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By Leonard Waldo

(New York Meeting, February, 1911.) THE recent and rapid development of the physics of engineering materials at temperatures as low as that of liquid air and as high is that of the electric are, has drawn renewed attention to the absence of tables, properly printed and spaced, for the convenient and accurate translation of temperature from centigrade to Fahrenheit scales and vice versa. It is to be noted that the Fahrenheit scale is the almost universal usage in foundries and shops in the United States, though the laboratories of the same works employ the centigrade notation. The growing use of the electric furnace in Germany and France calls for much American citation all in centigrade high temperatures, and while the arithmetical calculation is simple, it becomes burdensome when often repeated. I have been surprised at the numerous reprints of Table I. from centigrade to Fahrenheit degrees, first privately printed for personal use, which have been made by works, blue-prints, test-books, and technical journals, and I hope that Table II., from Fahrenheit to centigrade degrees, will be equally useful.

Jan 4, 1913

By E. C. Simmons

Uranium is an incompatible element with respect to the major rock-forming minerals crystallizing from granitic magma, entering instead trace minerals such as zircon. The relationship between the saturation limit (SL) for such a mineral and the bulk distribution coefficient (Do) for U is central to understanding the distribution of U and its availability to late-stage fluids that can form ore deposits directly, or labile U that can be remobilized later. Low SL values imply early crystallization of zircon, but in very small proportions, minimizing Do and maximizing the degree of enrichment of U in late-stage fluids. Thus, granitic rocks with low Zr contents (due to a low saturation limit for zircon) are most likely to evolve U-enriched differentiates; this will be reflected in a high U content of the zircons (but not necessarily high U abundances in whole-rocks). Thus, the ratio of the U content of zircon to the Zr content of the corresponding whole-rock is potentially a very useful parameter in identifying granitic rocks most likely to have U-enriched solutions associated with them. The granitic rocks associated with the U deposits of the Midnite mine area, Washington, have geochemical characteristics that fit the model presented very well. The rocks are very low in Zr (100 ppm) and contain zircons with extremely high U contents (3,000-4,000 ppm).

Jan 1, 1984

By G. W. Hodges

The Basic Oxygen Process shop at Gary Works is a three vessel shop tapping 220 ton heats. The larger portion of the heats are teemed into ingot molds with the remaining heats being continuously cast in a single strand continuous slab caster. Ingot production includes a wide range of carbon, alloy, and high-strength steels in many ingot sizes for bar, structural, plate and sheet and tin products. Individual ingot weights vary with the number of ingots per heat ranging from a high of 48 to a low of five. Caster production is primarily Riband, a proprietary low carbon grade for sheet and tin applications developed by United States Steel for continuous casting; some Riband steel is vacuum degassed prior to casting. Maintaining a satisfactory level of ladle performance on both ingot and caster heats with a high production rate and widely varied product mix is a demanding and exacting job requiring the best of equipment, materials, and, most importantly, personnel. The improving trend in ladle performance in the No. 1 BOP shop at Gary is due to a combination of factors, which will be described in the following presentation.

Jan 1, 1972

By George M. Rigg, Samuel M. Cassidy

During 1937 a program was begun to mechanize and modernize the then 28-year old Isabella mine of the Weirton Coal Co., which is on the Monongahela River, in Fayette County, Pennsylvania, at one edge of what is generally known as the Coke Region. Weirton Coal Co. is a subsidiary of the National Steel Corporation, and produces metallurgical grade coking coal for the Weirton Steel Co., Weirton, W. Va. Improvements subsequently made included a cleaning plant for washing the entire mine output, shovel-action track-mounted machines for mechanically loading all the coal, universal-type track-mounted cutting and shearing machines, post drills, 8-wheel mine cars of 10 tons capacity, cable-reel gathering locomotives and other auxiliary equipment. This paper presents the factors, reasons and results of decided changes from the mining system generally prevailing in the region, as well as abandonment of selective mining practices in favor of complete seam extraction. Coal-seam Conditions Fig. 1 illustrates the Pittsburgh coal seam on the property. Cover over the seam averages 450 ft., and 675 ft. is the maxi- mum. Main roof varies from very weak to medium strong; usually it disintegrates rapidly on exposure to air. The "wild" coal makes a fairly strong immediate roof if supported by crossbars and if unbroken affords a seal to the main roof. The draw slate is very weak and treacherous. The floor is characterized by numerous irregular bottom rolls, or "horsebacks," protruding from a few inches up to 3 ft. into the coal. Some are soft, but many are hard and flintlike. Although the bottom slate usually is hard, the underlying fire clay causes it to buckle and heave readily with any moderate increase in roof pressure or where damp. As a whole, the bottom is weaker than the main roof. The coal is characterized by numerous closely jointed face and butt cleats and a woody, springy nature when shot, both having a decided influence on face practices. As shown in Fig. I, at both the top and bottom of the main coal seam is a layer of coal of higher ash and sulphur content than the body of coal in the middle. Factors That Influence the Mining System Equipment was bought and organization for mechanical loading was made on the basis of working each mechanical unit as near its full capacity as possible, to lessen investment cost and obtain best operating efficiency. This led to combination double and triple-shift operation at the start, and, very shortly, to all sections being triple shifted.

Jan 1, 1947

By Samuel M. Cassidy, George M. Rigg

During 1937 a program was begun to mechanize and modernize the then 28-year old Isabella mine of the Weirton Coal Co., which is on the Monongahela River, in Fayette County, Pennsylvania, at one edge of what is generally known as the Coke Region. Weirton Coal Co. is a subsidiary of the National Steel Corporation, and produces metallurgical grade coking coal for the Weirton Steel Co., Weirton, W. Va. Improvements subsequently made included a cleaning plant for washing the entire mine output, shovel-action track-mounted machines for mechanically loading all the coal, universal-type track-mounted cutting and shearing machines, post drills, 8-wheel mine cars of 10 tons capacity, cable-reel gathering locomotives and other auxiliary equipment. This paper presents the factors, reasons and results of decided changes from the mining system generally prevailing in the region, as well as abandonment of selective mining practices in favor of complete seam extraction. Coal-seam Conditions Fig. 1 illustrates the Pittsburgh coal seam on the property. Cover over the seam averages 450 ft., and 675 ft. is the maxi- mum. Main roof varies from very weak to medium strong; usually it disintegrates rapidly on exposure to air. The "wild" coal makes a fairly strong immediate roof if supported by crossbars and if unbroken affords a seal to the main roof. The draw slate is very weak and treacherous. The floor is characterized by numerous irregular bottom rolls, or "horsebacks," protruding from a few inches up to 3 ft. into the coal. Some are soft, but many are hard and flintlike. Although the bottom slate usually is hard, the underlying fire clay causes it to buckle and heave readily with any moderate increase in roof pressure or where damp. As a whole, the bottom is weaker than the main roof. The coal is characterized by numerous closely jointed face and butt cleats and a woody, springy nature when shot, both having a decided influence on face practices. As shown in Fig. I, at both the top and bottom of the main coal seam is a layer of coal of higher ash and sulphur content than the body of coal in the middle. Factors That Influence the Mining System Equipment was bought and organization for mechanical loading was made on the basis of working each mechanical unit as near its full capacity as possible, to lessen investment cost and obtain best operating efficiency. This led to combination double and triple-shift operation at the start, and, very shortly, to all sections being triple shifted.

Jan 1, 1947

By W. P. Lass

Discussion of the paper of W. P. LASS, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 103, July, 1915, pp. 1443 to 1447. ROBERT M. KEENEY, Somersville, Conn. (communication to the Secretary *).-There is not only a possibility of improvement in present methods of treatment of the byproducts of refining in the cyanide plant by the use of the electric furnace, but also in melting and refining of gold precipitate. This interesting paper by Mr. Lass shows an electric furnace in successful operation in a large plant for the treatment of by-products. Electric melting of cyanide precipitate is a cheaper form of treatment in many cases than any of the combustion methods now used because of the high cost of oil, coke or coal in many camps, while on the other hand electric power may be had cheaply, especially in a place where there is possibility of development of high-head hydro-electric plants for power purposes. Also, if the oil-fired tilting furnace is used for direct melting of the precipitate, as is the case at many small mills, a great saving in cost is made by the use of the electric furnace because of the high crucible cost in melting with the tilting furnace. A study of this paper indicates the cost of the operation approximately. Consider all the fluxes to be turned in as byproducts and coke at $18 per ton.

Jan 12, 1915

By E. N. Mazza, H. S. Kalish

The effect of sintering types 302, 3028, and 430 stainless steel powder compacts in hydrogen and dissociated ammonia was investigated. It was found that sintering in dissociated ammonia resulted in as much as 0.5 wt pct increase in the nitrogen content of stainless steel even though the dissociation of the gas was complete. Sintering in hydrogen, on the other hand, reduced the nitrogen content of the stainless steel to less than 0.01 wt pct. In the case of the 302-type stainless steel, the low nitrogen content resulted in a material that was largely ferritic, whereas the high nitrogen content rendered the material fully austenitic. Sintering in dissociated ammonia resulted in lower density, generally lower tensile strength, less ductility, and higher hardness than sintering under equivalent conditions in hydrogen. The reduction of oxides on both stainless steel and iron particles was found to be effected by hydrogen partial pressure in the sintering atmosphere. Compacting pressure was found also to effect oxide reduction during sintering. DISSOCIATED ammonia often is used as a substitute'.' for hydrogen in sintering and in annealing, since economic advantages sometimes can be obtained by such a substitution. In addition, anhydrous ammonia contains very little impurity. Thus, dissociated ammonia gas is very dry whereas tank hydrogen often must be freed of oxygen and water vapor prior to use in many applications. The sintering of stainless steel powder compacts as well as bright annealing is well recognized as requiring a hydrogen atmosphere and for the foregoing reasons dissociated ammonia is frequently substituted. It has generally been overlooked, however, that the nitrogen in dissociated ammonia might have an important effect on the sintering process and on the properties of stainless steel compacts. Considered an inert gas in many applications, nitrogen, on the other hand, is very reactive with cer- tain metals. Dissociated ammonia could not be used for hydriding zirconium or titanium. Nitrogen reacts with columbium, tantalum, chromium, uranium, thorium, and many other active metals. Iron and iron-base alloys are, for the most part, inert in nitrogen but there are many borderline cases. It has been reported that stainless steel stabilized with columbium or titanium should not be sintered in dissociated ammonia.3 olybdenum has been reported as reacting with dissociated ammonia to a minor extent.' Although most of the reactions with iron-base alloys are attributed to the action of un-dissociated ammonia and the action of nascent nitrogen, Uhlig4 showed how readily pure molecular nitrogen reacts with and diffuses into 18-8 stainless steel at 1150°C. He also pointed out how readily nitrogen diffuses out of 18-8 stainless steel when heated in pure dry hydrogen, and these thorough investigations on the subject show that commercial stainless steels are nitrogen-bearing, since they are melted in air. The effects of nitrogen in stainless steel, particularly the 18-8 Cr-Ni type, previously have received considerable attention." In 1926, it was pointed out

Jan 1, 1956

By Edward K. Landis

Our Transactions contain so many suggestions of apparently trivial, yet really important, contrivances for the saving of time and

Jan 1, 1893

By R. S. Shoemaker, D. L. Harris

Past investigations into the possibility of concentrating the low-grade iron ores of the Gogebic Range in Wisconsin have been hampered by the complex association of the constituent minerals. In part the problem arises from the fact that the iron occurs essentially as two minerals, hematite and goethite, having nearly the same chemical composition but exhibiting different physical properties. Individual grains of these minerals are usually so small that the ore must be ground to a size finer than 325 mesh if substantial liberation of the minerals is to be secured. Appraisal of beneficiation tests on this iron ore requires, therefore, some method of determining quantitatively the contents of constituent minerals in the various products of the beneficiation. Because of the chemical similarity of the two iron minerals, chemical analyses do not provide a means of differentiation. Although the minerals are different physically, they are both opaque and friable, and as the ore must be ground to a very fine size for liberation to be secured, quantitative microscopic methods of analysis are extremely difficult at best. In an effort to overcome these analytical problems, a quantitative X-ray diffraction analysis method has been developed at the University of Wisconsin for the research program on iron ore beneficiation.

Jan 5, 1955

By Edgar G. Tuttle

The accompanying figures show a jig arranged for separating the middle product or middlings obtained in the concentration of certain ores, minerals, coal, etc. In the preparation for sizing, prior to jigging, of ore-bearing minerals, coal, etc., with their impurities, it is generally desirable to avoid reducing them to unnecessarily small sizes. Where the impurities adhere to the mineral particles or are disseminated through its mass, it is generally necessary to crush to such a fineness as will unlock the minerals from the gangue. If a considerable proportion of the material consists of mixtures of the minerals and gangue, each in large size, and a lesser proportion consists of a mixture of the two, in smaller sizes of various dimensions, it is not always desirable to reduce the whole to such size as would be required to liberate completely the pieces of ore and gangue in the finest mixtures. In such a case it is preferable to reduce all the material to such an

Jan 1, 1897

By E. J. Nielsen, P. R. Strutt

A study has been made of the progressive changes in the distribution of etch-pit structures occurring during high-temperature creep in copper + 7 wt pct Al single crystals oriented with a [113] tensile axis. The two equally stressed glide systems with the highest Schmid factor would be expected to form subboundaries of the type predicted by Kear.2 The alignments of etch-pits on sections parallel to different (111} planes consistent with these types of boundaries were not observed. However, they were consistent with planar subboundaries (on a macroscopic scale). From an analysis of Amelinckx1 it may be shown that stable cross-grid dislocation boundaries may form in the primary slip planes. These boundaries form when dislocations with a Burgers vector not in the slip plane move into the plane by combination of climb and glide. THE geometry of subboundaries formed by the interaction of dislocations of two glide systems has been analyzed by Amelinckx,1 and the particular types produced by deforming fee crystals are predicted by ear.' In this paper types of boundaries which may be formed when climb as well as glide occur are discussed as this is relevant in high-temperature creep. It is assumed in the present investigation that the etch-pits observed in Cu + 7 wt pct A1 on surfaces parallel to {111} planes delineate the sites of dislocations. Although there is no direct evidence for this previous work on a-Cu/Al single crystals by Mitchell, Chevrier, Hockey, and Mon-aghan,3 would show this assumption to be reasonable. The alignments of etch-pits which form during creep are studied on sections parallel to each {111) plane. It is then deduced that these alignments are consistent with a specific type of planar subboundary. The Cu + 7 wt pct A1 single crystals had a [113] tensile axis and Fig. 1(a) shows schematically the relation of the slip planes and slip directions (as represented by tetrahedron ABCD) with reference to the tensile axis. The two equally stressed glide systems with the maximum Schmid factor namely ß-AD and (a-BD, from the analysis of Kear,2 would be expected to form the boundaries shown in Fig. l(a) and (b), also Fig. 5(a) and (b). EXPERIMENTAL PROCEDURE The a-Cu/Al single crystals were grown and annealed in a "gettered" argon atmosphere. Chemical analysis showed the aluminum content to be uniform in each crystal and the difference between crystals was maintained to an accuracy of ± 0.25 wt pct. The initial dislocation density and mean subgrain diameter after annealing was -106 cm-2 and 250 µ, respectively. Surfaces parallel to (111) planes were produced by specially developed electrolytic machining processes. The {111} faces were next electropolished for 5 min in a solution consisting of 25 g chromium trioxide, 113 ml glacial acetic acid and 40 ml water; the applied potential was 8 v. Dislocation etch-pits were revealed using l an etchant described by 1 ml bromine, 45 ml HCl, and - 250 ml water. RESULTS In crystals strained into secondary creep at higher stresses (443 and 750 g - mm-2 at 650° C aligned rows of etch-pits parallel to slip plane traces were evident in sections parallel to the (1111, (ill), and (111) planes, see Fig. 3. As well as the longitudinal alignments in Fig. 3, well formed randomly oriented arrays indicative of an equiaxed subgrain structure are evident. At the lower stresses (100 to 230 g . mm-2) only an equiaxed structure formed during creep. The sections in Fig. 3 are from a crystal crept for 70 hr at 650°C with a CRSS of 443 g.mm-2. Two identically oriented crystals were also deformed at the same temperature and stress for 5 min and 4 hr. In the crystal crept for 5 min, the etch-pits were randomly distributed with no tendency for directional alignment, see Fig. 2(a). As shown in Fig. 2(b) aligned arrays were evident after 4 hr creep but they were not nearly so well defined as in Fig. 3. The alignments (parallel to the arrows) in Fig. 3 are consistent with the existence of boundaries in the two main slip planes a and ß. The way in which this is deduced is seen by reference to Fig. l(c), where the existence of boundaries in the a and ß planes is verified by sectioning parallel to a,ß, and d. The (111) and ß(111) planes intersect the d(111) plane along BC [101 ] and AT [011] and alignments parallel to [101] and [011] are clearly evident in Fig. 3(c) in a section parallel to the d(111) plane. Similarly the a, and ß planes in Fig. l(a) intersect each other along DC [110] and hence there will be an alignment parallel to [110 ] in sections parallel to the a-plane and the ß-plane; this is evident in Fig. 3(a) and Fig. 3(b). It is interesting to note that alignments of etch-pits consistent with the boundaries predicted by Kear2 were not observed; see Figs. l(a) and l(b). The geometry of boundaries in {111} planes as shown in Fig. l(c) is discussed later. In Fig. 4(a) the individual etch-pits are resolved and the alignments are exactly parallel to the slip trace direction [101]. However, in some areas alignments deviate away from the slip trace direction by as much as 10 to 15 deg, this is evident in Fig. 4(b), and in Fig.

Jan 1, 1969

By J. W. Rutter, K. T. Aust

In previous studies of grain boundary migration in zone-refined lead, the authors used bicrystal specimens consisting of a striated crystal which was grown from the melt, and an adjacent striation-free crystal, introduced by artificial nucleation and growth.1 While this method permits the study of the motion of individual grain boundaries, it does not provide control of the relative orientations of the grains. The present note will describe a technique for controlling the orientations of the two crystals in this type of specimen. The technique consists essentially of placing a striated crystal and a striation-free crystal of controlled orientations end-to-end in a graphite trough, then melting a short zone at the junction of the two crystals and allowing it to freeze to form the desired grain boundary. The apparatus used to carry out this process is illustrated in Fig. 1. It consists of a trough milled from high-purity graphite,with grooves in the underside for the placement of thermocouples. The graphite piece fans out on one end at the level of the bottom of the trough; the sides of the trough are completed in this region by the attachment of a mating plate with a slot cut at any desired angle to permit reorientation of the crystal placed at this end of the assembly. The joint between the crystals is made at or near the point where the slotted plate joins the rest of the trough. The thermocouple slots are deepened in this region so that the thermocouples are separated from the melt by only 1/32 in. of graphite. An induction heater, with suitable temperature control, is used to obtain the molten zone. The two single crystals used are first chemically polished in a solution consisting of eight parts glacial acetic acid and two parts 30 pct hydrogen peroxide. They are then placed in the trough with the ends to be joined at the position of the thermocouples. Next, cooling is applied to the two crystals by means of air

Jan 1, 1962

By Joseph W. Leonard

Evidence is presented to show that certain coals can be super-cleaned, using present coal preparation processes, to reduce sulfur below levels that are commonly believed to be possible. The evidence points to the need to develop continuous sorting methods by which coal coming from a mine can be segregated so that different raw coal types can be processed separately to produce a super-clean coal in addition to coals cleaned to more common levels of sulfur. Evidence is presented and techniques discussed that may be applicable for making the method feasible.

Jan 1, 1976

SINCE I promised you above when speaking of the melting of metals to teach you to make small crucibles and shells for melting, I do not wish to fail in my promise. For, in truth, since they are instruments that are much used for this procedure, they increase the work if they are not good, and often cause great extra expense as well as necessitating repetition of the work. If they are good they save everything. Therefore, if you have to make them, do it so that they, are greatly aided by art. It is first necessary to have the clay of a good nature, that is, resistant to the force of the fire by its own natural virtue, either when it is lean or when its viscousness is mixed with much talc, and whether it is yellow or white. This should be well freed from small stones and beaten well with an iron, and then thoroughly mixed by hand. With this should be mixed an eighth part of finely ground and sifted iron scale,* and also some [145] young ram's-horn ashes. These things should be well mixed together by hand and by beating them. If this clay should not be strong enough by itself, it is mixed with another lean clay, with crushed peperino, flintstone, or some other stone that in your judgment seems to be arid and resistant. Crucibles are worked on a low potter's wheel turned by hand, or on a high one turned by foot, just as plates are made. Both large and small ones are made. Most of them are given a triangular shape at the mouth, and the shells have a kind of spout for ease in pouring out the metal. This done they are well dried, and baked in furnaces like pots or other vessels. At the end, when they have been thus made they are used for melts.

Jan 1, 1942

By D. J. Carney, J. Chipman, N. J. Grant

G. A. Moore—The tin-fusion method has been a very favorable possibility for many years. The authors apparently have settled the question that delayed the method for a long time by showing that no hydrogen is absorbed in the tin. This, of course, is very important. I want to make a few remarks concerning the absolute accuracy of analysis, which must be the final basis for deciding among the various methods. From the figures in the paper, there seems to be some remaining slight discrepancy on the actual amount of hydrogen present in various samples which may be presumed essentially identical. (This is of the order of the precision of individual analyses but appears in averaged results.) From the analyst's viewpoint, the tally of hydrogen content can be regarded as occurring in three portions. First is a large portion which comes off easily and automatically during sample storage and later on heating in the apparatus. This is fairly easily analyzed. Second is an item which may be either positive or negative in the tally sheet. In warm or hot evolution, this is a portion which, in practice, can never be re-

Jan 1, 1951

By Tuncel M. Yegulalp, Peter G. Zambas

In planning an underground room-and-pillar mine, the selection of the shaft or portal location and the orientation of the main haulage arteries is of paramount importance, particularly in view of the high dependence of the cost of truck haulage on the proper definition of these parameters. In an effort to facilitate this selection a computer program was written which, by relating the truck characteristics to the areal configuration of the property or ore body, derives the volume-weighted total fuel and time requirements for hauling ore from every panel within the property to a specified portal or shaft location through a predetermined gridwork of haulage drifts. By varying the size and orientation of the gridwork and the location of the portal or shaft access, an infinite number of configurations can be investigated. The results of this analysis can be plotted to indicate the optimum conditions.

Jan 1, 1974

By R. Maddi, I. R. Kramer

C. S. Roberts (Dow Chemical Co., Midland, Mich.)— In this study we have seen another example of how modern electronic instrumentation can be of great value to metallurgical research. The authors have shown much ingenuity in their experimental work. However, I wish to point out that anelasticity theory tells us that we must be cautious when we use pulse methods for measurements which are to be correlated with knowledge of static stress-strain behavior. The basic stress calibrations used by the authors depend on the use of static moduli combined with the pulsed strains. No recognition of a possible modulus defect has been indicated. The general agreement of critical resolved shear stresses may indicate that a

Jan 1, 1953

By William Y. Mo

The OPEC oil embargo and the subsequent higher prices for oil have drawn public attention to the critical problems associated with security of supply of oil and other key industrial materials, especially nonfuel minerals. This concern has stimulated the interest of decisionmakers in analyzing policy options to cope with the emergency situations resulting from a sudden foreign- induced supply interruption or a cartel price increase. Several policy options are available to counteract foreign-initiated embargoes or cartel price actions. The type of response will differ depending on the commodity action intiated. A mathematical model that measures the impact of foreign-induced commodity actions on the domestic economy is formulated. The paper also presents a computer method that can be used to determine the optimum policy response to counteract such actions.

Jan 1, 1977

By Henry A. Stiff, Lawrence E. Davis

A graphic method was developed which can be used to predict the tendency of oil field waters to precipitate calcium Sulfate under a variety of conditions. Application of this method is made to the prediction of sulfate scale formation in heater treaters. boilers. oil wells. cooling systems and water injection wells. INTRODUCTION A solution may be said to be in equilibrium with respect to a given salt when the concentration of that silt in equal to its solubility. If for any reason the concentration of the salt is increased or its solubility decreased. the equilibrium is upset and precipitation of the salt takes place. Thus, if the concentration of a salt in a particular solution is known and its solubility can be calculated for a given set of conditions, the tendency of this salt to form a precipitate under these conditions can be predicted. Based on these principles a method has been developed for determining the tendency of oil field waters to form calcium Sulfate precipitates under various conditions. THE SOLUBILITY DIAGRAM Calcium sulfate precipitation most frequently occurs when two waters are mixed: one containing calcium ions. and the other sulfate ions. As one of these waters is added to the other a point may be reached where the concentration of calcium Sulfate is greater than its solubility. thus causing the formation of a precipitate. The solubility diagram is a graphic device for determining the location of such points, thereby making possible a prediction of the tendency of such a system to deposit sulfate scale. A similar diagram can be used to solve many other problems involving the precipitation of calcium sulfate. Fig. 1 shows a solubility diagram representing the mixing of two waters. Water "A" contains a high concentration of odium, magnesium, and sulfate ions together with a small amount of calcium. Water "B" contains a high concentration of calcium ions together with sodium, magnesium and a small amount of sulfate ions. The percentage mixture of these waters is plotted along the abscissa of a system of rectangular coordi-

Jan 1, 1952

By A. S. Venkatadri, H. B. Bell

The equilibrium sulfur distribution between molten iron and Ca0-Mg0-Al203 slags containing iron oxide was investigated at 1550°C. The results were used to derive the iron oxide activities at low iron oxide concentrations in the slag by combining the sulfide capacity data obtained from gas-slag work with the free energies of both the sulfur solution in iron and the iron oxide formation in slag. The derived ferrous oxide activities were compared with values based on Tem-kin's kin's and Flood's ionic models. One difficulty in using these models is that the nature of the aluminate ion in slag is uncertain. Nevertheless, such indirect methods, in particular, those described in the present paper, are of value because of the difficulty of measuring small amounts of oxygen in liquid iron in equilibrium with slag. It is shown that these methods confirm the consistency of thermodynamics data on liquid iron and slags. It is well established that decreasing the iron oxide activity in the slag increases the desulfurization of molten iron at constant slag basicity. This effect is most pronounced at the very low iron oxide activities, characteristic of blast furnace slags. Yet a precise quantitative determination of the significance of low iron oxide contents in slag in blast furnace desulfuri-zation is not possible for the following reasons: a) difficulty of separation of iron "shots" from the slag, and b) errors in chemical analysis of small amounts of iron oxide in slags. In view of these obstacles, one must resort to indirect methods of calculating iron oxide activities. EXPERIMENTAL TECHNIQUE The apparatus for providing the sulfur equilibrium data has been described previously1 and was similar to that used by ell' in connection with the study of slag-metal manganese equilibrium. The procedure consisted of: a) melting about 50 g of Armco iron in a magnesia crucible in a platinum furnace, b) adding a mixture of about 15 g of lime-alumina slag and varying amounts of Fe2O3 and CaS, and c) maintaining the temperature at 1550°C for more than an hour in an atmosphere of argon to enable the sulfur equilibrium to be attained. Several melts were made using lime-alumina slags with basic composition 55, 50, and 45 pct lime. During the experiment the temperature was controlled manually using a Pt/10 pet Rh-Pt thermocouple. After the experiment, the Power was shut off and the flow rate of argon was increased to freeze the melt as quickly as possible. The analysis of sulfur in the metal was carried out by the oxygen combustion method3 using uniform drillings from the top and bottom of the metal button. After crushing and grinding and removal of any iron particles with the aid of a hand magnet, the slag was analyzed for sulfur by the CO2 combustion method.4 The E.D.T.A. method was employed for the analysis of lime5,6 and magnesia,= the ceric sulfate method7 for the analysis of slag iron oxide, and the perchloric acid dehydration method5 for the analysis of silica. The remaining amount was taken to be Al2O3 precipitation with ammonium hydroxide in several preliminary melts had confirmed the propriety of using this simple procedure. RESULTS The activity of iron oxide in binary, ternary, and more complex slags has been the object of numerous investigations, and the two experimental methods for its determination are: 1) Equilibrating the metal with the slag in question and measuring the oxygen content of the metal. The ferrous oxide activity is then given by aFeO L%OJSat where [%0]sat is the oxygen content of the metal in equilibrium with pure iron oxide slag. This method was used by Chipman et al.8,9 2) Equilibrating the slag in iron crucibles with known partial pressures of H2/H2O or CO/CO2 mix-tures.10-12 This method is limited to temperatures between 1265" and 1500°C. The very low oxygen content of the melts in this investigation made it impossible to derive the ferrous oxide activity by the first of these methods. Therefore, the iron oxide activities were computed by means of: Sulfide capacity data from the gas-slag work" Temkin's concept14 Flood's approach15 a FeO from Sulfide Capacity. The method of calculating the aFeO involves the sulfide capacity of the slag (c,), the sulfur distribution coefficient (Ls), the free energy of dissolution of sulfur in iron, and the free energy of formation of iron oxide in the slag. Bell and Kalyanram13 have investigated the sulfur absorption characteristics of lime-alumina slags containing magnesia by the Carter-Macfarlane method16 (based on comparing the sulfide capacity of the slag in question with that of a standard slag of unit lime activity) and have derived lime activity values. The relation between sulfide capacity and their lime activity a'CaO is given by: Cs= 3—: Xa'CaO at 1500°C

Jan 1, 1970