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By S. K. Basu, H. H. Kellogg

THE physical-chemical behavior of the system Pb-S-0 is of prime importance to the understanding of lead smelting processes, yet little accurate information is available on either equilibrium or kinetic behavior in this system. This paper is the first report of a program designed to fill gaps in our knowledge of this system. In the total ternary Pb-S-0, the region of greatest metallurgical interest is that bounded by the compositions Pb-PbS-PbS0,-PbO-Pb. Systems richer in sulfur, or richer in oxygen,* than those essentially pure SO2. This conclusion follows from the fact that all systems are in a highly reduced state, since either PbS or Pb is a constituent of all the equilibria. The content of 02, SO3, S2, S6, S8, and so forth, can be shown to be negligible compared to SO, in all such systems.* corresponding to this region can only be obtained at gas pressures exceeding 1 atm, a condition seldom met in lead smelting practice. Not only is the present study limited to condensed phases within this portion of the total system, but it is limited to temperatures at which all phases are pure solids, except for lead, which is liquid. In this limited system the following seven condensed phases are known to exist: Pb(l), PbS(c), PbO(c), PbSO,(c), PbSO,•PbO(c), PbSO4 • 2PbO(c), and PbSO, -4PbO(c). PbO exists in two crystal modifications,' but only the high-temperature yellow form is considered here. Schenck and co-workers2-4 reported the compound PbSO4 3Pb0 to be stable at high temperature, but the more recent work of Lander,5 and the present work, prove that the tetra-basic sulfate, rather than the tri-basic sulfate is stable. Fig. 1 shows the composition diagram for the binary PbO-PbSO2, based primarily on the work of Lander. In this study the univariant boundaries and invariant points existing among these seven condensed phases and the gas phase have been determined. In a ternary system, the phase rule indicates that an invariant point involves the simultaneous equilibrium of five phases—four condensed phases and the gas phase. A univariant relation involves four phases—three condensed phases and the gas phase. The gas phase in the systems studied is The following stable univariant equilibria between SOz and the condensed phases were identified: (a) PbS + 7PbS04 = 4(PbSO, - PbO) + 4SO2 (b) PbS + l0(PbS04 • PbO) = 7(PbSO4- 2PbO) + 4SO2 (c) PbS + 8(PbSO4 • 2PbO) = 5(PbSO4 . 4PbO) + 4SO2 (d) Pb + PbSO, • 4PbO = 6PbO + SO2 (e) 3PbS + PbSO4 . 4PbO = 8Pb + 4SO2 (f) 3PbS + 16(PbS04 PbO) = 7(PbSO4 . 4PbO)+ 12SO2 (g) 2PbS + PbSO,2PbO = 5Pb + 3SO2 (h) Pb + 3(PbSO4 . 2PbO) = 2(PbSO,. 4PbO) + SO, Of these eight univariant equilibria, five were measured in this work (a, b, c, d, and g) and the behavior of the other three (e, f, and h) was calculated by thermodynamic analysis of the measured data. Two invariant points were found corresponding to simultaneous equilibria as follows: Point 1: PbS, PbSO4PbO, PbSO4.2PbO, PbSO, - 4PbO, and SO2 Point 2: Pb, PbS, PbSO, . 2PbO, PbSO, - 4PbO, and SO2, From the measurements it was also possible to calculate the thermodynamic properties of the three basic sulfates of lead at 298.16°K. EXPERIMENTAL Apparatus—The experimental method consisted of the measurement of the gas pressure exerted by a given reaction mixture at a given temperature. An iridium crucible was used to contain the reaction mixture. There was no evidence of attack of the iridium,* but after use at high temperature for a week

Jan 1, 1961

By Gerald J. Anderson

The Marquette District of Central Northern Michigan is the oldest of the Lake Superior iron districts with a mining history dating from 1852 up to the present. The total production of all types of ore through 1965 was 338,120, 146 long tons. Emphasis up to the 1950's was on mining the direct shipping ores; however, demands for higher-grade and better-structured ores in the last decade has resulted in a complete shift in emphasis to beneficiating the lowgrade Negaunee Iron-formation to produce high-grade iron ore pellets. The Precambrian sediments of the Marquette Range have been correlated with the Animikie Series of the Thunder Bay District, Ontario, and are contained in a westward plunging synclinorium that is approximately 3 3 miles in length and 3 to 6 miles in width. -The rock unit of major economic importance is the Negaunee Iron-formation that reaches a thickness of 2500 feet near the City of Negaunee. The primary iron content of the Negaunee Iron-formation averages 26 per cent, whereas the altered iron-formation approximates 31 per cent. The Negaunee Iron-formation has been divided into three principal types: diagenetic, oxidized, and metamorphic. The ores produced to date fall into four categories: high-grade soft ores, high-grade hard ores, siliceous ores, and concentrates and agglomerates (pellets). The soft ores generally are found in synclines and in fault-trough structures, bounded by mafic dikes along at least one side, and are mainly found in the basal portion of the Negaunee. In contrast, the hard ores occur in the uppermost portion of the Negaunee and are controlled by structural features such as folds, faults, and dikes. Iron-formation that has undergone diagenetic and metamorphic alteration makes up the main beneficiating ore types. Studies on the Negaunee Iron-formation have played an important role in the formulation of many of the theories on the origin of the Precambrian iron-formations.

Jan 1, 1968

By H. C. Theuerer

GeC14 may be purified by extraction with HCI and chlorine. The process is as effective for the removal of AsCI:, as the more cumbersome distillation methods usually used for this purpose. GERMANIUM for semiconductor use contains impurities at levels no higher than a few parts in ten million. Material of this quality is obtained from highly purified GeC1, by hydrolysis to the oxide and reduction of the oxide in hydrogen. When purifying GeCl,, AsC1, is the most difficult impurity to remove. This is usually accomplished by multiple distillation procedures.1-3 AsC1, may also be removed from GeC1, by extraction with HC1.1-4 Reducing the arsenic to low concentrations is not practicable, however, because of the large number of extractions needed. This paper discusses a new method for the removal of arsenic from GeC1, by extraction with HC1 and chlorine. The method is rapid, leads to little loss of germanium and is at least as efficient as the distillation procedures currently being used. Theory of Extraction Procedures In the simple extraction of GeC1, with HC1, the following reaction occurs ASCl8G8C1 D AsCl3rc1 at equilibrium CA/Cn= K, where K is the distribution coefficient, and C, and C,, are the molar concentrations of AsC13 in HC1 and GeCl,, respectively. The materials balance equation for this reaction is VACA + vncn = VnC,, where V, and Vn are the volumes of HC1 and GeCl4, respectively, and C, is the initial concentration of AsC13 in GeC1,. From this it can be shown that for multiple extractions where C,, is the concentration of AsC13 in GeC14 after n extractions, and r is the ratio of V, to V,,. It is assumed that r is maintained constant, that equilibrium is established during each extraction, and that K is independent of the AsCl3 concentration. By saturating the system with chlorine, the following reaction occurs in the aqueous phase AsCl3 + 4H2O + Cl2 D H5AsO4 + 5HC1 at equilibrium K' = ------------ ai - a4 h2u - aet2 where a is the activity of the various components. The effect of this reaction is to reduce the concentration of the AsC1, in the aqueous layer and, therefore, to promote further extraction of this component from the GeC1, layer. If the arsenic acid remains entirely in the aqueous phase, the net effect of this reaction is to promote the removal of arsenic from the GeC11. The materials balance equation for extraction with HC1 and chlorine with the foregoing reaction is, then, VaCC + VACA + VACn = VnCo where C,. is the molar concentration of H3AsO, in the HC1. With the added assumptions that the activities of AsC13 and H8ASO4 in the aqueous phase are equal to their molar concentrations, it can be shown that for n extractions Cn/Cu = (1/rkK + rK + 1) n where k - K1 a4h2o - acl2/aoncl. It can be seen by comparing Eqs. 1 and 2 that if k is large, the removal of AsC1, by HC1 extraction will be greatly improved by the addition of chlorine. Dilution of the HCI used in the extraction with chlorine would also favor the separation. This, however, would increase the loss of GeCl,, which is undesirable. Experimental Procedure Germanium prepared from oxide of semiconductor purity is n-type with resistivities greater than one ohm-cm. The resistivity is controlled by the donor concentration, which is —lo-: mol pct. Germanium prepared from material with added arsenic will have lower resistivity commensurate with the arsenic concentration. With such material, at arsenic concentrations above 10-1 mol pct the resistivity is controlled by the added arsenic, and effects due to other impurities initially in the oxide are negligible. In this investigation GeO, of semiconductor purity was converted to GeCl,, and -0.01 mol pct As was added. This material was used for the extraction experiments and the purification attained determined by a comparison of the resistivity data for samples of germanium prepared from the initial and purified GeC1,. A method for calculating the arsenic concentration from the resistivity data is discussed later. The details of the experimental procedures used are as follows: Two hundred and thirty cu cm GeC1, were prepared by the solution of GeO, in HC1, followed by

Jan 1, 1957

By R. J. Charles

SEARCH for a consistent theory to explain the relationship between energy input and size reduction in a comminution process has accumulated, over the years, an enormous amount of plant and laboratory data. Although some correlation of these data has been possible for purposes of engineering design and for the advancement of research in fracture, there is still great need of a means of predicting behaviour of a solid when it is reduced in size by mechanical forces. The best known hypotheses proposed to describe the energy-size reduction relationships in crushing and grinding stem from a common origin. The present article analyzes problems of comminution in the light of the precepts of this origin. Its object is to reconcile points of difference between these well known hypotheses and to present relationships more widely applicable to comminution studies. Theoretical Considerations: Most existing relationships between energy and size reduction of a brittle solid stem from a single, simple, empirical proposition.&apos; Although this proposition can be demonstrated by observation and experiment, no theoretical derivation is yet possible. Mathematically, the proposition may be stated as follows: dE = -Cdx/xn [1] where dE = infinitesimal energy change, C = a constant, dx = infinitesimal size change, x = object size, and n = a constant. Eq. 1 states that the energy required to make a small change in the size of an object is proportional to the size change and inversely proportional to the object size to some power n. No stipulations are placed on the exponent n in either magnitude or sign. In 1867 Rittinger2 postulated that the energy required for size reduction of a solid would be proportional to the new surface area created during the size reduction. As far as can be determined there is as yet no physical basis for Rittinger&apos;s hypothesis. Rittinger&apos;s hypothesis can be stated mathematically as follows: E, = K(oa-a-0 . [2] Er = energy input per unit volume, K = a constant, <ti = initial specific surface, and o2 = final specific surface. In the size reduction of particles of size x, to particles of another smaller size, x2, Eq. 2 becomes the well known relation: ET = K&apos; {l/x2-l/xx) [3] where K&apos; is a constant. Eq. 3 may be arrived at from the proposition given in Eq. 1 by integrating and by assigning a value of 2 to the exponent n. J dE = J - C dx/x2 E = Kt (1x - 1x) where K&apos; = C. In 1885 Kick3 proposed the theory that equivalent amounts of energy should result in equivalent geometrical changes in the sizes of the pieces of a solid. For example, if one unit of energy reduced a number of equal-sized particles to particles of one half the size, then the same amount of energy applied to the particles resulting from the first test should result again in a size reduction of one half or a final size one quarter the original size. The Kick concept may be expressed as follows: Ek = K" log x1/x2 [41 K" = a constant and E, = energy per unit volume. The expression for Kick&apos;s law may be arrived at by again integrating Eq. 1 and in this case assigning a value of 1 to the exponent n. dE= J - C dx/x Eh = - C In {x/x2) = K" log (x,/x,) where K" = 2.3 C. Application of Kick&apos;s and Rittinger&apos;s laws to comminution has met with varied success. Gross and Zimmerley4 and Piret5 have shown that Rittinger&apos;s equation applies under certain conditions of experimentation. Walker and Shaw6 express the belief that in metal turning and shaping and in grinding of both metals and minerals the production of very fine particles (less than lP) follows Kick&apos;s hypothesis, whereas Rittinger&apos;s concept is valid for the size reduction of coarse particles. For the practical case of crushing and grinding, however, neither of the above hypotheses has received general acceptance. Bond&apos; has lately proposed that since neither Kick&apos;s nor Rittinger&apos;s hypotheses seem correct for plant design work, an energy-size reduction relationship somewhere between the two would be more applicable. The fundamental statement of Bond&apos;s work

Jan 1, 1958

By Gilbert Soler

Page Introduction. By Gilbert Soler.........................657 Deoxidation of Basic Open-hearth Steel. By T. S. Washburn.............658 Slag-metal-oxygen Relationships in the Basic Open-hearth and Electric Processes. By J. S. Marsh. (With discussion)...........................672 The Total Oxygen Content of Plain Carbon Open-hearth Steel during Deoxidation and Teeming. By Michael Tenenbaum and C. C. Brown. (With discussion)......685 The Occurrence of Oxygen in Liquid Open-hearth Steel—Sampling Methods. By T. E. Brower and B. b. Larsen..........................712 Effect of Deoxidation on the Strain-sensitivity of Low-carbon Steels. By H. K. Work and G. H. Enzian. (With discussion)........................723 The Relation among Aluminum, Sulphur, and Grain Size. By C. E. Sims.......734 Some of the papers and discussions that appear on the following pages were presented at the meeting of the Iron and Steel Division in Cleveland, Ohio, on Wednesday, October 18, 1944. with L. F. Reinartz and H. K. Work as Chairmen; the remainder were scheduled for the New York Meeting of the Institute in February 1945, which was canceled.

Jan 1, 1945

By C. K. Leith

IN telling the story of Canada&apos;s minerals many interesting and spectacular details will be passed over to permit pointing out some of the significant inter- national aspects. No country now has enough of all minerals for its own use. The problems of satisfaction of both national and world demands under these conditions have become international in scope, and history supplies no obvious solutions. The minerals of Canada are coming to play a prominent part in such problems. Production and Reserves In the last decade Canada has rapidly advanced in mineral production. In 1928 the total value of mineral products from Canadian sources reached 273 millions of dollars. Canada ranks first in production of nickel, first in asbestos, second in cobalt, third in gold and silver, fourth in lead and copper, and sixth in zinc.

Jan 1, 1929

By R. J. Wasilewski

The resistivity of single crystal and of polycrystalline metal has been determined between 77° and 1500°K. At comparable purity, the resistivity of the poly crystalline metal differs from that calculated from the axial resistivity values. The observed anisotropy is briefly discussed. A zone refined titanium rod was obtained from F. J. Darnell.1 The hardness of this material varied between 52 and 64 Bhn, indicative of its high purity. Single-crystal specimens were cut out from a few large grains, elongated predominantly along <1120>. Resistance measurements were taken with specimens immersed in liquid nitrogen, solid CO,, and acetone, and at ice point, and then recorded continuously between room temperature and 1200" to 1250°C, throughout at least one full heating and cooling cycle at a rate of l° to 3°C per min. Four probe measurements were taken using spot-welded Pt wire 0.003 in. in diam as potential terminals, and the electromotive force drop was determined poten-tiometrically. A standard resistance, in series with the specimen, served to determine the dc current (generally about 80 ma) in the circuit. In order to eliminate spurious thermal electromotive forces, the circuit polarity was automatically reversed at 5-min intervals, and the mean of the two adjacent readings taken as the true electromotive force value. The discrepancy between the readings at reversed polarities was generally of the order of a few µ v, as all the spot-welded joints were contained within a volume of some 5 mm cube. The relative resistance (R T/R 273o) variation with temperature is tabulated below, and shown in Fig. 1, as measured during the first heating run. The discontinuous drop in resistance, corresponding to the a — ß transformation, started for both initial orientations at 1170°K; i.e., some 15°K above the accepted value of 882°C (1155°K). Judging by the temperature ranse of transformation—some 30°K for the single crystal and 20°K for the polycrystal-line specimen—this difference is believed caused by the solution of the oxygen present initially on the surface of the specimens. The general trend of the resistance vs temperature shown in Fi,;. 1 is in qualitative agreement with that previously reported for polycrystalline titanium metal. 2,3 Significant anisotropy is, however, indicated by the crossing over of the curves for <1120> and <0001> orientations at 273°, 650°, and 1000°K. This difference is most startlingly shown in Fig. 2, where instantaneous temperature coefficients (l/R273 x dR /dT) are plotted for both the first heat-

Jan 1, 1962

I-Institute of Metals Division* PAUL D MERICA, Chairman ZAY JEFFRIRS, Vice-chairman W M CORSE, Secretary Executive Committee T R FREEMAN JR, Local Section S SKOWRONSKI, Papers Committee R S ARCHER Non-ferrous Data Sheets H C JENNISON, Membership Committee C BAIN, Journal Committee L W SPRING Local Section Committee J R FREEMAN, JR, Chairman R J ANDERSON Cincinnati R L DOWDELL Minneapolis R S WILLIAMS, Boston H CLAMER, Philadelphia W A SCHEUCH, Chicago R F WOOD, New York Papers Committee S SKOWRONSKI, Chairman H S ARCHER-Aluminum W K FRANK-BRONZE F W HARRIS-Copper H BASSETT-BRASS G O HIERS-Lead Alloys M CORSE-White Nickel Base Alloys PAUL D MERICA-Nickel

Jan 1, 1923

By C. C. Harris

An analytical solution of the integro-differential equation of batch grinding is proposed as a first appoximation to the xYt surface. The size distribution equation (xY plane) is a three parameter equation previously suggested. Possible refinements are outlined. Comminution kinetics research is presently following several related courses. Some are equivalent, in that they represent different ways of viewing the same facet of the problem, though the entire endeavor cannot be described as being completely integrated. The purpose of this note is to propose and discuss a framework into which the various approaches might be fitted. This must clearly be founded upon an analysis of the xYt surface.&apos; (See also Fig. 1 of Reference 26.) The investigations referred to above comprise mainly researches into the following: (1) The kinetics of the creation of the finer sizes during relatively small grinding times. This is the Fahrenwald-Arbiter-Bhrany 2-3 approach which leads to equations equivalent to a special case of the charles4 relationship. It emerges that initial production of fines follow essentially zero order* kinetics. (2) Disappearance kinetics of the coarser fractions. This appears to be a first order relationship.5-6 (3) Prediction of the xYt surface via the selection and breakage functions utilizing computer-programmed or approximate solutions of the integro-differential equation of batch grinding.5,8-17 A recent discussion by Mika et al.5 references the relevant literature up to about 1966. In addition to these main-stream researches there is some work on the minor topic of extremely long grinding time considered as a limiting case.18-19 The field is supported by investigations into the size distribution of fragments produced by breakage processes, some of this work being most valuably statistical-mechanical in nature.20-25 Better fitting equations, however, are obtained by statistical and curve-fitting methods.26 This

Jan 1, 1969

By R. H. Richards, A. E. Woodward

In Rittinger&apos;s Aufbereitungskunde of 1867 occurs (p. 195) the following table, which shows the rate of falling in water of fragments of minerals, of irregular shapes and of five different specific gravities: Diameter of particles in millimeters. 10 8 6 4 3 2 1 .5 Sp. Or. Velocity in meters per second. Auriferous silver, 16..9 .8 .7 .57 .5 .4 .29 .20 Galena,. ..7.5 .62 .55 .48 .39 54 .28 .20 .14 Pyrites,. ..5.0 .49 .43 .38 .30 .26 .22 .15 .10 Quartz,. ..2.6 -30 .27 24 .19 .17 .14 .10 .07 Coal,. ..1.3 .13 .12 .10 .08 .07 .06 .04 .03 With the purpose of extending this valuable table, to cover a larger number of minerals and sizes of each mineral, and of making it more easy of application in deciding upon a sieve-scale for any group of minerals, we have prepared the curves of velocity of fall of bodies in water shown in Plates I., XI., 111. and IV., using Rittinger&apos;s formula V= 2.44d(8 —1) where V= velocity in millimeters per second. " D = diameter of particles in meters. " 8 = specific gravity of the mineral. These curves embrace a large number of specific gravities, and for each specific gravity the relation of the diameter of the mineral particle to the velocity of its fall in water is given for all diameters and velocities used in practice. The second diagram is an enlargement of the lower left-hand corner of the first, the third bears the same relation to the second, and in like manner the fourth to the third. Plate I, therefore, covers the work of the coarsest jigging 2 inches in diameter; and under

Jan 1, 1890

By C. H. Mathewson

CONSIDERABLE progress has been made during the last few years in analyzing the action of plastic deformation in metallic crystals. This is due largely to the development of X-ray spectrographic methods for studying changes in the orientation of single crystals, or of conglomerates, as they occur during the process of plastic deformation, but partly to the widespread knowledge of suitable technique for preparing large (single or variously combined) crystals for direct crystallographic observation under stress or in various conditions of strain. These two methods of studying changes in the crystalline structure of metals may of course be used in conjunction with features of mutual support, but unfortunately the advantage of direct crystallographic observation is lost when we proceed to the study of severely cold-worked structures, owing to the occurrence of real or apparent crystalline discontinuities which become more and more complicated as the amount of plastic action increases. Furthermore, the X-ray methods do not appear to be adequate, at least in their present stage of development, to fix definitely the character of structural alteration in the parent crystal lattice by plastic deformation. The principal question at issue concerns the nature of the crystalline particles that remain after plastic deformation. These are generally known in our American metallurgical literature as crystalline fragments,&apos; and they seem, indeed, to diffract as individuals causing the Hull pattern of a severely cold-worked metal to resemble the pattern of a fine powder,2 with certain features of preferred orientation among the particles deter- mined by the manner and intensity of cold working. We must freely concede that there are conceptions of lattice alteration, apart from that of simple fragmentation, which would account for an increasing number of lattice positions according to X-ray spectrographic observation as the degree of deformation increased.

Jan 1, 1927

By S. D. Strauss

The marketing of nonferrous metals and of the ores and concentrates from which these metals are recovered is a fascinating trade, international in character, sensitive to every change in the economic tide, and complex in its organization. Each individual metal has its own marketing mechanism; no two are exactly alike. The differences sometimes are a matter of tradition rather than of necessity, but usually they have developed because of the very nature of the problems of producing or consuming the individual metal. This description, because of limitations of space, can do no more than indicate the major aspects of the trade and touch lightly on the marketing structure of each metal. The dictionary states that a market is a "meeting of people for selling and buying." In the case of nonferrous metals this meeting may occur on a half-dozen different occasions between the time the ore has been first mined and the time the refined metal is available for use by industry; or it may not occur at all until after the metal itself has been rolled, drawn, stamped, cast, or forged into a useful semifabricated shape. To illustrate: A Chilean miner may sell his small ore production to a custom mill, which produces concentrates that are sold to an ore dealer, who finances the shipments of the concentrates to a United States custom smelter, which buys these&apos; concentrates for conversion into blister, which is subsequently refined into electrolytic copper and sold. Conversely, much of the production of aluminum is in the hands of integrated concerns that mine bauxite, convert bauxite to alumina, smelt the alumina to produce aluminum, and then fabricate the aluminum into semifinished or even finished products before title to the material changes hands for the first time. Some nonferrous ores are not converted into metal at all but are sold by the miners or dealers directly b the ultimate consumers. A good example would be chrome ores used by the chemical industry. And of course a substantial part of the commerce in nonferrous metals is in scrap, which is the reconversion into useful form of metals that have long since been mined and smelted. Thus, one-third of all the lead used in the United

Jan 1, 1959

By H. I. Aaronson, H. A. Domian, G. M. Pound

The thernodyna,nics of I the Proeutectoid ferrite re-action ha1.e been investigated on the bases of three diifevent descviptions of the statistical thernzodynamics of interstitzal solid solutions. Especially at low ternperatures, substantial dijeretzces are found in the valltes of the extrapolated y/y + a and cr/a + y equilibriurn curls, and in the To- co7nposilion metastable eqliilibriunz curl-es thus co,npited. Although neither actiztity nor phase-diagram date are able to distingrish udeqiutely among the various descviptions, the statustics of Lacher, Fouller, and Guggenheinz provide the ?nost conplete epresentation az3ailable of the single carbon-ctrbon interaction energy (w) nzodel of an intevstitiril solid solution, and the relationships deduced frojrl then2 are accordingly pre.ferred. The findings tlzut w in austenite &apos;aries significu?ztly uith tenpevntrue and that phase-diagawr data arc not accurately con?palible usith eqcrctions deduced on the basis of actility infoation indicate, hou&apos;e13er, that a wzore cornplex nlodel of the uustenite , und pvobably of the .feyrite, solirl solutions will have to forn the basis of f4tuve statistical t1.eat1nents. Some suggestions for such a ruodel arc advanced. Althoug11 w represents a vepltlsio energy in austozite, it was found to corvcsporzd in ferrite to a binding energy, in qualitatit.e accord zc,itlz the internal-friclion results of Keefer and wert. ThE transformation of austenite to proeutectoid fer-rite is becoming recognized as an exceptionally useful vehicle for quantitative studies of the kinetics of phase transformations.&apos;" Reasons for this popularity include well-characterized microstructures which develop on a convenient scale with acceptable kinetics within a considerable temperature-composition region, the absence of great sensitivity to common impurities, and, especially. the availability of a unique wealth of the ancillary information indispensable for the quantitative interpretation of kinetic measurements, including phase diagram,3 crystallographies diffusivity,5 inter-facial energy,=17 elastiit," specific vlume, &apos;&apos;&apos; and ativity&apos;-&apos; data. Development of considerable amounts of additional thermodynamic information from activity data is of particular importance with respect to kinetic studies, since much of this information is needed in temperature-composition regions not directly accessible to presently available techniques for the measurement of equilibrium properties. A generally useful approach to the thermodynamics of solid solutions, which is of especial value in this situation, is based upon the formulation of the free energy of such solutions as a function of temperature and composition. The free energy of solid solutions has been resolved into many components. Particularly in the case of interstitial solutions, with which we shall be concerned in the present study, however, only the positional entropy component has been intensively studied. The other components are conventionally taken into account by fitting equations for the activity of the interstitial species or the temperature-composition path of phase boundaries, derived principally from positional entropy considerations, to experimental information on these quantities through adjustment of one or more constants in the equations. A number of studies of the thermodynamics of interstitial solid solutions have been made primarily on this basis,&apos;"25 but only Kaufman, Radcliffe, and cohenZ2 (hereafter KRC) and ener&apos;&apos;% ave applied the results of such studies to develop relationships for the thermodynamic quantities of interest in the austenite —- proeutectoid ferrite transformation. KRC made use of a model developed by cheil&apos;&apos; (on the basis of a previous study by ohansson&apos;), and subsequently rede-rived correctly by Speiser and retnak,&apos; in which a carbon atom is considered to inhibit occupancy of a certain number of its nearest-neighboring interstitial sites. schei120 determined the number of sites in austenite thus excluded by matching calculated and experimentally measured curves for the variation of carbon activity with the mole fraction of carbon. zener17 used a different approach. He assumed that the positional entropy of carbon is ideal both in austenite and in ferrite (i.e., no excluded interstitial sites), and included all other contributions of carbon in a temperature-independent "free-energy change" accompanying the transfer of 1 mole of carbon between the two phases. This quantity was determined by "pinning" an equation derived for the boundaries of the a + y region to experimental data on the compositions of these boundaries at a single temperature. In the present investigation, three different approaches to the thermodynamics of the proeutectoid ferrite reaction are examined comparatively: I) the method of Zener; 2) the model employed by KRC and predecessors; and 3) the more detailed statistical thermodynamic treatment of the same model developed by acher and Fowler and uenheim, &apos; in which the problem of overlapping regions of influence of individual interstitial atoms is resolved. In order to make these comparisons, it is necessary to undertake an extension of one aspect of Zener&apos;s method; since the Lacher- Fowler -Guggenheim (LFG) treatment has not been previously used in the present context, the necessary thermodynamic "superstructure" for this treatment will be developed in parallel

Jan 1, 1967

Arizona E. P. MATHEWSON, Chairman W. V. DECAMP. First Vice-chairman H. W. ALDRICH, Second Vice-chairman E. D. GARDNER, Secretary-Treasurer, Care U. S. Bureau of Mines, Tucson, Ariz. F A. AYES, J. P. HODGSON W L DU MOULIN WILLIAM KOERNER Boston Meets first Monday each winter month GEORGE B WATERHOUSE, Chairman GEORGE A PACKARD, Vice-chairman F. LEROY FOSTER, Secretary-Treasurer Room 8-219, Mass. Inst. of Tech , Cambridge, Mass. F K MORRIS F S MULOCK

Jan 1, 1923

By G. P. Moore

BOLIVIA still remains among the oil countries that have proved oil acreage but no production which is being marketed. No steps have been taken during the past year to provide facilities for transport of Bolivian oil to market nor are any known to be contemplated for 1930. The only active operator to date is the Standard Oil Co. of Bolivia, subsidiary of the Standard Oil Co. of New Jersey. The potential production from completed wells is practically unchanged from the 1928 figure of 6000 bbl. daily. As far as is known, there has been only one completion during the year 1929. This is the Machareti well, which is about 50 km. north of Villa Montes along the road to Charagua. The well is reported at about 250 bbl. daily initial production. The gravity of the oil is not known but is presumed to be about 40" Bé., the average for the region. The Standard Oil Co. of Bolivia has five strings working on various parts of its concession. No new locations have been made definitely. Company Activities There was no change in the situation of American holdings in Bolivia during 1929. The oil rights of an English company, acquired under a special colonization contract with the Bolivian Government, are being negotiated in New York and may mean the entrance of another of the large American oil companies in Bolivia. The Sucre Syndicate sold its holdings to the Standard Oil Co. of Bolivia during the past year. .A local company called the "Aguila Doble" was formed during 1929 to drill a well or wells near the town of Cochabamba on structures mapped by a local geologist. It is reported that the Government is buying about one-fourth of the capital stock of this company for 500,000 Bolivianos (about $180,000). The company has not yet raised sufficieht funds to buy drilling equipment so that no operations have been started. According to the statements published in La Pas, this company has acreage on seven anticlinal structures near Cochabamba. This area lies about 8500 ft. above sea level on the eastern Hank of the Andes Moun-

Jan 1, 1930

By Leonard R. Weisberg

HE procedure of directional freezing by the Bridgman technique1 is frequently used in crystal preparation. On those occasions where the crystal is regrown, it can be advantageous to Crop part of the ingot before regrowth to achieve purification. This note describes some simple, yet interesting, observations concerning the effects of cropping an ingot between successive freezes. First, it is not effective to Crop the front end of an ingot, whether or not the distribution coefficient, k , of the impurities is greater or less than unity. This can be shown as follows. The concentration C, of an impurity in a directionally frozen ingot of length d with a uniform cross section is given by where x is the distance along the ingot, and C0 is the initial concentration per unit length. It is assumed in deriving this equation that diffusion is negligible in the solid, is complete in the melt, and that k is constant. Consider that a section of the ingot Ad is removed from the front end. Then the average impurity concentration in the remaining (d- Ad) section of the ingot can be shown by integration to be given by When the ingot is remelted and refrozen, the new impurity distribution is given by where xl is the distance along the refrozen ingot. Substituting the value of c into Eq. [3], one finds This is identical to Eq. [11 when x = (x, Ad), which represents the original impurity distribution in the (d - Ad) section of the ingot after the first directional freeze. Therefore, the cropping and re-freezing accomplished nothing. This can also be seen physically by realizing that the average impurity content in the melt after the first Ad section is frozen, is identical to that after the resulting ingot has been cropped and remelted. Hence, it is assumed in the following sections that only the tail end of the ingot is cropped. However, it must be realized that for impurities with k greater than one, the pieces cropped from the tail end are purer, and are therefore saved. After cropping an amount Ad from the tail end of an ingot, the average impurity concentration of impurities in the remaining portion of the ingot is given by wheref= d/d. For the case of k < 1, the purification is defined as c,/c. It is obvious from Eq. [5] that the purification increases asf increases, but the increase in purification is not large. For example, iff is doubled from 0.1 to 0.2, the purification increases by only 10 pct for k = 0.5, by only 24 pct for k = 0.1, and by 32 pct for k =0.01. Much smaller values off than 0.1 are not desirable since insufficient purification is achieved. These figures indicate that much larger values off do not lead to substantial improvement, especially considering that much of the original ingot is lost. Therefore, it is generally useful to Crop about 1/10 of the ingot to achieve purification. As compared to doubling the value off, it is much more helpful to remelt, refreeze, and crop the ingot twice. Using Eq. [51 reiteratively, and assuming f= 0.1, it is found that the purification after this process is found to be increased over the purification after a single freeze and cropping by 33 pct for k= 0.5, 450 pct for k = 0.1, and 4100 pct for k = 0.01. This indicates that considerable purification can be obtained by this procedure. However, if purification is the main goal, one should resort to zone refining,3

Jan 1, 1962

By T. R. Ingraham

The thermal decomposition of Nickel (II) sulfate was examined by determining the total pressure of SO3, SO2, and O2 developed over a sample when it was heated in an evacuated system fitted with a Pyrex-bellows mercury manometer. The equilibrium pressures were combined with previously published data on the oxide and sulfide systems to establish a predominance volume diagranz for the Ni-S-O system over the normal range of roasting temperature and gas composition used in the treatment of nickel minerals. The protective coating of NiSO4 which forms on the oxide during roasting, and which causes the sulfation reaction to almost cease, may be disengaged readily by temperature cycling. When nickel sulfide is roasted in air, either nickel sulfate or nickel oxide may be formed by altering the experimental conditions. Because of the differing stabilities of various metal sulfates and oxides, possibilities exist for separating some of the constituents of mineral mixtures by the technique of selective sulfation and oxidation roasting. The experimental information required to make reasonable predictions of the possibilities of this technique is incomplete and, in some cases, in conflict. As part of a general program of providing some of the required information, a study EXPERIMENTAL Materials, Apparatus, and Procedure. Fisher certified reagent-grade nickel sulfate hexahydrate was used in the source material for both nickel sulfate and nickel oxide. The manufacturer&apos;s analysis indicated: 0.001 pct Fe, 0.005 pct Cu, 0.003 pct Co, 0.001 pct C1, other 0.15 pct. The material was dehydrated, before use, by heating at 420°C for 5 hr. The oxide was prepared by roasting the sulfate in an open tray in a muffle furnace for 10 hr at950°C. Preliminary experiments which were made by thermogravimetric analysis and X-ray diffraction analysis established that only one crystal form of nickel oxide and one of nickel sulfate were involved in the equilibrium shown in Eq. [I]. The apparatus used in the experiments was described previously.1,3 The main feature is a corrosion-resistant, flexible Pyrex bellows which is used to protect the mercury in a u-tube manometer. Before a run was begun, the apparatus was washed thoroughly with hot hydrochloric acid and water and dried by heating under vacuum. The mixed sulfate -oxide sample was contained in a platinum bat rest-

Jan 1, 1967

CHARLES KIRCHHOFF, Chairman. ALBERT SAUVEUR, Vice-Chairman. HERBERT M. BOYLSTON, Secretary, Abbot Bldg., Cambridge, Mass. John Birkinbine, J. Esrey Johnson, Jr., Felix A. Vogel, William H. Blauvelt, William Kelly, Leonard Waldo, James Gayley, . Richard Moldenke, William R. Walker, Henry D. Hibbard, Joseph W. Richards, - William R. Webster. Henry 1%1. Howe, E. Gybbon Spilsbury, Frederick W. Wood. Robert W. Hunt, A. A. Stevenson, The Board of Directors of the Institute has authorized the holding of a meeting under the auspices of the Iron and, Steel Committee in New York City, October 16 and 17, 1913. Gratifying responses have been received to the request of the Committee for contributions, the following papers being already assured: 1. H. M. Howe, Equilibrium Temperature for A, in Carbon Steel. 2. H. M. Howe, The Divorcing of the Eutectoid in Meteorites. 3. H. M. Howe and A. G. Levy, Determination Of the Position of Ae3, in Carbon-Iron Alloys. 4. G. .K Burgess, J. J. Crowe and H. S. Rawdon, Thermal and Microscopical Examination of Professor Howe&apos;s Standard Commercial Steels. 5. H. Dl. Hove, Discussion of the Existing Data as to the Position of Ae3,. 6. J. H. Hall, Shock Tests of Cast Steel. 7. H. F. Miller, Jr., The Design of Regenerators for Open-Hearth Furnaces. 8. E. Stütz, Paper on the "Scoria Process." 9. Albert Sauveur, Mayari Steel. 10. Felix A. Vogel, Briquetting. 11. J. E. Johnson, Jr., Paper on " Cast Iron."

Jan 6, 1913

By W. R. McMillan, E. A. Gulbransen, K. F. Andrew

Annealed and electrolytically polished pure iron was oxidized between 650° and 850°C at oxygen pressures of 0.1 to 2 microns Hg. Electron optical studies showed that oxidation occurs discontinuously over the surface and orients crystallographically with the substructure of the metal grains. IN previous papers&apos;, " the authors described the formation of oxide films on high purity iron at norrnal pressures and at temperatures below 300°C. Electron optical studies showed that the oxide film consisted of many individual oxide crystallites having nearly random orientation on each metal grain. The size of the oxide crystallites depended upon the temperature and upon the extent of oxidation. In these studies the crystallite size varied from 250 to 1800Å. Recently, Bardolle and Benard3 studied the crystal habit of the oxide crystallites formed on Armco iron between 650" and 850°C in what might be defined as a "poor vacuum" atmosphere in which the pressure could be varied between 10-1 to 10-3 mm of Hg. Their results showed that, at 850°C and a vacuum of l0-2 to 10-3 mm of Hg, a few well oriented nuclei of oxide were formed on the metal grains. At pressures between l0-1 to 10-2 mm of Hg, many oriented nuclei of oxide were formed. At 750°C the metal surface was bright although an oxide was present. Unfortunately, the extent of oxidation, the oxygen pressure, and the influence of carbon in the metal were not determined, and it was, therefore, impossible to give a theoretical interpretation to the very beautiful light micrographs. Bardolle and Benard used the light microscope to determine the crystal habit of the oxide and X-ray diffraction to determine the orientation relationships. It was believed that the use of controlled amounts of oxidation at high temperature is an important method for the study of the initial stages of oxidation of metals at high temperatures. This paper presents the first results of an electron optical study of this problem for iron. Since the electron microscope and electron-diffraction methods using stripped oxide films and surface replicas yielded finer details of the crystal habit and structure of oxide film, these methods were used in this study. Two types of iron having different carbon contents were used: Puron and Armco* iron. A com- parison of the results for these materials made possible a study of the influence of the surface oxide-carbon reaction on the initial stages of oxidation. Before discussing the experimental results, the thermodynamic equilibria of 1—the oxidation reaction, 2—the surface oxide-carbon reaction, and 3—the solubility of oxygen in iron, will be considered. In addition, it is important to consider the kinetic-theory predictions on the rate of collision of oxygen with the iron surface. Thermodynamic and Kinetic-Theory Calculations Only one type of reaction is usually considered in the oxidation of iron at normal pressures at high temperatures: Fe(a) + 1/2O2(g) = FeO(s) 3Fe(a) + 2O2(g) = Fe3O4(s) 2Fe(a) +3/2O2(g) = a-Fe2O3(s). [11 However, two other reactions may occur: FeO(s) + C (solid solution in Fe) + Fe(a) + CO(g) [2] and Fe(a) + O2(g) e Fe(a) (solid solution of 0,). [ 3 ] In addition, iron will react with the higher oxide at certain temperatures to form FeO. For a complete interpretation of the oxidation of iron at low pres-

Jan 1, 1955

By P. Nyul, S. Caplan, M. F. Lamorte, T. Gonda

Therrnal resistance is measured on GaAs laser diodes in the temperature range 77" to 300°K. These data show that typically the thermal resistance increases fifteen times from 77 to 300°K. The increase is attributed to the decrease in thermal conductivity of Gds. Nornzalized thermal-resistance experimental and calculated from published thermal-conductivity data) values are compared and good agreement shown. In many practical applications, it is desirable to obtain high average power output from laser diodes. Average power output is determined in large measure by the external efficiency and thermal resistance of the diode.&apos;-3 The average input power with which a laser diode may be pumped is dependent on the thermal resistance. Thermal resistance has been studied over the temperature range from 77" to 300°K which is usually of interest in practical applications. This correspondence presents data on thermal resistance for GaAs laser diodes and compares them to values calculated from thermal-conductivity data. Junction heating arises from three distinct components: 1) joule heating, 2) nonradiative recombinations, and 3) reabsorption of radiation. In high-threshold lasers, joule heating predominates.4 Typically, the nonradiative recombination is not negligible and contributes significantly to junction heating. The loss caused by reabsorption may be of the order of the joule-heating loss.&apos; The fabrication and the geometry of laser diodes have been described in other publications.5 The data presented were obtained from diodes which were fabricated from the same region of a wafer to minimize differences. Fig. 1 shows four types of heat sinks employed in this study. In types 1 and 2, the laser cavities are alloyed; pressure contacts are employed in types 3 and 4, and indium is plated on the inside faces to improve the intimacy of contact between the diode and the heat sink. The thermal resistance R is defined by the following relationship: where AT is the junction-temperature rise above the heat-sink temperature for the diode power dissipation Pd. For measurement of thermal resistance, a direct current is passed through the junction, in the range from 1 to 50 pct of threshold. The diode is placed in the laser mode by superimposing a current pulse of low-duty cycle on the direct current.3 Junction-temperature rise is obtained from the time-resolved laser spectrum at the leading edge of the current pulse.&apos; Typically, the laser line shift is 2.5A per OK. The resolution employed in these experiments is 0.5A; therefore, the accuracy in the temperature measurement is 0.2K. Typically, the temperature rise is 2" to 20°K. The power dissipation is the difference between the dc power input, and the radiation power exiting the diode. The measurement accuracy is less than 1

Jan 1, 1968