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By P. Datta, L. L. Handy

For a wetting phase displacing a nonwetting phase from a porous medium the distribution of the residual fluid may depend on displacement conditions. Although this subject has been debated in the literature, only a few experiments have been cited to support the various conclusions. Experimental results presented in this paper show that fluid distributions are dependent on imbibition pmcedures. Results agree qualitatively with predictions from the pore doublet model. If the rate of water imbibition is restricted, the nonwetting phase is trapped preferentially in .the larger pores as expected. But if the rate of water imbibition is unrestricted, trapping occurs somewhat more in the smaller pores. These conclusions were deduced primarily from relative permeability measurements. INTRODUCTION Relative permeabilities are known to depend on the saturation history of the porous medium. For either continuously increasing or continuously decreasing wetting phase saturations, however, they have normally been assumed to be single-valued functions of saturation. Severat investigators have compared relative permeabilities measured by different methods and have reported acceptable agreement.1-5 Studies of simple models of the displacement process suggest that the distribution of residual fluids can be influenced by the displacement method. If this is so, relative permeabilities also should depend on the method of displacement. These predictions have not been supported by experimental data. The object of this paper is to investigate experimentally some of the predictions of these model studies. The particular question of importance is whether steady-state and unsteady-state methods should be expected to give the same values of relative permeability. Much of the reported data showing agreement between steady-state and unsteady-state methods have been obtained on un consolidated sand. Johnson, Bossler and Naumann, however, compared steady-state and unsteady-state results for Weiler sandstone and found no significant differences.5 Levine made a detailed study of pressure and saturation distributions for a laboratory waterflood in a consolidated system but made no attempt to calculate performance from steady-state relative permeability data Bail and Marsden in a somewhat similar set of experiments did attempt a comparison of observations with predictions but the results were inconclusive.7 Excluding gravity, two forces affect the distribution of wetting and nonwetting phases during an unsteady-state, immiscible displacement: viscous and capillary forces. If relative permeabilities are indeed the same when measured by steady- or unsteady-state methods, the fluid distributions at the same fluid saturations must be similar for both methods. Furthermore, the implication is that the relation between capillary and viscous forces is the same for both methods insofar as the effect on microscopic fluid distributions is concerned. Unsteady-state displacements are normally run at high rates to maximize the ratio of the viscous to capillary forces. The objective is to reduce the effect of capillary forces on macroscopic fluid distributions. For floods in which the phase which wets the porous medium displaces the nonwetting phase, capillary forces compete with viscous forces in determining fluid distributions.8 The residual nonwetting phase is discontinuous. Competitive aspects of viscous and capillary forces and the resulting effect on water-oil distribution in porous media have been illustrated in an elementary way using a pore doublet model. This model and predictions from it have been discussed at considerable length by Rose and Witherspoon, Rose and Cleary and by Moore and Slobod.9-13 Rose and Witherspoon show that so long as water invades the model at a rate equal to or greater than the free imbibition rate, the water will move through the larger capillary of a doublet first and trap oil in the smaller capillary. On the other hand, if a negative pressure is applied to the water

Jan 1, 1967

By R. F. Mehl, W. Batz, C. Wells

Diffusion coefficient values for carbon in austenite covering a wide range of temperature and composition have been determined employing statistical methods. In addition, the relation between concentration and each of the following, D (diffusion coefficient), Q (activation heat of diffusion), and A (the constant in the diffusion equation), has been obtained. A study of the rates of diffusion of austenite was published in Metals Technology in 1940.' The present investigation is an extension of the earlier work, undertaken (1) to obtain values of the coefficient of diffusion, D, over a much wider range of carbon concentration, and (2) to provide data in all ranges of concentration and temperature in such abundance that statistical methods could be employed to evaluate the accuracy of the data with unusual precision. Composition of Materials: Composition of materials used in this research program are listed in table I. These materials, all forged to about 1 1/4 in. rounds, consist of a high-purity iron, Armco iron, a large number of laboratory-made plain carbon steels containing amounts of impurities normally expected in high-quality commercial steels, and three silicon steels. Since it was known at the time these steels were being made that impurities in the amounts present were unlikely to affect carbon diffusion rates' significantly, the effort made to obtain high-purity steels was not as persistent as it otherwise would have been. Procedure: In general, the procedure followed by Wells and Mehl and described' in detail in an earlier publication' is the one used by the present authors. However, certain modifications have been made which it is believed allow diffusion data to be interpreted more objectively and correctly. These are described completely under appropriate subheadings which follow. Experimental Procedure: Experimental procedure includes (1) the preparation of specimens by welding steels of different carbon contents, (2) the heating of these for certain times at selected temperatures in order to diffuse carbon along the specimens across the welded "interface," and (3) the determination of the carbon distribution across the diffusion zone. Preparation of Specimens: Prior to welding steel of one carbon content to iron or steel of another carbon content, surfaces to be welded are machined perpendicular to the longitudinal axis of cylinders which are about 3/4 in. in diam and 1 1/2 in. long. The prepared, flat, parallel surfaces are brought together and butt-welded electrically. Evidence of a good weld is given in fig. 1. Welding temperature

Jan 1, 1951

By R. G. Ward

The temperature gradient in the subhearth metal or "salamandern of the iron bhst furnace results in the establishment of gradients in the concentrations of silicon, manganese, carbon, and sulfur. The temperature and compositional variations observed in three blast furnaces are analyzed according to irreversible thermodynamics and the systems appear to be close to the steady state condition. Apparent heats of transport, Q, for silicon, manganese, carbon, and sulfur are found to be respectively -17.5, -5, -2.1, and+22k cal per g mol. In conclusion the significance of thermal diffusion in extraction metallurgy is briefly discussed. INCREASING interest has been shown in recent years in the application of irreversible thermodynamics to metallurgical problems. In particular studies have been made of the transport of matter in thermal gradients1-' and under chemical gradients imposed by a binary solvent However, no detailed example in extraction metallurgy has been reported although gradients are the essence of many extractive processes. The case of the distribution of elements in molten blast furnace iron under a thermal gradient is discussed here. DATA In blast furnace operation the hearth bottom is often extensively destroyed by molten metal, and the metal may penetrate perhaps 10 ft into the furnace foundations forming a "bear" or "salamander". Several hundred tons of molten metal may thus exist beneath the level of the conventional tap hole and remain relatively undisturbed for several years under a thermal gradient. This system is subject to little convective stirring because the temperature decreases from top to bottom, and mechanical stirring due to movements in the stack and to tapping operations is unlikely to penetrate far into the metal. The system may thus be regarded as static

Jan 1, 1963

By C. D. Rubert, W. J. Parton

Large quantities of fine anthracite with associated impurities are discharged with the waste water from the coal-cleaning plants in the Pennsylvania anthracite region. Furthermore, for many years this fine material has accumulated and formed silt banks. The difficulty of removing the impurities from the fine material and the lack of adequate markets are responsible for the waste of this material. In view of a larger demand for fine coal, mainly for pulverized fuel, the Lehigh Navigation Coal Co. Inc. decided to investigate the froth flotation process for recovery of fine coal from these waste solids. A test plant was constructed and operated for six months during 1942 in order to determine the practicability of recover ing coal from the waste water of a a plant (breaker) by froth cleaning and to obtain operating data for designing a commercial plant if the results were favorable. Preliminary Investigation Before the pilot plant was constructed information was obtained by field and small-scale laboratory tests to serve as a guide in the design and operation of the pilot plant. Size and ash analyses of a representative sample of the material discharged in the wash water from a cleaning plant are given in Table. The refuse content increases progressively as the size of the particles decreases The larger particles (+35 m.) are low in ash content and could be marketed without cleaning. Since these solids are discharged from the breakers with 90 to 95 per cent water by weight, the first step in the recovery of the coal was that of reducing the quantity of water so that water in excess will not have to be handled. Furthermore, it was found that the removal of most of the minus 200 mesh high-ash material was desirable to permit the most efficient flotation of the cod. Classification tests were run and showed that a hydroseparator overflow rate of 12 ft. per hour* was sufficient to elimi-,late much of the minus 200-mesh material while allowing the coarser material to settle and be thickened,

Jan 1, 1944

By C. D. Rubert, W. J. Parton

Large quantities of fine anthracite with associated impurities are discharged with the waste water from the coal-cleaning plants in the Pennsylvania anthracite region. Furthermore, for many years this fine material has accumulated and formed silt banks. The difficulty of removing the impurities from the fine material and the lack of adequate markets are responsible for the waste of this material. In view of a larger demand for fine coal, mainly for pulverized fuel, the Lehigh Navigation Coal Co. Inc. decided to investigate the froth flotation process for recovery of fine coal from these waste solids. A test plant was constructed and operated for six months during 1942 in order to determine the practicability of recover ing coal from the waste water of a a plant (breaker) by froth cleaning and to obtain operating data for designing a commercial plant if the results were favorable. Preliminary Investigation Before the pilot plant was constructed information was obtained by field and small-scale laboratory tests to serve as a guide in the design and operation of the pilot plant. Size and ash analyses of a representative sample of the material discharged in the wash water from a cleaning plant are given in Table. The refuse content increases progressively as the size of the particles decreases The larger particles (+35 m.) are low in ash content and could be marketed without cleaning. Since these solids are discharged from the breakers with 90 to 95 per cent water by weight, the first step in the recovery of the coal was that of reducing the quantity of water so that water in excess will not have to be handled. Furthermore, it was found that the removal of most of the minus 200 mesh high-ash material was desirable to permit the most efficient flotation of the cod. Classification tests were run and showed that a hydroseparator overflow rate of 12 ft. per hour* was sufficient to elimi-,late much of the minus 200-mesh material while allowing the coarser material to settle and be thickened,

Jan 1, 1944

ATHOUGH the open-hearth charge contributes CO, CO2, and water vapor to the combustion gases and absorbs oxygen from them, in the main the thermal effects in the melting charge and molten bath can be considered independently of those in fuel combustion, the latter being regarded simply as the source of any extra heat required to finish a heat of steel. First of all, it should be remembered that a large percentage of the heat supplied to the bath is furnished by oxidation of the various elements in the charge itself. If this charge consisted of 80 to 100 per cent of hot metal and the oxidation were obtained by blowing in air or oxygen, as is the case in the Bessemer converter, then the net heat absorption would be negative, that is, the bath would contribute part of the heat required to keep the melting chamber hot, in addition to that contained in the finished steel and slag. In actual open-hearth practices, probably the nearest approach to this is in the duplex furnace, charged with Bessemer-blown metal and some hot metal, where very little heat is required to complete the refining and nearly all the heat energy from fuel combustion is used to keep the roof and walls of the melting chamber up to around 2900 to 3000°F. (1600 to 1650°C.) so that the bath will not cool off during the refining. The other extreme is with all-cold charges containing around 80 per cent steel scrap and 20 per cent cast iron or cold pig iron, in which case a very large proportion of the heat in the bath at tap is supplied from the fuel combustion. THERMAL EFFECTS IN MELTTNG In the previous chapter it was pointed out that in a typical heat, the fuel furnishes about four million B.t.u. per ton of steel produced. The heat required for the metallurgical processes is not easily defined in useful manner (as is shown later), but it ranges downward from about one million B.t.u., depending not only on the charge but on the manner of calculation. In any event this requirement appears quite small in comparison with the heat furnished by the fuel and invites

Jan 1, 1944

By V. K. Karra, A. J. Magerowski

An overview of the scope of a computer program meant for aiding the design of crushing circuits is presented. Effect of circuit variables like the screen separation size and the crusher setting is illustrated. For a better understanding of the logic behind the circuit sizing, a detailed commentary in the case of a starting example is given.

Jan 1, 1982

By E. P. Pfleider, W. G. Pariseau

This paper reports the theoretical and experimental results of an analysis of ore pass drawdown as a problem in soil plasticity. The method of analysis developed appears to be a promising technique of investigating the mechanics of fragmented materials. A reconstructed plasticity theory brings experiment and theory into reasonable agreement, and hence may provide the foundation needed for rational ore pass design. The gravity-induced movement of broken rock through ore passes is an economical method of transporting fragmented materials through large vertical distances in underground mines, provided the ore pass is well designed. Unfortunately, the design procedures now followed do not very often result in ore passes that function properly. On the one hand, the huge accumulation of empirical data pertaining to the movement of materials in gravel bunkers, storage bins, deep grain silos and other structures that have features in common with ore passes remains uncorrelated. On the other hand, there is a dearth of experimental data substantiating theoretical models of material behavior. Consequently, reliable generalizations encompassing the broad spectrum of problems involved have not been forthcoming. AS an initial step towards improving the situation, a detailed case study of two-dimensional ore pass drawdown was made. The mechanics of the process were analyzed theoretically as a problem in soil plasticity and tested experimentally through observations of a laboratory ore pass model. THEORY Taylor1 defines a soil as a "mass commonly considered to consist of a network or skeleton of solid particles, enclosing voids of varying size." Broken rock in an ore pass is such a material. In plasticity theory this material is replaced by an idealized substance that deforms elastically up to some state of stress at which slip or yield occurs,2 For com-pressive states of stress, the Mohr-Coulomb criterion is a satisfactory yield condition. After the yield point is reached, the ideal soil deforms in accordance with the concept of plastic potential.4 Under plane strain conditions the governing equations separate into a system of stress equations and a system of velocity equations.' Only stress variables appear in the stress system. The velocity system, however, contains a stress variable. The two systems are, therefore, coupled. Both systems are hyperbolic, and each has two real, distinct families of characteristic curves that coincide according to the classical theory of ideal soil plasticity. The

Jan 1, 1969

By S. Grinsfelder

Although wildcatting was hampered by the general overproduction and low price of crude, several developments, worthy of note in the history of the petroleum industry in the Rocky Mountain region, were made in 1927. This district records production from six new fields, two of these having been heretofore productive of gas. Deeper pay horizons were found in two other oil fields. In order to facilitate transportation from fields, six new oil pipe lines were completed or in the course of construction at the end of the year, and one line is proposed for 1928. Four gas lines were completed, one was under construction, and one was proposed for 1928. The total production in 1927 in the Rocky Mountain district was 29,591,379 bbl.,' a decrease of 7,771,991 bbl., or 21 per cent., fro111 the previous year. This was occasioned by natural decline and the general curtailment of production and drilling. A review of the development by states follows. Colorado Production from horizons in the Morrison and Sundance at Craig and at Ilrs Dome, and the bringing in of the deepest producing well in the Rocky Mountain district on North McCalluin anticline (Waltlrn) in Jackson County are the outstanding developments for the year in Colorado. In March the Midwest Refining Co.'s Parkinson 21 SD, SW SE, Sec. 22 T p. 4 N R 92 W, Iles Domr, Moffat County Colorado, found gas in sands in the Morrison estimated at 15,000,000 cu. ft., and at 3242 ft. an oil sand was encountered in the Sundance. Initial production from this horizon was 2575 bbl. in this well. This structure previously was only productive of water in the sands of the Dakota group but has been producing shale oil from horizons in the Benton. The second well completed by the Midwest Refining Co., No. 18 SD in Sec. 23 was also productive of gas in the Morrison and made an initial of 300 bbl. from sands in the Sundance. By the end of the year three other wells wrrc nearing the completion stage but none of them indicate that they will be as big producers as the discovery. To date the productive area has

Jan 1, 1928

By Huntington Adams

The arrangement of a flow of cyanide-pulp through Pachuca tanks in agitation, so as to permit a continuous process, instead of alternate filling, agitation, and emptying, has been proposed by various writers within the last two years, and more particularly by A. T. Grothe, agent for the Brown patents on Pachuca tanks in Mexico. It was first put into practice, I believe, by M. H. Kuryla at the Esperanza mine in El Oro, Mexico. The starting of agitation in Pachuca tanks after filling may offer no serious difficulties with ores which do not settle rapidly in such tall tanks; and the adaptation of the tanks to continuous agitation under such conditions may give simply a somewhat more convenient method of treatment and greater agitation-capacity for a given number of tanks, because of the saving of time lost in filling and discharging. But in the treatment of pulp which tends to settle rapidly, as in the cyaniding of concentrates or of the whole pulp of ores containing heavy sulphides, the packing of the slime at the bottom may cause much trouble. The use of the radial air-pipe attachments near the top of the cone and of the air-valve outside of the air-lift tube at the bottom may obviate the difficulty to some extent; but the action of the radial air-pipes on the cone-sides is that of a sand-blast, and their continuous use cuts through the tanks. Moreover, even when these pipes are used, some pulps will pack tightly below them in the cones. Under such conditions the use of Pachuca tanks with intermittent filling and discharging becomes a troublesome process. Time is lost in starting agitation; large quantities of compressed air are wasted; pulp is blown over the tank-tops; and not infrequently it may be necessary to dig out the bottoms of tanks by hand. This trouble is the only important one occurring in the use of Pachuca tanks; and, since it is caused by intermittent filling, the arrangement of a continuous flow of pulp from tank to tank,

Jan 1, 1912

By G. S. Hume

IN. THE autumn of 1922, British Petroleums Ltd. found oil of 14° Baumé in a sand 17 ft. thick in its. No. 2 well at Wainwright, 120 miles southeast of Edmonton. This greatly encouraged drilling in the Wainwright-Irma area and this past summer several wells were started, three of which are now completed and the others still being drilled. Of the three completed, No. 4 British Petroleums contains oil; No. 3 British Petroleums gave a show of oil but so far has not given much hope, of becoming a commercial producer; and No. 1 Maple Leaf Co., as now finished, is a. gas well with a daily flow of gas of about 2,500,000 cu. ft. at a closed pressure of 700 lb. An oil sand is reported to have been encountered below the producing gas horizon in the Maple Leaf well but has not been tested. Operations on this well have been suspended for the winter. The Geological Survey of Canada this past summer undertook a geological investigation of this area with the object of defining the structures with which the oil and gas are associated. The structure underlying this portion of the plains was supposed to be a terrace with the western edge dipping into the Alberta syncline and with a monoclinal structure to the east. By accurate leveling on known geological horizons on this terrace, a number of gentle folds were located and -it is in these folds that the oil and gas are found. At the British Petroleums Nos. 2 and 4 oil wells, the western flank of the fold has a gentle dip of only a few feet to the mile to the southwest whereas the strata on the eastern flank dip to the northeast about 40 ft. in ½ mile, the strike of the fold being northwest and southeast. How far oil will be found down the gentle southwest dip is unknown but probably the productive part of the fold will not exceed 1 mile in width, and possibly less. No. 3 British Petroleums well is on the strike of the fold 1 mile southeast of the two oil wells. The sand that was productive in Nos. 2 and 4 wells was not present in this well or, if present, was very thin and unproductive. Two other sand horizons, however, were encountered. The upper of these

Jan 3, 1925

By H. W. Clark

Electricity must be safeguarded everywhere that it is used. The conditions that exist underground make the use of safeguards more essential there than almost anywhere else. Electric Shock Electric shock is the greatest danger in connection with the use of electricity in mines, because conditions existing underground are so favorable to its occurrence. Men are often obliged to work in more or less uncertain light near bare wires that are carrying dangerous potentials. The fact that the men are standing on the earth practically connects them to one terminal of the electric generator. The moat dangerous piece of electrical equipment underground is the trolley wire. It is necessarily bare and extends for long distances throughout a mine, often less than a man's height from the track rail. Sometimes the making up of trips of cars must be done near low-hanging trolley wires. All 'bare wires offer the same danger that troIley wires do, although not to the same extent. Apparatus that has accidentally come in contact with the ungrounded side of an electric circuit is almost as dangerous as the trolley wire. A severe and even fatal shock may be obtained by coming in contact with the frame of a motor or a switch box that has become charged with electricity, or "alive," as it is usually termed. It is also possible to obtain . shocks from the frames of locomotives and cars if track sanding, poor bonding or a similar cause has put a high resistance to earth in the path of the current. Fires Caused by Electricity The danger from fires caused by electricity arises principally from defective installation and careless upkeep or from injuries to equipment resulting from falls of roof or similar causes. Fires may be started by unrelieved short cifiuits, or grounds, by the blowing of open fuses, and by the overheating of resistances. Incandescent lamps can produce heat enough to ignite combustible materials if the dissipation of the heat from

Jan 1, 1915

By J. K. Stanley

IT has been known for many years that the magnetic properties of a ferromagnetic material are very sensitive to internal strain. Any structure-sensitive property such as ferromagnetism, which is a-function of the regularity of the atomic arrangement, and discontinuities such as grain boundaries must show deviations from an equilibrium state when the regularity of the lattice is disturbed. Experience has shown that such distortions have a marked effect on the magnetic properties of a ferromagnetic material. The purpose of this paper is to show the feasibility of using magnetic methods in detecting internal strains. More specifically, it will be shown how such properties as permeability, remanence, and coercive force change on cold- working of aluminum iron and how these magnetic properties change during the annealing below the recrystallization temperatures. This work was conducted for two reasons. One was the desire to see in what manner strains are relieved in aluminum iron at low temperatures-a subject of practical importance in soft magnetic materials-and the other was the feeling that a study of cold-working and strain relief might shed some light honour understanding of what takes place in the deformation of metals DEFINITION IN TERMS It is necessary to define the terminology used in this paper because magnetic nomenclature is usually unfamiliar to the metallurgist, and certain other terms, such as recovery, have been used ambiguously by metallurgists and others. Magnetic terms are best explained by reference to the common hysteresis loop of ferromagnetic materials (Fig. I). In Fig. I the coordinates are magnetic induction, B, (ordinate) and magnetizing force, H, (abscissa). The c.g.s. unit for the magnetic induction is the gauss, the number of flux lines per square centimeter, and the unit for the magnetizing force is the oersted, the number of lines of force per centimeter in air or vacuum. If one starts with a completely de- magnetized specimen and magnetizes it, a typical virgin magnetization curve beginning at the origin is obtained. This curve is also the locus of tips of a family of smaller hysteresis loops. From this curve it is to be noted that the induction is not proportional to the magnetizing force, and that it appears to approach a limiting induction called the saturation value, and does so for values of H of 1000 oersteds. The ratio of the magnetic induction (gauss) to the magnetizing force (oersteds) is called permeability, p. Thus µ = B/H and if the magnetizing force H (oersteds) is specified as 10 or IOO oersteds, the permeability is written as µ10 or µ100. This is the accepted notation, and will be used in this paper. The values of permeability for H = 10 or 100 are chosen as indices for

Jan 1, 1945

Jan 1, 1934

By T. M. Yegulalp

This article summarizes some of the results of the continuing research activity at the Henry Krumb Schools of Mines, Columbia University, directed towards a better understanding of the stochastic behavior of slurry flows in underground coal-slurry pipeline systems. Fundamental ideas supported by field observations are presented and a Semi-Markov model of the slurry flows is developed. As a result of this formulation, behavior of combined slurry flows from N independent coal faces can be expressed in analytical form. The contents of a slurry surge tank receiving slurry flows with certain stochastic characteristics is investigated in a function of discharge pump characteristics and time.

Jan 1, 1983

To control the slag in an iron blast furnace is to control the quality of the pig iron produced (and to a certain extent the tonnage), and to control the whole operation of the furnace itself, including a large part of the cost of production. The character of the slag is the determining factor in the character of the pig iron as to the controllable limits of sulfur, silicon, and, to a certain extent, the manganese; it has an influence on the proportions of combined and graphitic carbons.

Jan 1, 1935

To control the slag in an iron blast furnace is to control the quality of the pig iron produced (and to a certain extent the tonnage), and to control the whole operation of the furnace itself, including a large part of the cost of production. The character of the slag is the determining factor in the character of the pig iron as to the controllable limits of sulfur, silicon, and, to a certain extent, the manganese; it has an influence on the proportions of combined and graphitic carbons.

Jan 1, 1935

By B. M. Larsen, T. E. Brower

THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slag-metal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the con- tinual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process. In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium. On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. Probable Chemistry of Desulphurization Since there is little evidence that sulphur atoms in the iron solution are aasociated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* (FeS) ? [FeS], [I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) ? (CaS) + (FeO), [2] and, (FeS) + (MnO) ? (MnS) + (FeO). 131

Jan 1, 1949

By B. M. Larsen, T. E. Brower

THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slag-metal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the con- tinual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process. In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium. On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. Probable Chemistry of Desulphurization Since there is little evidence that sulphur atoms in the iron solution are aasociated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* (FeS) ? [FeS], [I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) ? (CaS) + (FeO), [2] and, (FeS) + (MnO) ? (MnS) + (FeO). 131

Jan 1, 1949

By Clemens Jones

THE analytical history of phosphorus in its relation to the metallurgy of iron is an interesting study, the progress of which runs parallel with the development of the greatest industry in the world. Without the means of finding out how much phosphorus crude pigiron contained, the Bessemer steel process would have been impossible. To do this was originally tedious and slow work. On the other hand, the " direct" process of to-day, as well as the various special processes for steel or iron, have demanded the utmost rapidity in the operations of analytical chemistry. In general, any rapid process for the conversion of unrefined metal into a product of standard composition depends upon the rapidity of some accurate means employed to control it. Moreover, in our modern practice, it is not improbable that the differences in physical properties among the various makes of iron or steel are affected, if not produced, by the use of different methods of analysis. Recourse is always had for correction to the ((standard methods," but I incline to think that these methods are susceptible to error. It is very certain that the system of duplicates would not be resorted to, if the fact were otherwise. Even when duplicated, under the most careful and skilful manipulation, these standard methods produce disagreements. In proof of statements like these, which may sound. heretical, I hope, further on, to cite some evidence worthy of attention. I do not now mean to lay claim to the distinction of discovering the ultimate corrective. That result will come, no doubt, in. time, as the product of the experience of many workers. In the case of phosphorus, as of the other ingredients of iron or steel, a great deal has been done to accommodate the methods of analysis in rogue to the growing necessity for more rapid procedures: Much of this work has concerned what might be called the incidents of method. There is no better example of the accumulation of these incidental improvements than the work done on phosphorus; and I

Jan 1, 1890