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By Robert T. Howard, Morris Cohen

THE purpose of this paper is to direct attention to the lower part of the austenite transformation diagram, or TTT curves, where considerable uncertainty still exists as to the blending of the bainite and martensite reactions. The dissimilarities between these two low temperature trans- formations have been summarized recently by Troiano and Greninger.1 Of particular importance to the present work is the fact that martensite formation, unlike bainite formation, is not suppressed by the fastest quenching rates attainable. However, most of the investigations in this direction have been concerned primarily with the start of the martensite transformation [(M,)] during cooling, rather than with the quantitative aspects of the subsequent reaction on either further cooling or isothermal holding. Several years ago, Cohen2 suggested a form of transformation diagram which reconciled, at least schematically, the isothermal characteristics of the bainite transformation with the insuppressible nature of the martensite transfoi mation. In essence, the diagram consisted of a family of horizontal lines (representing the progress of the austenite-martensite reaction during quenching) which were interrupted in point of time by the bainite family of C-curves extending down from higher temperatures. This picture received later support by metallographic3 and dilatmetric4,5 studies, but the techniques employed were not sufficiently critical to substantiate some of the details. Elmendorf6 and Grange and Steward7 have shown that the Greninger-Troiano metallographic techniques may be used not only for [M,] determinations, but for studying the course of further austenite decomposition. In fact, the latter investigators have observed the amount of martensite formed as a function of temperature below [M,] in fourteen commercial steels. In the present paper, the Greninger- Troiano technique has been combined with the lineal method of Howard and Cohen9 to provide a unique, quantitative treatment of the austenite-martensite reaction. Furthermore, isothermal transformations have been similarly measured on holding at temperatures above and below M,, thus permitting a fairly detailed presentation of the lower part of the conventional austenite transformation diagram. EXPERIMENTAL DETAILS Materials The steels, listed in Table I, were selected for study because they exhibit a satisfactory range of M, temperatures and have not received as much attention as the lower carbon grades. They were prepared as 30 lb induction furnace heats in the laboratories of the Vanadium-Alloys

Jan 1, 1947

The following list comprises the names of those persons who became members during the period of Mar. 10, 1918, to Apr. 10, 1918. ADAMS, NOAH- :.. Geol.,. E. N. Gillespie & Co., Box 1875, Tulsa, Okla. ALVAREZ, PEDRO Asst. Met., American Smelt. & Refin. Co., Blue Hill, Maine. BARTRAM, JOHN G., Pet. Geol., Roxana Petroleum Co. of Oklahoma, Cheyenne, Wyo. CHANEY, S. E Supt.., Arizona Binghamton Copper Co., Stoddard, Ariz. CLEVELAND, EARL C Mgr., Deadwood Min. Co., Mogollon, N. M. DENNIS, HOWARD B Min. Engr., Empire Mines, Grass Valley, Cal. FOWLER, ARTHUR A., Partner, Rogers, Brown &- Co., 30 Church St., New York, N. Y. FRIEDMAN, L. A Pres. and Gen'l Mgr., Rochester Mines Co., Lovelock, Nev. GUIBERSON, S. ALLEN, JR 923-24 1. N. Van Nuys Bldg., Los Angeles, Cal. KROHN, ARTHUR Mine Supt., Missouri Metal Corpn., Mine La Motte, Mo. KURSELL, H. A., Mgr., Altai Mines Ltd., Zmeinogorsk, Altai Gov't, Siberia, Russia. LANE, L. RAY Mine Examinations, Galiano 24, Aptd. 1066, Havana, Cuba.

Jan 5, 1918

By B. E. Sundquist

The various methods based on solution models for obtaining free energies of mixing from miscibility-gap data have been applied to a number of binary-alloy systems. For nine of these systems there exist experimental thermodynamic data that permit a comparison of the results to experiment. It was found that the method of van der Toorn and Tiedema almost invariably leads to results that are physically unacceptable and that vary drastically with small changes in the miscibility-gap parameters. The subregular solution model is found in all cases, except the Al-Zn, Fe-Cr, and Cu-Pb systems, to exaggerate the free energy of mixing by 30 pct or more. The model developed by Lumsden is found to give results that are often in excellent agreement with experiment and which exaggerate the free energy of mixing by no more than 30 pct. These results and others give evidence that the Lumsden treatment of the effect of unequal atomic sizes and of imperfect configurational randomness due to deviations of AB bond energies from the mean of AA and BB bond energies is adequate for most systems. ANALYTIC expressions are frequently proposed for the dependence on composition of the activities of the components of a solution. Because the development of solution theory is incomplete, these expressions contain parameters which must be determined by experiment. The measurement of activities is often difficult and consequently such measurements are less readily available than are measurements of phase equilibria which, under certain conditions, can also be used to evaluate these parameters. For example, suppose it is known that two structurally dissimilar phases, each of known composition, in an n-com-ponent system are at equilibrium at a given temperature and pressure. n equations can be set up in terms of these parameters expressing the equality of the chemical potential of each component in the two phases. In addition, one can write the Gibbs-Duhem equation for each phase that also contains these parameters. Thus, if these n + 2 equations contain n + 2 parameters, these parameters can be determined (at the temperature in question) from the phase diagram alone. If the average number of parameters in each expression for the activity of a given component in a given phase is V then there will be 2nV parameters involved. Equating 2nV to n + 2 shows that, for n + 2, V = 1. If the temperature dependence of each parameter were to be expressed in some explicit form one could use equilibrium conditions at a number of temperatures to increase V. The situation is much improved when the two phases in equilibrium are structurally similar. It can then be assumed that, stably or metastably, two phases will become one at higher temperatures. Thus the number of parameters involved becomes nV instead of 2nV. Hence, V = 2 for n = 2 using only one temperature. (It is implied here that the activity expressions used are valid over the entire composition range.) In this investigation only the equilibrium of two structurally similar, two-component phases (miscibility-gap systems) will be considered. The various proposed solution models will be applied to a number of these systems and the results compared with available experimental results. All of the analytic expressions that have been proposed for the free energy of mixing of a two-component system are of the form where ?Gmix is the free energy of mixing per mole of solution, N1 and N2 are the mole fractions of components 1 and 2, respectively, and f(Ni, T) is some function of composition and temperature. In the "ideal" solution model f = 0. In the "regular" solution model f = a constant. Since these two models permit only a symmetric equilibrium diagram they will not be considered further here. The simplest model that permits a nonsymmetric miscibility envelope is the so-called "subregular" solution model proposed by Hardy.1 This model gives where the Ci(T) are functions of temperature only. The same expression for f is obtained from the "linear a function" model proposed by Darken and Gurry2 and applied to miscibility-gap systems by Wriedt.3 This model requires that the a function defined by be a linear function of composition (yi is the activity coefficient of component i). This model is not purely hypothetical for it has been found2 to hold true for a number of systems. It is readily shown3 that the f(Nl, T) obtained from this model is of the form given in Eq. [2]. It will be noted that the subregular solution model contains only two parameters and hence both of them can be determined at any desired temperature below the critical temperature, Tc, for a miscibility-gap systems in the manner described previously. At T, the two constants can be determined by equating the second and third derivatives of ?Cmix with composition to zero. Another two-parameter model was proposed by Lumsden4 who set

Jan 1, 1967

PAST AND PRESENT CHAIRMEN OF DIVISIONS Institute of Metals Iron and Steel Mineral Industry Industrial Minerals Year Division Petroleum Division Division Coal Division Education Division Division 1918 W. M. CORSET 1919 " 1920 W. H. BASSETT 1921 " 1922 W. B. PRICE RALPH ARNOLD 1923 E. DEGOLYER 1924 G. B. ELLIOTT 1925 F. JULIUS FOHS 1926 P. D. MERICA 1927 11 JOHN. M. LOVEJOY 1928 S. SKOWRONSKI A. W. AMBROSE RALPH H. SWEETSER ' 1929 " J. B. UMPLEHY G. B. WATERHOUSE 1930 ZAY JEFFRIES C. V. MILLIKAN W. J. MACKENZIE HOWARD N. EAVENSON 1931 SAM TOUR C. E. BEECHER F. M. BECKET 1932 C. H. MATHEWSON EARL OLIVER F. N. SPELLER THOMAS G. FEAR C. H. FULTON 1933 T. S. FULLER W. E. WRATHER JOHN JOHNSTON ELI T. CONNOR " 1934 J. L. CHRISTIE H. D. WILDE, JR. L. F. REINARTZ " T. T. READ 1935 W. M. PEIRCE HARRY H. POWER A. B. KINZEL JOHN T. RYAN SAMUEL H. DOLBEAR 1936 E. H. DIX, JR. HALLAN N. MARSH C. E. WILLIAMS EUGENE MCAULIFFE WILLIAM B. PLANK OLIVER BOWLES 1937 A. J. PHILLIPS M. ALBERTSON FRANCIS B. FOLEY J. B. MORROW " CHESTER A. FULTON 1938 R. F. MEHL G. B. CORLESS J. T. MACKENZIE PAUL WEIR FRANCIS A.THOMSON J. R. THOENEN 1939 R. H. LEACH W. H. GETS J. HUNTER NEAD C. A. GIBBONS " M. M. LEIGHTON 1940 E. M. Wise T. V. MOORE F. T. SISCO C. E. LA WALL W. R. CHEDSEY W. M. WEIGEL 1941 D. K. CRAMPTON E. A. STEPHENSON C. H. HERTY, JR. JULIAN E. TOBEY " PAUL M. TYLER 1942 CARL E. SWARTZ HARRY P. STOLZ E. C. SMITH NEWELL G. ALFORD A. F. GREAVES-WALKER B. L. MILLER

Jan 1, 1943

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 ROBERY W HUNT 1883 JAMES C, BAYLES 1884-1885 ROBERT H RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B POTTER 1888 RICHARD PEARCE 1889 ADAM S HEWITT 1890 JOHN BIRKINBINE 1891-1892 H M HOWE 1893 JOHN FRITZ 1894 J D WEEKS 1895 E G SPILSBURY 1896 THOMAS M. DROWN 1897 CHARLES KIRCHHOFF 1898

Jan 1, 1937

By S. J. Aresco, George E. Keller, J. Visman

INTRODUCTION The accurate sampling of coal, as with most minerals, is a difficult task. Coal is a very heterogeneous material made up of different types of coal and varying amounts of mineral matter. The product as mined may contain all of the layers of coal and impurities found in the seam as well as portions of the strata above and below the coal seam. The preparation plant is the device to size, crush and/or remove impurities so that the coal may be shipped as a saleable product. Sampling may be needed at many stages in the preparation process. Although this chapter is mainly concerned with sampling in connection with preparation processes, the principles will apply to all coal sampling. The main reasons for sampling in connection with coal preparation are: 1. To determine the washability characteristics of the raw coal by means of float and sink tests. These may be used for the design of a preparation plant, prediction of results to be obtained or for monitoring raw coal delivered to the plant. 2. To check the performance of various operating units in the plant, either by float and sink tests or chemical analyses. 3. To determine the analytical characteristics of the products produced, such as moisture, ash, Btu, sulfur, etc. HISTORY The earliest accepted methods of sampling coal in the United States were given in U. S. Bureau of Mines publications by J. A. Holmes,1 G. S. Pope2 and A. C. Fieldner.3 The American Society for Testing and Materials more or less adopted the methods proposed by the U.S. Bureau of Mines in their Standard D-21-1916, and it remained a standard for many years. Briefly, the standard called for a 500 pound sample for coals less than. 3/4 -in. in size and a 1,000 pound sample for all coals over ?4 -in. in size. No mention was made of increments but there was an instruction that the sample should spread over the coal to be sampled. Sample preparation was by hand crushing with the alternate shovel method for reduction to 250 pounds followed by coning and quartering below 250 pounds. Obviously, with the amount of work involved, this method of sample preparation was rarely followed. This method of preparation resulted in samples that were practically air dried because of long exposure while crushing, shoveling and quartering. In the late nineteen twenties and early nineteen thirties, studies for more practical methods were begun. Dr. E. S. Grummell4, Imperial Chemical Industries, Ltd, London, summarized the work to date at the

Jan 1, 1968

By G. Derge, Lo Ching Chang

The chemical and physical propertties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use. These processes are carried out at high temperatures and involve such complex chemical systems that funda-mental scientific knowledge of the Properties and behavior of these slags is inadequate. Various hypotheses have been Proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenckl and the recent Papers of Chipman and co-authors. Another proposal is that these compounds dissociate by com-plete6 or partial ionization, the evidence for which has been reviewed by Martin and Derge.? whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: 1. Studies of solidified 51% samples by X ray diffraction, petrography, and similar methods that can be used at room temperature. The correlation of this information with the high-temperature properties of the molten slag is uncertain. 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature. However, even these data present problems of interpretation because they require a complete knowledge of the metal phase. 3. Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret. Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information. The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems cao-sio2 and cao-120,-SiO2 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1948

By G. Derge

The chemical and physical propertties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use. These processes are carried out at high temperatures and involve such complex chemical systems that funda-mental scientific knowledge of the Properties and behavior of these slags is inadequate. Various hypotheses have been Proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenckl and the recent Papers of Chipman and co-authors. Another proposal is that these compounds dissociate by com-plete6 or partial ionization, the evidence for which has been reviewed by Martin and Derge.? whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: 1. Studies of solidified 51% samples by X ray diffraction, petrography, and similar methods that can be used at room temperature. The correlation of this information with the high-temperature properties of the molten slag is uncertain. 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature. However, even these data present problems of interpretation because they require a complete knowledge of the metal phase. 3. Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret. Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information. The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems cao-sio2 and cao-120,-SiO2 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1948

By H. M. Morse

This report on oil and gas development in Mississippi covers the period from Jan. I, 1944, to Dec. 31, 1944: Salt Domes During the year six salt domes were drilled for sulphur, but no commercial sulphur deposits were found. One salt dome, the Bruinsburg, in Claiborne County, has produced gas- at 935 to 940 ft' in Moody's Branch marl. The Stringer salt dome in Smith County and the Ruth salt dome in Lincoln County both had a slight showing of heavy oil. Other salt domes have been dry. In addition to the Bruinsburg dome, the Allen salt dome, in Copiah County, and the Richton salt dome, in Perry County, were discovered in 1944; also the Sumrall dome, in Covington County. New Oil Fields Baxtemille Oil Field.—The Baxterville oil field was discoveredby the Gulf Refining Co, in sec. 7, T. I N., R. 16 W., Lamar County. At the end of the year this field had one oil well, with two active operations. Production for 1944 was 1047 bbl. of oil. GwinvilLe Field.—Gwinville field was discovered by S. W. Richardson, in sec. 24, T. 9 N., R. 19 W., Jefferson Davis County. This discovery well was a gas-distillate well, the oil being crystal clear. At the end of 1944 there were two gas wells and one oil well in the field. The oil well is approximately 2 1/2-miles from the gas- distillate wells. Gas production was 55,801 M cu. ft. and the distillate production was 2644 barrels. Heidelberg Oil Field.— The Gulf Refining Co. discovered the Heidelberg field in sec. 30, T. I N., R. 13 E., Jasper County, in January 1944. This field has by far exceeded the other 1943 and 1944 discoveries, having approximately 56 oil wells, 7 dry holes, and 10 active wells at the end of the year. Production to Jan. I, 1945 was 1,441,192 bbl. of oil. Mallalieu Oil Field.—The california Company discovered the Mallalieu oil field in set. 10, T. 7 N., R. 8 E,, Licoln. County. At the end of the year there was one well in the field with three active operations. Production was 32,303 bbl. of oil. Old Oil Fields Brookhaven Oil Field, in Lincoln County, has one oil well, which produced 2590 bbl. of oil during 1944. CarY Oil Field, Sharkey County1 has only one producing well, which produced 11,818 bbl- of oil during the Year- In Cranfield Oil Field, dams County, II oil wells and two gas-distillate wells were drilled in 1944 and there were five active wells on Dee. 31, 1944- The total production for the Year was 5251422 bbl-of oil. The gravity of the oil is 40" to 54.9'- In Eucutta Oil Field1 Wayne County1 34 oil wells were completed during 1944. There were five dry holes and six active wells at the end of the year.. The field produced 454,332 bbl. of all d the average gravity is 25" Flora Oil Field, Madison County, pro-

Jan 1, 1945

By J. T. Price

The study was undertaken to investigate the effect in the charge to a blast furnace of zinc and alkali contents, which tend to form accretions and scaffolds in the upper sections of the furnace. Commercial iron oxide pellets were reduced in a CO:N2, 40:60 gas mixture in a 5-cm by 5-m counter-current reactor (Rist-type apparatus) designed to simulate blast-furnace conditions. Pellets from a commercial magnetite concentrate were prepared in the laboratory with zinc (1% ZnO) and alkali (1% KOH) additions to the concentrate. Reducibility, crushing strength and swelling tests were carried out and the results compared with test data from pellets prepared without additions. The results indicated normal behaviour for those pellets containing zinc, whereas those containing alkali swelled catastrophically under the same reducing conditions.

Jan 1, 1977

By A. F. Nylander, J. H. Jensen

Magnesium, in its combined forms, is the sixth most abundant element and the third most abundant metal in the earth's crust, but it is so reactive that it is never found in nature in the elemental state. As part of the rock-forming minerals like magnesite, dolomite, olivine, and serpentine, it is combined in virtually insoluble forms. As part of soluble minerals like kainite (KC1 MgS04 - 3H20), leonite (K2S0, MgSO, 4H20), langbeinite (K,SO, 2MgS04), and carnallite (KC1 . MgCl? 6H20), it is found in evaporite deposits, generally of marine origin, deep within the earth's crust. Since these minerals are soluble, they are found only in deposits protected from the percolation and leaching action of ground waters by an insoluble and impermeable mantle. Usually this mantle is from several hundred to many thousands of feet thick. Finally, as a solute in marine-like brines, magnesium is common in surface and subterranean waters throughout the world. The oceans, which contain 0.13% Mg, illustrate the inexhaustible nature of the reserve. The recovery of magnesium from the rock-forming minerals, usually by thermal decomposition, and from dilute brines such as sea water by precipitation with lime, are frequent industrial practices. But the recovery of magnesium as magnesium chloride from evaporites or natural brines of concentration greater than sea water has been of little industrial significance for economic and technological reasons. The present US capacity is preponderantly based on the sea-water magnesia process with thermal reduction capacity in second place. No present magnesium capacity is dependent on recovery from the stronger natural brines. But projected capacity, although still weighted in favor of the sea-water magnesia process, is partly based on the recovery of magnesium chloride as a byproduct of potash operations.

Jan 11, 1964

Jan 1, 1917

By J. Ostachowicz, B. Holynska, M. Lankosz

The paper presents an analyzer and the method for the continuous determination of weight percentage of ore grains with diameter smaller than 75 µm in mineral slurries. The method is based upon the measurement of characteristic x-rays of copper excited by primary radiation of two different energies 16.5 keV and 60 keV from Pu238 and Am241 sources respectively. Additionally the backscattered primary radiation is measured in order to correct the variations of the solids content in the slurry. Since the particle size distribution of slurry can be described by the Rosin-Rammler formula, some calculations have been carried out in order to evaluate the influence of distribution parameters upon the results of the measurements of weight percentage U75 of particles smaller than 75 µm. The influence of solids content and of the copper concentration variation on the results has been also evaluated.1 It resulted from the calculations that the ratio rl/rz, where rl and r2 are the relative intensities of copper characteristic x-rays excited with 16.5 keV and 60 keV photons respectively does not depend on the copper content within the range 1 % to 4% of copper and is slightly dependent on the solids weight fraction and its chemical composition. The change of the dispersion parameter of the Rosin- Rammler distribution from 0.5 to 0.9 results in a change of value of U75 of approximately 3.0%. The results of calculations have been confirmed by the results of laboratory experiments. Therefore, a prototype of industrial analyzer for continuous determination of weight percentage of particles smaller than 75 µm has been designed and made. Its schematic drawing is shown in [Fig. 1]. Slurry is flowing down through steel flow-cell of the length equal to approx. 2 m. In the center, two XRF measuring heads (1) and (2) are located. Each of the heads comprises a rigid waterproof cover (3) with the mylar window (4), in which a proportional counter of resolution 15% for 6.4 keV is mounted with a preamplifier (5). The low- energy isotope source (6) is centrally located above the detector

Jan 1, 1980

By A. L. Bailey, B. A. Landry

W. W. ANDERSON and G. E. KELLER*—We want to compliment the authors on this very thorough paper. It gives information which the coal industry has needed for some time. We hope that the additional information which the authors are collecting will he available shortly. The mixing and riffling procedure that was followed for experimental purposes is obviously not practical in routine float-and-sink testing because of the particle size degradation which would result in handling the sample so many times. It is important to obtain our tloat-and-sink fractions with a minimum amount of handling of material. A statement is made in the paper (p. 80) that "the variable most likely to affect the size of sample required to meet a given preassigned accuracy would be the state or degree of mixing of the coal." We agree that this is a large factor, but do not believe it is the most important factor. Our own opinion is that the most important single factor governing the total gross weight of sample that must be collected is the percentage of the weight of material in the smallest fraction that results from the screening and float-and-\ink operations. In other words, size of sample is governed by the total number of fractionations that must he made, and the distribution of material within the fractions. We can imagine a coal with perfect mixing, but with such a small amount of material in some float-and-sink fraction in one of the coarse sizes that a much larger sample would have to be taken than would be the case with very poorly mixed material, but with a large percentage of coarse material more evenly distributed in all float-and-sink fractions. Our own observation of many float-and-sink tests that we have run in our own organization on many types of coal is that the size of sample that must be used on fine size float and sink is governed more by the requirements for weight of material to be used for analysis in the laboratory than by weight of material necessary to obtain accurate float and sink percentage of weight values. In other words, it is our opinion that very small samples can be used for float-and-sink fractionation in the fine sizes, but that accurate analysis of the fractions will depend on a larger weight of sample being pulverized for the laboratory than is necessary to establish the float-and-sink distribution with respect to weight. A. L. BAILEY and B. A. LANDRY (authors' reply)—The authors thank Messrs. Anderson and Keller for their comments based on long experience. It is agreed that the involved mixing and riming technique used may be disadvantageous from the standpoint of degradation. Fortunately, the paper does point out that the extended riming was unrewarding in causing further mixing. Two large unknowns remain, however: (1) how much of the mixing from the presumed highly unmixed state in the bed was achieved toward the random state during blasting, loading, transportation, screening, and further transportation to the point where the gross sample was taken, and (2) how much of the mixing took place during the preparation described preceding riming. As has been pointed out by one of the authors.6 the degree of mixing has a very large effect on the size of sample required and there are still too few experimental data to show at what stage of coal handling most of the mixing occurs. The discussion states that the weight of material in a screened fraction, or in a float-and-sink fraction, is more important than the mixing factor. We do not believe that these factors are comparable in this instance inasmuch as our purpose was to give minimum sampling requirements to achieve a preassigned accuracy in the percentages of float, middlings, or sink, and nothing more. The gross sample had already been screened and no further division by screening was made or contemplated; also, it was not intended that the middlings and sink fractions would necessarily be adequate for percentage ash or other determination. In other words, the sample obtained by the method outlined is not intended for washability studies but only for preparation plant control. Further experimental work has been done, since the paper was prepared, to investigate the effect of increasingly larger top and bottom sizes on the variability of float, etc., of a double-screened coal from Western Pennsylvania. Results will be published and eventually attention is to be given to the preparation of sampling specifications. E. H. M. BADGER*—I should like the authors to explain more fully the fundamental assumptions on which their Eq 4 is based. The equation is of the form s2 = p(l - p) which is the usual expression for the (standard deviation)2 when the chance of finding a particular kind of particle in the sample is proportional to the number fraetion, p. But instead of the number fraction, the authors have used the weight fraction, WF/W. The chance of finding a particular kind of particle in the sample can only be proportional to the weight fraction, if the average ?eig?ts of all kinds of particles, that is, float, midlings, or sink, are the same. Surely a much more justifiable assumption would be that the average volumes of the particles are the same, and, if this is so, Eq 4 would not be true. This may be demonstrated as follows: Let be the weight fraction of float, middlings, or sink, dl the density of this fraction, and d2 the density of the rest of the coal. Then assuming that the average volumes of the pieces in the three classes are the same, the number fraction, p, is given by ? P = d1/l-?/d2 + ?/d1 = ?d2/d1 + ?(d2-d1) The weight fraction, w, in terms of p is given by ? = pd1/(l-p)d2 + pd1 = pd1/d2 + p(d1-d2) _____ [61

Jan 1, 1950

E. K. Landis, Philadelphia, Pa. (communication to the Secretary) : Mr. Firmstone's paper is of great interest; but he has unfortunately otnitted to state the most important point, viz., the percentage of sulphur in the two materials he compares; and this omission vitiates the conclusions which he draws. Comparing by grade, instead of silicon-contents (as in his Table III.), the iron made using limestone with that made using dolomite, we find for gray-forge the average of four analyses under limestone to be, Si, 0.644; S, 0.089 ; while one analysis under dolomite gives Si, 0.508 ; S, 0.070. For No. 2 iron, the limestone flux gives, as an average of 19 analyses, Si, 1.107; S, 0.051; while the average of 4 analyses made with dolomite flux gives Si, 0.630; S, 0.056. It will be observed, that no No. 1 pig is given under limestone, while 14 analyses appear under dolomite, averaging Si, 0.950 ; S, 0.028. As nothing is said about changed conditions, it is Fair to presume that the ore and fuel, as well as the blast-temperature (which is stated to have been uniform at about 750' F.) remained practically the same; and since the sulphur in the two fluxes is not given, it is impossible to know whether the lower sulphur for equal silicon-contents is due to the use of dolomite or to other conditions. The use of dolomite would produce a more fusible cinder, and the furnace would be hotter than when using limestone; therefore, we might expect to see a grayer iron. The amount of So. 1 iron made with dolomite seems to confirm this supposition; and, under these conditions, we might expect more of the sulphur to be volatilized, and to pass off in the gases. The easier fusibility of the cinder would also permit more rapid driving; and this should reduce the amount of silicon and sulphur in the iron, as the amount of reduced metalloids in the pig is directly proportional to the length of time it remains in the reducing-zone.

Jan 1, 1895

By Ursula E. Wolff

The precipitation of carbides from an alloy containing 33 pct Ni, 21 pct Cr, balance iron, was investigated electron microscopically by means of extraction replicas and thinned metal foils. Annealing temperatures ranged from 565°to 870°C and up to several thousand hours. M23C6 precipitated in pain boundaries, incoherent and coherent twin boundaries in that sequence. The orientation relationship between carbides and austenite matrix was determined and correlated with the morphology of the carbides and with the type of boundary in which precipitation occurred. In large-angle grain boundaries, as well as in coherent twin boundaries, the carbides had the same orientation as one of the adjacent pains. These carbides formed sheets of individual flakes with shapes related to the orientation of the boundary. In incoherent twin boundaries carbides precipitated in ribbons composed of pavallel rods. An unidentified subcarbide was found to precede precipitation of M23C6 in these boundaries. The M 23 C6 rods had a kind of fiber texture with (110) parallel to the long dimension of the rods and ribbon, and with orientations of both of the adjacent twin-related austenite crystals Predominant in the texture of the carbide. A hard sphere crystal model has been used to discuss orientation and morphology of the carbides in terms of free volume and vacancies available in the boundaries. A number of papers have dealt with the morphology of chromium carbide (M23 C6) precipitated in austenitic stainless steels.1"7 In all these investigations, the carbides were examined in the electron microscope by means of extraction replicas. With this technique, the carbides retain the spatial distribution they had in the bulk sample. However, since the matrix is dissolved in the process, the particles can turn in an unpredictable way; and the orientation relationship between matrix and carbides cannot be established. In this paper the results of studies on extraction replicas and on thinned metal foils are reported. These studies were undertaken to determine the matrix-to-car bide orientation relationship, and to correlate the orientation of the carbides with their morphology. PROCEDURE The material used was an austenitic alloy with 33 pct Ni, 21 pct Cr, balance iron, containing approximately 0.05 pct C. Coupons of 1.25-mm sheet were first solution-annealed at 1050°C for 15 min and air-cooled. Then, to precipitate the carbides, samples were isothermally annealed in the range from 565" to 870°C for times up to several thousand hours. All further specimen-preparation procedures were carried out after the final anneal. Carbon extraction replicas from polished and etched surfaces were made with 10 pct bromine in methyl alcohol.' Thin foils were prepared from punched-out 3-mm-diam disksg which fit into the electron-microscope holder. The disks were prethinned by grinding to approximately 0.5 mm thickness, and then electro-polished in a polytetrafluoroethylene holder1' with a solution containing 5 pct perchloric acid in acetic acid to which 10 g per 1 Cro3 and 5 g per 1 nickel chloride were added (etchant modified from that of Briers et al."). This solution dissolves neither the carbides nor the austenite around the carbides preferentially. By using extraction replicas, electron micrographs and selected-area electron-diffraction patterns were taken from the same carbide arrays. By using thin foils, electron micrographs were made from a grain boundary area containing carbides. Electron-diffraction patterns were then taken from the same area and from each of the adjacent grains separately. In this manner, the orientation of each grain could be determined without interference by the carbide pattern. A peculiarity of extraction replicas should be pointed out. After the matrix is etched away, the carbide arrays float freely in the etching and washing solutions, and are held in place only at the anchoring points in the carbon replica. When the replica is picked up with a screen the carbide arrays tend to flip to one side. Thus, while the surface features are preserved, the original arrangement of the carbides may severely and unpredictably be disturbed whenever the specimen contains large amounts of interconnected carbides. Nevertheless, it is possible to correlate the different morphologies of the carbides with the type of boundary in which they have precipitated. RESULTS 1) Extraction Replicas. Fig. 1 shows that the grain boundaries usually are curved, multicornered surfaces of random orientation. The coherent twin boundaries (which are (111) planes) cut a grain into parallel slices. Incoherent twin boundaries occur at the ends and on the steps of twins and are often narrow, parallel-sided strips which are much longer than they are wide. Different morphologies can clearly be distinguished for the M23Ce carbides precipitated in each of these types of boundaries, and agree well with those observed by kinzel.2 The kinetics of this precipitation has been investigated." The first carbides precipitate in junctions of three grain boundaries and fan out from there into the adjoining boundary surfaces, Fig. 2(a). These carbides are oriented randomly, Fig. 2(b), and become coarser and thicker as annealing time increases. The large-angle grain boundaries are next to fill

Jan 1, 1967

By Edwin F. Brush, John Chipman

Published data on the activity of carbon in binary and ternary austenite at 1000°C are reviewed. The composition variables are . The coefficient, Vj, has the value for substitutional elements but may be assigned a ualue -1 for silicon to effect a simplification on the mathematical treatment. The activity coefficient PC = is obtained from gas equilibrium data. For the ternary systems studied the Henrian activity coefficient is given by the expression: The principle advantage in cornparison with the analogous expression in terms of atom fractions is found in the fact that for most systems the final term and in many the last two terms are zero. Values of the interaction parameters are tabulated and the graphical comparison of the equation with experirt~ental data is sho,wn in several figures. The thermodynamic properties of the solid solution, austenite, are of considerable importance in the heat-treatment of alloy steels and in other aspects of ferrous metallurgy. Early studies embodied in the Fe-C diagram have been extended to include other binary and some ternary diagrams. Our best hope of obtaining a useful thermodynamic treatment of reactions in complex alloy steels will not be found in quaternary and quinternary phase diagrams but in determinations of activities and interaction relations among the several solute elements. The foundation for such a development was laid by smith' in his early studies of the activity of carbon in Fe-C alloys and his subsequent work on Fe-C-Si, Fe-C-Mn, Fe-C-Ni, and Fe-C-Co solid solutions.2"4 Other observers have also made noteworthy contributions and these will be discussed and correlated here in the light of a somewhat simplified mathematical treatment of solute interactions. Fe-C AT 1000°C In a recent review of the thermodynamic properties of binary Fe-C austenite it was shown that the simple mathematical treatment employed by smith' was capable of describing all the published results on this solution. The treatment utilizes the atom ratio, yc = nC/nF,, rather than the atom fraction. The activity of carbon is proportional to the equilibrium gas ratio, either measured on a scalk in which the activity of graphite is taken as unity or, alternatively, aC may be set equal to yc at infinite dilution. In either case the ratio aC/y = (PC, the activity coefficient. It was found that the experimental data of smith1 and those of Diin-wald and wagner; Bungardt, Preisendanz, and Lehn-ert,' and Scheil, Schmidt, and Wiinnings at temperatures of 800" to 1200° C as well as reliable data on the solubilities of graphite and cementite could be represented by the equation for which graphite is the standard state: The data on alloyed austenite have been obtained at 1000°C. For this temperature, the "Henrian" activity coefficient (which is unity at infinite dilution) is: FOr an interstitial solute such as carbon in austenite it has been shown by statistical mechanicsg that the activity in the infinitely dilute solution is proportional to the ratio of the number of lattice sites occupied by carbon to the number of yet unfilled lattice sites. A variable zz proportional to this ratio serves as a useful measure of concentration:" in which b is the number of lattice sites provided by each atom of solvent; in austenite b = 1. The Henrian activity approaches zz at infinite dilution and the ratio a is the activity coefficient. The effect of a change in concentration is then given by: It has been shown further that in some systems the derivative in Eq. [4] remains constant over a wide range of concentrations. In such a case second-order terms become negligible and the Henrian activity coefficients is:

Jan 1, 1969

By N. A. Gokcen, S. Fujishiro

The dissociation pressure of Cr3C2 has been measured in the range of 1908" to 2237°K by means of graphite Knudsen effusion cells. It has been found that Cr3C2 vaporizes according to the following reaction: 1/3 Cr3C2 (s or 1) = 2/3 C (graph.) + Cr (g). The equilibrizcm pressure, P, of Cr (g) is found to be log Ps=- - (21,194/T) + 6.525 over solid Cr3C2 and estimated as log P, = - (19,535/T) + 5.76 over liquid Cr3C2. CARBIDES of chromium are of great importance in alloy steels and cemented carbides. The published data on their therm odynamic properties at high temperatures, however, are meager. The heat capacity and change in entropy of Cr3C2 were determined calorimetrically by Kelley and Moore1 in the range of approximately 50" to 300°K, and by Oriani and Murphy2 from 297" to 1188°K. The standard entropy of Cr3C2at 298.15°K, obtained by Kelley.7 was later confirmed by DeSorbo.4 Equilibrium in the reaction was investigated by Boericke.5 A recent tabular summary

Jan 1, 1962

By Victor V. Damiano

THOMPSON1 proposed a very convenient nomenclature in which an imaginary regular tetrahedron was used to facilitate the analysis of dislocation interactions in fcc materials. The faces of the tetrahedron were constructed parallel to four different sets of (111) planes, and the six edges of the tetrahedron then represented the six 1/2 [110] Burgers vectors. The lines which joined the midpoint of a tetrahedron face with the ends of one of its edges represented the Burgers vectors of the partial dislocations into which the six 1/2 [I101 Burgers vectors dissociate. Using Frank&apos;s2 notation, all of the dislocations and their partial dislocations were identified and numerous possible interactions were postulated. The case of hexagonal crystals is unfortunately more complex, but it appears convenient to introduce a system similar to that of Thompson1 to describe the various slip planes and Burgers vectors encountered in cph structures. The system proposed has limited application but serves to identify the following slip systems {0001} <l20>, {1010} <1120>,

Jan 1, 1963

T. R. HARRISON, Washington, D. C. (written discussion). *-Mr. Kowalke shows that a high resistance millivoltmeter is subject to smaller errors, due to change in resistance of the thermocouple to which it is attached, than is a low-resistance instrument. He uses as examples instruments having resistances of 30 and 2 ohms, respectively. At the Bureau of Standards, resistances above 300 ohms would be considered high and 30 ohms rather low. In the tests on calorized-iron thermocouples, a difference between the first and third calibrations of the couples serves to show changes due to the intermediate heat treatment and only under certain conditions would changes in calibrations due to changes in the wire be detected by ,a recalibration after 1 1/2 in. had been cut from the hot-junction end of the couple and the ends rewelded. The calibration of a couple depends only on the thermoelectric prop-erties of that part of the couple which lies within the region of non-uniform temperature, i.e., the temperature gradient; hence, so long as the temperature gradient falls along wires of similar thermoelectric properties no change in the electromotive force is produced by altering the metals of those parts of the circuit that are at uniform temperature. Usually at the cold-junction end of the circuit, copper leads, brass binding posts, manganin resistance coils, and various other materials form part of the circuit, but so long as all are at a uniform temperature (or if for each junction between unlike metals there is a similar opposing junction at the same temperature) no resultant thermoelectromotive force will be produced thereby. Likewise, if a length of several inches at the hot-junction end of the couple is at uniform temperature, it matters not if this section is unlike other parts of the couple, so long as there is good metallic connection and no source of e.m.f. other than thermoelectric is present. Cutting off part of the hot end of the couple within such a region of uni-form temperature would not alter the e.m.f. of the couple.

Jan 12, 1919