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By Henry A. Wriedt, John Chipman

Equilibrium in the reaction of hydrogen gas with oxygen in liquid nickel, iron, and their alloys has been studied at temperatures of 1500° to 1700°C. The equilibrium con^stant, 0/p, [% O], is greater in nickel then in iron by a factor of 45 at 1594 C. In the alloy steel range, the activity coefficient of oxygen is slightly increased by the presence of nickel. NICKEL is more resistant to oxidation than is iron, in both the solid and the liquid state. The solubility of oxygen,' however, is greater in nickel than in iron. The two metals and their liquid alloys constitute an interesting series of solvents in which the chemical behavior of oxygen can be studied by methods similar to those used for liquid iron.' Experimental Method The furnace assembly, including the tube for preheating the entrant gas, was the same as that described by Gokcen and Chipman. " controlled mixture of water vapor, hydrogen, and argon preheated to approximately the melt temperature impinged upon the surface of the liquid metal. The charge, weighing about 35 g, was held in an alumina crucible at constant temperature in the gas stream for a prolonged period, then quenched in a stream of cold helium, sampled, and analyzed for oxygen by the vacuum fusion method. The temperature of the liquid metal was measured by a Leeds and Northrup optical pyrometer which had been checked against a similar instrument certified by the National Bureau of Standards. The freezing point of electrolytic iron in hydrogen, taken as 153j°C, was used for frequent checks. This point and the emissivity determined by Dastur and Gokcen" established the transmissivity of the optical system. The emissivities of Fe-Ni alloys at 1535" are known from the experiments of Smith and Chipman,h nd it was assumed that the variation with temperature is parallel with that of iron. Recorded temperatures are probably accurate within k5"C. Preparation of Gas Mixtures—Since the ratio H,O:H, had to be much higher for nickel than for iron, it was found convenient to construct two separate systems for gas preparation. In both cases, the ratio of argon to the sum of the other two gases was at least 4, the proportion of hydrogen and water vapor being varied to produce H,O:H, ratios from 0.2 to 70. The primary purpose of the argon was to diminish the errors caused by thermal separation' in the gas phase. In addition, its presence lowered the saturation temperature required for a given H,O:H, ratio and minimized the difficulty of preventing condensation. Both systems were modifications of the one used by Dastur and Chipman.' For H,O:HI ratios greater than 2, welding-grade argon purified by passage over magnesium chips at 620°C was mixed with hydrogen produced in the electrolytic cell shown in Fig. 1. The design was based on a cell used by Bodenstein and Pohl," the important features of which area nickel wire cathode and sodium hydroxide solution as the electrolyte. The rate of hydrogen evolution was controlled by a calibrated ammeter and a rheostat in the circuit, the current efficiency being taken as 100 pct. Precise control of the argon flow rate at about 300 ml per min was achieved by means of a capillary flowmeter having a controlled pressure drop. The molar flow rate was measured volumetrically before each run, and a constant flowmeter setting was maintained thereafter. The A-H, mixture passed through a water saturator of the type previously described," the saturation temperature being maintained automatically with a fluctuation of k0.04"C. The tube between saturator and furnace was heated by a resistance winding. The system was of all Pyrex construction with the exception of the stainless steel tube containing magnesium chips. This was connected with the glass tubing at the upstream end by

Jan 1, 1957

By B. M. Larsen, T. E. Brower, J. W. Bain

A mass of circumstantial evidence is presented to indicate that the main source of alloy losses in open-hearth tapping is oxidation by air, with the steel apparently reacting with an amount of oxygen equivalent to about 30 times its own volume of air. The effect is erratic from heat to heat, depending largely on turbulence and distance of free fall of the stream of liquid metal. THIS paper reports another phase in a general study of oxidation in the open-hearth, various aspects of which have already been discussed in previous papers.1,2,3 It is based on experiments conducted on commercial, basic open-hearth furnaces at various times when opportunity offered, beginning about 1938, in an attempt to determine the mechanism and measure the amount of air oxidation during the flow of the tapping stream through the air into a ladle. This effect is closely connected, not only with alloy losses and control of chemical analysis, but possibly with various questions regarding inclusion content and steel quality and with a true picture of the deoxidation of steel in general. Thus it is believed that discussion of a large part of the results to date may be of assistance to others who are studying problems related to deoxidation or to steel cleanliness and quality. The literature reveals that strangely little attention has been devoted specifically to the effect of pouring steel through open air. Bardenheuer and Henke4 in 1939, in a paper devoted largely to overall losses of manganese in the basic open-hearth, reported that for a number of heats tapped into a tilted ladle held just beneath the runner so that the maximum distance of drop of the stream through the air was held to less than about 30 in., there was in most cases almost no loss of manganese from furnace to ladle. Hultgren,5 in 1945, showed that in high-carbon basic electric steel deoxidized in the furnace and containing no large inclusions as it left the furnace, large silicate inclusions, often rich in manganese oxide, were present in samples dipped from the pool in the ladle; also that the rise in content of large inclusions (above 0.01 mm dim) was greater when the metal stream was made to spray or flow in a turbulent manner. Our interest in this phase of oxidation in the open-hearth was first aroused by a study of alloy efficiencies on ladle additions. The frequency curves of manganese efficiency (net recovery of metal added in ladle) given in fig. 1 are of interest in this connection. Lowest, and also most variable (47 to 95 pct), recovery was in low-carbon heats having no coal additions to the ladle, progressing upward to a maximum average and least variable (82 to 97 pct) recovery in high-carbon heats killed with aluminum and silicon. Both coal additions and higher carbon contents in the tap stream, as well as additions of silicon and aluminum, help to lower the amount of manganese loss. But the most interesting point is the amount of manganese oxidized in many heats tapped at 0.50 to 1.06 pct carbon. It has been shown in a previous paper3 that the amount of oxygen in the tap stream in such heats is very small, usually below 0.01 pct, too small to oxidize any appreciable amount of manganese. Also, the fact that manganese should be oxidized at all in a metal solution containing such more stable oxide-forming elements as aluminum and silicon is an indication of some rather intense oxidizing effect such as could be caused by reaction with the air during ladle filling. Oxygen Balances from Tap Stream to Teeming Stream: Data in the form of alloy efficiencies, such as those shown in fig. 1, are not a proper measure of such a general oxidation effect. Having available

Jan 1, 1951

By E. T. Turkdogan

This is a compilation and a critical review of the data on the Fe-Ca-0 ternary system. Using the results on the reductiorz-equilibria, an oxygen potential diagram is drawn for the greater part of the system. A number of univariant systems and invariant points, not determined experimentally, are evaluated by making use of the theorem on univariant curves intersecting at an invariant point. The formation of solid solutions and ternary compounds and the crystal structures of some of the phases in the composition-diagram are given for a feu! temperatures. DURING the past thirty years there has been a continued interest in the study of the Fe-Ca-0 system. A detailed literature survey made by white1 in 1943 indicated that further work was required to clarify the phase relationships; in fact, the work carried out in the subsequent years, reviewed by Burdese2 in 1954, made a valuable contribution to a better understanding of this subject. Most of the data were obtained by the step-wise reduction of mixtures of iron oxides and calcium ferrites. However, there is some uncertainty about the phase relationships in this system, arising mainly from insufficient use of thermodynamic concepts in the construction of phase diagrams. In this paper an attempt is made to establish the invariant points from the available data. OXYGEN POTENTIAL DIAGRAM Schenck and coworkers3,4 were the early investigators who studied part of this system by the step- wise reduction method and suggested the formation of two ternary compounds, CaO.FeO.Fe2O3 and 2Ca0.5Fe0.2Fez03, the latter being referred to as point X. They also deduced from their results that the phases Y (8.74Ca0.32.5Fe0.8.74Fe2O3 and Z (2.02CaO-97.98FeO) were formed near the w?stite corner of the system. Martin and voge15 postulated the existence of the compounds CaO.9FeO and 4Ca0.3Fe3O4; the former is very close to the composition of point Z and the latter to that of CaO.FeO-Fe2O3. The most valuable contribution to the presen knowledge on this system was made by Cirilli and Burdese6-8 who showed by X-ray and chemical anal yses that there were two ternary compounds, CaO-Fe0.Fe2O3 and CaO.3FeO-FezO3; the former is the same as that suggested by Schenck et al. and the latter is close to their point X. The results of Cirilli and Burdese show that the phases Y and Z postulated by Schenk et al. are solid solutions of calcium oxide in w?stite. In most of the above-mentioned reduction-equilibria measurements carbon monoxide-carbon dioxide mixtures were used and in a few cases hydrogen-water vapor mixtures were employed. Using the

Jan 1, 1962

By W. D. Forgeng, R. L. Folkman, D. C. Hilty

The solubility of oxygen in molten Fe-Cr alloys has been determined at 1550° , 1600°, and 1650°C for alloys containing up to alloyshasbeenabout 50 pct Cr and found to decrease as chromium increases to 6 pet and then to increase gradually. Phase relations in the Fe-Cr-0 system at steelmaking temperatures have been evaluated and two previously unreported oxides have been identified. OPERATIONS in the melting and refining of chromium steels are dependent to a major degree on the reactions of chromium and iron with oxygen and are primarily directed toward controlling and modifying these reactions to secure maximum advantage in the utilization of chromium. Although fairly effective practices have been developed empirically, understanding of the specific reactions is limited. Moreover, the ability of molten steel to dissolve oxygen that subsequently precipitates as oxide inclusions during solidification is well known, so that clarification of the effect of chromium on the nature and mechanism of formation of these inclusions is desirable. Study of the problem indicated that increased knowledge of the fundamental Fe-Cr-0 system is essential to further technical and economic improvement. Consequently, an investigation of the influence of chromium on the solubility of oxygen in molten iron and of phases and phase relations in the Fe-Cr-0 system was undertaken at the Metals Research Laboratories of the Electro Metallurgical Co. as part of a general program on the effective utilization of chromium in chromium steel production. Experimental Procedure All of the experimental runs made during this investigation were carried out in the rotating crucible induction furnace which has been described in detail in a previous publication.' In review, the principle underlying this furnace is that rotational forces in the crucible cause the molten metal to assume a concave shape in such a manner that the slag is contained in the molten metal cup, thereby minimizing slag/crucible contact and subsequent reaction. Practically all of the heats were melted in commercial-quality magnesia crucibles of the type usually furnished for laboratory induction furnaces. All of the runs were made under an argon atmosphere after the furnace chamber had been degassed. Bath temperatures were controlled by Pt—Pt-10 pct Rh thermocouples. The basic furnace charge consisted of a premelted 12 to 15 lb electrolytic iron slug which had been cast to a shape convenient for fitting into the rotating furnace crucible. A typical analysis of the electrolytic iron slugs is given in Table I. For certain runs, it was desirable to melt down charges containing high initial chromium contents. In these cases the chromium was added to the electrolytic iron during the premelting operations. Chromium was added to the rotating furnace bath in the form of electrolytic chromium of the analysis given in Table 11. In all of the constant temperature runs, the standard procedure was to melt down the electrolytic iron or alloy slug under vacuum, admit argon to slightly greater than atmospheric pressure, and adjust rotational speed to develop a well formed "cup" on the bath surface. The melt was then saturated with oxygen by an addition of ferric oxide and the temperature of the bath adjusted to within +5°C of the desired level. At this point the heat was permitted to come to equilibrium prior to sampling or further addition. This time interval was varied from 15 min to 2 hr but generally was about 20 min. After sampling, the desired chromium addition was made and the bath again equilibrated prior to subsequent sampling. This cycle of addition and sampling continued for the duration of the run which lasted from 4 to 8 hr. At the end of this period, power was shut off and the bath allowed to solidify in the furnace. Quenched metal samples were taken from the equilibrated melts by means of the "Taylor sampler" which has been described by Taylor and Chipman.' Before being submitted to chemical analysis, all samples were carefully examined for surface slag occlusions and cold shuts. Later in the study, each sample was radiographed and examined metal-lographically in cross-section to determine the presence of internal defects. On the basis of these examinations, sound and apparently clean specimens were selected from the Taylor samples for chemical analysis.

Jan 1, 1956

By S. R. Goodman, Hsun Hu, R. S. Cline

The quenching technique has been used to study phase relations in the composition area 2FeO.SiO2-FeO-SiO2-MnO.Si02-ZMnO.SiO2 of the system iron oxide-manganese oxide-silica under strongly reducing conditions such as exist in a gas mixture consisting of equul parts of carbon dioxide and hydrogen. Liquidus and solidus temperatures of most mixtures in the composition area studied are in the range of 1173° to 1345°C. EQUILIBRIUM relations existing among the oxides of iron, manganese, and silicon are of particular interest in two areas of steelmaking: slags and ingot inclusions. Mixtures of these oxides represent about 90 pct of the slag in the acid steelmaking process, and so dominate the chemistry of the whole refining process. These constituents also play an important role in the early slags existing at the time of the "lime boil" in the basic open hearth process. If these slags are liquid, they "wet" the lumps of lime rising from the bottom of the bath, and react with them. A liquid slag rich in CaO is then formed at the very beginning of the refining. Because the temperature is still low, all conditions for a good dephosphoriza-tion are fulfilled at this stage of the operation. Metal deoxidized with ferromanganese or silico-manganese is likely to contain, as inclusions, phases made up from among the oxides of iron, manganese, and silicon. A knowledge of stability relations existing among the phases present in this system, therefore, enables one to predict the hardness of the inclusions encountered. Moreover, because the shape of the inclusions in steel has a profound influence on the physical properties of the metal, it is important to establish whether or not the oxidic material is present as liquid or crystalline phases during heating and rolling of the steel (-1150 to 1350°C). A knowledge of melting relations in synthetic mixtures of iron oxide, manganese oxide, and silica will give a clue to these problems. Methods for determining such relations and the results obtained are described iln this paper. I) PREVIOUS WORK A number cf previous studies have dealt with the three "binary"* systems bounding the system iron oxide-mangar,.ese oxide-silica. The system iron oxide-silica was studied by Bowen and shairerl in 1932. Their data were obtained by equilibration of mixtures in contact with metallic iron. Phase relations for the system iron oxide-silica ill atmospheres of different oxygen pressures car1 be derived from data on the system FeO-Fe2O3-SiO2 as determined by Muan.2 The diagram shown iri Fig. l is a section of this system in an atmosphere of CO2 and H2 in ratio 1:l. The system manganese oxide-silica has also been the subject of several investigations. Most of the early studies suffered from a lack of proper control of the atmosphere under which the equilibrations were carried mt. Phase diagrams for the system at two well defined levels of oxygen pressures have been determined recently. Glasser3 determined stability relations in an atmosphere consisting of carbon dioxide and hydrogen in ratio 5:1, diagram Fig. 2, and Muan4 studied phase relations in the system in air.

Jan 1, 1962

By A. Muan

Liquidus data are presented for mixtures in the ternary system FeO-Fe2O3-SiO2 in equilibrium with a gas phase with O2 pressures ranging from 10-10.9 to 1 atm. Data obtained are combined with previously published data to construct lines of equal 02 pressures and lines of equal CO2/H2 mixing ratios along the liquidus surface. Courses of crystallization of selected mixtures under conditions of constant total composition, constant O2 pressures, and constant CO2/H2 mixing ratios are discussed. PHASE equilibrium studies of silicate systems where iron is one component are complicated by the fact that iron readily occurs in three different states of oxidation: Fe3+, Fe2+, and Fe0. Success or failure in work with iron silicate systems is to a large extent dependent on control of the oxidation state of iron and all investigations therefore must be carried out under carefully controlled atmospheric conditions. Silicate systems containing only strongly electropositive metals (like Na+, Ca2+, Mg", etc.) can, for simplicity, be treated as condensed systems, that is, the gas phase can be neglected and the phase relationships discussed in terms of the phase rule written in the well known simplified form P + F = C + 1. In the case of iron silicate systems, however, the composition of the condensed phases varies with the gas composition, and a complete picture of phase relationships can be obtained only by varying the gas composition over a wide range. In order to understand the phase relationships in the more complicated multicomponent silicate systems with iron oxide as one of the constituents, a knowledge of the ternary system FeO-Fe2O3-SiO2 is essential, since it constitutes a bounding portion of all such systems. It was with this in mind that the present study was undertaken. Previous Work A considerable amount of work has been done on various aspects of the chemistry and metallurgy of systems containing silica and iron oxides. The two bounding binary systems FeO-Fe2O3 and FeO-SiO2" The first attempt to obtain information on phase relationships of iron oxide-SiO, mixtures at different 0, pressures was made by Greig.' Darken" determined the melting points of iron oxide on solid silica under various atmospheric conditions. Darken did not determine experimentally the composition of the melts at liquidus temperatures but discussed very ably the principles involved in applying the phase rule to the system. In a recent study Schuhmann, Powell, and Michal8 determined experimentally the liquidus surface of a portion of the ternary system and combined the new information with data in the literature to construct a phase diagram. Their method was briefly as follows: Homogeneous mixtures with various contents of SiO2, FeO, and Fe2O3 were made up by melting together stock mixtures in various proportions. Samples of the homogeneous mixtures, the compositions of which were determined by chemical analysis, were then heated in platinum crucibles in an inert atmosphere until equilibrium among the condensed phases was achieved. The samples were quenched to room temperature and the phases present determined by microscopic examination. Assuming that no change in composition takes place during the equilibration run in inert atmosphere, the liquidus surface can be determined, but no information is obtained regarding the partial pressures of 0, of the gas phase in equilibrium with the condensed phases. The author's method, to be described in the next section, permitted the location of points at the liquidus surface as well as a calculation of the corresponding partial pressures of O2. Experimental Method General Procedure: The standard quenching technique was adapted for a study under controlled variable atmospheric conditions. Premelted mixtures of silica and iron oxides in platinum envelopes were held at constant temperature under chosen atmospheric conditions until equilibrium was reached among solid, liquid, and gas phases. The sample was then quenched to room temperature, the phases present identified, and, for the most significant runs, the composition was determined by chemical analysis. The corresponding partial pressure of 0, was calculated from known equilibrium constants of the gas reactions occuring in the furnace atmosphere. Materials: Starting materials were oxides of commercially highest available purity; cp silicic acid was dehydrated by heating to 1350°C for 6 hr and cp Fe2O3 was dried at 400° C for the same length of time. Samples of 10 g were made up by mixing

Jan 1, 1956

By J. B. Wagstaff, R. A. Buchanan, J. F. Elliott

High speed photography through blast-furnace tuyeres showed coke particles moving rapidly. Model studies showed a raceway was formed and gave quantitative results which were correlated with actual blast furnaces. Another study showed the similarity between hanging and the flooding of a packed column. This was explored by models. THE combustion zone before the tuyere in an iron blast furnace is a vital region because here are generated: 1—most of the gases on which the furnace depends to carry out its basic operation of reducing iron ore to the metallic state, and 2—the major fraction of the heat required in the nearby regions of the furnace for the various reduction reactions, the fusion of the slag, and the melting of the iron. Since the greater part of the coke is consumed in this region, the descent of the burden must be greatly affected by the characteristics of the tuyere zone. This region then would seem to be a profitable field for study. Fortunately, a view into this important zone is available to the operator through the tuyere peep sight. Here he sees relatively dark pieces of coke "dancing" in the blast. What he sees is of considerable help in interpreting the behavior of the furnace at a given time but the very rapidly moving particles and the intense radiation obscures what is happening very deep in the zone. This investigation was initiated in the hope that a better understanding of the combustion region could be obtained by using a high speed camera with a maximum speed of 3000 frames per sec. It seemed the best practical method of "slowing down" this characteristically violent action within the highly luminous field. Model studies and tuyere probing also have been used to aid in explaining the observed phenomena. Above the combustion zone, but below the fusion zone, there is probably a region in which the coke is comparatively stationary. Here are zones in which the gases must flow up through the granular bed counter to descending liquid slag and metal. There is no easy way to observe this zone in a blast furnace, but model studies have been of some help in explaining the nature of the zone and the laws governing the flow of the fluids involved. The whole problem is difficult and involved and any approach to a complete solution may require long investigation. This preliminary report has been written, therefore, because it is believed that appreciable progress has already been made that would be of interest to others. Tuyere Studies, Chemistry and Kinetics It is well known from the early work of Kinney and coworkers1,2 that combustion of carbon before the tuyeres appears to occur in two zones: Zone A: C + O, = CO2; AH77°F. = — 14,108 Btu per lb of carbon [I] Zone B: CO2 + C = 2CO; H77°F = + 6,183 Btu per lb of carbon [2] Zone A (Fig. 1) is close to the tip of the tuyere and zone B is somewhat farther back; there being a transition region in which both reactions occur. It is interesting to estimate the rate at which coke is burned before a tuyere with a wind rate of 90,000 cfm in a modern furnace having 18 tuyeres. Approximately 0.55 lb of carbon is consumed by eq 1 per tuyere per sec. A like amount disappears by eq 2 for a total consumption of 1.11 Ib per sec per tuyere. Assuming the coke is 85 pct C and has a bulk density of 30 lb per cu ft, this figure can be converted to a total of 1.30 lb of coke with a bulk volume of 0.043 cu ft disappearing per sec per tuyere. At the temperatures prevailing in the combustion zone (according to Kozlovich,³ he maximum is about 3400°F), the rate at which carbon is con-

Jan 1, 1953

By J. A. Elias, R. H. Heyer, J. H. Smith

Plastic anisotropy determined by the ratio of width strain to thickness strain in tensile specimens of low-carbon steels is strongly related to crystallographic preferred orientation. Using(222) Pole figures, a method was developed which permits rapid Predictions of plastic anisotropy for any crystallographic texture or orientation. The method is applied to low-carbon steel sheets in which four different crystallographic orientations were produced by variations in cold rolling and annealing treatments. AnISOTROPIC behavior of metal sheets during plastic deformation has long been evident. A familiar example is earing in cup type draws. During tension testing of sheet specimens, anisotropy results in a difference in width strain as compared with thickness strain. Carpenter and Elam1 observed this phenomenon in single crystals of aluminum for both sheet and rod samples. Lankford, Snyder, and Bauscher2 made tension tests on sheet samples of aluminum-killed low-carbon steel to determine the ratio of the width-to-thickness strains, and showed that this ratio was related to drawing performance. Burns and Heyer3 calculated theoretical ratios of width strain to thickness strain for two specific orientations of the bee system, using <111> as the operative slip direction. These calculated values were in fairly good agreement with the ratios determined by tension tests of low-carbon steel sheets in which these preferred orientations existed. The high degree of plastic anisotropy of silicon steel sheets could also be predicted from their crystallographic structure by these calculations. The present study has been made to show that the anisotropy observed in plastic tensile straining is strongly orientation dependent and can be adequately predicted for many orientations and textures. PLASTIC STRAIN RATIO R In the region of uniform elongation of a tension test specimen the plastic deformation may proceed at different rates in the width and thickness directions. Such anisotropy has been described in the past by the plastic strain ratioR:

Jan 1, 1962

By A. W. McReynolds

One characteristic of plastic deformation which distinguishes it from elastic strain is the essential inhomo-geneity of plastic strains. Elastic strain varies continuously through a material, and average relative displacements of initially adjacent atoms are only small fractions of their initial spacing, (strains of the order of 0.01 or less). On the other hand, plastic flow corresponds to the appearance of discontinuities in strain of the lattice, such as dislocations or slip bands, where local strain, on an atomic scale, is several orders of magnitude higher. These discontinuities are visible on a microscopic scale as the familiar slip lines (Fig 1). In spite of this obvious microscopic inhomogeneity, however, macroscopic measurements almost invariably show a smooth curve of stress vs. strain (Fig 2b) even if measurements of linear strains be made to an accuracy of one part in 107. This macroscopic homogeneity of strain indicates that the discontinuities in strain on slip planes occur in increments too small or too slow to be recorded individually, and further that they occur sufficiently independent of one another so that the small increments add at random to a smooth stress-strain curve. The present paper describes observations of plastic strain in aluminum of commercial purity and in high purity Al-Cu alloys, where there exists a strong coupling between slip in various regions of the specimen such that once initiated it spreads rapidly through a large volume. The total effect is that of relatively large, rapid, and regularly spaced steps of strain followed by periods of only elastic strain. Fig 2a illustrates the type of "stair-step" stress-strain curve which results. The properties of this cooperative slip phenomenon will be described further in the section on results: in par- ticular it will be shown that each step corresponds to the propagation of a wave of plastic deformation through the specimen. Some interpretations of the mechanism by which it occurs will be made in the following section. Although the type of plastic wave phenomena to be described has not previously been reported, there are numerous cases of related effects in the plastic yielding of metals: YIELD POINT PHENOMENA The most familiar of such effects is the "yield point" observed in low carbon steels, brass, duralurninum, and the like. It consists in the sudden termination of the elastic portion of the stress-strain curve by a large plastic strain. Since the usual tensile machine is such that yielding of the specimen relieves the load, the resulting curve is as shown in Fig 3. As the strain continues, deformation occurs at a lower stress for some time, then follows a rising curve, but with no further sudden yielding. This effect has been observed in brass by Sachs and Shojil and later by many others. Edwards, Phillips and Jones2 made extensive studies of the effect in steel, and of the role of various alloying elements. Although there seems to be fairly clear evidence that the yield point is caused by a hardening of the material by precipitation of impurities, no satisfactory explanation for the sudden yielding has been given. Winlock and Leiter3 have shown that the strain. level of the upper yield point depends strongly on the rate of loading, the yield point increasing by almost a fac- tor of two as the strain rate goes from 0.002 in. per in. per min. to 4.4 in. per in. per min. This effect would seem to imply an incubation period before yielding is initiated at a certain stress. On the other hand, by going to very slow loading rates, Edwards, Phillips and Jones2 showed that the yield point does not become lower and eventually disappear as might be expected, but, on the contrary, begins to rise at loading rates below about 25 Ib per in. per min. becoming much higher than at rapid loading rates. STRAIN AGING If, instead of continuing straining of a specimen after occurrence of a yield point, the load is removed and the specimen aged, resumption of the test results in occurrence of another yield point as shown by the dotted curve of Fig 3. The new yield stress is generally higher than the previous maximum applied stress. This hardening of the material by straining and subsequent aging is undoubtedly related to quench age-hardening resulting from the aging of a specimen quenched from high temperature. Since neither effect is observed in pure metals, it is generally accepted that quench-aging in all cases is the result of hardening by precipitation of a supersaturated alloying element, and that strain-aging is probably a similar precipitation, accelerated by disruptions of the lattice by previous strain. Pfeil4 has shown that strain-aging does not occur in iron from which all of the carbon has been removed, but that only a very small carbon content, around 0.003 pct, is necessary to cause strain-aging. In accord with this observation is recent work by Dijkstra5 in this laboratory showing that the solubility limit of carbon in iron is extremely low, less than 0.001 pct at 400°C. Edwards, Phillips and Jones2 have shown that the strain-aging effect is also removed by the addition of small quantities of elements such as Mo, Mn, Ti, and the like, which readily form carbides. Their results demonstrate the

Jan 1, 1950

By A. W. McReynolds

E. OROWAN*—I observed the phenomenon of jerky yielding many years ago with zinc25 and cadmium single crystals. A significant point was that the jerks occurred not only when the stress was raised but also (sometimes, after a pause of many minutes during which no trace of creep was observable) at constant stress. The phenomenon may be closely linked with the inertia of the testing machine and of the specimen, although the inertia alone cannot account for it. If, during the test, the resistance of the material to plastic deformation suddenly diminishes while the applied force remains constant, a sudden deformation follows until the yield stress has risen, by strain hardening, to the level of the applied stress (= the value of the previous "upper yield point."). When this is reached, the rate of deformation has attained a maximum value because, up to this moment, the applied force was higher than the plastic resistance of the specimen, and the difference was used for accelerating the moving parts of machine and specimen. The kinetic energy accumulated is now transformed into plastic work by further deformation; that is. the deformation overshoots the point at which the plastic resistance equals the applied static force. When the kinetic energy has been used up, therefore, we are left with a specimen the yield stress of which is higher than the applied stress, and no further deformation can occur (apart from a little creep) until either the applied stress has been raised to the new yield stress level, or the yield stress has fallen by thermal recovery to the level of the applied stress. While this occurs, a new upper yield point can develop, for example, by precipitation.26

Jan 1, 1950

By Frederick C. Langenberg

A method is presented for computing the solubility of nitrogen in molten alloy steels. Examples are given to illustrate the procedure, and comparisons are made between predicted and measured nitrogen solubilities. THERE is an increasing use of nitrogen as a major alloying element in steels, or as a partial substitute for other alloying elements. Nitrogen is a potent austenite stabilizer, and Cr-Mn-low Ni-N steels, or even Cr-Mn-N steels, are being considered

Jan 1, 1957

By Donald A. Corrigan, John Chipman

It is shown that the heat of solution of nitrogen in liquid-iron alloys is Proportional to the interaction coefficient. This proportionality forms the basis for a method of predicting nilrogen solubility at any temperature when the interaction coefficient is knoun at 1600°C ov when the solubility is known at some one temperature. A method for predicting the solubility of nitrogen in liquid steels, including alloy steels, was proposed some years ago by Langenberg.&apos; Since the data available at that time were restricted to temperatures of about 1600°C, his predictions were similarly restricted. More recently, Nelssonz devised an approximate method for estimating nitrogen solubilities at higher temperatures. It is the purpose of the present paper to present a method by which the solubility of nitrogen at any temperature within the steelmaking range may be predicted from the known interaction coefficients at 1600°C. Nitrogen in iron and in all of the alloys to be considered here is known to obey Sieverts&apos; Law; hence the activity of nitrogen in an alloy of fixed composition is proportional to its concentration, here expressed in weight percent. The activity of nitrogen is defined as equal to its weight percent in the binary Fe-N solution at any temperature. Its activity coefficient in any alloy is the comparison being made at equal values of T and PN2. In all alloys the activity coefficient changes with composition, log fN being a linear function of the percent of alloying element at low concentrations. In the following calculations the alloy compositions are restricted to those in which this linear relation is exhibited. For most systems this is a fairly wide range, for example up to 5 pct V and to 10 pct Cr or Ni. For this composition range. complex alloy is the same as that in the Fe-N-j ternary solution. Langenberg&apos;s method of prediction was based on Eq. [3], the values of log fN for various additions being taken from a graph. Instead of using the simple addition indicated in Eq. [3], he used a more complex method suggested for Fe-S-j alloys by Morris and Buehl.3 For the composition ranges in which Eq. [2] is valid the two methods are equivalent. Nelson extended the prediction to other temperatures on the assumption that logfN is inversely proportional to absolute temperature. It may be shown that inverse proportionality would result if the partial molal entropy of nitrogen were unaffected by addition of the alloy element, an assumption which Nelson designated as a "regular" solution. It has been shown recently by the authors4 that this assumption is not a good approximation. The heat of solution of nitrogen (N2) in an alloy may be obtained if the solubility is known as a function of temperature. Measurements of this nature have been reported recently by Beer5 for Fe-Mn alloys, by Nelsson2 for Fe-C, by El Tayeb and parlee6 for Fe-V, and by Pehlke and Elliott7 for many alloys embracing a wide range of compositions. In connection with the work of the last named authors it is noted that their Fig. 22 gives the heat effect per half mole rather than per mole of N2. In using their data we have shifted some of their values slightly by using the best straight line in preference to their curve. Their data, supplemented by others from the literature, are summarized in Table I. In Fig. 1 the heat of solution of nitrogen is shown as a function of composition for the several alloy systems. The difference between the heat effect in the alloy. AH; and that in pure

Jan 1, 1965

By R. C. Buehl, M. B. Royer

High manganese slags of low phosphorus and iron content are produced by air oxidation of high phosphorus spiegeleisen in a basic-lined converter. Control of phosphorus and iron within specification limits for ferromanganese ore feed is obtained by a unique cyclic operating procedure. Various types of slags, or synthetic manganese ore, can be made. AN affiliated paper&apos; describes the production of high phosphorus spiegeleisen containing 14 to 23 pct Mn and up to 4 pct P in an experimental blast furnace from open-hearth slag or manganiferous iron ore. This phosphorus content is too high for use of the spiegel in normal steel-production operations. Consequently, a preferential separation must be effected whereby the manganese is concentrated in a product that is usable in industrial operations. The preferential separation methods being investigated for this phase of the work are confined to pyrometal-lurgical processes for ready incorporation into steel-plant operations. It is fortunate that manganese is more actively oxidizable than iron or phosphorus, and therein lies a preferential separation method for isolating manganese from these two elements. Silicon is more strongly oxidizable than manganese, and its oxidation precedes, or occurs simultaneously, with manganese. Therefore, manganese and silicon are separable into a high manganese oxide slag phase while the phosphorus and iron remain in the molten metallic state. Complete separation of these elements represents an ideal condition which is not generally attainable in actual operations. This pyro-metallurgical method for separating manganese from phosphorus and iron by preferential oxidation was investigated by blowing 500 lb of metal in a basic-lined vessel to obtain preliminary information on the effectiveness of the procedure. Certain conditions of attainment in the separation process are desirable in any method for removing manganese from high phosphorus spiegeleisen, such as: 1—High recovery of manganese in the oxidation product; 2—the product to be of equal or better quality than ferromanganese-grade ore—48 pct Mn minimum, less than 10 pct SiO2, and Mn-P ratio of 300:1; and 3—attainment of the enumerated objectives in a product amenable to industrial handling, such as a slag of high manganese content that will flow from the processing vessel and of sufficient fluidity for ready separation of metallic granules that may have become mixed with the manganese slag phase. Previous Work Recovery of manganese from low grade ores and industrial byproduct slags by smelting to spiegeleisen, with subsequent oxidation to synthetic ferro-manganese-feed ores, has been a subject for periodic investigation during the past four or five decades in the United States and Germany. Joseph&apos; and associates of the Bureau of Mines North Central Experiment Station, Minneapolis, Minn., smelted manganiferous iron ores of the Cuyuna range, Minn., to spiegeleisen and subsequently tried air and ore oxidation procedures for concentrating the manganese into synthetic ferrograde manganese ore. Joseph&apos;s results on the operation of a side-blown basic-lined converter for air oxidation of manganese from molten spiegeleisen were so discouraging that the procedure was abandoned after 11 blowing tests. Much slag was thrown from the converter vessel; phosphorus content was four to five times the maximum allowable for ferro ore; and a manganese-iron ratio of only 2 or 3:1 was obtained in the slag instead of the required 8:1. Oxidation of manganese from spiegeleisen with about 0.5 pct P, by adding iron ore to molten spiegel in an experimental open-hearth furnace, proved moderately successful in Joseph&apos;s experiments. The main drawback to the operation was the necessity for over-oreing for effective oxidation of the manganese with consequent too high iron oxide residual in the slag. Furthermore, the phosphorus content was proportional to the iron concentration and therefore much too high, so that several hours of reduction by a carbonaceous material were required to adjust the iron and phosphorus to the desired content of high grade ferro feed. A troublesome feature of the slag product of the spiegel oxidation process was its lack of fluidity if the silica content was less than 10 pct, the concentration considered desirable for the synthetic ore. Approximately twice the desired concentration of silica was required to impart enough fluidity for transfer from the vessel by pouring. The acute shortage of manganese in Germany

Jan 1, 1953

By R. C. Buehl, M. B. Royer

A three ton per day blast furnace using blast temperatures up to 2200°F was operated to recover manganese from open-hearth slag and manganiferous iron ore. The spiegel product containing 12 to 24 pct Mn was blown in a basic converter to high manganese oxide slag as described in the paper which follows this one. HE steel industry, which uses over 900,000 short tons of contained manganese yearly, depends on the maintenance of supplies of manganese from foreign sources such as India, Gold Coast, and Union of South Africa. Domestic ores furnish less than 10 pct of the yearly requirements of metallurgical ores and, unfortunately, the United States has no large, or even moderate, grade deposits that could supply a major portion of the requirements for many years. It may be necessary to obtain manganese from low grade materials, even though the cost is appreciably higher than when imported ores are used. An American Iron and Steel Institute questionnaire prepared in 1949 revealed the startling fact that open-hearth slags contained about as much manganese as is imported annually. The quantity of slag produced each year by integrated steel plants (not including cold-melt shops) and the manganese contained in the slag follows: Flush slag, 4,500,000 net tons a year containing 408,000 net tons Mn; tap slag, 7,230,000 net tons a year containing 364,000 net tons Mn; for a total of 772,000 net tons Mn. Some of this slag is returned to blast furnaces but about 75 pct would be available for the recovery of manganese. In several decades, when many of the present sources of high manganese ores have been depleted, open-hearth slag and manganiferous iron ore may become the major source of the manganese required for steel production. In 1948, manganese-ore imports from the U.S.S.R. were 427,000 net tons or 34 pct of the foreign ore. Imports from this source were only 81,000 tons in 1949. It became evident that adequate stockpiles of manganese could not be accumulated for many years. The Bureau of Mines initiated an extensive research program on methods for increasing domestic production of manganese and entered into a cooperative agreement with the American Iron and Steel Institute for recovering manganese from open-hearth slags whereby the Institute provided additional research funds and trained operating personnel. Description of Process and Equipment Numerous pyrometallurgical and hydrometallur-gical processes and combinations of the two can be applied to the recovery of manganese from open-hearth slag and manganiferous iron ore. The process being developed at the Pittsburgh Station of the Bureau of Mines consists of: 1—Reduction of open-hearth slag in a blast furnace to recover the iron and manganese as spiegel-eisen with 12 to 24 pct Mn. 2—Selective oxidation of the manganese from the blast-furnace metal in a basic-lined converter to produce a high manganese slag with up to 60 pct Mn content, which is a synthetic ore for the production of ferromanganese. This process has the advantage over other processes in that the equipment which would be used, such as blast furnaces and converters, has been highly

Jan 1, 1953

By S. Ramachandran, N. J. Grant, T. B. King

MANY investigations of the rate of the sulfur transfer reaction between carbon-saturated iron and blast furnace type slags have been made." It is evident that the reaction is complex, the rate being affected by the presence of elements dissolved in the metal that are readily oxidized and therefore capable of existing in the slag phase. Thus Goldman, Derge, and Philbrook- have shown that carbon, silicon, manganese, and aluminum, in order of increasing effectiveness, accelerate sulfur transfer from iron containing these elements to blast furnace type slags. Quantitative information is still, however, not available on the relation between what have been termed side reactions, such as silicon transfer and CO evolution, and the sulfur transfer reaction itself. In other words, the stoichiometry of the reaction has not been investigated. In the present investigation, the transfer of all reacting elements and the evolution of CO have been measured simultaneously in order to establish the mechanism of the reaction which occurs in practice. Information of this nature cannot be deduced from equilibrium studies. It should be pointed out that in kinetic studies of this type quantitative conclusions are applicable only to the system studied. This restriction should be borne in mind when attempts are made to compare results from different investigations. Apparatus The apparatus used enables slag and metal samples to be taken at frequent intervals and also provides a continuous record of the amount of gas evolved. A sketch of the apparatus is given in Fig. 1. It may be considered in three sections: 1) furnace section, 2) blank volume section, and 3) pressure measuring section. The furnace section is shown in detail in Fig. 2. It consists of two graphite crucibles, C and D, super-

Jan 1, 1957

By V. Koump, T. F. Perzak, R. G. Olsson

Jan 1, 1965

By W. O. Philbrook, L. D. Kirkbride

IN the normal operation of the iron blast furnace, reduction of the iron oxides is accomplished almost entirely above the tuyeres.&apos; Blast furnace slags usually contain less than 0.5 pct FeO, although higher values may occur with abnormal operation. There is reason to conjecture, however, that incompletely reduced ore may sometimes reach the hearth and enter the slag as a result of heavy slips or, perhaps, even from cores of excessively large lumps of a charge material of poor reducibility. The possibility of reoxidation of iron droplets falling in front of the tuyeres has been considered by several writers. It would be of interest, to know how rapidly iron oxides reaching the slag for any of these reasons could be reduced by reaction with coke or with the high carbon liquid iron in the hearth. In comparison with the hundreds of papers that have appeared on various aspects of the reduction of solid iron oxides by gases and in the presence of several forms of carbon, little work has been published on the reductioin of liquid oxides or slags. Dancey measured rates of reaction of the pure liquid oxides, both FeO and Fe,O,, with molten iron containing about 4.3 pct C. The oxide was dropped into the cup formed in the upper surface of the iron by rotating the crucible and melt. Under these conditions, reduction of either FeO or Fe,O., was completed in less than 10 sec. The present study was concerned with the reduction of FeO from blast furnace-type slags containing less than 5 pct FeO and melted over carbon-saturated iron in stationary graphite crucibles. The results were considerably different from those found by Dancey, as will be discussed later. Although this work is of interest in relation to hearth reactions in the blast furnace, interpretations must be made with caution because the experimental conditions do not duplicate those within a furnace and may not even lead to the same reaction mechanism. The authors were motivated in undertaking this work by an additional interest—the part played by FeO reduction in the mechanism of de-sulphurization of iron by slags under similar experimental conditions. Derge, Philbrook, and Goldman eveloped detailed experimental evidence to support a three-step mechanism for desulphurization like that originally proposed by Holbrook and Joseph&apos; (These reactions are written in molecular form for convenience, but this is not intended to imply the existence of molecules of FeS in the bulk metal phase nor to deny the likelihood of ionic reactions in the slag.) Earlier work by Chang and Goldman" had shown that the overall reaction follows first-order kinetics with respect to sulphur and that the rate of reaction is proportional to the slag-metal interface area, which observations have been confirmed by subsequent work. Later studiese,&apos; have established the influence of al.loying elements on the first and last steps of the reaction. This paper reports a study of step 3 alone, uncomplicated by the simultaneous process of sulphur transfer. Apparatus and Procedure The experiments were made in a conventional high frequency induction furnace powered by a 35 kva Hg spark gap converter. The graphite crucibles used for most of the runs were 14 cm (5.5 in.) deep and 4.8 cm (1.9 in.) ID with 0.75 cm (0.3 in.) wall. An insulating cover with a small opening for withdrawing samples was used to minimize heat loss and infiltration of air into the furnace. The crucible was charged with 300 g of carbon-saturated iron and either 65 or 100 g of prefused slag analyzing 38.0 pct SiO,, 15.4 pct A10 and 47.1 pct CaO. To obtain the cleanest possible interface at the start of the reaction, the metal and slag were brought to temperature together to prevent the rejection of kish graphite that would have been caused by the chilling effect of a large addition of cold slag to carbon-saturated iron. After temperature control had been established, the desired amount of iron oxide was added in the form of a prefused slag of composition 73.6 pct FeO, 7.7 pct AWX and 19.0 pct SiOl. This slag addition was observed to be molten in somewhat less than 1 min, and a very vigorous reaction proceeded for 1 to 2 min after its introduction. Zero time was taken as 2 min after the ferrous silicate slag addition. Slag samples weighing about 0.5 g each were taken periodically by a copper chill sampler." The weight of the initial slag was large relative to the weight of samples removed, so that the slag weight never varied by more than 5 pct during any run. Temperature was measured by a calibrated W/Mo thermocouple immersed in the metal, with a graphite tip cemented over the fused silica protection tube to prevent attack by slag and metal. After some difficulties with uncertain temperatures during the first two runs, the practice adopted to position the thermocouple for reproducible results was to lower the protection tube to touch the bottom of the crucible and then raise it 0.5 cm. The apparent temperature gradient between the bottom of the crucible and the top of the slag was found to be 15°C (27°F). but much of this spread was probably the result of inadequate immersion of the protection tube to off-set conduction losses along the graphite tip when the thermocouple was inserted only into the slag. The temperature of the bath was controlled within 25°C (9°F) during a run.

Jan 1, 1957

By Hillary W. St. Clair

An equation is derived for the rote of reaction of a sphere of metal oxide in a restricted enclosure through which a reducing gas is flowing. The equation takes into consideration the reaction rate coefficient, transport through the gas and through the porous shell of reduced oxide, the rate of gas flow, THIS paper describes a mathematical study of the chemical and physical processes that determine the rate of reduction of solid metal oxide with a reducing gas. The study was a part of a theoretical study leading to the development of a mathematical model for the simulation of the thermochemical behavior of the iron blast furnace. An essential feature of such and the volume of- space surrounding the sphere available for gas flow. The equation is applied to experimental data on vote of reduction of iron oxide in hydrogen. The equation serves as a model for predicting the course of reduction of a particle of. metal oxide in a shaft furnace. a model is an adequate mathematical relationship defining the rate of reaction in terms of all the important chemical and physical phenomena that affect the rate of reaction. This includes not only the reaction rate coefficients, equilibrium ratios, gas composition, and temperature, but also the relevant physical properties of the oxide, rate of gas flow, and relative volumes occupied by gas and solid. In many previous experimental studies of the rate of reduction of oxides by hydrogen or carbon monoxide, the rate of reduction was assumed to be controlled primarily by the chemical reaction at the

Jan 1, 1965

By R. D. Burlingame, T. L. Joseph, Gust Bitsianes

DESPITE almost fifty years of commercial practice, the sintering of iron ore has received little fundamental study. Much of the theoretical work1-&apos;has dealt with the constitution of sinter produced under widely varying conditions. While these studies have broadened our knowledge of the changes that occur in the sintering zone and in the freshly formed sinter during the early stages of cooling, they provide little insight into the changes that precede the formation of sinter. These preliminary changes merit study as a part of the overall process. Hessle. working with beds of Swedish magnetite concentrates, was one of the first investigators to study the sintering process in its entirety. On the basis of temperatures observed at various levels of the bed during sintering, he postulated a number of distinct reaction zones to account for the chemical changes leading to the formation of sinter. A more direct method of attack is that of arresting the sintering zone after it has progressed part way through the bed. A study of a vertical cross section through such a quenched bed provides direct information on the changes taking place at various levels. This method was used by McBriar et al.&apos; to show that several well-defined zones of chemical change existed within beds that were typical of British sintering practice. The same general method of attack was developed independently in the present investigation to study partially sintered beds typical of American practice. Experimental Sintering Equipment The sintering operation was carried out on an experimental scale with the equipment shown in Fig. 1. The refractory-walled sintering chamber A was 11 in. deep and averaged 9 in. in diameter. Air was introduced through a tapered flow section B, which contained the orifice C for accurate metering of the incoming air. This section was located directly above the square ignition housing D, which in turn rested upon the sintering chamber A. The bed was ignited with burner E. The required suction for the operation was furnished by a fan F, which had an air capacity of 500 cfm (stp). Hot exhaust gases from the sintering chamber were cleaned in the dustcatcher G before entering the exhaust fan. In the study of partially sintered beds, it was essential to find some technique for removing the entire charge from the sintering pot without disarranging the unsintered bottom portion. This problem was finally solved by sintering the charge in a removable basket, which snugly fitted the sintering chamber. This basket was constructed of two thicknesses of window screen and was lined with a 3/16-in. layer of asbestos paper. The bottom of the basket consisted of two thicknesses of wire screen, which were fastened to the basket wall. For high fuel mixtures, additional insulation was provided by a somewhat thicker layer of asbestos cement. Preparation of Partially Sintered Mixtures The moist feed was carefully placed in the sintering basket, to prevent segregation of the particles, which varied widely in size and composition. A thermocouple was placed in the center of the basket with the hot junction halfway down, and the mixture was evenly distributed around it. During ignition and throughout the sintering of the upper half of the bed, the hot junction temperature increased very little. When the sintering zone reached the halfway point, as indicated by the sudden increase in the hot junction temperature, the charge was quenched. During quenching the suction was turned off and the orifice was tightly stoppered to prevent further influx of air. At the same time, nitrogen was admitted to the sintering chamber through the orifice tap. As soon as the nitrogen had displaced the air and products of combustion, the charge was removed from the sintering pot for immediate dissection. It is impossible to preserve the exact zone structure of the bed at the instant that combustion is arrested unless the downward transmission of heat is also immediately stopped. Fortunately, heat transfer is very slow in beds containing a stationary fluid, especially if the particle size is small. It follows that the minimum quantity of nitrogen should be used to displace the air and that static conditions be established as soon as possible. A very steep temperature gradient across the combustion zone for some time after the quench was evidence of in-

Jan 1, 1957

By Arnulf Muan, Hobart M. Kraner

Ferromanganese alloys react with aluminu-silica brick in blast furnace hearths and cause the formation of new phases with low refractoriness and consequent failure of the refractory lining. The nature of these reactions is explained on the basis of petrographic observations, thermodynamic data, and Phase equilibrium considerations. Animproued hearth design resulted from these findings. The production of ferromanganese in blast furnaces presents many problems which are not encountered in the production of iron in the same furnaces. One of the most serious of these problems is the rapid failure of refractories caused by their reaction with the ferromanganese metal. The present paper describes such a "hearth attack", its symptoms, causes, and cure. Following an introductory discussion of operating practice in ferromanganese blast furnaces, results are presented of a petrographic examination of samples from a furnace which had to be shut down because of refractory failure. The causes of this failure are then analyzed on the basis of petrographic observations combined with thermodynamic and phase equilibrium data available in the literature. The latter type of data were subsequently used as a guide in recommending improvements in hearth designs which have since proven themselves successful in practical operations. I) FERROMANGANESE BLAST FURNACE PRACTICE It is considered good practice to blow in a furnace on iron and operate it in this way for a period of time preliminary to producing ferrornanganese. During this time, iron generally penetrates the bottom refractories six or more feet below the original working surface of the hearth. Not only does this metal pervade the joints to these depths, but the pores of the refractories are usually also filled by molten iron. The high throughput of the iron furnace provides ample heat to maintain a high temperature in the hearth refractories. This, together with a high ferrostatic pressure, causes porous clay brick of the hearth to shrink. During subsequent use of such a furnace in ferromanganese production, the iron in the pores of hearth brick if; replaced to some extent by ferromanganese. The replacement is usually not complete. This is probably due to the lower metal throughput and lower prevailing temperatures resulting from this in the brick of the hearth bottom. When the ferrornanganese furnace is banked—or when the temperature in the furnace falls due to a furnace delay—-manganese oxidizes even though the atmosphere is largely CO. Considerable expansion accompanies this oxidation of manganese from metal to oxide. The hearth refractories are then subjected to the disintegrating forces of the volume expansion. These forces may in extreme cases be large enough to lift the furnace off its mantle supports as was described in a previous paper.&apos; When cooling takes place slowly, however, and the temperature remains at a fairly high level, the refractories undergo fluxing action by the MnO. This latter reaction and the reduction of SiO2 of the clay brick is the general subject of the present paper. The observations to be described herein were made on a ferromanganese furnace located at the Johnstown plant of Bethlehem Steel Co. The furnace was lined entirely with clay refractories and had operated on iron for 266 days and on ferromanganese for 96 days prior to being taken off because of a hearth wall failure. II) PETROGRAPHIC EXAMINATION AND CHEMICAL ANALYSIS The photograph reproduced in Fig. 1 shws a cross section of the upper part of an 18 by 9 by 4-1/2 in. bottom block removed from the blast furnace. This brick came from a depth of approximately 6 ft below the original working face of the bottom. It will be noted that the 4-1/2 in. dimension is almost the same as when the brick entered the furnace. Three characteristically different zones marked I, II, and III on the print of Fig. 1 are apparent. Results of chemical analyses of the original brick and samples from each of these zones are listed in Table I. Petrographically the various zones were characterized as follows: The central zone marked I was essentially un-reacted brick. The microstructure consisted of fine needles of mullite, and the pores in this entire area were filled with iron. This is characteristic of

Jan 1, 1962