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By D. C. Hilty, W. Crafts

J. Chipman—It has been my privilege to discuss this work with the authors on several occasions and to observe at first hand the experimental methods employed. I wish, therefore, to emphasize certain points which they have mentioned only briefly with regard to the experimental techniques. The rotating induction furnace as here employed interposes liquid metal between slag and refractory thus preventing the two nonmetallic parts of the system from reaching equilibrium with one another. It is therefore impossible for the metallic phase to be completely in equilibrium with both the slag and the crucible. The metal also acts as a partially permeable membrane allowing certain components, including oxygen, to diffuse from slag to crucible. This transfer results in building up on the face of the crucible a layer of material whose composition is in part dependent on that of the bath. Reactions between the layer and the solid refractory are slow, as evidenced by the rather good life of the crucible. Hence it seems probable that the layer is more nearly in equilibrium with the metal than with the underlying crucible material and that, once it is established under a bath of a given composition, its further reactions with that bath are slow. Additions to slag or bath may be followed by changes in the layer; and time must be allowed for virtual completion of such changes, before it can be assumed that slag and metal are in equilibrium. We may judge from the results reported that, in general, this was the case and that the data represent at least quite close approximations to slag-metal equilibrium. Data on deoxidation and on oxygen solubility are no better than the analytical methods employed. The vacuum fusion method as used by the authors seems entirely adequate for the samples analyzed. I have had frequent occasion to compare results with their laboratory, always with very satisfactory agreement. The determination of aluminum at very low concentrations is perhaps an even more difficult procedure. Here also the colorimetric method used has been worked out with great care and is undoubtedly the most dependable method available. The discrepancy between observed and calculated deoxidation or solubility lines is not to be explained as the result of experimental errors, either in the sampling or analysis of the metal. Nor is it to be blamed upon inaccuracies in the several kinds of indirect data upon which the calculated results were based. It is true that both the observed and the calculated lines admit of some uncertainty as to their exact locations, but the uncertainties are small compared to the wide gap which separates the two lines. The authors have pointed out the real cause of the discrepancy. In all of their experiments the solid phase was not Al2O3 but a mixed oxide containing iron and aluminum. This suggests an extension of the calculated values to include equilibrium with the spinel FeO . A12O3. The free energies of FeO and A12O3 are known, that of the spinel is not. However, it cannot differ greatly from that of its component oxides for even in the more stable spinel, chromite, the free energy of formation from the oxides is less than 10,000 cal. For purposes of calculation we shall call this free energy X and solve for values of X lying between zero and 10,000 cal. The other data required are taken from the forthcoming revision of "Basic Open Hearth Steelmaking" and are given in the following equations in which underlined symbols indicate elements dissolved in liquid steel and the standard concentrations are 1 pct. ?F° at 1600°C, cal ?LA = 2 Al + 3 O; + 107,200 FeO = Fe + 0; + 5,460 FeO + A12O3 = Fe + 2A1 + 4 0; + 112,660 — X The corresponding equilibrium concentrations are shown in fig. 21. The line marked A12O3 corresponds to the first equation, those marked FeO . AL2O3 correspond to the last, with X = 0, 5000 and 10,000 cal, respectively. The two upper lines represent the data of Hilty and Crafts and of Wentrup and Hieber. The points are the observations of Hilty and Crafts in the presence of 0.50 pct Mn.

Jan 1, 1951

By E. T. Turkdogan

In this theoretical paper, a transport-reaction mechanism is suggested for the enhancement of the rate of vaporization of metals, or other materials, brought about by the process of convection and condensation. Based on theoretical reasoning it is predicted that, when there is a temperature gradient surrounding the heated object, a slight increase in the rate of vaporization brought about by natural convection is enhanced further as a result of condensation of the vapor close to the surface of the object. In order to derive the effective vapor-concentration profile, consideration is given to the super saturation of the vapor necessary for the homogeneous nucleation of the condensed phase from the vapor. For the formulation of the rate equation based on this mechanism, adequate information should be available on the transport properties of gases and vapors at elevated temperatures and the method of calculating nucleation pressures of the vapor. The methods of deriving such data are discussed in the paper and a rate equation is calculated for the vaporization of iron in helium for various temperature gradients in the boundary layer. Considerations are also given to the effect of oxygen on rates of vaporization of metals under isother ma1 and nonisotherma1 conditions. THE study of the methods of enhancement or retardation of basically transport-controlled vaporization reactions is of theoretical interest with possible practical implications. There are several ways of bringing about such effects. For example, Turk-dogan, Grieveson, and Darken1 demonstrated that the rates of vaporization of metals under isothermal conditions were increased by several orders of magnitude, up to the maximum rate attainable in vacuo, by introducing some reacting gas into the inert atmosphere surrounding the metal. Such an effect is brought about by the interaction of the counter-diffusing reacting gas and metal vapor in close proximity of the metal-gas interface. Another case which is often experienced in practice is that of vaporization affected by natural convection. Although several theoretical and experimental studies of this problem have already been made, no detailed consideration has been given to the possible effects of condensation of the vapor in the boundary layer on vaporization rates, which constitutes the subject matter of this paper. BASIC CONCEPT OF ENHANCED DIFFUSION-LIMITED VAPORIZATION When a heated object, for example a metal sphere, is submerged in a fluid medium, heat is transferred from the surface of the object to its surroundings by four simultaneously occurring transfer processes: i) free-molecular conduction at the gas-solid interface over the distance equal to the mean free path of the gas, ii) conduction and convection through the fluid-dynamic boundary layer, iii) latent heat of mass transferred, and it!) radiation. The free-molecular conduction becomes pronounced only when the total pressure in the system is very low, e.g., below 1 mm Hg. Therefore, this term may be neglected for ordinary pressures. At low mass-transfer rates, due to vaporization of the object, the contribution of process iii) to the heat transfer can also be neglected. Finally, since the temperature profile is not affected by radiation, the latter need not be considered. The natural convection is brought about by gravitational body forces arising from a decrease in the

Jan 1, 1964

By Philip D. Anderson, Ralph Hultgren

Heat contents of extremely pure iron were measured over the range 300"to 1433"K, using a diphenyl ether calorimeter. Results from three samples containing widely differing impurities agreed with one another and with Previously reported results at higher temperatures (1184 ° to 1809°K) by Olette and Ferrier. From these data a table of heat contents of iron has been Prepared which is believed to be more accurate than those previously available. CP values have been derived which are consistent with these heat contents, with the best experimental Cp data, and with the thermodynamic conditions of equilibrium between bcc and fcc iron. The opinion is expressed that low-temperature extrapolations of presently known Cp values for y-Fe are not reliable. It would seem that the thermodynamic properties of iron, which is by far our most important metal, should have been well established long ago. This is not the case, however. As discussed by Olette and Ferrier,' there is objection to every earlier heat content measurement. While the best true Cp determinations agree well at temperatures below the Curie point, there is wide divergence at higher temperatures. Several investigators have examined available data and attempted to calculate thermodynamic functions for iron that are consistent with the two equilibrium temperatures of bcc and fcc iron. The two primary efforts were those of Austin' in 1930 and Darken and smith3 in 1948. The recommended values differ considerably; integration of Austin's Cp values leads to a heat content at 1100°K which is 300 cal per g-atom higher than the value recommended by Darken and Smith. The compilation of Fisher4 in 1949 was based on the selection of Austin. In 1956, Weiss and Tauer obtained yet another set of values by resolving Cp values into components due to dilation, lattice vibration, electronic excitation, and magnetism. The magnitude of contribution by each component and its dependence on temperature was estimated by semiempirical means. Their values are not self-consistent in that they do not form smooth curves when plotted vs temperature; moreover, their calculations cannot easily be repeated since they do not give the values of some of the parameters used. Clearly, experimental values for iron were in a most unsatisfactory state. The presently described measurements of the heat content of iron were therefore undertaken, covering temperatures as high as 1433°K. While the work was in progress, the high-temperature (1193" to 1789"K) heat content measurements of Olette and Ferrier' were published; in the region of temperature overlap the present results agree with Olette and Ferrier well within experimental accuracy. It is believed that the present results, combined with those of Olette and Ferrier, provide for the first time a reliable set of heat contents of iron from room temperature to the melting point. From these data, guided by available Cp measurements, it proved possible to derive Cp, entropy, and free energy function values for @-iron from room temperature to the melting point, and for y- iron in the temperature region of its stability. Exhaustive study led to the conclusion that extrapolations of y-iron functions to room temperature were not reliable enough to be useful; hence these have been omitted from the tables. EXPERIMENTAL Materials. Three samples of extremely high purity iron from different sources, containing widely different impurities, were measured. The first of these, designated "Chipman", was kindly supplied by Dr. K. K. Kelley of the U. S. Bureau of Mines from a lot which was made many years ago by Dr. John Chipman of the Massachusetts Institute of Technology. The second, designated6'Teddington", was supplied by the National Physical Laboratory, Teddington, England, from a lot zone-refined by them. The third sample, designated "Irsid", was supplied by the Institute de Recherches de la

Jan 1, 1962

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

SINCE the beginning of this century it has been known that hydrogen contributes to the porosity of steel and that it is harmful to its mechanical properties. The evidence for this has been largely qualitative. Steel to which hydrogen was purposely added. in sufficient .amounts was shown to be either porous or brittle or both, whereas similar steel of low hydrogen content was shown to be free of porosity and to possess normal physical properties. There have been a considerable number of qualitative experiments of this type. Also, early in this century, a few attempts were made to measure the amount of hydrogen normally dissolved in commercial steels. This was usually done by placing the sample under an inverted liquid column such as mercury and collecting the evolved gas. These attempts, while not successful in measuring actual amounts of dissolved hydrogen gas, were able to prove that this gas will diffuse out of steel at room temperature, and that the amount of hydrogen dissolved is normally very small. On the basis of such qualitative evidence, hydrogen has been and still is blamed for a great number of the troubles encountered in the steel industry. In recent years, partial solutions for many steel-working problems have been obtained. These have led to increased interest in accurate quantitative work on hydrogen in steel, with the expectation that the results might possibly answer a few of the remaining unsolved problems. Commercially, two of the obvious questions which are in need of an answer are: (1) what are the most important sources of hydrogen, and (2) what quantity of hydrogen can be tolerated in various steels? There are many other unanswered questions. To begin to find the answers it seemed logical to start at the beginning of steel production with the liquid metal. Further, it seemed almost imperative to solve first the problems of analysis and sampling of the metal for hydrogen. Once these problems have been solved, it would be possible to answer more of the important commercial problems mentioned above. As a consequence, it was decided to design an analytical apparatus and, upon satisfactory completion of this, to develop an accurate method of sampling liquid metal for hydrogen.

Jan 1, 1951

By N. A. Gokcen, M. Ohtani

Thermodynamic intevaction pararnetevs of elements E2(2), for dilute binary solutions of a component "2" in liquid iron, i.e., E(22) = 9 In f2/?N2 where f2 is the activity coefficient and N2 the mole fraction, and E(3) 2 = In f2/ N3 dilute ternary solutions of "2" and "3," and the carbon saturation parameter sc(3) (In f c/ N3) N c/N Fe for N3 - 0, are critically examined and correlated. It has been found that the interaction parameters and the atomic numbers of alloying elements follow regular periodic putterns. PHYSICO-chemical behavior of alloying elements in molten iron have become the subject of numerous investigations during the past 25 years. Consequently, the mutual effects of elements in the iron-rich solutions Fe-C-X, Fe-N-X, Fe-H-X, Fe-O-X, and Fe-S-X where X represents an alloying element, have gradually become better understood. These effects for a given temperature and pressure may be expressed by the interaction parameter of Wagner1, 2 derived briefly in the following manner. The complete differential of the Gibbs free-energy equation at constant temperature and pressure is dF = Fl dn, + F2 dn, + F3 dn3+ . . . [ 1] where F is the free energy; F 1, the partial molar free energy of "I"; and n,, the number of moles of "i." Cross-differentiation of this expression* *Cross-differentials are obtained as follows: Since the order of differentiation of F with n2 and n3 is immaterial, the left sides of the second differentials are equal, hence the derivation of Eq. [2] is obtained. For a dilute solution of components 2 and 3 in solvent 1, with the substitution of RT In f i = Fi xs for Fi where fi is the activity coefficient, and Fixs is the excess partial molar free energy, Eq. [2] becomes O) [3] where N2 and N, are the mole fractions. The interaction parameters are defined by

Jan 1, 1961

By Avnulf Muan, Egil Aukrust

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

Jan 1, 1964

By Avnulf Muan, Egil Aukrust

Activity-composition curves jor cobalt oxide and manganese oxide in solid solutions with spinel-type structure have been determined by studying the equilibrium between the spinel phase and a coexisting solid-solution phase in the tewzperature range 1100" to 1400"C. Within limits of experimental error, the system displays the behavior of a regular solution. The excess integral free energy of mixing is represented by the equation . The standard free energy of formation of cobalt manganite, CoMn,O,, from the oxide components COO mzd Mn2OS at 1200°C is calculated to be -8.6 kcal. AMONG the technologically and theoretically most important oxide phases are those which crystallize with the same structure type as the mineral MgO . A120,. Although the name spinel originally was used only for this mineral, the term is generally used today to designate the whole group of oxide phases with this same structure type. It is in this wider meaning that the term is being used in the present paper. The previous literature on spinels is very extensive. There are two aspects of spinels which have attracted particular attention: the structure, including the nature and distribution of the cations present, and the physical properties (electric, magnetic). The status of knowledge in these fields has been well-summarized in recent review articles.1'2 By contrast, thermodynamic properties of spinels are virtually unknown. Delineation of the activity-composition curve over the whole composition range of a solid-solution series with spinel-type structure is the objective of the present work. The system at elevated temperatures (>1000"C) constitutes such a series. The activity-composition curves for this system can be calculated from a study of the equilibrium between the above spinel solid solution and a solid solution (Co,Mn)O with sodium chloride-type structure. Data for the latter solid solution have become available recently.3 The system, in contact with metallic CO at 1200°C, obeys Raoult's law. The determination of the activity-composition curve for the spinel phase is based on the following relations. Consider the reduction-oxidation equilibrium for cobalt ions according to the equation: Because it is impossible in practice to measure single activities of electrically charged constituents, we will treat the equilibria in terms of electrically neutral components. Eq. [I] can then formally be written as follows: where and the activities of cobalt oxide in the (Co,Mn)O and the spinel solid-solution phases, respectively, K is a constant at constant temperature, and Pa is the oxygen pressure of the gas phase. The numerical value of K can be determined from a determination of the oxygen pressure P& for the equilibrium coexistence of Cos04 and COO in the binary system Co-0. Under these circumstances be set equal to 1, and hence K = [Po Eq. [3] can therefore be written

Jan 1, 1964

By C. W. Sherman, J. Chipman, H. I. Elvander

THE pronounced and usually deleterious effects of sulphur on all ferrous metals and the resultant necessity for its control in metallurgical processes have stimulated many investigations of the system iron-sulphur. The data required for thermodynamic study of the behavior of sulphur in molten iron and steel include the activity and free energy of the dissolved sulphur and its heat of solution. Such data are also of theoretical interest since there is all too little information available concerning solutions of nonmetallic solutes in metallic solvents. It was the purpose of this investigation to attack the problem very directly by a study of equilibrium at several temperatures in the reaction H2 (gas) + S = H2S (gas) [1] K1 = PH2S /PH2 as where the sulphur is present in the liquid iron in amounts up to several percent by weight. Such a method of attack is not new since several careful studies have already been reported. It is planned, however, to extend the study to other metallic solvents and particularly to determine the effects of the various alloying elements on the activity of sulphur in liquid iron. This paper presents the results on molten iron-sulphur alloys containing up to 4 pct sulphur in the temperature range 1530°-1730°C. Literature Review The significant researches on dilute molten solutions of sulphur in iron include those of Chipman

Jan 1, 1951

By H. F. Ramstad, F. D. Richardson

The equilibria (a) SiOz +Hz =SiO +H20 and (b) Si + SiO, = 2Si0 have beet1 studied at temperatures of 1425"to 1600°C ad 1310°to 1485°C respectively. The stattdard free energy changes for the tzrro reactions are given by the equatiotts Combination of the results for both equilibria leads to tiotz removes certain anomalies in existing high-terlzperature data for equilibria involving silica and silicon in iron. In many metallurgical processes and in many laboratory investigations silicon monoxide undoubtedly plays an important role. It is unfortunate therefore that wide differences exist between the results obtained by different investigators1-7 in their studies of such equilibria as In an attempt to put our knowledge of SiO on a surer basis, an exhaustive study has been made of equilibria [I] and [2] at temperatures ranging from 1300" to 1600°C. Reaction [I] was studied by measuring the amounts of silica which could be condensed from streams of Hz or Hz + HzO which had previously been brought into equilibrium with silica at temperatures ranging from 1425" to 1600°C. Reaction [2] was studied by measuring the material that could be condensed from streams of Hz or argon which had been brought into equilibrium with mixtures of silicon and silica at temperatures ranging from 1310" to 1485°C. EXPERIMENTAL Materials. The silicon was "superpure" grade and contained less than 0.1 pct impurities. The silica was prepared from pure mineral quartz; this was crushed and treated with concentrated hydrochloric acid to remove particles of iron, washed with water, and finally dried at 120°C. For the hydrogen + silica reaction, the silica was sized to —20+100 mesh. For the silicon + silica reaction, the two materials were ground to a fine powder in an agate mortar. The hydrogen and argon were commercial oxygen-free gases. The gas streams were controlled with capillary flow meters and the volumes were measured by wet gas meters. After passing through the meters, the gases were partially dried by silica gel. The hydrogen for the HZ + SiOz reaction was then passed through palladised asbestos at 300°C and dried with magnesium perchlorate. The efficiency of oxygen removal was checked throughout the experiments by passing the gas over an electrically heated strip of nichrome, used as an indicator as described by Rathman and de itt.' When mixtures of HZ + Hz0 were required, the partial pressures of water vapor (1.8 to 22 mm) were obtained by passing the hydrogen through oxalic acid dihydrateg' lo held at various controlled temperatures, O.l°C, by means of a water bath. The hydrogen for the Si + Si02 reaction was purified by passing it over a mixture of 3 parts of magnesium to 5 of lime heated to 600°."l1 u The argon for this reaction was passed through titanium powder (-3/16 in. + 100 mesh) heated to 900°C. The nitrogen used to prevent the reaction products escaping from the condenser (see later), was deoxidized by copper or iron at 600°C. All these gases were finally dried with magnesium perchlorate. Furnace, Temperature Contr01, and Measurement A molybdenum resistance furnace was used for both sets of experiments. The reactions were conducted inside a high-grade alumina tube, 36 in. long and 1 in. in diam as indicated in Fig. 1. With this arrangement an even temperature zone (2"C) 4 cm long was satisfactorily obtained. The temperatures were kept constant by means of a proportional controller actuated by a Pt-Pt 13 pct Rh thermocouple. This was placed between the two alumina tubes, so that the temperature at the junction was 1400" to 1450°C. Up to 1485"C, the temperatures were measured with Pt-Pt 13 pct Rh thermocouples. For higher temperatures an optical pyrometer was used, this being sighted (through the glass window 1 in Fig. 1) on the end of the alumina tube, that held the SiOz or Si +SiOz mixture, 10 in Fig. 1. The optical pyrometer was recalibrated whenever a change was made in any part of the apparatus situated in the hot zone. Successive readings with the optical pyrometer were reproducible to within 1"C. Equilibrium Apparatus and Procedure. Hydvogen and Silica Reaction. The apparatus is shown in Fig.

Jan 1, 1962

By AIME AIME

BEFORE proceeding with the papers scheduled for the ore and foundry session*, the teller's report on the election of officers for the ensuing year was presented, a; follows: Chairman. G.C. F. MacKenzie; vice-chairmen, C.S. Robinson, J. T. MacKenzzie, C. E. Meissner; executive committee, A. L. Field, R. F. Harrington, E. F. Kenney lit. Waterhouse announced that the fall meeting will be devoted to alloy steel. This meeting will be held in Chicago the week of Sept. 22 in connection with the National Metal Congress. He also announced that oxygen in steel will be the central idea of the meeting which will be held in New York next February. The first paper, entitled "Sintering Limonitic Iron Ore at Ironton, Minn.," was presented by Perry G. Harrison (T. P. 284), the author. Sintering was first un¬dertaken in 1024 to treat Cuyuna range iron and manganiferous ores low in silica and high in moisture and containing objectionable qualities of fine... A Dwight-Lloyd machine was first installed. This machine was replaced by a larger one having a width of 72 in. The power cost was decreased from about $11.22 per ton of sinter on a 42-in. machine to about X0.14 for the 72-in. machine. The tons of sinter per man-shift was increased from 11.86 to 16.77. Improvements embodied in the larger plant reduced the cost of sintering to $0.41. The analyses of iron ore and manganiferous ore and the sinter produced from these materials was used to show the increase in value at the mine resulting from sintering. Crude iron ore actually unsalable was increased in value f.o.b. mine from a theoretical figure

Jan 1, 1930

By AIME AIME

THE first meeting" of the Iron and Steel Division was held Tuesday afternoon, Feb. 17, with nearly 100 men present and C. B. Murray as chairman. This was a round table discussion of iron ore beneficiation and of its relation to blast-furnace operations, and only one paper was presented, by Clyde E. Williams. Mr. Williams discussed the future of the Lake Superior district in its relation to the iron and steel industry. He stated that although estimates had shown that the total life of the present known iron ore reserves of the Lake Superior district was 20 to 30 years and that many believed that as a result of this depletion foreign ores would be brought to the Atlantic Seaboard, thus causing a displacement of the steel industry to the East, he believed that the Lake Superior district would continue to be the important producer of iron ore used in this country for decades beyond the predicted time before the exhaustion of the present known reserves. He described the three general types of ores that required concentration and pointed out the needs for research and the proper methods to be used in processes for the beneficiation of these low-grade materials. He discussed the effects of fine concentrates and the use of agglomerated ores in the blast furnace. This general summary led to interesting and valuable discussion on the various economic, ore-dressing, and blast-furnace problems in large-scale development of beneficiation. Perry Harrison described recent developments in sintering and the properties of iron ore sinter. T. B. Counselman and W. H. Coghill discussed the merits of classification of iron ore previous to tabling. Robert Faulkner and J. E. Little described the beneficiation plant of the Bethlehem Steel Corporation.

Jan 1, 1931

THE first session, on alloys, took place on Feb. 20, Mr. Hibbard presiding in Mr. Campbell's absence. The session covered papers on manganese, chrom-ium, and silicon-iron systems. The paper by Mr. Wohr-man was presented by title. This paper showed that manganese produced many of the effects generally at-tributed to carbon and indicated that our ideas on manganese-bearing carbon steels will have to be modi-fied. Mr. Krivobok discussed this paper at length, the gist of the discussion being that Mr. Wohrman had not taken sufficient precautions in carrying out some of his work, particularly as to the effect of silicon content. Mr. O'Neill's paper was also submitted by title and no discussion was presented. Mr. Kinzel showed an accu-rate determination of .the carbon-free chromium-iron loop obtained by means of a specially constructed tele-scopic dilatometer. The loop ends at 12.2 per cent chromium and the A-3 line at 900° is unaffected by chromium content. The A-4 line runs from 1400° to 900° at 12.2 per cent chromium as an oblique hyperbola. Mr. Armstrong noted that the brittleness in high chromium alloys is often attributed to the gamma trans-formation and, according to Mr. Kinzel's diagram, this was impossible, as the alloys contain a great deal more than 12 per cent chromium. Mr. Kinzel pointed out that the presence of carbon in the commercial alloys caused the elongation of the loop and made possible local austenite transformation. Mr. Styri discussed the relations of the coefficients of expansion as shown in Mr. Kinzel's diagram. Mr. Corson presented the iron-silicon diagram as he has worked it out, showing a pre-viously unknown intermetallic compound, Fe3Si, to-gether with characteristic martensitic microstructure varying with the heat treatment. This compound formation is the real cause of brittleness in certain re-gions of the iron silicon system. Dr. Hoyt believed some of the evidence presented by Mr. Corson to be in contradiction to the phase rule. Mr. Corson, however, explained that true equilibrium does not exist under the conditions at hand so that the diagram was accurate in spite of the discrepancies. The meetings of the subcommittee on the physical chemistry of steel making were interspersed through-out the day. Mr. Feild presided and a program of future activities was outlined. This includes plans for a symposium at the next annual meeting and methods for interesting physical chemists, particularly those in the universities, in the steel man's problems. This committee has been newly formed and bids fair to be especially active. The Iron and Steel Committee met at lunch at the Engineers' Club at noon, with Dr. Mathews presiding. After disposing of the food the report of the Nominat-ing Committee was called for, and the following were elected as officers for 1928: R. H. Sweetser, chairman; F. C. Langenberg and W. J. Priestley, vice-chairmen; and T. T. Read, secretary. The report of the commit-tee appointed at the last meeting to consider publica-tion and general policy for the committee was then called for and freely discussed, after which it was unanimously voted to instruct the new chairman to se-cure from the Board of Directors the necessary author-ization for the Committee to recognize as a Division. This action was reported to the Board at its meeting the following night and the authority granted.

Jan 3, 1928

By Clyde E. Williams, JAMES L. GREGG

THIS review of the past year's progress in iron and steel metallurgy presents examples of only a few of the interesting or important accomplishments made in the United States. In the field of iron ore concentration increased attention was given to the study of the more difficultly separated wash ores and some progress was made in tabling. One difficulty with the table, in concentrating iron ore where the percentage of concentrate in the feed is large, has been the removal of fine silica from the thick layer .of concentrates in the cleaning zone. One company has -Made an important contribution toward the solution of this problem by an extension of the well-known plateau principle. By a special riffling of the plateau section of the table, the concentrates are crowded together. This action forces the fine silica to the top of the bed in the cleaning zone, whence the cross-flowing currents of water -can wash it into the middling product. Some work has been done on the application of froth flotation to the concentration of iron ores. Laboratory experiments were made at the Colorado School of Mines in which hematite was, successfully floated. Using oleic acid as a frothing and collecting agent and sodium carbonate as the conditioning agent, a high recovery of rich ,concentrate was obtained. A laboratory flotation unit is in use at Taconite, on the Mesabi range, and a commer-

Jan 1, 1932

By G. B. WATERHOUSE

THE year 1929 was exceedingly busy and prosperous for the iron and steel industry in the United States. The lake shipments of ore were approximately 65,000,000 tons, steel ingots produced were about 57,000,000 tons. Plants were very active. operating for many months well over their rated capacity, slowing down during the last quarter following the severe break in the stock market. The ore tonnage mentioned above was the greatest ever shipped by lake from the Lake Superior region. The trend at the ore mines has been to supplement manual labor by mechanical appliances as much as possible. Mining methods have been greatly improved along the lines of safety as well as to increase the percentage of ore recovery. Crushing and grading of iron ores continued to gain in popularity inasmuch as remarkable blast-furnace operations and records were obtained with sizing and uniformity of raw materials. Progress was made along other lines. The Bradley process for the separation of manganese osicle and iron oside from siliceous manganiferous iron ore was cleuelopecl; also considerable work was clone on a process for the beneficiation of the Cuban laterite ores. Sintering of ores and concentrates increased in popularity. A new analytical method for the deter- mination of sulfur in iron ore was worked out which reduced the time required appreciably. The ore re- serves of the Lake Superior district continued to receive considerable attention and played an important part in the recent mergers which have taken place in the iron ancl steel industry.

Jan 1, 1930

By Clyde E. Williams

THIS review of the progress made in iron and steel metallurgy during the past year is confined to developments in this country. It attempts to give examples to illustrate progress made rather than to appraise results. As a result of the gradually diminishing supply of rich iron ores and of predictions made as to the probable life of the iron-ore reserves of the Lake Superior District, attention of iron and steel executives was directed to the question of beneficiation of iron ores. Laboratory and plant-scale experimental work was conducted on the wash ores .of Minnesota and an investigation, was, begun on the Old Range low-grade ores.

Jan 1, 1931

By AIME AIME

T HE Institute of Metals Division and the Iron and Steel Division will meet jointly at the Stevens Hotel, Chicago, during the week of the American Metals Congress, Sept. 22-26. The Iron and Steel Di- vision of the American Society of Mechanical Engineers, the American Society for Steel Treating and the American Welding Society meet at the same time. but the sessions have been arranged to conflict as little as possible. A rich program of papers and plant visits has been arranged for the members and guests of the two Institute Divisions. The annual dinner and a pro- gram of entertainment are being arranged by the Woman's Auxiliary of the Chicago Section. Members are urged to register immediately up011 arrival and to make dinner and plant visit reservations at the same time.

Jan 1, 1930

By L. Su, S. Liu, K. Jiang, K. Xie

The reduction of iron dissolution and acid consumption is fairly important in the extraction of Ni and Co from laterite ores from both economic and efficiency perspectives. BGRIMM conducted detailed research to investigate the behavior of iron in a nickel laterite leaching process. The mineralogy of Ni and Co was studied. In limonite ore about 76% of nickel is present in goethite while in saprolite ore 79% of nickel is associated with magnesium and silicon minerals. Test work revealed that limonite can be decomposed completely with enough acid concentration during atmospheric leaching. More than 98% of Ni and Co were leached into solution while 85% of the iron was also dissolved with 130-140 g/L iron in solution. Iron precipitates as hematite in the temperature range 250-270?C without neutralization reagents. That’s why limonite is treated by high pressure acid leaching (HPAL) technology to achieve nickel extraction and iron precipitation in the same autoclave. BGRIMM’s test results indicated that the remaining acid in atmospheric leaching solution and acid released by iron precipitation at a lower temperature was enough to leach saprolite efficiently. The so-called inverse leaching technology leaches limonite at atmospheric condition and the leaching slurry combined with saprolite is pumped into an autoclave to leach saprolite at 150-170?C. In the autoclave iron precipitates as hematite without acid consumption. Total nickel and cobalt extractions in the test program were more than 90% with iron content in solution below 8 g/L. In this inverse process iron dissolves in the atmospheric leaching stage and precipitates as hematite in the low temperature leaching stage. Compared with HPAL the leaching temperature is reduced to 150-170 ºC from 250-270 ºC. Compared to atmospheric tank leaching acid consumption is reduced from 850-950 kg/t ore (atmospheric) to 550-650 kg/t ore (inverse).

Jan 1, 2016

By G. W. Josephson

WHILE methods of utilizing blast-furnace slag have been developing, a great deal of literature on the subject has accumulated, but no comprehensive summary of information that would be helpful to engineers, contractors, architects, chemists, and others in under-standing and more successfully using this byproduct of the iron and steel industry has been published in the English language. The National Slag Association recognized the need for such a publication, and the Problems Committee of the Association under-took in 1943 to accumulate the necessary material. Over a period of several years this committee compiled pertinent information in manuscript form, and in 1948 the Bureau of Mines and the National Slag Association made an agreement whereby the Bureau was to prepare the data for publication as a cooperative bulletin of the Bureau of Mines and the National Slag Association.

Jan 1, 1949

By Cripps-Clark CJ, Deague TK

In order to study conditions under which SiO(g) may be formed in a blast furnace, equilibrium phase diagrams were constructed for the combustion of high and low ash cokes with oxygen-enriched blast and oil injection under conditions of high and low raceway pressures. Free energy minimisation techniques were used to calculate the composition of gaseous and condensed phases. Where coke ash is assumed, for simplicity, to comprise Si02 only, the coke can be comple- tely gasified, mainly to SiO and CO, under restricted conditions of coke to blast ratio and at temperatures greater than 1600 - 1650¦C, depending on system pressure. The formation of SiO(g) is partially suppressed by the introduction of alumina into the ash, because of the formation of solid and liquid alumino- silicate compounds. The minimum temperature for complete silicon gasification is raised to about 1700¦C. The results of the equilibrium calcula- tions are related-to actual raceway conditions. It is proposed that virtually all silicon in the coke ash is gasified such that, on condensation, it affects hot metal chemistry and slag properties and secondly, that the effects will be greater with higher ash cokes.

Jan 1, 1980

By W. H. Caruthers

ECONOMIC utilization of all by-products has long been the goal of American industry. One of the first groups that was popularly supposed to have achieved its aim was the meat-packing industry, which reputedly found a use for everything except the squeal of the hog. To the metallurgist, slag has always been the principal wasted by-product, representing a loss not only of material, but of heat. Slag does not possess many qualities that appeal to man's imagination or suggest a romantic influence on the daily life and progress of a community or nation. It is a bulky product, and space for its disposal within reasonable hauling distance of a smelter is not always available; the iron-ore smelter especially has been wont to find space for slag disposal at a premium. Therefore, the success that has been attained in recent years in finding a use for iron blast-furnace slag is notable. It has become a vital economic factor in the construction industry in areas where it is available. Its use may suggest further possibilities of an economic outlet for the slags from nonferrous smelting as well.

Jan 1, 1940