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By P. A. Larssen, P. R. Gage, R. W. Bartlett

The kinetics of formation of intermediate sili-cide compounds from MoSi2/Mo and WSi2/W couples were studied using a cylindrical sample configuration. Concentration profiles of the constituent metals were deter mined from electron-microprobe analysis of cross-sectioned samples after isotlzernzal diffusion annealing. These data also yielded hand widths of phases. Growth of intermediate phases depends on diffusionin them and obeys a parabolic rate law. The rates of formation of the intermediate phases decrease in the order Mo5Si3 > W5Si3 > Mo3Si. Crowth rates. for the isomorphous phases Mo5Si3 and W5Si3 had the same activation energy. 43 kcal per mole. SILICIDE coatings employed to protect refractory metals from high-temperature oxidation are usually formed by a diffusion process requiring concurrent transfer of silicon to the refractory metal surface. For a simple binary system and a coating thickness of one or two mils, the coatings on molybdenum and tungsten are primarily the disilicides WSi2 and MoSi2, respectively. During use of the coated re- fractory-metal system at high temperatures, in the absence of the silicon source, further diffusion causes growth of lower silicide compounds and depletion of the disilicides. Recent investigations have shown that the lower silicides are less effective than the disilicides in forming a glassy oxide film which impedes oxidation.' Consequently, failure of coatings at high temperatures may coincide with complete conversion of the disilicide phase. The purpose of this part of the study is to investigate the growth kinetics of the intermediate compounds in the W-Si and Mo-Si systems. There are three intermetallic compounds in the Mo-Si system: MoSi2 with a tetragonal structure

Jan 1, 1964

Discussion of the paper of E. L. deGolyer, to be presented at the Colorado meeting, September, 1918, and printed in Bulletin No. 137, May, 1918, pp. 987 to1000. J. A. UDDEN,* Austin, Tex. (written discussiont).-I have read Mr. E. L. deGolyer's paper on The Theory of Volcanic Origin of Salt. Domes, with a great deal of interest. It seems to me a very able summary and discussion of the various theories set forth to account for the origin of our salt domes on the coast. It has always appeared to me that what we need is more observations on the facts involved and I regret very much that so far we have not been able to devote much time to the study of our salt-dome fields on the coast in this State. One feature that I do not find mentioned in Mr. deGolyer's paper is the so-called "cap. rock" overlying the salt. The nature of this rock seems to vary from a coarsely crystalline limestone to a fine-grained limestone containing sand and in which the limestone seems to be intersticially introduced material. We should be prepared to accept, if necessary, "more than one theory. To my mind, the igneous theory and the artesian theory, if I may so call it, may very well both be true. The "squeeze" theory and the artesian .theory may,, it seems tome also, jointly explain the phenomena. Neither the volcanic nor the salt "squeeze" theory explains the presence of the cap rock. The latter certainly does not explain the extensive sulphur deposits which occur in association with the cap rock. Whichever additional theory will be found best to explain the salt-dome structures, when we shall know them better, it seems to me that the theory first advanced by R. T. Hill and later elaborated by G. D. Harris, is not likely to be entirely replaced. Whatever cause has first set into action an upward circulation of gases and liquids in our salt domes, it seems to me that to a gentle circulation of the kind postulated by their theory is to be ascribed the uppermost and the later phenomena in our salt domes on the coast, with which we are most familiar; such as the cap rock, the sulphur, and the gypsum and anhydrite deposits.

Jan 7, 1918

By Robert Maes, Robert de Strycker

The Fe-Ni-As phase diagram has been established by the study of about a hundred alloys, by microscopic observation, and by thermal analysis, with arsenic contents up to 50 pct. The iron and nickel arsenides present extensive solid-solution fields, owing to the substitution of nickel by iron and vice versa; the extent of the solubility field of each compound has been determined with an accuracy of ±1 pct. In the investigated range of compositions, the solidification reactions were established, and the temperatures of the invariant reaclions detevmined with a preciston of iZ°C in the most favorable and ±5°C in the least favorable cases. The isothermal lines of the liquidus surface have also been drazum, with an accuracy estimated at i5°C. Reactions in the solid state, which take place for the formation or the decomposition of certain phases , were investigated in detail. ThE constitution diagram of the Fe-Ni-As system is fundamental for the understanding of the properties of nickel speiss; these by-products of the extraction of certain nonferrous metals indeed often contain the three elements iron, nickel, and arsenic as main constituents. The Fe-Ni-As system has already been the object of earlier investigations. In 1932, Guertler and Savels-berg' have presented some elements of the ternary phase diagram, for arsenic contents up to 55 pct (all percentages in this paper are given in weight percent), including the vertical section FezAs-Ni&s2. This investigation is, however, incomplete and certain anomalies suggested the necessity to verify the results published by these authors: the section Fe2As-Ni5AsZ, for example, is presented as quasi-binary, with a field of complete miscibility in the solid state, even though these compounds do not have the same structure. Recently, ~useck' established an isothermal section at 800°C in the Fe-Ni-As system by X-ray diffraction and microscopic examination of water-quenched alloys. These techniques are sometimes inaccurate for the determination of the fields where alloys are liquid at the investigated temperature, and they may lead to erroneous conclusions when a compound exists at the investigated temperature but is not stable at room temperature and cannot be maintained by quenching. LIMITING BINARY PHASE DIAGRAMS The Fe-As constitution diagram has been the object of several investigations which have been reviewed by Hansen and Anderko.3 For the Ni-As phase diagram, a recent study has been effected by Yund.4 In this system, Heyding and calvert5 have determined the existence of a compound of unidentified structure at arsenic contents slightly higher than those corresponding to Ni5As2 and at temperatures lower than about 200°C; by analogy with iron and cobalt arsenides, this compound could correspond to the formula Ni2As, as suggested by Kulle-rud; although this is not definitely established. In the region of arsenic contents from 35 to 55 pct, Fried-rich7 detected anomalies in the solidification reactions; an interpretation of these anomalies was given by Hansen ,8 which assumed that the solidification reactions in practice are not in equilibrium, but are meta-stable. The main features of the Fe-Ni constitution diagram are the existence of a complete miscibility field, at least at high temperatures, for the fcc phase (which will be designated by My in the remainder of this work) and of a limited solubility field for the bcc phase (designated by Ma). EXPERIMENTAL METHODS The fundamental technique used in this investigation was microscopic observation, which allowed the determination of the reactions occurring during solidification of the alloys, and possible reactions in the solid state.

Jan 1, 1968

By C. R. Ramachandra, C. C. Patel

Flotation of chalcopyrite from a low grade ore was studied by using different xanthates and dixanthogens as collectors and by conditioning the flotation pulp with oxidizing gaseous systems. The improvement in the recovery of chalcopyrite with the oxidizing systems was mainly due to the auto-activation of chalcopyrite, leading to the enhanced adsorption of xanthates and dixanthogens even when the latter were formed by oxidation of the xanthates. With air or oxygen as oxidizing system, the amount of ethyl xanthate required at pH 8.5 was much less than normally employed in the industry, the recovery being 97-99% of chalcopyrite with a concentrate of 24% copper. With isopropyl and isoamyl xanthates, the recovery was improved but the grade was lowered. By conditioning the pulp with air-CO2 or oxygen-CO2 mixture, the recovery was lowered with ethyl xanthate only, mainly due to the depressant action of bicarbonate formed. Flotation with dixanthogens gave cleaner concentrates of chalcopyrite. because iron pyrite did not float with these collectors. Of the dixanthogens tried, diisopropyl dixanthogen gave the highest recovery, 99% chalcopyrite with a concentrate containing 28.5 to 30% copper, when the pulp at pH 8.5 was condi-tioned with air. Isopropyl dixanthogen was found to be the best collector of all the xanthates and dixanthogens studied. It was found that the adsorbed ethyl, isopropyl and isoamyl xanthates at chalcopyrite surface, activated by cupric sulfate, and at iron pyrite surface were oxidized to the corresponding dixanthogens to different degrees in presence of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture.' The dixanthogen formed at chalcopyrite surface was, however, firmly adsorbed while that at iron pyrite surface was easily desorbed. Since dixanthogens formed have greater hydrophobicity than the corresponding xanthates, as revealed by contact angles,1,2 the former were expected to improve the flotation results. It was, therefore, thought desirable to find out the effect of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture on the selective flotation of chalcopyrite when individual xanthates were used as collectors. The effect of direct use of dixanthogens as collectors on the selective flotation of chalcopyrite was also investigated. For these studies, low grade chalcopyrite ore, received from the Indian Copper Corp., Ltd. (I.C.C.), Ghatsila, Bihar, was employed. At the milling plant of the I.C.C., chalcopyrite is floated at a pH of 8.5, employing ethyl xanthate as collector. EXPERIMENTAL Materials Employed: XANTHATES - Ethyl, isopropyl and isoamyl xanthates of potassium were prepared in a pure state by the methods described earlier.4 A 0.03% aqueous solution of a xanthate was freshly prepared in air-free distilled water for flotation studies. DIXANTHOGENS - Diethyl, diisopropyl and diisoamyl dixanthogens were prepared by the oxidation of xanthates by iodine and purified by extraction with petroleum ether. A 0.03% alcoholic solution of dixanthogen was used as a collector. FROTHER - A 0.2% solution of pine oil in ethyl alcohol was employed. SODIUM CARBONATE - A 0.4 N solution was used. ORE - The composition of the -100 +200-mesh size (Tyler standard) powdered ore, as determined by standard methods of analysis, was: copper 1.57%, iron 10.29%, sulfur 3.15% and acid insolubles 66.10%. Iron present as chalcopyrite (CuFeS2) was 1.38%, while that present as iron pyrite (FeS,) was 1.37%. Both chalcopyrite and iron pyrite were found to be liberated from the gangue minerals and from each other, as observed under a microscope. Flotation of Chalcopyrite with Xanthates in Presence of Different Gaseous Systems: Fifteen grams of -100 + 200-mesh size ore were shaken well with 100 ml of distilled water. The pH of the pulp was adjusted to 8.5 by the addition of sodium carbonate solution. Then 0.1 ml of xanthate solution (0.005 lb xanthate per ton of the ore) was mixed with the pulp, and the latter together with washings transferred to a

Jan 1, 1963

By G. A. Crowe, W. T. Bishop

WHILE the literature in the United States on general polarographic technique is extensive, very little appears to be directly applicable to the analysis of flotation tailings. For this reason, it seemed worth while to present a few polarographic methods of ore analysis that have been in constant use in the laboratories of the Hercules Experiment Station for the past few years. At the time of our initial investigation of the polarographic method, there was little or no mention of its specific application to flotation tailings. It was therefore necessary for us to establish suitable conditions for the analysis of our flotation tailings and to consider possible interfering constituents. The polarograph, or dropping mercury electrode, method was discovered in 1925 by J. Heyrovsky and M. Shikata,1 of the Charles University, Prague. This method has since received extensive development and the literature contains many articles on the use of the polarograph for the quantitative determination of metals as well as anions, oxygen in solution, and reducible organic compounds. Kolthoff and Lingane,2 by the publication of their book, "Polarography," in 1941 did much to advance the knowledge and use of the polarograph. In chapter 25 of that book, methods for the polarographic analysis of brass, steel and iron products, alloys, and zinc ore are given. Aluminum,3 cadmium,3.4 cobalt,4 copper,3-9 gold,10 iron,3,11 lead, 3,12,13 molybdenum," nickel,4.8,9 tin,15 and zinc3,4,5,7 in ores have been analyzed by the polarograph. However, most of the work on tailing samples has been published in Russian journals and translations are not yet readily available. In this paper we will describe the method that was developed and used in our laboratory for the determination of copper, zinc, and lead in flotation tailings. PRINCIPLE OF THE METHOD The polarograph is an instrument for applying a potential to a mercury pool and a dropping mercury electrode separated by a solution, and for measuring the resultant electrical current. The procedure is essentially a small-scale electrolysis, in which the voltage required to reduce or oxidize the material identifies it qualitatively and the current measures the concentration quantitatively. Different constituents in a sample may often be determined simultaneously provided they reduce at sufficiently different voltages. An example is the determination of copper and zinc in the same solution. The reduction potentials are quite far apart, as shown in Fig. I. The polarographic method is particularly useful in the range of concentration between those normally determined by spectographic and chemical methods. In

Jan 1, 1946

Discussion of the paper of E. C. HARDER, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 94, October, 1914, pp. 2573 to 2586. I. C. WHITE, Morgantown, W. Va.-I have seen some of the great iron-ore deposits described in this paper. -One of these in the State of Minas Geraes appears to be an immense mountain of iron ore about 2,000 ft. in height. All over its surface from bottom to top may be seen large masses of rich iron ore, varying in weight from a few pounds to several tons, and from all that one can judge without exploitation, the quantity of available ore is certainly very large in this particular mountain. Whether it will prove a mere surface deposit or shell, like the famous Iron Mountain of Missouri, is for future exploration to determine. The question of transportation is the main factor in determining the availability for exportation of these Brazilian iron ores. There is no coal in Brazil that can be manufactured into coke without expensive previous treatment, since the best of the raw coal in the States of Rio Grande do Sul, Santa Catharina, and Parana, contains about 35 per cent. of ash, of which about 6 per cent. is sulphur, and coal of this composition cannot be utilized in iron smelting without purification. When I was chief of the Brazilian Coal Commission in 1904 to 1906, I had a cargo of this coal shipped to Balk, Germany, and treated in the great coal-testing plant of the Humboldt Engineering Works, located just across the Rhine from Cologne. It was found that by crushing and washing the Brazilian coal, it yielded 33 per cent. of briquetting coal, containing only 10 to 12 per cent. of ash (of which 1 per cent. was sulphur), and 42 per cent. of slack coal, with 25 per cent. of ash and low in sulphur, so that about 33 per cent. of the Brazilian coal could be converted into coke of fair quality, as shown by the following average of three analyses, using air-dried coal, of briquets made from the Barro Branco coal bed, State of Santa Catharina: Moisture 1.56 Volatile matter 31.66 Fixed carbon 56.73 Ash : 10.05 Total 100.00 Sulphur 1.34 Phosphorus 0.003 B.t.u 13,395

Jan 4, 1915

By George Sachs

I deeply appreciate the honor of being selected to deliver the twentieth Annual Lecture of the Institute of Metals Division. The subject of my paper is extremely involved and voluminous, therefore I shall discuss only some more recent experimental material and speculate somewhat on the physical and mechanical fundamentals of these changes. The flow and the rupture of a solid material are rather different phenomena. It is therefore surprising that up to a rather advanced stage in metallurgical science these two fundamental phenomena have been simultaneously treated and forced into the general conception of the "failure" of solid material. Only in this century, and particularly during the last 20 years, have the very different physical meanings of flow and rupture been clearly recognized. Several hundred of the more recent publications deal with these subjects.1 LAW OF SIMILARITY The basic values commonly considered responsible for the mechanical behavior of any material are the stresses. From this standpoint both a large and a small article made from the same homogeneous metal and of geometrically similar shapes should behave identically, i.e., they should deform geometrically in a similar manner, if subjected to the same stress values at corresponding points. This "law of similarity" was introduced about 60 years ago simultaneously by Barba2 and Kick3 and was derived from the classical theory of elasticity. As far as the plastic behavior of a metal is concerned, this rule appears to be valid. The conventional properties of large and small tension or compression test bars, machined from larger sections, are identical; while the force required to deform a section is proportional to its cross-sectional area and the work consumed in deforming geometrically similar articles in a geometrically similar manner is proportional to its volume. The general trend of the stress-strain diagram of a metal is independent of the section size (Fig. I). No exceptions from this rule are known. However, if the deformation of a metal is continued until rupture occurs, and the breaking stress or the work consumed is measured, a test bar of large cross section appears to fail before or at lower stresses than does one having a small cross section. Thus, the specific impact energy has been often found to decrease with increasing size of the test specimen, particularly for materials with a limited ductility.4 Another exception from the rule of similarity is offered by fatigue-strength values, which usually decrease with increasing section size. 5,6 The conclusion must be drawn from these experimental facts that the ductility of a homogeneous metal decreases with increas¬ing section size (Fig. x). This effect has been actually confirmed by Docherty,7 who observed that in static notch bending tests large specimens failed earlier and in a more brittle fashion than small specimens ma-

Jan 1, 1941

By J. C. McKinnell

The appraisal of an oil lease may often be mad,? through production decline analysis, which requires description of the functional relationship between the oil production rate and either cumulative production or time. Heretofore, attempts to define the function appropriate to a given set of production data have depended to some extent on subjective procedures. The purpose here is to introduce an objective solution, obtained by combining the principle of least squares with the theory of equations. MATHEMATICAL ANALYSIS The fundamental differential equation appropriate to a general class of decline curves may be written. Solution of Eq. 1 for general boundary conditions may be written in terms of either the cumulative oil production or time: These equations constitute the mathematical expression of the so-called hyperbolic decline. Their complete description for a given set of production data requires the numerical evaluation of the three parameters1.', n, D, and (go),. For the special case of n = 0, Eq. 2 becomes q. = (q.), - DiN with the corresponding expression in terms of time being q. = (qa),e...........(5) Similarly, for the special case of n = 1, Eq. 3 becomes with the corresponding expression in terms of cumula- tive oil production being q. = (q.),e " '.......(7) Eqs. 4 and 5 constitute the mathematical description of the so-called exponential decline; Eqs. 6 and 7 are the mathematical description of the harmonic decline.',' Returning to the hyperbolic expressions, Eqs. 2 and 3 may also be written, q: = sNp + b........ (8) and where a = 1 - n; s = (n— 1)D,(q0);"; b = (go):-"; a'=-n;s/= nD,(qo);"; and b' = (go);-. Note that both Eqs. 8 and 9 are linear in either time or cumulative production with respect to an exponential function of the production rate. In other words, a straight line relationship results for both variables when associated with the appropriate power of q,. This fact is of prime importance in the application of statistical analysis. . STATISTICAL ANALYSIS For a given oil lease, the time, production rate and cumulative production are recorded records. To establish predictive formulas from Eqs. 2 and 3, it remains to determine numerical values for the three parameters [n, D, and (q,) .] through an investigation of the past history. Upon interpreting a, s and b as parameters, Eq. 8 may be expressed for every time interval of interest, i, over the past history as follows. (q,): = s(Np), + b........(10) In general, Eq. 10 will not be satisfied exactly, because of the assumptions in the expression of Eq. 1, and the errors and anomalies universally associated with production data. It will instead define the residual, s(Np), + b- CO=d......(11) Squaring both sides and summing over all the data points, m, under consideration yields

By F. H. Wilson, R. M. Brick

With the papers of Palmer and Smith1 and of Burghoff and Bohlen,2 published in 1942, understanding of the problem of the development of ears on deep-drawn brass cups was brought to the point where, from a practical standpoint, producers of brass sheet could keep earing under control. However, these very practical results raised questions concerning the reasons for the observed behavior. Since plastic deformation is fundamentally a function of crystallographic slip, these reasons must be considered in the light of the textures to be found in the annealed sheet. Various attempts have been made. to interpret the mechanism of ear formation by correlation with the preferred orientation and the anisotropy of the sheet. However, none of these has satisfactorily explained why ears are usually found in the rolling and transverse directions for copper but at 45' to these directions for brass. This paper offers additional data on these two related subjects and has been divided into two sections The first section provides a survey of the recrystallization textures of brass as affected by annealing temperatures and prior reductions, and an account of the caring behavior which accompanies these textures. The second section reports new data on the anisotropy that accompanies a characteristic texture for brass and endeavors with partial success to establish the factors that account for the difference in earing behavior between copper and brass Earing BehavioR oF Brass Review of Textures The recrystallization texture of severely rolled brass was first reported by Bass and Glocker.3 The preferred orientation to which this texture, obtained from metal annealed at 500°C., was most akin was (II3)[I12] This texture has been confirmed by Bauer, von Göler and Sachs;4 Brick;' Brick, Martin and Angier;6 and Cook and Richards7 who, in general, used annealing temperatures under 500°C. Bass and Glocker3 also reported the recrystallization texture at 850°C. to be the same as at 500°C. They analyzed their textures by means of single photograms obtained with white radiation. The photo-grams for both temperatures are reproduced in their paper, and there is a strong similarity between the two. However, for the latter temperature, the number of spots registered on the film was remarkably large for the grain size to be expected, and the authors made no mention of using a technique that would integrate a large enough area of the specimen to produce so many spots. The only other attempt to determine textures resulting from high temperature

Jan 1, 1945

By J. Murray Riddell, George A. Morrison

THIS paper is a companion to the one by George A. Morrison on Mining a Deep Limestone Mine in Ohio.[+] Barberton is 8 miles west of Akron, Ohio, and 23 miles south of Cleveland. The underground mining of limestone at Barberton constitutes the world's deepest limestone mine. The stratigraphy is as follows: 0-20 ft. Loam, clay, sand and gravel. Water bearing. 20-40 ft. Fractured. sandstone. Water bearing. 40-110 ft. Sandstone with interbedded shale, slightly fractured. Water bearing. 110-314 ft. Sandstone with interbedded shale, slightly fractured. Water carrying. 314-2197 ft. Shale with occasional seams of sandstone, which varies in thickness from a few inches to 4 feet. Dry. 2197-2247 ft. Limestone. Dry. 2247-2742 ft. Dolomitic limestone. Dry. 2742-2767 ft. Salt. Dry. 2767- Dolomitic limestone. Dry. All of the strata dip to the southeast, about 0.5 per cent from the horizontal. The top 110 ft. of the crust is water-bearing. The rock strata are naturally fractured to a depth of 314 ft., sufficient to allow the passage of water. In the shaft-sinking operations, a stra was encountered at a depth of 520 ft., and flows of methane gas were pierced at depths of 1350 and 1952 feet. Specifications for the mine plant called for, in part, the sinking of two vertical shafts and a hoisting plant capable of producing at the rate of 300 tons per hour. No. I shaft is 550 ft. west of No. 2 shaft. Each shaft measures 8 by 17 ft. outside of steel. General features of the design (Fig. I) are: Principal set members, 6-in. H-section; connecting angles (studdles), 3/8 by 4 by 4-in. angle irons; spacing of sets, 8 ft. centers; spacing of bearer sets, generally, 160 ft.; bearers, of 12-in. I-beams. Each bearing set featured a concrete ring about the periphery of the shaft, steel to rock, and 8 ft. in height; permanent guides, 6 by 10-in. long-leaf yellow pine, 85 per cent heart. THE SHAFT-SINKING OPERATION The preliminary shaft-sinking work consisted of driving interlocked steel piling about the exterior of the shafts to depths of 35 and 32 ft., respectively, and of such horizontal dimensions as to ultimately permit the pouring of a concrete collar 2 ft. in horizontal thickness. Following the pouring of a shaft collar, a temporary wooden headframe for shaft-sinking purposes was erected. The head-frame, while ordinary, featured: (I) a storage pocket of 300 cu. ft. capacity with truck servicing facilities, and (2) pneumatically operated dump doors, which were actuated by the hoistman, thus caring for the dumping of the "ball-and-chain"

Jan 1, 1944

By C. G. Dunn, F. W. Daniels, M. J. Bolton

IN recent papers on interface energies in metals¹,² the concept of an equilibrium of forces has been used in the measurement of interfacial tensions. Mathematically the equilibrium of three forces is given by the relations: where the 2's are the interfacial tensions (interface energies per unit area of interface) of three phases or grains meeting at angles 21 22 and 23 (212 relates to the 1-2 boundary formed by grains 1 and 2;223 to the 2-3 boundary, etc.). If these relationships are valid, one can calculate relative values of the interface energies from measured boundary angles on specimens which have been brought to equilibrium. Since Eq 1 may be derived through a mathematical process of minimizing the grain boundary energy under the restriction that the ?'s be independent of boundary orientation: the concepts of surface tensions and equilibrium of forces are not particularly essential. To deal with the general case involving dependence of boundary energy on boundary orientation, it becomes desirable to drop certain concepts formerly held (namely that energy per unit area is identical with force per unit length or surface tension) and to use the energy concept alone. It is appropriate, therefore, to use E in place of ? in deriving and using the more general equations that express the anisotropic nature of the grain boundary energy. Herring3# ' recently has derived the required general equations using the principle of minimization of energy. Specifying the boundary orientations in terms of angles (4) measured with reference to crystal axes within the grains, Herring's equations take the form E23 + E21 cos?8 + E12 cos?2 — sin ?12 + sin?2-?E12/?12 =O [2] where the partial derivatives are measured in the direction of counterclockwise rotation of the boundaries. Eq 2 implies that an infinitesimal displacement of the triple point along the 2-3 boundary produces no change in the boundary energy. Similar equations apply for infinitesimal displacements along each of the other two boundaries. From such equations Herring obtains the following general relationship (1 + E1 E2) sin?8 + (E2 — E1) cos?3 ________ E38______________ = (1+ E2 E8) sin ?1+ (E3— E2) cos ?1 __________^5____________[3] (1 + E sin ?2, + (E1 — E8,) COS ?2 1 E28 where E1 = 1/E23- E25 and PC and c8 have similar expressions. It is apparent that Eq 3 reduces to Eq 1 when the c's vanish. Eq 3 also reduces to Eq 1 when the E'S are all equal. Shockley and Read' have pointed out one limitation to these equations. When E plotted versus 4 appears as an energy cusp, as their theory requires, for example, for the energy near a twin boundary position, then Eq 3 (and therefore Eq 1 also) no longer applies if one boundary is in the minimum energy position. One of the equations of form Eq 2, however, applies if the infinitesimal displacement is along the boundary associated with the energy cusp. From the foregoing treatment it will be apparent that equilibrium angles alone are not sufficient in general for calculating relative interface energies.

Jan 1, 1951

By E. B. Thornhill

(San Francisco Meeting, September, 1915) IN this paper on the recovery of mercury as sulphide, from the residues from the amalgamation and cyanide treatment of high-grade ores and concentrates, I will not discuss the many reactions, chemical and other- Fig. 1. wise, that take place in the general process, but confine myself more particularly to the methods of recovering the mercury. I submit charts of two amalgamation-barrel charges, Figs. 1 and 2, which are self-explanatory. The flow sheet of the high-grade and the mercury extraction plants is shown in Fig. 3.

Jan 8, 1915

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan' investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0'~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther' investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969

'T. C. MERRIMAN, New Haven, Conn. (written discussion *).-This most interesting paper gives much carefully obtained and valuable data. However, there are two points in connection with the commercial application of such data that might possibly be a source of trouble and mis-understanding. In the first place, the examination of thin sections of annealed brass, subjected to standard Brinell test.(500 kg. on a 10-mm. diameter ball) at thicknesses from 0.075 to 0.150 in. (1.9 to 3.8 mm.) indicates that cold work has been performed on the specimen during the application of the load sufficient to extend way through the section, and have the hardness of the metal affected by the backing. If the usual steel support is used, this effect is very evident. If a piece of soft brass is used as a support, there is an indentation in the surface of the support accompanied by a bulge on the under side of the tested specimen opposite the impression made by the 10-mm. ball. The result is that Brinell specifications (governmental or otherwise) on stock for a certain purpose may not be fair in all cases, since manufacturers, owing to differences in equipment, etc., may not all use precisely the thickness and conditions of stock on which the Brinell specifications were based. This would mean that the government Brinell specification might not give them the temper of stock best suited for their manufacturing methods. The concluding paragraph of this paper, stating that "the hardness of cartridge brass may be determined with greater accuracy by the Brinell hardness measurement than by attempting to judge it from the grain size" appears to be in line with the movement of the last year or so among brass manufacturers toward substitution of the Brinell test for microscopic examination as an acceptance test on cartridge brass. The statement may he strictly true that the Brinell test is the best test for hardness, but it is not, as the statement might readily be construed, a sufficient test of suitable condition. For instance, some cartridge brass might accidentally have been overheated to a point where it would be distinctly unsafe to use for the manufacture of small arms cases and then be so rolled (reduction 3 to 5 per cent.) as to pass perfectly proper Brinell specifications. Under such conditions the microscope would reveal its unsuitability where the Brinell test had failed so to do.

Jan 4, 1919

By Roshan B. Bhappu, Zeki M. Dogan

Two magnesite ores containing 3.15% and 8.73% SiO2 and a calcined magnesite product assaying 2.6% Si02 were first reduced in size to -20 mesh by roll crushing. 'They were then treated dry on a high intensity magnetic separator to reduce their silica content by rejecting iron-stained silicate minerals in the magnetic fraction and obtaining marketable magnesite or calcined magnesite as a nonmagnetic product.

Jan 1, 1975

The following is an incomplete list of members and guests who called at Institute headquarters during the period Apr. 10, 1919, to May 10, 1919. Arthur K. Adams, Spencer, Mass. Ensign Floyd D. James, U. S. S. Fulton. W. T. Bates, New York City, N. Y. J. Harry Johns, Thorsden, Woking, A. D. Brokaw, Washington, D. C. England. E. H. Clausen, San Francisco, Calif. W. F. Jones, Rock Springs, Wyo. W. M. Corse, Mansfield, Ohio. E. L. Lasier, Washington, D. C. E. O. Daue, Philadelphia, Pa. John M. Lovejoy, New Rochelle, N. Y. G. D. Dub, Washington,, D. C. 2d Lieut. James F. Magee, Lancaster, S. B. Eaton, Dover, N. J. Pa., Sherman Eaton, Smethport, N. C. Ernest Marquardt, Casper, Wyo. J. A. Endweiss, La Jolla, Calif. Geo. B. Marshall, Abangarez, Costa Edgar W. Engle, North Chicago, Ill. Rica. 2d Lieut. Maxwell E. Erdofy, New York Benj. L. Miller, So. Bethlehem, Pa. City, N. Y. Major Desaix B. Myers, Camp Mills. Chas. A. Fellencer, Allentown, Pa. Edmund Newton, New York City, N. Y. Arthur Feust, Joplin, Mo. Seely B. Patterson, Jr., Allentown, Pa. Ensign Harold P. Ford, U. S. S. Radnor. Wm. R. Pearson, New York City, N. Y. A. D. R. Galloway, Accra, West Africa. Harold C. Price, Langeloth, Pa. R. C. Gosrow, Milwaukee, Wis. T. C. Roberts, East. Orange, N. J. C. A. Grabill, El Paso, Tex. P. H. Royster, Washington, D. C. Hobart A. Hanks, San Francisco, Calif. W. H. Staver, New York City, N. Y. John L. Henning, Lake Charles, La. N. L. Wimmler, Bangkok, Siam. 1st Lieut. J. Parke Hook, Philadelphia, Capt. Jay P. Wood, New York City, Pa. N. Y. An item in the May Bulletin made it appear that Frank W. DeWolf had just become connected with the State Geological Survey of Illinois. This was one of the inadvertences of war. Mr. De Wolf has been Director, or Chief, of the State Geological Survey for approximately ten years. Through the courtesy of the Governor of Illinois, lie was loaned to the Bureau of Mines for about seven months, after which period he resumed his former position.

Jan 6, 1919

Discussion of the paper of DAVID COLE, presented at the New York meeting, February, 1915, and printed in Bulletin No. 9S, February, 191.5, pp. 431 to 444. R. H. RICHARDS, Boston, Mass.-The Butchart riffle seems to violate, according to our preconceived notions, some of the very essential principles of the Wilfley riffle, and therefore ought not to succeed, but it does. On this account it must conform to other very important principles, or it would not succeed. It would beinteresting to know what these principles are which enable it to succeed. E. P. MATHEWSON, Butte, Mont.-I cannot, explain the principles on which this riffle acts, because I have not given it personal attention. All I can say is that I first saw the riffle in operation several years ago at the Steptoe Valley mill in Nevada, and I was told that a man had been around there guaranteeing that these riffles would make the table do twice as much work and do it better than with the ordinary Wilfley riffles. I heard nothing further about it for a long time. I heard about a year ago, from David Cole, the author of this paper, that the riffles were a success, and that he was using them at Morenci, and if, we were interested he would send the inventor to show us how they worked. As we knew of David Cole's reputation, we invited Mr. Butchart to come up and show us how his riffles worked. We did not have sufficient confidence in the invention to guarantee Mr. Butchart his traveling expenses, but lie came up entirely at his own expense and put in a set of the riffles on one table. It was known as a roughing table in our No.

Jan 5, 1915

By D. Moskowitz

IN the course of a general investigation of boride systems, sponsored by the Office of Naval Research, various vanadium boride powders of relatively good purity were prepared which could be used for a determination of the phases present. The X-ray pattern of one of these lots showed, in addition to the known VB1 and VB22 phases, an additional phase, almost certainly of composition V3B4, isomorphous with Cr3B4, Cb3B4, Ta3B4, and Mn3B,. Its pattern fitted in well with the indices worked out by Kiessling for Mr3B4.3 The unit cell for this new compound is orthorhombic, with the dimensions a = 3.030A, b = 13.18A, c = 2.986A7 V=119.2A.' Table I lists the X-ray diffraction data for V.3,.

Jan 1, 1957

By L. S. Castleman, L. L. Seigle

THE formation and growth of intermetallic phase layers is of considerable practical importance to metallurgists interested in diffusion bonding and cementation processes and has been the subject of extensive qualitative investigation. In contrast, it is somewhat surprising that so little quantitative data have been amassed. The need for additional fundamental work was pointed out by Mehl in 1936,' and persists to a large extent to the present day. The early studies have been reviewed by Rhines,2 and his conclusions have been summarized by Lustman and Mehl3 substantially as follows: 1) All phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two metals; however, in some cases, certain of the phases may be too thin to be observed and identified easily. 2) The isothermal growth of intermetallic phases generally obeys a simple parabolic equation of the form X2 = Kt, where x is the thickness of the alloy layer, K the temperature dependent reaction rate constant, and t the time. 3) The rate of thickening varies with temperature according to the Arrhenius equation k = Ae -Q/RT , where k is the parabolic rate constant, A, a temperature independent constant, Q the heat of activation for the process, R the gas constant, and T the absolute temperature. Subsequently, Lustman and Mehl made a quantitative study of the laws of growth in intermediate layers in a number of binary systems, in which one of the components was either zinc or cadmium, and the other component was one of the following: nickel, copper, silver, cobalt, gold, iron, or Monel metal; the interdiffusion times used were for the most part less than 24 hr. It was found that the simple parabolic law was not obeyed in general, but that a generalized parabolic law of the form xn = kt was valid, where n was a temperature dependent constant; also,

Jan 1, 1959

By Jean Bonnemaison

Societe Miniere & Metallurgique de Penarroya Noyelles-Godault works are located in the northern part of France. The complex includes a lead smelter, a zinc smelter, shops for production of manufactured products and all necessary general services. The zinc smelting complex described in this paper was designed in 1959 to replace an old horizontal retort distillation furnace and was first operated in May 1962. It includes: - a sinter plant producing the zinc sinter for the Imperial Smelting furnace : zinc, lead and bulk zinc-lead concentrates are sintered on a Dwight-Lloyd machine with a working area of 80 sq.m. Cadmium sludges are treated by the wet method in a separate plant for recovery of cadmium. Sulphur dioxide contained in gases goes to a gas washing tower and is subsequently made into sulphuric acid in a plant with a capacity of 550 m.t. per day. - a smelting plant where the process developed by Imperial Smelting Processes Ltd. is applied : the blast furnace which was modified in 1967 has an area of 17.5 sq.m. at the tuyeres level and a section of 24 sq.m. at the top of the shaft. It has a theoretical zinc capacity of 100,000 m.t. per annum. Air blast is heated by means of covers up to the theoretical temperature of 950ºC. Zinc produced is either directly cast into slabs for sale as standard 'good ordinary brand' zinc, or sent to a refining plant where the New Jersey process designed to produce 'special high grade' zinc is in application. Mixes of zinc containing various amounts of lead, cadmium or aluminum are prepared to customer specification in a mixing plant.

Jan 1, 1970