases to find the tem-perature of their kindling points.1 From the results of their experiments, the writer has culled the ignition temperatures of some hydrocarbon gases, and has tabulated them with other data, in Table 1.

Jan 10, 1919

By John A. Bonucci

AMAX Base Metals R&D, Inc. has developed technology for extracting and recovering platinum and palladium from spent automobile exhaust emission control catalyst. Our most promising route is a chloride-based hydrometallurgical flowsheet in which catalyst pellets or crushed monoliths are leached in HC1 with an oxidant at 95°C without agitation. Alumina co-dissolution can be limited by thermal pre-treatment of the catalyst. The leach solutions are treated by one of several precious metals recovery techniques to produce a high grade PGM concentrate. For the new generation of three-way catalytic converters which contain rhodium, an H2S04 preleach could selectively extract much of the rhodium while leaving the platinum and palladium behind. Capital and operating costs will be discussed.

Jan 1, 1984

By C. Dinis da Gama

In order to reduce the complexity of mechanisms influencing rock. fragmentation by blasting a simulation approach is proposed, using the capabilities of microcomputer interactive graphics. Situations involving cratering end bench blasting are simulated, and both jointed and intact rocks can be subjected to explosive action, taking into consideration its breakage mechanisms. Size analysis curves relating rock distribution before and after the blasts are determined and compared with field data.

Jan 1, 1984

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Jan 1, 1925

By Richard Moldenke

So far as the quality of the product is concerned, the history of the production of pig iron for foundry purposes is one of constant retrogression. The steps in this deterioration began with cold-blast charcoal pig iron, then anthracite iron, coke iron; then gradually warm to hot-blast coke iron, with the charcoal furnaces also heating their blast to get greater tonnages, and finally the present-day hot-blast coke irons with scrap additions to the ordinary burden that, according to one European report, have gone as high as 65 per cent. Parallel with this quality retrogression is the enormous increase in furnace tonnages from about 15 to over 1000 tons per day in excep tional instances of modern practice. The key to this situation is economic pressure. The effect is a growing differentiation between furnace production for gray iron and malleable foundries and for the production of commercial steel. As the foundry is often compelled to draw upon the pig irons made for steel purposes, for economic reasons, whereas the steel industry does not draw upon foundry pig irons proper, the situation is resolving itself into one of grave consequence for the life of the gray-iron castings industry, and hence the intensive present-day feeling in foundry circles for rigid specifications to govern the quality of pig irons sold for foundry use. In the discussion of a paper on the use of scrap in the blast furnace held recently in the Institute, a very pertinent remark was made by one of the participating furnacemen, who confessed that "the things found wrong by the foundryman with his iron were beyond his depth." It may be added that those things are also beyond the depth of most foundrymen who, however, know from their results that they are getting poorer castings today with many pig irons than they did with those same brands in former years. Under the former fracture buying, the foundryman at least could select the strongest metal, as judged by the sledge, from various brands of similar fracture and pig section, and his results proved

Jan 1, 1927

By E. A. Gulbransen, A. Pebler

Pressure-composition isotherms have been determinedfor the systems ZrMo2 -H2 between 0" and 900°C at hydrogen pressures between 10-4 and 760 Torr. Tkese studies plus X-ray diffraction analyses of selected compositions show that these intermetallic compounds form a complete series of hydrogen solid solutions within this temperature and pressure range. The partial molar enthalpies and entropies of solution of hydrogen in the three intermetallic compounds were calculated. The solubility of hydrogen in these Laves phases can be related to their free electron concentration. ThE reaction of hydrogen with inter metallic compounds of zirconium with Laves phase-type structure has both theoretical and practical interest. The in-termetallic compounds have structures different from any of the pure metals. In addition the electron to atom ratio of the intermetallics varies appreciably. In the nuclear materials field, these materials are of interest since intermetallic compounds may exist as precipitates in commercial zirconium alloys with transition metals. From studies on the hydrogen reaction, one can establish the stability of the intermetallic compounds relative to the hydrides of the component metals. The intermetallic compounds may also be used as getters for hydrogen and as materials for hydrogen storage. This paper will present the results of equilibrium and structural investigations of the ZrCr2-H2, the ZrV2-H2, and the ZrMo2-H2 systems for the temperature range of 0" to 900°C and the pressure range of Torr to 1 atm. A complete thermochemical analysis will be made of the measurements. Some of the results have been referred to in a survey paper' covering the types of hydrogen behavior observed in zirconium alloys. LITERATURE ZrCr2 is the only intermetallic phase in the Zr-Cr system.' It exists in two allotropic modifications. Between 900" and 1000°C the hexagonal MgZa (C14) structure transforms into the cubic MgCu2 (C15) structure. Beck4 has previously shown that the intermetallic ZrCrz takes up hydrogen into solid solution up to a composition H/ZrCr2 = 1.14 at room temperature and 1 atm hydrogen. A ZrCr2 hydride was stated to have a fcc structure. The binary Zr-V system has been investigated by williams5 although Rostoker and Yamamoto 6 had given earlier a partial phase diagram. ZrV2 was the only intermediate phase found in the system. wallbaum7 reported earlier that the compound ZrV2 hp the MgZm (CJ4) type structure with a = 5.288A and c = 8.664A. This was not comfirmed by Elliot8 nor by Matthias, Compton, and corenzwit9 who reported that ZrV2 has a cubic MgCua LC15) type structure. The latter authors gave a = 7.429A. Also, several authors do not agree on the temperature of the peri-tectic horizontal. It appears that ZrV2 may exist in several modifications. A high capacity for occluding hydrogen was reported by Beck4 who found H/ZrV2 = 1.38 at room temperature and 1 atm of hydrogen. ZrMoz is the only intermetallic phase in the Zr-Mo system.10 ZrMoa is formed by a peritectic reaction of the melt with a molybdenum-rich solid solution. ZrMo2 has the C15-type structure with a = 7.59A. MATERIALS High-purity chromium, vanadium, and molybdenum were used together with grade 1 crystal bar zirconium to prepare the alloys. Table I lists the chemical analysis and the sources for the metals. Ten-gram alloy compacts were levitated and melted in an inert argon

Jan 1, 1968

By T. L. McCall

THE late Walter Herd1 in 1929 gave a full description of past and present conditions in No. 2 mine, Springhill, Nova Scotia, developed theories regarding the cause of these bumps and made certain suggestions regarding possible methods of future development. Recapitulating briefly from Mr. Herd's paper, the seam is bituminous coal, averages 9 ft. in thickness and has a well defined parting containing fusain about 14 in. from the roof. This roof coal is somewhat stronger than the rest of the seam and has a tendency to cling to the roof. The pitch of the seam where it is now being worked is about 20°. The first manifestations of bumps began when the room and pillar workings had reached a depth of cover of 1900 ft. and under continuously increasing depth of cover these bumps increased to such an extent, both in number and severity, that in the year 1924 it became apparent that some change in the system of extraction was necessary. After closely studying all the factors involved and benefiting largely by valuable out-side advice obtained by the Provincial Department of Mines of Nova Scotia,2 the system of working was changed from room and pillar to longwall retreating. Mr. Herd's paper described in detail three remarkable bumps in the year 1928 in April, July and October that affected the 5700-ft. and 5900-ft. East levels, the last bump being so severe both in intensity and in extent of damage done that this district was abandoned. The longwall workings to the west of the slope had been stopped in the year 1926 owing to an inbreak of water, coming from the flooded waste of No. 3 seam lying some 400 ft. vertically overhead. This inflow was not excessive, but a large quantity of water being impounded in the old workings it was considered advisable to take the prudent course and not incur the risk of possibly increasing the flow by further working. This district has remained idle ever since.

Jan 1, 1934