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By Richard Franchot

DISCUSSION of a paper is sometimes more in-teresting in what has not been said than in what is said. In the present case the paper is mainly directed to certain thermo-dynamic relation-ships in the blast furnace. Careful reading of the dis-cussion fails to show a single use of the term, heat unit, or its equivalent. If we wish to know very-much about the furnace action it is necessary to count calories or B.t.u. Nothing much is. said about the availability of heat at high temperatures, although it will be generally admitted that in seeking underlying limiting factors in the furnace economy the hearth heat relations offer-the most promising clues. Those discussing the paper, with exceptions of course, apparently have failed to recognize an outstand-ing fact. It is a fact that the heat actually generated by the air oxygen in CO formation (including the blast heat) is in excess, after charging off radiation, etc., by from 70 to .90 per cent over the heat absorbed in melting the iron and slag and calcining the stone reduction by CO absorbing no heat. The fact stands out as plainly as does the fact that the furnace functions largely as a gas producer. The surplus heat is there. It is in the picture. Why not take a look at it, face the fact? That the surplus heat is necessitated by the hearth conditions admits of very little if any doubt. The furnace is really two separate pieces of apparatus: the hearth, doing certain work, and the superimposed shaft, doing certain other work. The combustion of fuel in the hearth, primarily serving the hearth pur-poses, generates much more heat and gas than the shaft requires, or can use, in smelting work. The result is surplus heat makes still more gas in the heat-absorbing reaction between CO, and coke; what is left of the surplus going to top heat. Here we have a simple yet adequate sketch of the furnace action. Having obtained a fairly comprehensive view of the existing heat relations of both hearth and shaft, the way to improvement seems quite plain. Either do more of the work above the hearth or put more heat into the hearth. Since there is already a great surplus of heat above the hearth, probably little needs to be done by way of increasing the proportion of the work done in the shaft. The shaft can, however, probably do much more work than it is now doing provided that a way, can be found to get more work, done in the hearth. The hearth heat is nicely balanced. Losses by radiation and water cooling and other losses are already taken care of. Any increase of hearth heat development could be utilized in taking care of increased smelting work. Aside from the possibility of increased blast heat, there is one sure way of putting more heat into the hearth, and this is to blow more air. And since the shaft already has more gas than it needs, the increased gas resulting from the greater blast volume can be withdrawn from the bosh after it has done its work in the hearth. Now an increase of burden will cool the shaft, cut down solution loss and thereby supply addi-tional coke in the hearth to burn with the additional air blown. The hearth heat per pound of coke charged will be proportionately increased. The balance between hearth and shaft will be better. Gruener's ideal will be more nearly attained, if not exceeded. Most inter-esting of all perhaps, the more the burden is increased, the more coke will reach the hearth and the more burden can be added. The effect is to be cumulative.

Jan 3, 1927

By T. J. Lutz, L. Yan, J. R. Srednicki, J. A. Yonkey, G. T. Homce

"Federal regulations require the installation of refuge alternatives (RAs) in underground coal mines. Of the in-use RAs, over 95% are mobile RAs with the remainder being built-in-place (BIP) RAs. Heat/humidity buildup has been one of the major concerns with mobile RAs. For BIP RAs, however, there is a lack of in-mine heat/humidity test data to determine the extent of heat and humidity buildup. To quantify heat/humidity buildup in BIP RAs, the National Institute for Occupational Safety and Health (NIOSH) performed a series of heat/humidity tests on a 60-person BIP RA with and without a borehole air supply. At various times during the year, tests were performed with cooled, heated, or unconditioned borehole air to examine how various outdoor temperatures may affect the thermal conditions inside a BIP RA. The results show that the air supplied to a BIP RA may require heating and cooling, depending on the outside air temperatures and the temperature of the mine. For example, during tests with an external ambient temperature above 70°F and a humidity that reached 90 %RH, providing 55°F dew point air was able to keep the internal apparent temperature below the mandated 95°F. Results for each test case are presented. INTRODUCTION The Mine Safety and Health Administration (MSHA) has required the installation of refuge alternatives (RAs) in underground coal mines since 2008 [1]. MSHA requires that RAs provide an environment with breathable air for entrapped miners for a 96-hour period. Heat buildup inside an occupied RA is a serious concern. Without a means to dissipate the heat and humidity generated by the occupants and the carbon dioxide scrubbing system, the temperature and humidity inside RAs could lead to severe discomfort or heat stress depending on the mine ambient temperature before and during occupation of the RA. In its 2006 report, the West Virginia Mine Safety Technology Task Force recommended an apparent temperature limit of 95°F for RAs [2]. In 30 CFR 7.504, MSHA specifies a maximum apparent temperature of 95°F inside an occupied RA [3]. The apparent temperature is calculated using both air temperature and relative humidity [4]. To determine if their RAs meet the apparent temperature limit, RA manufacturers have been performing 96-hour-long heat and humidity tests in laboratories. During these tests, a heat input of 117 W (400 BTU/hr) per person is used to represent the metabolic heat of a single miner [2]. The heat generated by the RA’s carbon dioxide system is also accounted for in testing. To account for this heat, 50 W (170 BTU/hr) of heat per miner is used for a lithium hydroxide scrubbing system, or 30 W (100 BTU/hr) of heat per miner is used for a soda lime scrubbing system [5]. In these tests, air velocities around the RA are minimized to represent the worst-case scenario of an interruption in mine ventilation that might occur in a mine disaster."

Jan 1, 2017

By R. W. Bartlett

The rates of oxidation of tungsten have been determined at temperatures between 1320" and 3170°C and oxygen pressures to 1 amn using a surface -recession measurement technique. Above approximately 2000°C and 10-6 atm the rate is independent of temperature and can be calculated from gas collision theory assuming a constant reaction probability, e, of 0.06. Oxygen molecules react at surface sites where oxygen atoms have previously chemisorbed. This provides a direct pressure dependence at low pressures but at high pressures tungsten oxide molecule s form an adjacent gas boundary layer which lowers the PO2 at the tungsten surface. A correction for this effect using free-convection theory fits the rate data over the entire oxygen-pressure range from 10-8 to 1 atrn as well as data using O2-A mixtures. Below 10-6 atrn and above 2000°C, e decreases with increasing temperature because of desorption of oxygen atoms. Below 2000°C the rate decreases with decreasing temperature at all oxygen pressures following an apparent activation energy of 42 kcal per mole and depending on (Po2)n with n varying between 0.55 and 0.80. MOST of the previous tungsten oxidation studies have employed gravimetric methods and have been limited to temperatures below 1000°C where the weight loss associated with evaporation of tungsten oxides is negligible compared with the weight gain from oxidation.' At higher temperatures, oxygen-consumption rates have been determined from pressure measurements, usually at constant flow rates, by Langmuir,2 Eisinger,3 Becker, Becker, and Brandes,4 and Anderson.5 The sensitivity of this method decreases with increasing pressure and, with the exception of Langmuir's work, these investigations were confined to pressures below 10-6 atm. Above approximately 1300°C, depending on the oxygen pressure, the rate of oxide evaporation is greater than the oxide-formation rate and the recession of the tungsten surface can be measured optically without interference from an oxide layer. This was first done by Perkins and crooks6 who heated tungsten rods in air pressures from 1 to 40 torr at temperatures between 1300" and 3000°C. The present investigation of the oxidation kinetics of tungsten at high temperatures emphasizes oxygen pressures from 10-6 to 1 atm. This is the range of interest for earth atmosphere re-entry applications of tungsten for which little data were previously available. APPARATUS The apparatus is a modification of the type used by Perkins and crooks.' Ground tungsten seal rods, 6 in. long by 0.125 in. diam, were mounted vertically between two water-cooled electrodes, one fixed and the other having free vertical travel. The movable counter-weighted electrode is prevented from undergoing horizontal displacement by three sets of runners mounted at 120-deg intervals. Electrical contact is made by means of a water-cooled mercury pool. A 24-in. vacuum bell jar having a volume of approximately 267 liters was used as the reaction chamber with the sample holder mounted in the middle of the chamber. Power was supplied from an 800-amp dc variable power supply. Temperature readings were made by means of a Latronics automatic two-color recording pyrometer. With this instrument, corrections for emissivity are not necessary provided the spectral emissivi-ties at two closely spaced wavelengths are equal. Supporting measurements were made with a micro-optical pyrometer corrected for emissivity of bare tungsten and window absorptivity. The micro-optical pyrometer was calibrated against a National Bureau of Standards calibrated tungsten lamp and both pyrometers were periodically checked against the melting points of tungsten and molybdenum using the oxidation apparatus. Above 10-6 atm, pressures were measured with an Alphatron gage calibrated against a McCleod gage. At 10-6 atm, a hot-filament ionization gage was employed. A magnified image of the self-illuminated tungsten rod was formed using a 360-mm objective lens mounted outside the bell jar. When the experiment exceeded 1 hr, the image was focused on a ground-glass plate about 10 ft from the tungsten rod at about X8 and the recession of the thickness of this image was monitored with a Gaertner cathe-tometer. When faster rates were encountered, a 35-mm time-lapse cinecamera with a telephoto lens and bellows extension was substituted for the ground-glass plate and cathetometer. Diameter recession rates were determined from the photograph image projected on the screen of an analytical film reader. EXPERIMENTAL PROCEDURE After installing the rod in the apparatus and cleaning it with acetone, the system was evacuated to 5 1 x 10-5 torr. Before oxygen was introduced,

Jan 1, 1964

By Edna A. Dancy, Gerhard J. Derge

The specific conductance of FeOx,-CaO melts in contact with iron was found to decrease from 200 ohm-1 cm-1 for FeO, to 40 ohm-1 cm-1 for a melt containing 26.3 pct CaO at 1400°C. The temperature coefficient was positive at all compositions, but became smaller at high CaO contents. Current efficiencies for electrolysis increased from 2.5 pct in FeOx to 17.3 pct at the high CaO composition, indicating a change from predominantly electronic conduction to conduction with a substantial ionic contribution. It was shown that Ca++ ions as well as Fe++ ions carry the ionic current. A subsidiary investigation on the apparent effect of atmospheres of argon, helium, and nitrogen on the electrical conductivity showed that this could be correlated with surface temperature losses, which varied with the thermal conductivities of the gases and resulted in precipitation of metal by the reaction 3 Fe++ = 2 Fe+++ + Fe. The work described in this paper is offered as a contribution to the general fund of knowledge concerning metallurgical slags. Measurement of electrical conductivity and electrolysis are comparatively trouble -free methods for investigating molten materials, but, although these methods had been used for complex slags, it was not until the work of Bockris et al.1 that the approach of examining simple binary slag systems was employed, and CaO-SiO2, MnO-SiO2, and Al2O3-Si9 were studied. Two groups have performed work of particular relevance to the present investigation. Inouye, Tomlinson, and chipman2 studied the conductivity of wustite as a function of temperature and of the addition of 5 mol pct of a number of oxides, including CaO. They concluded that molten FeOx in equilibrium with iron is a semiconductor. Simnad, Derge, and ceorge3 demonstrated the ionic nature of liquid iron silicate slags and also concluded that, although the conductivity of FeOx in equilibrium with iron is predominantly electronic in nature, there is a small ionic contribution. The work reported here on FeOx,-CaO slags consists of three main parts, namely, the determination of the specific conductance over a wide composition range, an investigation into the nature of the conductivity through current-efficiency measurements over the same composition range, and an attempt to identify the current-carrying ions, as well as a subsidiary investigation on the apparent effect of the nature of the inert atmosphere on the conductivity. EXPERIMENTAL Materials. The slags, varying in composition from FeOx to 27 pct CaO, were prepared by heating reagent- grade Fe2O3 in an ingot iron crucible with a suitable amount of CaCO3 and, in some cases, powdered iron, in air. This prefused material was then used for the runs. At the end of each run the cell was removed from the furnace and quenched by immersing the bottom half in water. After crushing, the slags were analyzed for calcium and total iron by the usual wet methods. The oxygen content was obtained by difference. Specific Conductance: Apparatus and Method. Fig. shows the experimental setup, with the conductivity cell and leads of ingot iron. The standard four-probe method for measuring high conductivities was used. In this, the potential drop across the unknown resistance is compared with the potential drop across a known resistance connected in series, i .e., same current through both resistances. Thus there are both current and potential leads to the center electrode and to the crucible, which acts as th other electrode. Both ac and dc circuits were available for the measurements; they have been described in earlier work performed in this laboratory.4,5 The geometry of the cell was such that the center electrode was equidistant from the bottom and sides of the crucible. This ensured that the current path was the same irrespective of the magnitude of the conductivity of the material in the cell. Cell constant were measured with KC1 or NaCl solutions, which have considerably lower conductivities (0.0013 to 0.25 ohm-' cm) than the slags, and this precaution in design made sure that the determined cell constants applied to the cells with contents of any conductivity. The cell-constant determinations were made with the ac measuring circuit to prevent polarization. The four-probe method eliminates lead resistance but not the resistance of those parts of the center

Jan 1, 1967

By E. Miller, J. M. Eldridge, K. L. Komarek

The liquidus curve of the Mg-Pb system was accurately redetermined. The compound Mg2Pb decomposes peritectically at 538.2° ± 0.3°C to liquid and to a compound p' which melts congruently at 35.0 at. pct Pb and 549.0° ± 0.3°C. The solidus curve of ß' was determined. X-ray diffraction studies indicate that 4' has an orthorhombic structure. Activity values of magnesium calculated from the phase diagram agree with those published in the literature. EXPERIMENTAL thermodynamic properties of binary metallic systems have to be consistent with values calculated from the phase diagram. In systems forming intermetallic compounds the shape of the liquidus curve near a compound is determined by the thermodynamic properties of the coexisting solid and liquid phases. Hauffe and Wagner' neglected the temperature dependence of the chemical potentials and obtained the potential differences of the components of the liquid alloys, relative to stoichiometric liquid. Their calculations were based on the liquidus curve and on the heat of fusion of the compound, and were only valid near the congruent melting point. Steiner, Miller, and Komarek2 developed equations which account for the temperature dependence and obtained the chemical potentials of liquid Mg-Sn alloys over the entire phase diagram from the liquidus and solidus curves and from enthalpy values with the pure components as the standard states. The Mg-Pb phase diagram has been studied by several investigators whose results have been compiled and critically evaluated by Hansen.3 Although the liquidus curve was poorly defined, the general features of the diagram, i.e., one congruent melting compound, Mg2Pb, of essentially stoichiometric composition, two eutectics, and limited terminal solid solubilities, seemed to be suitable for a similar thermodynamic analysis. A careful redeter-mination of the liquidus by thermal analysis revealed, however, the existence of another compound. The liquidus curve between the two eutectics was precisely delineated and the structure and solidus curve of the new compound were investigated. The revised phase diagram was thermodynamic ally analyzed to evaluate the activity of magnesium in the liquid alloys. EXPERIMENTAL PROCEDURE The magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) had a purity of 99.99+ pct; lead (American Smelting and Refining Co.) contained 99.999 pct Pb. Most experiments were carried out in graphite crucibles. Several experiments were made in high-purity alumina (Triangle R.R., Mor-ganite, Inc.) and in Armco iron crucibles to test the inertness of the graphite crucibles. Chemical analysis of magnesium and detailed description of the procedure for thermal analysis have been given previously. For the determination of the solidus curve of the compounds, specimens of initial composition Mg2Pb were equilibrated in a closed isothermal system with magnesium vapor. The source of the magnesium vapor was an alloy which had a gross composition lying in the 0' + L field at the temperature of equilibration. As equilibrium was approached, the specimens lost magnesium to the two-phase reservoir thereby lowering the activity of magnesium in the specimens until activity and composition equaled that of the ß'/ß' + L boundary. Crucibles (1.9 cm ID by 2.2 cm OD by 4.1 cm high) and tightly fitting lids were machined from a molybdenum rod; small, shallow trays were fashioned from thin (0.005 in.) molybdenum sheet, and all the molybdenum components were degreased in hot carbon tetrachloride and then dried. The pieces were then degassed in vacuum at 950°C for about 6 hr. The two-phase alloy was placed at the bottom of the crucible and small specimens of the Mg2Pb compound, weighed on an analytical balance, were placed in two molybdenum trays above the two-phase alloy. The crucible was closed by forcing its lid on and then inserted in a titanium crucible. This crucible was evacuated, flushed twice with argon, and welded under argon. The specimens were equilibrated for about 1 week in a resistance furnace regulated by a Celectray controller, and the runs were terminated by water quenching. The specimens were again weighed and the equilibrium compositions were calculated on the basis that the weight losses were solely due to a loss of magnesium to the two-phase alloy. The structure of the B' phase was investigated by the Debye-Scherrer X-ray diffraction technique. Selected ingots from thermal-analysis experiments containing about 35 at. pct Pb were re-melted, slowly cooled, and crushed in an argon-filled glovebox until the entire ingot passed through a 50-mesh sieve. The powder was thoroughly

Jan 1, 1965

By John R. McWilliams

This is one of a series of reports being published by the Bureau of Mines on mining methods and costs at various mines throughout the United States. Including the Holden mine in this series is particularly appropriate at this time. The mine was operated on a low-cost, large-scale production basis to compensate for low-grade ore. Even with the best conditions and the most efficient methods, the margin of profit was small. Under the present situation of rising costs and lowering metal prices, the profit margin vanished. On June 28, 1957, the mine operations ceased; therefore, this report can review the entire life span of the mine.

Jan 1, 1958

By Carl G. Hogberg

To the casual observer there is probably no simpler appearing operation in the mineral industry than a limestone quarry. It might seem that the entire operation - from the drilling, blasting, and loading of the stone, its transport to a mill for crushing, washing and sizing, to loading into boats, railroad cars, or trucks for delivery to customers - can be comprehended at a glance. But no first impression could be more misleading. It is one of the purposes of this presentation to sketch the broad outlines of the extensive limestone industry in the United States which, measured in terms of volume of production since the end of World War II, has grown almost 300 per cent to a national level in 1957 of 384 million net tons.1 Another objective will be to discuss in more detail this industry in the State of Michigan. For this latter purpose, the Michigan Limestone Division plants at Calcite and at Cedarville will be used as examples. These descriptions will, we believe, show that the limestone business has complexities to match its size.

Jan 1, 1962

By L. R. Fyffe, D. R. Lentz, S. H. Mcclenaghan

"Abstract - The Eel River area in the southwestern Miramichi terrane of New Brunswick contains a complete calc-alkaline suite of volcanic rocks that are interlayered with intervals of sedimentary and polylithic fragmental rocks, and are overlain by a thick sedimentary sequence. This package, collectively referred to as the Meductic Group, was deposited in a submerged volcanic arc setting interpreted to be part of the Popelogan arc. Rifting of this arc led to the development of the Tetagouche-Exploits back-arc basin, and formation of volcanogenic massive sulfide deposits in bimodal volcanic rocks of the Bathurst Mining Camp in the northeastern Miramichi Terrane. Unlike the Bathurst Mining Camp, volcanic rocks in the southeastern Miramichi Highlands form a continuous calc-alkaline suite characterized by increasing Zr/TiO2 with increasing SiO2, in part resulting from progressive coupled assimilation and fractional crystallization of nested magma systems. Slumping of semi-consolidated volcanic and sedimentary rocks in topographically unstable areas resulted in numerous slumps and debris flows that are preserved throughout the Eel River area. In the early 1990s, the discovery of a large sulfide clast in a road cut along the Benton road sparked interest in the volcanogenic massive sulfide potential of the Eel River area. Subsequent drilling intersected smaller fragments, one clast of which graded 16.7% Zn, 5.6% Pb, 90 ppm Ag, and 220 ppb Au. The intersection of thin lenses of stratiform sulfides in another drillhole indicates favorable conditions for the preservation of massive sulfides. Their subsequent incorporation into synvolcanic debris flows resulted in the transport and deposition of sulfide clasts from hydrothermal vents to more distal locations. Similar to the Buchans deposits of Newfoundland, tracing these debris flows back to their source would be beneficial from an exploration perspective. Approximately 15 km to the southwest of the Eel River area, gold-bearing base metal sulfide clasts (11.1% Zn, 6.13% Pb, 0.19% Cu, 108 ppm Ag, and 1100 ppb Au) occur within intermediate-composition volcanic rocks at Monument Brook in eastern Maine. Sommaire - Le secteur d’Eel River dans le sud-ouest de la terrane de Miramichi au Nouveau Brunswick contient une séquence complète de roches volcaniques calco-alcalines interstratifiées avec des roches sédimentaires et fragmentaires polylithologiques, sous une épaisse couverture sédimentaire. Cet assemblage constitue le Groupe de Meductic, et a été déposé dans un environnement d’arc insulaire interprété comme une partie de l’arc de Popelogan. Le rifting de cet arc à mené au développement du bassin d’arrière-arc de Tetagouche-Exploits, et à la formation de gisements de sulfures massifs volcanogènes dans les roches volcaniques bimodales du Camp Minier de Bathurst dans le nord-est de la terrane de Miramichi. Contrairement au Camp Minier de Bathurst, les roches volcaniques des hautes terres du sud-est de Miramichi constituent une suite calco-alcaline continue caractérisée par un accroissement du rapport Zr/TiO2 à des valeurs croissantes de SiO2, résultant en partie de l’assimilation progressive et de la cristallisation fractionnée de systèmes magmatiques superposés. L’effondrement de roches volcaniques et sédimentaires semi-consolidées dans des secteurs topographiquement instables est à l’origine des nombreux slumps et coulées de débris qui sont préservés dans le secteur d’Eel River. Au début des années 1990, la découverte d’un large claste de sulfures le long de la route Benton provoqué un intérêt pour le potentiel en gisements de sulfures massifs volcanogènes dans les secteur d’Eel River. Des forages ont par la suite recoupé des fragments plus petits, dont un claste qui a retourné des teneurs de 16.7% Zn, 5.6% Pb, 90 ppm Ag et 220 ppb Au. Le recoupement de minces lentilles de sulfures stratiformes dans un autre forage indique des conditions propices à la préservation des sulfures massifs."

Jan 1, 2006

By Ana E. Bohé, Georgina De Micco, Juan P. Gaviría, FEDERICO J. POMIRO, Gastón G. Fouga

Chlorination and carbochlorination processes have industrial applications in metallurgical activity for extraction and purification of uncommon metals such as rare earth elements (REE). This study reviews the chlorination and carbochlorination reactions of light REE (LREE) oxides with chlorine considering the thermodynamic, stoichiometric, and kinetic aspects of the reactions. Lanthanides between lanthanum to gadolinium were considered as LREE, in agreement with previous literature, and the results were detailed in this review. LREE were analyzed taking into account their oxidation states and were divided into three groups accordingly. The results presented show that, although the LREE are chemically similar, their behaviors during the reactions with Cl2 and Cl2–C, and the different LREE-O–Cl compounds formed, have particularities. It was observed that gadolinium, in both thermodynamic calculations and experimental results, presents some differences, and it can be considered intermediate between light and heavy REE; i.e., reactions between LREE2O3 and Cl2(g) begin at approximately 250 °C, except for Gd2O3 that begins at 327 °C. The present work will contribute to a better understanding of the chemistry of LREE oxides and Cl2 under different conditions and the products obtained in the LREE–O––Cl2(g) and LREE–O–C–Cl2(g) systems.

Oct 15, 2021

By P. Wynblatt, J. E. Dorn

The effect of strain rate, temperature, and interstitial impurity concentration on the flow stress was investigated in a poly crystalline Fe-2 pct Mn alloy. The temperature dependence of the flow stress was found to be independent of the interstitial impurity concentration, removal of interstitials merely decreasing the atherma1 stress level. Below 160%, the large temperature dependence of the flow stress was interpreted in terms of the Dorn-Rajnak theory of the Peierls mechanism of plastic deformation. Above 160"K, some other thermally activated intrinsic meckanisln seems to be operating. The strong temperature dependence of the flow stress of bcc iron at low temperatures has been studied by numerous investigators and interpreted in terms of several different thermally activated dislocation mechanisms. The following mechanisms have been proposed: a) interaction of dislocations with interstitial impurity atoms1 or with solute atoms in general; b) interaction of dislocations with clusters of impurity atoms;3 c) resistance to the motion of dislocations due to jogs on screw dislocations;* d) resistance to the motion of dislocations due to the Snoeck effect;' and e) interaction of dislocations with the intrinsic resistance of the bcc lattice or Peierls "hills". In previous work: it was found that the plastic behavior of polycrystalline iron containing 2 wt pct Mn (and 100 ppm C + N) is in good agreement with predictions based on the Peierls mechanismlo from 77" to 160°K whereas from 160" to about 370°K another as yet unidentified thermally activated mechanism is operative. The purpose of the present investigation was to determine the effect of interstitial impurities on the temperature dependence of the flow stress, by purifying the previously investigated alloy with respect to interstitial impurities. The investigation revealed that removal of the interstitial impurities to a level that eliminated Cottrell locking and the Portevin-LeChatelier effect (i.e., serrations in the stress-strain curve due to dynamic strain aging) affects neither the strong temperature dependence of the flow stress at low temperatures nor the general characteristics of the higher-temperature behavior. Such purification, however, lowered the athermal yield stress. I) EXPERIMENTAL PROCEDURE AND RESULTS The material used in this investigation consisted of an Fe-2 wt pct Mn alloy having the following additional elements present: 0.004 pct C, 0.006 pct N, 0.05 pct 0, 0.004 pct S, 0.003 pct P, and 0.001 pct Si. This was the same material as that studied in the previous investigation and will henceforth be referred to as the "impure material". The as received -jr by 2 in. hot-rolled bars were cold-rolled to 0.08-in. thickness, recrys-tallized under argon for 30 min at 80O0C, and further cold-rolled to 0.053-in. thickness. Flat tensile specimens 3 in. wide having a 1.625-in.-long gage section were machined from the sheet and then purified. The first stage of purification consisted of holding the specimens at 850°C for 24 hr in a stream of hydrogen saturated with water vapor at room temperature. Material prepared in this fashion will subsequently be referred to as "wet hydrogen purified material". It has been estimated that this type of treatment reduces the carbon content of iron to less than 5 ppm.' The second stage of purification consisted of holding the specimens in a closed system through which hydrogen was circulated past the heated specimens as well as a zirconium hydride getter. The specimens were held at 850°C and the getter at 800°C. The process was continued for 212 hr. The starting material for this process was wet hydrogen purified material. Material prepared in this manner will be referred to as "ZrHz purified material". The technique used was substantially the same as that described by Stein et al.' who have shown that the carbon level at the end of the process is reduced to about 5 parts per billion. The mean grain size of the three materials was found to be -60 C( for the impure material and -160p for the wet hydrogen and ZrHz purified materials. All tensile testing was carried out on an Instron Testing Machine either in controlled-temperature baths or at fixed-point baths such as boiling liquid nitrogen, and so forth. When fixed points were used the temperature was kept constant to better than *1°C whereas in all other tests the temperature variation was less than *2°C. Test of Purity. It was not possible to determine the purity achieved at each stage of the purification because the resulting level of interstitial impurities was near or below the limit of sensitivity of standard analytical techniques. It was possible, however, to obtain a qualitative measure of the extent of purification from the appearance of the stress-strain curves for the three materials. Fig. 1 shows the stress-strain curves for the three different materials tested at 300°K. It can be seen that the effect of wet hydrogen

Jan 1, 1967

By M. B. Bever, A. K. Jena

THE heats of formation ?H at 273°K of the compound AgMg as a function of composition have been measured by solution calorimetry.1 The value at the stoichiometric composition is -4.41 kcal per g-atom. From electromotive force measurements2'3 the heat of formation at 773°K of stoichiometric AgMg has been determined as -5.19 kcal per g-atom.4 The combination of these two values results in an unusually high negative temperature coefficient of the heat of formation d?H/dT = ?Cp = -1.6 cal per g-atom-OK. By contrast, published heat contents of the compound AgMg and the component elements above room temperature5 indicate that the temperature coefficient of the heat of formation of AgMg is nearly zero. In this communication calorimetrically measured heats of formation of A.K.JENA,Junior- MemberAIME,andM.B. BEVER,Member AIME, are Staff Member, Division of Sponsored Research, and Professor of Metallurgy, respectively, Massachusetts Institute of Technology, Cambridge, Mass. Manuscript submitted July 1, 1968. IMD AgMg below room temperature are reported and the temperature dependence of the heat of formation is discussed. The heat effects of additions of samples of the compound AgMg containing 50.1 at. pct Mg to liquid tin-rich solutions at 623°K were measured in a solution Calorimeter.6 The heat effects of additions plotted against the average of the atom fractions of solutes in the solution before and after each addition were a linear function of composition from which the heat effect at infinite dilution was obtained, Table I. The calorimeter was calibrated by additions of tin; the heat content (H623°K - H273°K) of tin was taken as 4.08 kcal per g-atom.4 The heat effect at infinite dilution of an addition of where heat of formation of AgMg at T°K, T = temperature from which samples are added (78°, 195°. and 273°K), Xi = atom fraction of i in AgMg, ?Hi = relative partial gram-atomic enthalpy of i in tin-rich solution.

Jan 1, 1969

By Arthur McKee

As HEAT is the controlling factor in all smelting operations, it will be .most helpful to make a new set of calculations on the basis of a .unit of fuel burned at the tuyeres to carbon monoxide. This ties together the only two factors in this operation that seem to be constant with respect to each other-the fuel at the tuyere and the air or its oxygen content. If our usual smelting operations, using natural air heated to reasonably obtainable temperatures, furnish sufficient heat above this critical temperature for the purpose, it is doubtful whether additions of oxygen will be of marked benefit. A unit of fuel will not produce a single heat unit more if burned with pure oxygen than if burned with natural air and less heat will be available per unit of fuel by the amount of heat that is carried in by the preheated nitrogen in the natural air of the blast. This is more readily apparent if considered in connection with a heat balance sheet per unit of fuel at the tuyere. The heat available in the stack, as shown by the committee's report, is less by reason of the lower fuel consumption per unit of output assumed in this calculation. The balance sheet for enriched air shows a shortage of the amount of heat usually carried in with the blast; also a lack in the hearth of sufficient heat to melt the 18 per cent. additional metal and slag and in the shaft to the extent of the shaft heat required to heat the 18 per cent. additional stock to the melting point. These heat deficiencies are provided for by the largely increased conversion of carbon monoxide into carbon dioxide, which is assumed, as shown by the following figures: Calculation for natural air: Carbon dioxide 18.4 per cent. (after having eliminated the carbon dioxide from limestone) and 20.8 per cent. of carbon monoxide. Calculation for oxygen-enriched air: Carbon dioxide 28.4 per -cent. and carbon monoxide 23.2 per cent. (no carbon dioxide from stone as lime is charged instead).

Jan 11, 1924

By John Norton

"This presentation will cover the physical properties of waste heat recovery. It is a two part presentation. The first deals with actually recovering the heat with new state of the art heat exchangers and applying that heat to the furnace combustion and the second part will cover what other processes you can enhance with this ""free"" heat. It will also talk about converting it to steam, hot air or electricity to be used or sold back to the utility company. The economics of various schemes will be reviewed. A brief discussion on State and Federal grants and subsidies will be presented.IntroductionThere are large quantities of wasted heat in the usual aluminum melting process. And, there are several techniques for reducing and/or using some of that wasted heat as you have seen. Any technique that can make use of wasted heat is a form of recovery. This can range from simply preheating aluminum billets prior to melting, to more complicated processes like air-to-air heat exchangers using the boiling and condensing characteristics of special fluids in “heat pipes.” The objective of this type energy recovery process is to move the wasted heat from the hot and dirty exhaust gas stream into some useful process.Waste Heat Recovery in the Aluminum Melting Furnace.There are considerations, of course:1) What might the value be of the recovered energy?2) Can the recovered energy be used within the process? Within the plant? Or by theneighbors?3) What is the capital cost?4) Is the recovery process complicated?5) Will it take additional staff?6) Will it cause additional downtime on the melting line?7) Will the operations staff need to be licensed?Ideally, the process will be simple and inexpensive, the recovered energy will be very valuable, and the whole effort will cause little distraction to the aluminum melting process itself. These would be ideal."

Jan 1, 2011

By J Mercuri, S Dunford, P Rothman, E Bartsch, J Snyder, D Newton, R Maron, D Cirulis

The purpose of a mineral comminution circuit with a ball mill running in closed-loop with a hydrocyclone classification cluster is to feed the downstream process with the target particle size. Maintaining the optimal particle size in the flotation feed can significantly improve plant cash flow. In particular, reducing the amount of coarse material is often a major challenge. Existing instrumentation to provide particle size measurement is considered standard equipment in most modern concentrator plants. However, availability is often very low, mainly owing to high maintenance requirements of the analyser and associated sampling system.CiDRA Minerals Processing has developed two novel and robust technologies that address this challenge by providing high reliability and very low maintenance systems for on-line measurement of coarse material in the overflow of individual hydrocyclones. The first system is non-invasive and measures pebbles and rocks greater than 6 mm. This paper focuses on the second system, which is a ruggedized wetted sensor design with no moving parts and provides a real-time trend of the desired target grind size parameter, such as percentage above 150 micron.Both systems have simple robust designs and measure in the primary overflow stream of the individual hydrocyclone. Individual hydrocyclone measurement enables identification of poor performing hydrocyclones in addition to providing a representative measurement of the whole hydrocyclone cluster. The systems do not require sampling and associated sample transfer piping circuits that are prone to plugging, thus avoiding high maintenance requirements.The wetted sensor will be described in detail along with its implementation in a robust control scheme in a major copper concentrator in North America. Plant data shows very high availability, achieved with very low maintenance, has enabled improved process control, thereby maintaining throughput and ball mill target power while reducing grind size.CITATION:Cirulis, D, Dunford, S, Snyder, J, Bartsch, E, Rothman, P, Maron, R, Newton, D, O’Keefe, C and Mercuri, J, 2015. Process optimisation using real-time tracking of coarse material in individual cyclone overflow streams, in Proceedings MetPlant 2015, pp 93–109 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Sep 7, 2015

By R. Grierson, L. J. Bonis

The high-temperature Strength oF TD nickel has been observed to be dependent upon the previons thermal and mechanical history of the material. Variations in both the level and the anisotropy of strength have been observed. 01 this paper- these variations are correlated with the storing of annealing resistant elastic strain energy in the matrix of the TD nickel. An x-vay line -broadening tecknique is used to measure the maLrTis elastie strain. THE inclusion of a finely dispersed second phase into a ductile matrix has long been recognized as an extremely effective method of strengthening the matrix both at high and at low homologous temperatures. It has been found, however, that the factors which determine the high-temperature strength are not the same as those which are important at low temperatures. Below 0.5 Tm the size and distribution of the second phase particles are of prime importance in determining the strength,')' while above this temperature the strength is mainly dependent upon the previous thermal and mechanical history of the alloy,3-7 This paper is primarily concerned with explaining the response of the high-temperature mechanical strength of one of these alloys (DuPont's TD nickel) to various thermo-mechanical treatments. It will be shown that this response is not associated with the occurrence of any form of dislocation substructure within the matrix of the alloy. It has been found, however, that a correlation does exist between the elastic strain level in the matrix and the previous thermomechanical history of the alloy and that the observed changes in elastic strain level parallel the measured changes in high-temperature strength. It therefore must be concluded that variations in high-temperature strength are a direct result of the variations in elastic strain level. MATERIAL TD nickel contains approximately 2 vol pct of Tho2 in an unalloyed nickel matrix. It is formed, as a powder, by a chemical technique and this powder is compacted to form ingots which are then extruded to give 21/2-in.-diam rod. Rod of smaller diameter is prepared from the as-extruded rod by swaging. In the studies reported in this paper, 1/2-in.-diam rod was used. This rod received an anneal of 1 hr at 1100°C prior to being used in any of these studies. EXPERIMENTAL TECHNIQUES Two methods were used to examine the structure of the nickel matrix of the TD nickel. These were: 1) transmission electron microscopy; 2) the analysis of the position and profile of X-ray diffraction lines obtained using the nickel matrix as the diffracting media. To prepare thin foils for electron-microscopical examination, slices of TD nickel approximately 0.050 in. thick were cut from the as-received 1/2-in.-diam rod. These were then chemically polished down to 0.045 in., rolled to 0.009 in., given a predetermined heat treatment, and thinned, using a modified Bollman technique, to provide the foils for observation. All observations were carried out at 100 kv, using a Hitachi HU-11 electron microscope. Specimens of the undeformed rod were prepared by grinding down the 0.050-in.-thick slices to approximately 0.015 in. and then thinning chemically and electrolytically to give the thin foils. The X-ray specimens were prepared by rolling 0.375-in.-thick rectangular blocks down to 0.075 in. The surfaces of the rolled material were ground flat, chemically polished to remove the layer disturbed by the grinding, and given a predetermined anneal in an inert atmosphere. They were then ground lightly to check their flatness and given a final chemical polish prior to being examined. The X-ray diffraction line profiles were measured using an automated Picker biplane diffractometer. A special specimen holder was built to allow a more accurate and reproducible positioning of the specimen. The line profiles were determined by carrying out intensity measurements at intervals of either 1/30 deg or 1/60 deg over a range of 3 deg on either side of the nickel peaks of interest. A piece of pure nickel which had been recrystallized to give a large grain size was used as a standard to give the X-ray line profile generated by a strain-free matrix. The analysis of the X-ray diffraction line profiles is a modification of that due initially to Warren and Aver-bach8and has been described elsewhere.3 This analysis gives a measurement of two parameters associated with the structure of the nickel matrix. These parameters are: 1) the size of the coherently diffracting domains within the nickel matrix; 2) the magnitude of the elastic strains in these domains. Both of these parameters are first determined in terms of a Fourier series. These series are obtained from other Fourier series which describe the measured profile of the X-ray diffraction lines. Thus, for both the coherently diffracting domain size and the elastic strain level, it is possible to plot Ft (the Fourier coefficient) against t (the term in the Fourier series), where t can be expressed in terms of a distance L and the Fourier coefficient Ft(S) (associated with elastic strain level) can be expressed in terms of the root mean square strain (e2)1/2. Thus a plot of (F 2)1/2 vs L can be obtained. Plots of this type are shown graphically in Figs. 6 and 8. Interpretation

Jan 1, 1968

By N. Razavinia

Most mining and metallurgical industries produce relatively large quantities of low grade waste heat which they vent, for the most part, to the environment. To date, little is being done to recover some of this heat and transform it from low grade to a high grade energy form such as electricity. A few decades back this was also true of paper, plastics and metals. Recycling was not a prominent activity. Today, we all know that it is and that recycling is a must for sustainable development. To this end, we feel that we are now at that point in time when the recycling of waste heat to electricity must be given serious consideration. By recycling waste heat one can achieve at least one if not two of the following benefits: 1) reduction in the carbon footprint ? by improving the overall energy efficiency of a process, and 2) production of electricity at an economically viable cost. We have developed a process that captures, concentrates and converts (3 C?s) waste heat to electricity. The process comprises 3 distinct interacting units. The first unit captures and concentrates waste heat using heat pipe technology. The second unit converts some of the concentrated heat to mechanical work which can then be readily converted to electricity. This unit is based on the classical piston/cylinder engine arrangement that is widely used by consumers to power systems with compressed air, for example. The third unit of the process dissipates the heat that the engine cannot convert to high grade energy. It also uses heat pipe technology to achieve this. The combination of the 3 units forms a unique system for recycling waste heat. This paper describes the system and it presents some results that show how the system can be made to be economically viable.

Aug 1, 2013

By Frank Mucciardi, Hujun Zhao, Pietro Navarra

"A heat pipe is a device having a very high effective thermal conductivity in which two-phase flow and heat transfer takes place. Recent research at McGill University has led to a new type of heat pipe that contains a flow modifier. This improvement has enabled the device to operate at the high heat fluxes encountered in the metallurgical industry.This paper summarizes the progress made to describe the fluid flow in the evaporator section of a McGill heat pipe with the goal of understanding how the flow modifier configuration is linked to the film boiling and dry-out limitations. A separated flow model, an instability analysis, a lift-off model and an energy balance model are used to calculate the theoretical CHF with varying flow modifier configurations and operation conditions. A summary of the current work to relate the flow modifier to the dry-out limitation is also given.Determining how the flow modifier affects both the film boiling and dry-out limitation will give insight into improving the flow modifier design so as to extend the operational range of McGill heat pipes in terms of maximum heat flux and heat load capabilities.IntroductionThe McGill heat pipe is a specialized two-phase heat exchanger developed for several metallurgical applications where temperatures and heat fluxes are typically close to or beyond the maximum safe range of conventional cooling technology.Over the last few years, several breakthroughs have brought this device beyond the proof-of concept stage and a series of industrial trials have been performed with success. These trials include two oxygen injection applications for the ferrous and non-ferrous industry [l], and two light metals permanent-mould casting applications [2,3]. Current projects include a blast furnace copper taphole cooling application [4], a copper smelting application and a thermal analysis probe application."

Jan 1, 2004

By Lon D. Santis

This paper describes a lightning warning system (LWS) in operation at the U.S. Bureau of Mines' (USBM) Pittsburgh Research Center (PRC) from December, 1989 to April, 1991. An electric field mill measured the DC atmospheric electrostatic field. Also, an economical on-line weather data service provided lightning location maps and other weather information. A system such as this can significantly improve the safety of explosive handling. The use of these two methods addresses the detection of thunderclouds building overhead and the prediction and tracking of developed storms. Warning reliability of the system was very good when data from both sources were considered. Experience showed, however, that use of either system alone would not provide adequate reliability in most situations. Some problems occurred with the field mill and there is some question whether the instrument is compatible with harsh mining environments or could be made portable. Another method ' of measuring electric field based on fiber optics is discussed. This technology may be able to overcome the problems with field mills.

Jan 1, 1993

By A. H. Larson, R. J. McClincy

Laboratory-scale decopperizing experiments with multiple sulfur addifions were conducted at 330°C on ternary Pb-Cu alloys containing, as the third elenlent, Sn, Ag, As, Sb, Bi, Zn, and Au, common impurities in lead blast-furnace bullion. For silver and tin, an increased rate and extent of 'cofifier removal was obsert3ed. The elements As, Sb, Zn, Au, and Bi had no effect or less effect as compared to sulfur additions with no i)npurily additions. THE production of primary lead in the blast furnace yields an impure lead frequently containing such impurities as copper. antimony. arsenic. tin, gold, silver iron, oxygen. and sulfur. By cooling this lead to a temperature near its melting point. most of the iron, sulfur, and oxygen and part of the other impurities are removed in the form of a dross. With incipient solidification of the lead, the copper concentration wil have been reduced to 0.02 to 0.05 pct. depending upon the concentration of the other impurities. according to Davey.' Since copper interferes with the treatment of silver after the desilverizing process, it is desirable to decrease the copper content of the lead still fur-ther before the lead is desilvered. The decopperizing of the lead is accomplished by stirring a small quantity. approximately 0.1 pct. of elemental sulfur into the lead at a temperature near its melting point, 330" to 360°C. The copper is removed as a copper sulfide which constitutes a small fraction of a voluminous dross consisting mostly of lead sulfide and entrained metallic lead. The residual copper concentration following the decopperizing operation is frequently as low as 0.001 to 0.005 pct. Thi fact has aroused considerable interest because the equilibrium copper concentration of lead in contact with solid PbS and solid Cu2S is at least an order of magnitude greater, 0.05 pct Cu at 330C. 1, 2 Most investigators have suggested that various impurities in the lead bullion are responsible for the very low copper concentrations frequently encountered in practice. There is little agreement, however? as to which of the impurities are helpful and which are not.3"11 Also. few investigators have sought to explain the mechanisms responsible for the removal of copper to very low concentrations. Willis and Blanks9 have proposed that a nonstoichiometric copper-deficient cuprous sulfide forms in place of the supposed Cu2S. Being copper-deficient, this sulfide phase would possess a low copper activity, and the diffusion of copper dissolved in the liquid lead into this phase would be greatly facilitated. Pin and wagner2 have investigated the removal of copper from liquid lead by studying the effect of impurity-doped lead sulfide on the decopperizing of pure Pb-Cu alloys. Samples of the doped PbS were held in contact with copper-saturated lead for 1 week at 33'7°C. They reported a beneficial effect on decopperizing with bismuth and antimony and no effect with tin or silver. which is directly opposite to the results observed in practice and those reported by Davey 3 and this studv. The purpose of this paper is to describe the effects of certain additive elements on the extent to which copper can be removed fro111 liquid lead by successive additions of sulfur. The impurity elements were added individually to prepared Pb-Cu alloys. The resulting ternary alloys as well as a binary Pb-Cu alloy were then decopperized with repeated additions of sulfur. EXPERIMENTAL Materials. Granulated test lead with a purity of 99.999 pct and the additive elements Cu. Ag. Sb. Bi. Zn. Sn. and Au with purities of 99.99 pct were American Smelting and Refining Co. research-grade materials. The major impurities in the lead were 1 ppm each of iron and copper. all others being less than 1 ppm. The arsenic used was a technical-grade arsenic of 98+ pct purity. Reagent-grade flowers of sulfur were melted under argon to provide small pieces free of fines. Apparatus. The decopperizing experiments were carried out in a 25-mm-OD by 375-mm-long Pyrex tube sealed at one end. The tube was mounted vertically in a resistance-heated. hinge-type tube furnace controlled to within ±lcC. Temperature measurement was accomplished by means of a standardized chromel-alumel thermocouple sealed into the base of a silica. paddle-type stirring rod. All decopperizing experiments were carried out under an argon atmosphere. Procedure. A Pb-Cu starting alloy containing 0.05 pet Cu was prepared under carbon and poured into cold tap water to produce shot. The ternary alloys were prepared by melting together 100 g of the starting alloy and a sufficient amount of the impurity element to yield the desired concentration. The resulting alloy was then homogenized in a Pyrex tube at 450C with continuous stirring. The furnace temperature was then lowered to the operating temperature of 330°C. When thermal equilibrium had been obtained at the operating temperature, individual additions of 0.2 pct (0.2 g) of solid sulfur were added to the melt and stirred in. Stirring was continued for a period of 3 min. discontinued for 5 min. and resumed for the remaining 2 min of a 10-min cycle. This cycle was repeated for as many sulfur additions as desired. When the decopperizing experiment had been completed the lead bullion was quenched and samples of the bullion and dross phases were taken for analysis. Results. The results obtained in the decopperizing

Jan 1, 1970

By R. J. Fruehan

The oxygen activity and concentration were measured in Fe-Cr-0 melts in equilibrium with an oxide phase at 1600°C (2912°F). The activity was determined by ,use of the following solid oxide -electrolyte galvanic cell CY-Cr8,(s) I ZrOz(CaO) I Fe-CY-G(saturated)(l) The oxygen concentration decreases with increasing Cr concentration to about 270 ppm 0 at about 7pct CY and then increases gradually. The activity coefficient of oxygen (fo) decreases with increasing Cr. In melts containing up to about 20 pct Cr, log f is approximately a linear function of wt pct Cr with a slope (e q 2) of —0.037. The activity of chromium was calculated and found to exhibit a small negative deviation from Raoult's law. From the activity and solubility data for low chromium melts, the free energy of formation of chromite, FeCr204, was found to be -79.8kcal per mole where pure liquid chromium and oxygen at I wt pct in Fe are the standard states. ThE effect of chromium on the chemical behavior of dissolved oxygen in liquid iron is of great importance in controlling the deoxidation of steels containing a significant amount of chromium. Chen and chipman' equilibrated Fe-Cr melts in the presence and absence of slag with hydrogen-water vapor mixtures. They concluded that at 1595°C chromite was the oxide phase in equilibrium with Fe-Cr alloys containing less than 5.5 pct Cr while at higher chromium concentration Cr,O, was the stable phase. In the composition range 0 to 10 pct Cr they found that the interaction coefficient, was equal to -0.041. Turk-dogan,' Schenck and Steinmetz,, and pargeter4 measured egr) in a similar manner and found the value to be -0.064,-0.04, and -0.052, respectively. McLean and Be11 evaluated egr) from their data on the equilibrium of Fe-Cr-Al-0 alloys with H2/H20 mixtures and found it to be -0.058. However, McLean and Bell's value should only be considered an estimate because the effect of aluminum on the activity coefficient of oxygen is about a hundred times greater than that of chromium. Consequently, an error in the value of egl) used, which at the present time is not well-known, or an error in aluminum analysis, which is present in very small quantities, will result in a significant error in egr). Fischer et a1.6 determined the interaction coefficient (eEr) in Fe-Cr-0 melts not in equilibrium with an oxide phase and containing less than 18 wt pct Cr at 1600°C electrochemically. They determined a value of -0.031 for egr). Hilty et aL7 measured the oxygen content of Fe-Cr melts in equilibrium with an oxide phase containing up to 50 pct Cr. They found that the solubility of oxygen decreased as the chromium content increased to about 6 pct Cr and then increased gradually. They concluded that the equilibrium oxide phase was chromite below 3 pct Cr, distorted spinel from 3 to 9 pct Cr, and Cr,04 above 9 pct Cr. Adachi and lwamotoa also investigated this system, but did not find Cr30,. They X-rayed the equilibrium oxide phases and did not find the presence of Cr,O,. They also X-rayed the oxide phase extracted from a 65 pct Cr melt which was heat treated and did not find metallic chromium as would be expected if Cr3O4 were the equilibrium oxide phase as indicated by the reaction : 3Cr3O4 — 4Cr2O:, + Cr [lj It was the purpose of the present investigation to determine the effect of chromium on the activity coefficient of oxygen in Fe-Cr melts by measuring the activity and solubility of oxygen equilibrated with an oxide phase in the composition range 0.18 to 50.5 wt pct Cr at 1600°C (2912°F). The activity of oxygen in the melts was determined by use of the following galvanic cell: The relationship between the partial pressure of oxygen in equilibrium with the melt and the reversible electromotive force of the cell (E) is where 11 = 4, F is the Faraday constant, pb, is the oxygen pressure in equilibrium with the meit and is the oxygen pressure in equilibrium with Cr203 as determined from the free energy data compiled by Elliott et al? The oxide phase in equilibrium with pure chromium was assumed to be Cr If Cr30, were the equilibrium phase the activities derived would be approximately the same, since the best estimated free energy of formation of Cr,O,, if it does exist, is approximately % the free energy of formation of The activity of chromium in Fe-Cr alloys at 1600° C was also determined from the measured electromotive force. The activity of chromium (aCr) is related to the electromotive force as follows: , The oxide phase in equilibrium with pure chromium and Fe-Cr melts from 10 to 52 pct is assumed to be Cr203 so that n equals three. If future work proves the existence of Crs04 in equilibrium with Fe-Cr melts and pure chromium, the experimental results can be reevaluated using a value of $ for n in Eq. 141. A value of ^ for n will make the activities about 10 pct higher. In order for Eqs. 131 and [4J to be valid the electrolyte, ZrOa(CaO), must exhibit predominantly ionic conduction at the temperature and oxygen partial pressure of its use. Previous work1' has demonstrated that ZrOz(Ca0) is predonlinantly an ionic conductor

Jan 1, 1970