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Discussion Of the paper Of GEORGE K. BURGESS, J. J. CROWE, H. S. RAWDON, and R. G. WALTENBERG, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin NO. 93, September, 1914, pp. 2433 to 2437. ALBERT SAUVEUR, Cambridge, Mass.-The Bureau of Standards has once more rendered a public service. Manufacturers and consumers of steel rails alike should welcome the important results now laid before them by Dr. Burgess and his co-workers. Personally I welcome these results all the more that in the past, as some of the members may remember, I have never failed, when occasion arose, to call the attention of rail manufacturers to the importance of controlling the finishing temperature of their rails. The pioneer metallographic work conducted at the South Works of the Illinois Steel Co. in the early '90s clearly brought out the close relations existing between the manufacture, properties, and finishing temperature of steel rails and I think I may say without fear of being contradicted that the results of this early investigation had considerable influence in drawing the attention of manufacturers to the importance of finishing temperature and of heat treatment in general. The results now before us should be, it seems to me, of great value to rail manufacturers in their efforts to produce a better and, above all, a safer rail. It seems to be demonstrated in this paper that there is no difficulty in installing in rail mills pyrometric outfits, making it possible to record, without interfering in the mill operations, the temperature of the rails as they leave the finishing rolls, or of the ingots as they are withdrawn from the soaking pits, or at any intermediate point in the process of manufacture. The inference necessarily follows that manufacturers should see to it that such pyrometric installations are made, in order that they may actually know, instead of guessing at, the temperature of their rails;, and, for obvious reasons, rail consumers should insist upon such installations. In the rolling of heavy sections especially should care be taken to lower their finishing temperature, seeing that the present tendency is to finish them at higher temperature, whereas, owing to the slower cooling of their central portions, which makes for coarseness of grain, they should, if anything, be finished at a lower temperature than lighter rails.

Jan 4, 1915

By R. G. Vardiman, M. R. Achter

Observations of dislocation structure in niobium are presented using two techniques. Triangular pits developed by electroetching are confined to orientations in the stereographic triangle between the (111) pole and planes of the (1ll) zone and require the presence of carbon. Some unusual electroetching phenomena at other orientations are noted. A chemical etch of dislocations decorated by the addition of carbon to 50 ppm reveals the complete dislocation line structure in a surface layer up to 30 p deep, with a resolution of less than 1 p. This effect is independent of surface orientation. The structure of subboundary nets may be resolved for misorientations up to about 1'. Dislocation structures found in strain anneal grown crystals, such as helices, prismatic loops, and high-density areas, are observed. The measurement of dislocation density is discussed and values obtained in different ways are compared. IN the course of some work on the response of refractory metals to thermal-mechanical treatments, it was desired to examine the defect structure of relatively low dislocation density crystals of niobium in bulk form. Surface and bulk methods for the observation of dislocations have been reviewed by ~melinckx,' and include etch pitting, decoration, and various X-ray techniques. The dislocation line structure has been developed by decoration in a few metals, although observations were limited to certain orientations, or by the coarseness and nonselectivity of the precipitate. The most commonly used technique is etch pitting. In niobium, etch pits have been developed chemically'0," in material of high impurity content and electrolyti-cally'' in relatively pure material. In this paper, etch pits developed electrolytically, and the dislocation line structure of a surface layer developed by decoration and chemical etching, are examined, and observations are presented from both techniques. EXPERIMENTAL METHODS Our starting material was electron-beam-melted niobium, swaged to 4 or -in.-diam rod. Chemical analysis is given in Table I. Single crystals were grown by a strain anneal technique using 1 to 2.5 pct of strain and growth temperatures of 1700" to 2300"~.'~ Some crystals grown by zone melting were also examined. The desired surface orientation was exposed either by spark machining or by sectioning with a cut-off wheel and prepared for etching by electro-polishing.

Jan 1, 1969

By P. M. Robinson, M. B. Bever

THE heats of formation at 273°K of the compounds InBi, In2Bi, and TIBi2 have been determined by metal solution calorimetry with bismuth as solvent. The published information on the thermody-namic properties of these compounds is limited. The structure of the compound InBi (mp, 383°K) is tetragonal of the PbO (B10) type.1 The compounds In2Bi (mp, 362°K) and TIBi2 (mp of highest-melting composition, 486°K) are now believed to have structures of the NizIn (B8) type273 and not the A1B2 (C32) structures reported earlier.4, 5 The compounds In2Bi and TIBi2 have limited homogeneity ranges at room temperature, while the compound InBi has no detectable homogeneity range.' Samples of the compounds were prepared from 99.99 pet Bi (Mallinckrodt Chemical Works), 99.999 pet in (American Smelting and Refining Co.), and 99.99 pet Tl (Amend Drug and Chemical Co.) by melting the components in sealed, evacuated Vycor tubes. The compounds InBi and in2Bi were of the stoichiometric compositions. The compound TIBi2 contained 40 pet T1; this composition was chosen because at room temperature the alloy of stoichiometric composition does not lie within the homogeneity range.' The melts were held approximately 50°C above the liquidus for 8 hr and then quenched into iced brine. The samples were homogenized for 48 hr at temperatures 20°C below the temperature of complete solidification. Metallographic examination of sections taken from the center and the ends of the ingots did not reveal second phases or segregation . The heats of formation were determined as the difference in the heat effects on solution of a compound and of a mechanical mixture of its components added from the reference temperature of 273°K to liquid bismuth at 623°K. The details of the calori-metric procedure and method of calculation have been described elsewhere? The calorimeter was calibrated by adding bismuth at 273°K to the bismuth bath at 623°K. The calculated values of the heats of formation of the compounds, listed in Table I, are based on a value of 4.96 keal per g-atom for the difference between the heat contents of bismuth at 273" and 623oK7 No published values are available for the heats of formation of the compounds InBi and In2Bi. Hultgren et a1.7 have calculated a value of -0.50 i 0.10 keal per g-atom for the heat of formation at 423°K of the compound TIBi2 containing 40 at. pet T1 from heat-content measurements in the range from 398" to 700°K and the heats of formation of the liquid alloy. The difference between this value and the value of -0.66 * 0.01 keal per g-atom at 273°K is too large to be attributed to a difference between the heat capacities of the compound and the components over the temperature range 273o to 423oK7 However, the direct determination of the heat of formation by a calorimetric method should give a more accurate value. The heats of formation at 273°K of the compounds InBi and In2Bi lie on a straight line when plotted as a function of composition, Fig. 1. The compound In2Bi, therefore, appears to be barely stable with respect to its neighboring phases. In order for the free energy vs composition curve to be concave towards the composition axis, the entropy change on formation of In2Bi must be more positive than that on formation of InBi. As the compounds are ordered,2, 3, 8 there is no configurational entropy change on formation. The difference between the entropy changes on formation of the two compounds, therefore, is probably associated with the vibrational entropies. In view of the low heats of formation, the changes in vibrational entropy, due to changes in bond strength on formation of the two compounds, are likely to be small. Owing to the volume contractions on formation of the two compounds,5 the vibrational entropies probably decrease slightly but the decrease of the vibrational entropy of InBi is expected to be larger than that of In2Bi.

Jan 1, 1965

By J. E. Forciea, O. E. Palasvirta, L. G. Hendrickson

AH pilot and commercial plants working with Mesabi Range taconite employ wet magnetic separation. Progress is being made with a dry magnetic process, but this has not yet been applied to taconite except in the laboratory and pilot plants. Flowsheets in all five plants are similar, including multiple stages of grinding, each followed by magnetic separation, which rejects a finished tailing. The flowsheet in Fig. 1 is used in the preliminary and commercial plants of the Erie and Reserve mining companies and in Unit C of Oliver's Pilotac plant. At Erie the desliming operation is omitted. In the Reserve plants two ball mills are used with each rod mill. Pilotac uses flowsheet 2 in Unit A-B and has also tested flowsheet 3. Principal differences in the three flowsheets are the number of grinding stages and the type of roughing. The terms open-circuit roughing and closed-circuit roughing are best defined by the diagrams. Special Test Data Given in Table I: For the Erie and Reserve commercial plants, Table I reflects routine conditions. Pilotac, the experimental plant, has been run with several flowsheets, including those followed at Erie and Reserve's commercial operations. Pilotac data for these last two flowsheets are similar to commercial plant results and are not repeated in Table I; statistics are given, however, for special test conditions. using other flowsheets. when the objective was to 'to extra-grade concentrate, Variations Among Taconites: Although crude ore tributary to these plants is generally classified as taconite, there are important differences in mineralogy and fineness of dissemination.

Jan 1, 1959

[ARIZONA Established July 10, 1915 ROBERT W. HUGHES, Chairman CHARLES R. KUZELL, First Vice-Chairman GILBERT C. DAVIS, Second Vice-Chairman W. CLARK MASON, Secretary-Treasurer Inspiration Cons. Copper Co., Inspiration, Ariz. LYLE BARKER ROBERT HIGH T. G. CHAPMAN P. D. I. HONEYMAN GEORGE M. COLVOCORESSES WALTER C. LAWSON EDWIN H. CRABTREE, JR. W. H. LOERPABEL WALTER I. GARMS ALBERT MENDELSOHN WESLEY P. Goss CARL E. MILLS H. C. HENRIE JOSEPH A. WILLCOX C. F. WILLIS]

Jan 1, 1946

By A. F. Melcher

THE present paper is a progress report. on an investigation of the physical factors of oil and gas and especially of their sands, I such as-pore space, size of pores or permeability, retentivity, viscosity of the oil, temperature, pressure, thickness and area of the pay sand, water relations, and capillarity. The purpose is to determine as many of these physical factors as possible, and to ascertain the relations existing, directly or indirectly, between these physical factors and the production of oil and gas. As yet only pore space2 and size of grains of pay sands have, been investigated, although an apparatus has been designed to determine the permeability of a sand to oil, water, or gas under definite drops of pressure between the entrance face and exit face of the sample. Messrs. E. W. Shaw, R. Van A. Mills, D. Dale Condit, G. B. Richardson, G. C. Matson, and C. H. Wegemann collected the samples upon which the physical determinations were made. Acknowledgment is made to my colleagues of the United States Geological Survey for many suggestions and criticisms; to Mr. Mills for the production data given of the oil wells from which some of the samples were collected; to Mr. A. W. McCoy of the Empire Gas and Fuel Co., Bartlesville, Okla., for many ideas.

Jan 4, 1920

By D. Walton, W. C. Winegard, W. A. Tiller, J. W. Rutter

It is shown that the cellular substructure observed in binary alloy crystals grown from a melt of known concentration can be eliminated by the proper choice of growth conditions. For a given solute concentration, there exists a critical ratio of temperature gradient G in the melt to the rate of solidification R of the crystal, i.e., of G/R, which must be exceeded before the cellular structure can be eliminated. A secondary substructure is observed which is related to the cellular substructure. IN crystals grown from the melt, a prismatic substructure has been observed by Buerger,1 Pond and Kessler,2 and Rutter and Chalmers." This structure is columnar in the direction of growth and appears as a network of hexagonal cells in the plane of the solid-liquid interface. Rutter and Chalmers3 have shown that this substructure occurs as a result of the presence of a layer of high impurity concentration in the melt adjacent to the solid-liquid interface. The formation of the substructure is accompanied by a redistribution of this impurity in the neighborhood of the interface. The structure can be controlled by proper adjustment of the variables in the solidification process such as a rate of solidification and the temperature gradient in the liquid. The redistribution of solute during the solidification of metal crystals has been treated theoretically

Jan 1, 1956

Discussion of the paper of EDWARD G. NORTON, presented at the New York meeting, February, 1915, and printed in Bulletin No. 97, January, 1915, pp. 93 to 102. G. D. HARRIS, Ithaca, N. Y. (communication to the Secretary *).¬Since I have on several occasions1 expressed at length my general views on this interesting subject, it seems fitting that I endeavor here to comment as briefly as possible on a few points suggested by the paper. Doubtless you all know of the rather extensive publications of Lachmann on mid-European salines and his scarcely successful, attempt to make the phenomena presented by our domes fit. into his "Exzeme" theory based on studies of European phenomena. This paper is a most welcome indication that scientific America is very much alive to the difficulties that have been encountered in attempts already made to explain the origin of the salt domes in the lower Mississippi embayment region. Praiseworthy, too, is the attempt to explain these phenomena by agencies still in operation. I may, perhaps, be permitted to state here that a former student of mine, and co-worker in Louisiana, A. C. Veatch, is now interested in the Algerian region, where it would seem similar dome-phenomena are to be found, and hopes may well

Jan 5, 1915

By Strathmore R. B. Cooke

That calcium will activate quartz for flotation with anionic collectors such as soaps has been known for a number of years,1 2 3 and the method has been applied to the concentration of various iron ore 4 5 6 as well as to other materials. Clemmer gives the permissible pH range for the activation of quartz by calcium as between 9.5 and 12.5 with an optimum value of 11.0, and Hertzog7 has determined the calcium abstraction of iron ores and of Ottawa sand, but otherwise little quantitative data are available. The purpose of the present investigation was to determine those conditions under which dilute solutions of calcium chloride will activate quartz for anionic flotation and to determine the amount of calcium ion adsorbed by quartz. Those variables, the influence of which was primary, such as calcium, sodium, and hydrogen ion concentrations, were studied. Other factors which influenced the results are discussed in the description of the experiments. Three different experimental methods were used to determine the activation of the quartz. The first method was to treat a sample of ground, deslimed quartz with solutions of calcium chloride and sodium hydroxide, and to determine the calcium adsorbed by chemical analysis of the solution. Ad- vantages are that a direct value for the

Jan 1, 1949

By Stanford O. Grodd

The Sanford Lake district encompasses an area covering 24 square miles in the central Adirondack Mountains of northern New York State. Discovery of the titaniferous magnetite deposits dates back to 1826. Several attempts to exploit the ores for iron prior to 1942 proved uneconomical because of difficulties with the associated titanium, lack of transportation facilities, and the isolated location. Since 1942, the National Lead Company has produced ilmenite concentrates for the titanium pigment industry, and a magnetite by-product used in the steel and refractory industries. Rocks of the area are Precambrian in age and of igneous origin. The area has a history of erosion, deformation, and metamorphism, subsidence, and finally uplift and glaciation. The resulting topography is extremely rough with drainage patterns controlled by a combination of fault patterns and glacial modifications. The district is within the large anorthosite massif making up the central high peak area of the Adirondacks. All of the various lowsilica rock types associated with the massif are found within the boundaries of the district. These consist of both the Marcy and Whiteface types of anorthosite and of gabbroic anorthosite, gabbro, and different grades of titaniferous magnetite ores. All of the rocks contain the same minerals and differ only in their percentages of these consitituents. Gabbro, and ore associated with it, demonstrate flow structure as both have foliation and lineation. Anorthosite and its associated ores are massive and show very little primary structure. Minor pegmatites and diabase dikes provide evidence of remobilization in selected areas and of late intrusion as well. Faulting is prevalent and follows a regional pattern of major faults trending northeastsouthwest and of minor faults at nearly right angles to them. There are four mineralized areas where an economic grade of ore has been found. Three of these have both gabbroic-type ore and anorthositic-type ore. The fourth has only gabbroic ore. Ores are graded according to their TiO, content, and these range from 9.5 per cent to over 30.0 per cent TiO,. Ore bodies of both types are related to gabbro and conform to the configuration of the gabbro bodies within the anorthosite. At least three distinct theories of ore genesis have been expounded by different investigators. Others propose some variations of one or more of these. Although complete agreement probably never will be reached, it is certain that no one process of ore emplacement can explain the complicated picture as seen today. Further understanding of the ores and their origin will require detailed mapping, sampling, and mineralogical studies of the entire district, and then it may never be understood without qualification.

Jan 1, 1968

By Gerald Greene

Tan various lead producers have given the subject of lead drosses much attention in recent years but the problem of their economical treatment is yet to be solved. Formerly the copper in the furnace feed was removed from the furnace in the form of matte. The speiss at that time consisted principally of the iron arsenide. The practice today is to roast off most of the sulfur and the copper in the feed forms a dross in the furnace, which is removed from the furnace with the lead. This material is poured into the drossing kettles and allowed to cool down to but slightly above the freezing point of lead. The copper dross, containing almost all of the arsenic and part of the antimony, is skimmed off and treated in a small reverberatory furnace at most plants. This is essentially a liquation process. The skimmed dross contains from 70 to 80 per cent lead, and much of this lead is liquated out. The products from this treatment are: (1) impure lead, (2) speiss and (3) matte. The speiss from the reverberatory furnace was studied in this research. The literature on the subject is of very little assistance, as almost no work has been done on the problem of establishing the exact identity of the various phases present. One author(1) states that speiss consists of a series of isomorphous compounds of the general formula FexAsy in which the Fe may be replaced by Ni, Co, Cu, Pb, Ag, Au, Pt, Zn, Cd and the As replaced by Sb, S and Bi. Hofman(2) states that the iron arsenide present is Fe5As.

Jan 1, 1935

By AIME AIME

MOTHER example of the broad field that is covered by the mining industry is the recent erection by the Phelps Dodge Corp. of a modern hospital building at Douglas, Ariz., and an identical one at the rejuvenated mining town of Morenci. Managers of even small mining properties are often called upon to build schools, houses, stores, maybe a jail, and provide sanitary arrangements, possibly the while acting as mayor of the town. Those who direct larger properties may have to build hospitals, as in the present instance, construct sewage disposal plants, and sometimes even build and manage railroads. A mining camp achieves its reputation among mining men not entirely by the grade or amount of its ore, or the skill of the operating staff in mining and milling it at a profit-the operation soon acquires a reputation as either a desirable or an undesirable place to live, regardless of its remoteness from what is euphemistically termed civilization. Such a community is indeed fortunate if it can boast of a good hospital.

Jan 1, 1940

Discussion of the paper of E. G. Woodruff, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 78, June, 1913, pp. 1001 to 1010. F. A. LINFORTH, Butte, Mont.:-I have not had an opportunity of reading this paper thoroughly, but I would like to call attention to the possible use of the contours on fault planes. It is obvious that if the contours of fault surfaces call be determined, we will be able to determine the axes of the hollows in the fault surface. It seems probable, and there are examples to point to the accuracy of, the assumption, that the axes of these hollows may be the direction of movements on the faults, and if that is true it will aid materially in locating faulted ore bodies or the shoots of ore on the opposite sides of faults. A few such contour maps of faults have been attempted on some of the faults of the Butte district, and those faults which are believed to have the nearly normal movement exhibit for the axes of these hollows a line nearly up and down in the plane of the fault, but in those cases where the throw is believed to bee nearly horizontal we find that the axes of the hollows are almost horizontal lines. In other words, the movements on faults, I believe, would be more nearly indicated by the larger grooves in the fault surfaces than by the small slickensides and minor hollows that are seen, so that contour maps might be valuable in geology in that way. C. W. GOODALE, Butte, Mont.:-I received a letter from Mr. Woodruff asking me to take part in the discussion of his paper, but I have not had time to give the paper any study. I can certainly add my opinion to that of all the engineers here that the topographic maps of the government are of great aid to the engineer. When I visit a new district, the first thing I do is to see if that district has been covered by the U. S. Geological Survey avid if topographic map has been issued. And I find that some of the younger engineers frequently come into my office to see if I have such maps. I know in some cases the reports made out by engineers contain copies of these topographic maps, or clippings from them. I am sure that. the topographic maps furnished by the government are of very great value to our engineers.

Jan 11, 1913

By R. W. Raymond

THIS meeting was held in the new home of the Institute, the United Engineering Society Building, 29 West 39th Street, New York City, directly following the Dedication ceremonies. The first session was held in the large Auditorium, Thursday, April 18. The meeting was called to order by Mr. John Hays Hammond, President of the Council, who said Before taking up the reading and discussion of papers, I will call upon Dr. Rossiter W. Raymond, the oldest living past-President of the Institute, who has been in harness almost continuously for thirty-six years, and who has contributed more than any one else to bring this society to its present great success and to establish the reputation of the American mining engineer the world over, for a few words supplementary to those which were uttered to engineers generally, during the sessions of yesterday and the day before. ADDRESS BY R. W. RAYMOND. The generally accepted Darwinian doctrine of the survival of the fittest is sometimes illustrated by persons who are supposed to be the fittest because they have simply survived. I fear that I come under that category. Almost all of my contemporaries in the early history of this Institute have passed away. Only one or two of the original founders remain, and I may fairly say that scarcely any remain who were active at that : time in shaping the organization and the future career of the Institute. In May, 1871, I was thirty-one years old. Next week I shall be sixty-seven years old. All the intervening years have been devoted to the service of this Institute almost continuously, either as President or Vice-President or Secretary. You may easily imagine, therefore, with what pleasure I greet you on this occasion. I am not here to extend to you the welcome of the City - of

May 1, 1907

By D. L. Rainey, E. R. Goter, W. R. Hudspeth

THE area in which spodumene-bearing pegmatites occur extends from Gaffney, S. C., in a northerly direction to Lincolnton, N. C., a distance of about 16 miles. The zone averages 2 miles in width. Interest in this area was first aroused by the discovery of small amounts of cassiterite in the pegmatites and in greissen which occurs on the walls of some of the pegmatites. Attempts were made from 1880 into the 1920's to mine and concentrate cassiterite, but there were no successful operations. In 1935 L. M. Williams became interested in the area and began prospecting by trenching and sinking several small shafts. He gradually gained control of a considerable acreage south of the city of Kings Mountain, N. C. Mr. Williams states that he produced some ore from a shaft which he shipped to the Maywood Chemical Co. in the late 1930's. In 1937 G. H. Chambers of the Foote Mineral Co. visited the area and examined several properties, but the lithium market was too small to support the necessary concentrating plant.

Jan 9, 1953

By J. B. Fletcher

The Miami mine first started operations in 1910. For convenience, the history of the orebody can be divided into the following categories (Fig. 1): 1) 1910 to 1925: 24.4 million tons of high grade ore, mined by top slicing, sublevel caving, etc. 2) 1926 to 1954: 102 million tons of low grade ore, mined by block caving.

Jan 1, 1961

Prior to any detailed discussion, I'd like to say that Dr. Aplan has made direct hits on two important considerations: 1) The most demanding need in Fine Coal research is to develop improved methods of sulfur reduction. 2) The areas of particle (impurity) liberation and froth flotation hold real near-term promise as techniques for improved sulfur removal. Digressing for a moment, I thin kwe can all remember the time when the biggest problem facing coal research was simply defined - "No money!" In the mid 70's we suddenly found ourselves dealing with a product worth five to seven times the value it carried in the mid60's. All of a sudden, we're talking about a high-profile, high- value commodity. The coal industry still hasn't made the complete psychological adjustment - especially in the operating areas (prep plants included). We have a valuable material at hand which is, in' many cases still being processed as though it were a two or three dollar per ton item. Simply put, I think that while the industry has made some major strides during this transition, a stronger commitment of attitude (and finances) needs to be made toward deeper definition of beneficiation work. Back to specifics - Dr. Aplan has really highlighted three areas where strong research efforts are needed. 1) Liberation processes - not limited to mechanical comminution - must be more fully studied.The industry certainly needs a better handle on value returned (improved ability to beneficiate) for dollars spent on improved liberation. 2) Flotation processes probably hold the most promise for near- term improvement in fine coal beneficiation technology. Dr. Aplan’s.

Jan 1, 1979

By Kalervo Rankama

UNTIL a few years ago, geological mapping, the study of ore boulders, and different geophysical methods were the principal means used in the systematic search for mineral deposits covered by a layer of disintegration products or soil. These methods have been developed to a high stage of perfection as far as the geometrical definition of the conductor is considered. Use of geophysical methods in prospecting is based on the fact that an ore body differs from the country rock not only geologically but also in its physical properties. The general drawbacks and complications included in the use of geophysical methods are well known to everyone who has been using them, so need not be entered into here in detail. One of the more important ones is the fact that geophysical methods are unable to furnish information concerning the chemical composition of the ore bodies responsible for the indications. Further, the ores of many metals, such as silver, gold, beryllium, zinc, mercury, tin, lead, vanadium, antimony, chromium. molybdenum, tungsten, manganese, cobalt, nickel, and the platinum metals cannot be directly located by known geophysical methods, owing to lack of physical characteristics suitable for distinguishing them from the country rock. Thus it is quite natural that efforts have been made to develop direct methods for prospecting and locating ore bodies of the elements named. Known as chemical, biogeo-chemical, and geobotanical methods of prospecting, these have been much improved during recent years. A brief review of these methods and of some results obtained with them will be presented in the following, on the basis of available information and my own experience.

Jan 1, 1947

By W. A. Tiller

The conventional techniques1 for determining the liquidus and solidus surfaces of an alloy system containing more than two components are extremely tedious to use and do not provide a complete picture of the equilibrium relations between solid and liquid alloys. These techniques are unable to yield "tie-line" information concerning solid and liquid phase equilibrium, a very important parameter in the solidification description of the liquid alloy and a very necessary parameter in the preparation of "zone-levelled" alloy crystals. The tie-line in a polycomponent system is analogous to the partition coefficient, k, in a binary system, it gives the composition of the solid, Cs, in equilibrium with a liquid of composition CL. That is, CS = kCL, where CL = [CO, c1,...Cn] denotes the concentrations of the n + 1 constituents, and k = [ko, kb ,...kon] denotes the gross partition coefficient for the elements between the two phases; thus, k is the tie-line in this system. To provide complete information concerning the two-phase equilibrium in a polycomponent system it is necessary to know both the liquidus surface and the gross partition coefficient. From these two the solidus surface is obtainable. The conventional techniques are unable to provide this information in other than a binary system so we must look elsewhere. In recent years considerable insight has been gained into the correct description of the liquid-solid transformation, 2,3 and controlled solidification experiments may now be designed to both facilitate and enhance equilibrium diagram studies. In the present paper consideration is given to two methods for obtaining the liquidus surface and the tie-lines in polycomponent systems. The methods to be described below deal with the solidification of an n + 1 constituent liquid alloy of initial composition [co, Co ,...Con], where the superscripts refer to the elements present and the Oth element is considered as the solvent in which the n solutes are dissolved. The general assumptions made in the treatment are the following: (i) the solid and the liquid at their interface are in equilibrium during the growth of the solid phase, (ii) there is no diffusion in the solid phase, and (iii) the liquid phase is completely mixed and is therefore homogeneous in concentration. METHOD I In this section a general experimental method will be described which, in principle, is capable of giving an exact description of the liquidus surface and tie-lines. Consider the unidirectional solidification of the liquid alloy specimens L cm in length (freezing either horizontally or vertically). Allow the sample to be frozen very slowly from one end, as indicated in Fig. 1, with complete mixing in the liquid, and then analyze the solid bar to determine its chemical constitution as a function of position, x, along the bar. Let Fig. 2 represent a possible distribution of the ith constituent along the bar. At the point x' the concentration of the ith constituent is C1/5(x'), and the average concentration of the rest of the bar between x' and L is given by C:(X' - L) where [ A(x) c1s(x)dx c1/s(x'-L) = f A(x) dx x * and A(X) is the cross-sectional area at x. In a similar manner. all the Cf(x' - L) may be determined. Thus, the gross artition coefficient k for liquid of composition [Cs(x - L),...Cs(X' - L)] is given by -ko= CUs')/Cos(x' - L)" k0 = csn{x')/cs(x'- L) During the freezing of a charge of length L, the liquid composition may vary over a wide segment of the phase diagram and the gross partition coefficient over this segment of the phase diagram may be determined from one, bar. Fig. 3 illustrates the magnitude of Cs(g)/C,' as a function of the fraction g of the bar which has Solidified.2 We can see that the concentration in the bar will vary over a range of about 15 wt pct for C,' = 10 wt pct and k0 = 0.5. It appears that 4 or 5 specimens would be adequate to study a simple binary eutectic phase diagram.

Jan 1, 1960

By J. Chipman, G. G. Hatch

One of the important functions of the iron blast furnace is the desulphur-ization of pig iron before it enters the steelmaking furnaces. However, the increasing concentrations of sulphur in the metallurgical coke, source of approximately 90 pct of the sulphur present in the blast furnace charge, and demands for higher rates of production within recent years have increased the need for greater desulphurization within the iron blast furnace. Furnace operators are beginning to look for desulphurizing agents other than blast furnace slag to accomplish the desired degree of desulphurization. A considerable amount of work has been done on desulphurization outside the furnace with soda ash, calcium carbide and various synthetic slags. Whether the desulphurization of pig iron is accomplished wholly inside the furnace or partly inside and the remainder outside, will be determined by the economics involved. Regardless of which is the case, it is believed that it is necessary to have a better understanding of the physical chemistry of desulphurization by blast furnace slags. To this end, it is the object of the present investigation to attempt what is believed to be the first equilibrium study of the distribution of sulphur between liquid pig iron and a wide range of blast furnace slag compositions. Review of Literature There is a considerable amount of information in the literature concerning the desulphurizing power of iron blast furnace slags, the solubility of various sulphides in the slags, and the effect on desulphurization of temperature, of elements dissolved in the liquid iron, and of viscosity. However, there is nothing to indicate that the equilibrium distribution of sulphur between liquid iron saturated with carbon and iron blast furnace slags has been studied experimentally. Wentrupl has made probably the most detailed study of the desulphurization of pig iron to date. He considered that there are three distinct aspects involved, namely: 1. Desulphurization within the blast furnace (by lime and manganese). 2. Subsequent desulphurization by manganese. 3. The effect of subsidiary reactions on the desulphurization by manganese. The experimental work carried out by Wentrup was devoted mainly to obtaining a better understanding of how desulphurization by manganese was accomplished in the mixer and the ladle. Particular attention was given to the part played by carbon, silicon, and phosphorus associated with manganese in the iron, and the effect of temperature on desulphurization. The experimental results indicated that desulphurization by manganese is purely a process of crystallization of manganese sulphide. The addition of silicon to iron melts containing 3.5 pct carbon and less than 0.5 pct manganese had no noticeable effect on desulphurization, but with 1-2 pct manganese the silicon additions improved the desulphurization. Additions of phosphorus also resulted in improved desulphurizati011 by manganese, but the effect was not as marked as in the case of silicon. It was also found that desulphurization by manganese was further improved by lowering the temperature. In order to explain desulphurization inside the blast furnace, Wentrup considered the system iron, sulphur, calcium, oxygen, manganese. (silicon). The distribution of sulphur between the metal and slag was represented by the following equation: (SS) _ (S)Fe + (S)Ca + (S)Mn .... [S] = [s] [1] The parentheses and the brackets represent the equilibrium concentrations in weight per cent of the slag and metal constituents, respectively. Since FeS D (FeS) _ (FeS) (S)Fe LfeS - [FeS] [S] [2] (CaO) + S e (FeO) + (S)Ca _ (FeO)(S)Ca. (S)Ca _ (CaO) Kl = (CaO)[S] [S] ~K1(FeO) [3] Mn + S D (S)Mn (S)Mn (S)Mn K' = [MnpT "1ST = *lIMnJ !4) Substitution of Eq 2, 3, and 4 into Eq 1 resulted in if = L- + *> (Sol + K^ (S) [51 Eq 5 was used to calcu1;lte -f^j and [S] at 1480°C for slags containing 30-50 pct lime, 0.1-2.5 pct iron oxide, 0-26 pct silica, 2 pct sulphur and iron analyzing 1.5 pct manganese. The value for LFaB at 1480°C was found to be equal to 4.5, based on the experimental work of Bardenheuer and Geller.2 The results of the calculations are shown in Table 1. Although the slags are hypothetical and do not represent the range of compositions found in ordinary blast furnace practice, the calculations indicate that lime is effective in controlling desulphurization only if the iron oxide and silica contents of the slag are kept low. Schenck3 did not claim K1 to be a true equilibrium constant, but an empirical value which varied with the silica content of the slag.

Jan 1, 1950