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By Carl F. Floe, John Chipman

THE system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or C02 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modem metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100° to 1500°C., and pressures from about 20 mm. of mercury to somewhat above atmospheric. REVIEW OF PREVIOUS WORK The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as 02, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: [2M -}-G2 = 2MGK =G) IYf X[I]] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: [MG = Ki Pa,[2]] Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: [6Cu + S02 = Cu2S + 2Cu20[3] K Cu2S X (Cu20)2(Cu)e(Psm)[4]] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: [K1 =or Vdo,= K2/PBO [5] PsO]

Jan 1, 1941

By Edwin M. Chance

During the last decade many conditions have been encountered that have materially increased the cost of the production of coal. As in most cases it has not been practicable to increase the selling price of such coal sufficiently to insure the necessary margin of profit, the mine management has been forced to avail itself of what might be termed unusual means that costs might be held at as low a figure as possible. The so-called efficiency engineer has been called upon, costly power plants have been built and machinery has been installed to replace manual labor wherever possible. Another aid used recently to secure economies through the more intelligent production of coal, is the chemist. As the coal industry, barring the production of byproduct coke, does not at once give evidence of its need of the services of the chemist, the writer will endeavor to point out a few of the services that this branch of the staff has been able to render. The preparation of coal in the past has been carried on entirely upon an empirical basis, that is, the criterion adopted has been an ocular inspection. Unfortunately, the appearance of a coal and especially of an anthracite, has but little relation to its fuel value, and as long as coal is purchased for the heat that can be obtained from it by its combustion, the quantity of such heat that is purchased must be one of the principal desiderata in selecting or preparing a coal. Were coals purchased for use as bric-a-brac or for exhibition in museums it might be both wise and just to purchase them upon their appearance. After 4 or 5 years of investigation the fact has been established that coals of very inferior appearance, and I now have special reference to anthracite, might and often did possess heating and burning properties superior to those possessed by bright coals which in the past had commanded considerable and uniform premiums in the market. This being the case the question arose as to whether the trade could be convinced of this fact. While at first some difficulty was experienced in establishing the quality of such dull coals, still it was found that the real obstacle to the sale of these materials in the past had been the fact that the coal producers' own sales departments felt convinced of the inferiority of this type of fuel and when complaints were registered they were given ready credence. Upon convincing the sales department of the quality of this type of fuel, but

Jan 1, 1917

By Clarence Zener

IT has long been known that the density of a metal usually decreases with cold-work. Thus O'Neilll observed as early as 1861 that cold hammering of commercial hot-rolled copper is accompanied by a decrease of density of 0.2 per cent, and that subsequent annealing restores the original density. The origin of this density change, however, has remained obscure. In particular, experiment has not yet decided whether it is due to the presence of small cavities and an increase in inter-granular surface or to an actual expansion of the lattice itself. This uncertainty in the origin of the change in density is a reflection of our uncertainty as to the changes induced in a metal by cold-working. One school regards cold-working as a breaking up of the original grains into a large number of perfect crystallites somewhat randomly orientated with respect to one another.2 According to this viewpoint, the mere introduction of a large intercrystallite surface induces a net volume expansion. Another school regards cold-working primarily as a distortion of the grains. It is not obvious that this second viewpoint will lead to a net volume expansion. The purpose of the present paper is to show that this is indeed the case, and that this expansion is of the right order of magnitude to explain existing experimental data. The physical basis for the association of an expansion with distortion lies essentially in the variation of the elastic moduli with volume. This variation is considerable. Thus from Table I we see that a I per cent increase in volume for the case of copper will decrease the bulk modulus K by 10 per cent, the shearing modulus µ by 3.8 per cent. If we thus twist a rod through a given angle, we shall do less work upon it if it increases slightly in volume, thereby reducing the torsion modulus that involves as a factor the shearing modulus. A general principle3 in physics states that the rod will so adjust itself as to have a minimum potential energy consistent with the end restraints. It will therefore expand. In order to obtain a quantitative comparison with experiment, we follow Maier4 in comparing the lattice expansion with the latent energy of cold-work. This latent energy has been measured directly by Taylor and Quinney5 on copper rods subjected to torsion, and may amount to as much as 15 per cent of the total work done upon the specimens. We shall assume that this

Jan 1, 1942

By C. E. Berry

Natural stone or manufactured porcelain pebbles are used as the grinding elements in pebble mills and the mills are lined with stone or porcelain blocks. Steel balls usually form the grinding medium in ball mills, and the mills may be lined with steel. Pebble mills are used to avoid contamination by metal of the material being ground, to avoid rapid wear due to corrosion, and for other specialized reasons. Belgian silex (silica) blocks formerly were used widely for lining pebble mills, because of their good resistance to wear, light color, and low cost, but the importation of these blocks was suspended early in the war. The stocks of Belgian silex diminished so rapidly that it was found desirable to compare the properties of a number of domestic substitutes for use in critical operations. Accordingly, a study was made to determine the best substitutes for fine grinding of white pigment and for certain heavy-chemical process work such as the disintegration of phosphate rock in weak phosphoric acid solution. A comprehensive survey of substitute lining materials was not contemplated. It was stipulated at the beginning of the investigation that only materials on the market, available in large quantities, would be tested and that these should be reasonable substitutes from a a ance viewpoint as determined from known physical characteristics. Marble and limestone, for example, could be eliminated immediately. Quartzite, granite and porcelain were selected as likely substitutes for Belgian silex and were subjected to quality tests. Materials Tested 1. Belgian Si1ex.—Sample blocks of a standard grade were taken from crates in which they had been imported. The stone was light gray in color and contained inclusions of small clusters of quartz crystals as well as light colored portions that might be calcite. This was a siliceous rock which appeared to be of igneous origin. 2. Quartzite.—Samples of quartzite were obtained from a quarry in Minnesota. The blocks exhibited a crystalline fracture. The stone was pink in color and composed of fine quartz crystals bound together with a siliceous cement. 3. Granite A was a fine-grained granite quarried in South Carolina. 4. Granite B was coarse-grained granite quarried in South Carolina. 5. Granite C was a coarse-grained granite quarried in North Carolina. 6. Porcelain A.—Sample blocks of the pebble-mill lining material were obtained direct from the manufacturer. It was white in color and of lower specific gravity than the natural materials. It did not have a crystalline structure. 7. Porcelain B.—Sample pebble-mill lining blocks of the porcelain were received direct from the manufacturer. It was white

Jan 1, 1948

By W. T. Cardwell, R. L. Parsons

This paper discusses the practical problem of estimating a single equivalent permeability for an oil reservoir, or a portion thereof, whose actual permeability varies in an irregular manner. Limiting averages for general types of permeability variation are developed, and illustrated by examples involving important, specific types of variation. Introduction The theory of the flow of fluids through porous media1"4 is becoming increasingly important in predictions of oil-reservoir behavior. In practical applications, however, reservoirs are seldom found to which simple theory strictly applies. Actual reservoirs have complicated shapes and nonuniform permeabilities and porosities. This paper discusses the problem of estimating a single equivalent permeability for an oil reservoir, or a segment of an oil reservoir, whose actual permeability varies in an irregular manner. The equivalent permeability of a reservoir segment is defined as the permeability of a homogeneous segment of the same dimensions that would pass the same flux under the same pressure drop- It is the permeability value that can be used in simple theoretical formulas to calculate the reservoir behavior. To the authors' knowledge, previous theoretical calculationst on systems of nonuniform permeability have been carried out only by Muskat'"; and he has not dealt with irregular variations, except in writing down the general differential equation for the pressure in variably permeable systems.lb In practical work, many calculations necessarily have been made to estimate equivalent permeabilities from the permeabiiity profiles obtained by core analyses. Regarding such calculations, Johnston and Sherborne6 say: Simple arithmetic and weighted averages have been tried on many wells and it has been found that, where frequent sampling has occurred, the arithmetic average is as satis- factory as a weighted average. It is possible that the application of statistical methods to the analysis of permeability data as recently presented by Law8 may prove fruitful. L,, has made a valuable contribution in showing how statistical analyses may aid in picturing the characteristics of a reservoir from those of a necessarily limited number of core samples. It is believed however that the particular problem of the estimation of equivalent permeabilities can be most directly approached from a fluid dynamical viewpoint as given in the present paper. An example is presented of the use of the conclusions herein in conjunction with Law's method. Theory In order to approach the problem of heterogeneity simply, it is interesting to consider a square block composed of four smaller, homogeneous, square blocks of porous medium, two of which have a

Jan 1, 1945

I. PRESIDING OFFICER. At all business meetings of the Institute the President, or, in his absence, the First Vice-President, or, in the absence of both of them, any other Vice-President or Director, chosen by the meeting, shall preside. At all other meetings of the Institute the President, or, in his absence, one of the Vice-presidents, shall preside. If none of these be present the meeting shall elect a Chairman. The President shall do and perform such other duties as may from time to time be assigned to him by resolution of the Board of Directors of the Institute. II. ORDER OF BUSINESS. At each business meeting of the Institute the order of business shall be as follows: 1. Reading of minutes of preceding meeting. 2. Report of the President. 3. Report of the Treasurer. 4. Report of the Secretary. 5. Election of Directors. 6. Reports of Standing Committees. 7. Reports of Special Committees. 8. Special Orders. 9. Miscellaneous business. This order of business may be changed at any meeting, by a vote of a majority of the Members and Associates present. At all sessions of the Institute, other than business meetings, the order of proceedings and the time of adjournment shall rest in the discretion of the presiding officer. III. SECRETARY OF THE INSTITUTE. The Secretary shall keep a record of the proceedings of all the meetings of the Institute. He shall be custodian of the corporate seal, of the minute books and of all the legal documents belonging to the Institute. He shall have charge on behalf of the Institute of all correspondence. He shall notify all Officers and Directors and all members of committees of their election and appointment; shall issue notices of all meetings of the Board, and of the annual and other business meetings of the Institute; and shall, in calling special meetings of the Directors, specify the objects of such meetings. He shall act as clerk at all the meetings of the Board of Directors and at all meetings of the Institute. The Secretary shall be custodian of all technical or scientific papers submitted to the Institute for its consideration and shall have general charge and supervision of the editing and proof-reading of all material published by the Institute, and of the distribution thereof. The Secretary shall be the custodian of all back numbers of the Transactions and other publications of the Institute. There shall be kept under his direction an account

Jan 1, 1925

I. PRESIDING OFFICER. At all business meetings of the Institute the President, or, in his absence, the First Vice-President, or, in the absence of both of them, any other Vice-President or Director, chosen by the meeting, shall preside. At all other meetings of the Institute the President, or, in his absence, one of the Vice-presidents, shall preside. If none of these be present the meeting shall elect a Chairman. The President shall do and perform such other duties as may from time to time be assigned to him by resolution of the Board of Directors of the Institute. II. ORDER OF BUSINESS. At each business meeting of the Institute the order of business shall be as follows: 1. Reading of minutes of preceding meeting. 2. Report of the President. 3. Report of the Treasurer. 4. Report of the Secretary. 5. Election of Directors. 6. Reports of Standing Committees. 7. Reports of Special Committees. 8. Special Orders. 9. Miscellaneous business. This order of business may be changed at any meeting, by a vote of a majority of the Members and Associates present. At all sessions of the Institute, other than business meetings, the order of proceedings and the time of adjournment shall rest in the discretion of the presiding officer. III. SECRETARY OF THE INSTITUTE. The Secretary shall keep a record of the proceedings of all the meetings of the Institute. He shall be custodian of the corporate seal, of the minute books and of all the legal documents belonging to the Institute. He shall have charge on behalf of the Institute of all correspondence. He shall notify all Officers and Directors and all members of committees of their election and appointment; shall issue notices of all meetings of the Board, and of the annual and other business meetings of the Institute; and shall, in calling special meetings of the Directors, specify the objects of such meetings. He shall act as clerk at all the meetings of the Board of Directors and at all meetings of the Institute. The Secretary shall be custodian of all technical or scientific papers submitted to the Institute for its consideration and shall have general charge and supervision of the editing and proof-reading of all material published by the Institute, and of the distribution thereof. The Secretary shall be the custodian of all back numbers of the Transactions and other publications of the Institute. There shall be kept under his direction an account

Jan 1, 1925

ARTICLE I NAME AND OBJECT SEC. I. This Institute is incorporated under the Membership Corporations law of the State of New York; its corporate name is American Institute of Mining and Metallurgical Engineers, Inc.; and its objects are such as are stated in its Certificate of Incorporation. ARTICLE II MEMBERS SEC. 1. The membership of the Institute shall comprise four classes, namely: 1. Members; 2. Honorary Members; 3. Associates; 4. Junior Associates. All members shall be equally entitled to the privileges of membership, excepting that Honorary Members, Junior Associates, and Members and Associates whose residences shall be outside of the United States, Mexico, and Canada shall not be entitled to vote. Members and Associates residing within the United States of America, Mexico, and Canada, .and not in arrears for dues, shall be entitled to vote in person at the meetings of the Institute, or, as hereinafter provided for, by letter ballot. SEC. 2. Members shall comprise all those persons who on the third Monday of February, 1918, were members of the Institute, and in addition thereto, all those thereafter elected or transferred into the class of Members. A person to be eligible for election or transfer into the class of Members must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. Graduation from the scientific course of a college, approved by the Committee on Membership, shall be considered equivalent to two years' employment, as required in the previous sentence. Employment as a teacher of engineering, mining, geology, metallurgy or chemistry, if in direct charge, may be considered a position of responsibility as specified in the second paragraph. Persons employed in research or any scientific literary work or in teaching in the scientific departments of colleges, approved by the Committee on Membership, who at the same time are engaged in consulting or in the active practice of mining, geology, or metallurgy, shall be entitled to consider the time so spent in active practice as equivalent to an equal length of time of employment in positions of responsibility, provided the work done or the positions held seem to the Committee on Membership to warrant the equivalency. The requirement of three years' employment in positions of responsibility maybe waived by the Committee on Membership in the case of persons who have done notable original work in mining, geology, or metallurgy, or have won distinction by

Jan 1, 1925

By John Chipman, Carl F. Floe

The system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or CO2 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modern metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100" to 1500ºC., and pressures from about 20 mm. of mercury to somewhat above atmospheric. Review of Previous Work The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as O2, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: 2M+G2=2MG K=(MG)2 /M2 X PG2 [I] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: MG = K1 vPG2 [2 Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: 6Cu + SO2 = Cu2S + 2Cu2O [3] K= Cu2S X (Cu2O)2 i - (Cu)6(Pso2) [4] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: K1 =V3SO2 /Pso2 or

Jan 1, 1941

By John S. Brown

As a part of a symposium on the relations of structure to ore deposition, in February 1938, the writer presented some tentative opinions derived from his experience with a number of important lead-zinc replacement deposits. These ideas were set forth, as a basis for discussion and a stimulus to further inquiry, in a mimeographed leaflet that read as follows: Intimate acquaintance with a number of lead and zinc deposits in metamorphosed limestones seems to indicate the existence of certain common features from which can be established some general principles governing the localization of ore in this type of formation. It is suspected that these principles can be applied, with modifications, to mineralization in unmetamorphosed limestone. In metamorphosed formations, some observed rules are as follows: 1. Bands or masses of pure limestone are very resistant to replacement by ore solutions, and are likely either to contain no ore or to resist replacement until near the end of mineralization. The reason for this apparently is physical, not chemical, since microscopic data indicate that when ore is deposited by far the greater part of it substitutes for carbonate. The chief factor is believed to be a lack of porosity in massive limestone that has undergone flowage and recrystallization. 2. Masses of intensely siliceous or silicated rock are likewise unfavorable ore receptacles. This seems to be accounted for by two factors: (a) chemical unsuit-ability or resistance to replacement, and (b) physical resistance to small-scale brecci-ation, which might faeilitate the opening of effective channelways for solutions. Some low-grade ore may occur, however, and also sporadic fracture fillings. 3. The optimum condition for ore reception appears to be found in bands or areas containing carbonate and silicates (or quartz) intimately mingled in something like equal proportions. In this situation movement is likely to result in mixed flowage and fracture, producing a finc-textured porosity that admits solutions freely and provides access to an abundance of replaceable carbonate. Cleavage cracks in some minerals such as diopside are believed to facilitate the penetration of solutions. 4. Certain minerals or assemblages are regarded as favorable impurities in a limestone and others as unfavorable. Original quartz, and subsequently developed diopside, and perhaps garnet, are typical favorable pre-ore gangue; in general rather equidimensional, brittle minerals. Tremolite, biotite, and probably wollastonite, are typical unfavorable pre-ore gangue; in general highly elongated and somewhat flexible minerals likely to develop under strong shearing stresses. 5. Tentative opinion is that the ratio of lime and magnesia in a limestone is of little or no importance.

Jan 1, 1941

By Arthur L. Christenson, Clarence E. Jackson

In the establishment of the relationship between weldability and hardenability, two methods have been employed in correcting for the grain growth produced in the heat-affected zone: first, the hardenability calculated from chemical composition* may be corrected to the grain size observed in an actual weld? or, second, a hardenability test may be made on the steel quenched from a temperature high enough to produce a grain size comparable to that found in the heat-affected zone.8 In order to obtain grain sizes in the end-quench hardenability bar comparable to those resulting in the base metal from the welding cycle, a quenching temperature of 2Ioo°F. has been used. In studies of the end-quench hardenability specimen quenched from 2Ioo°F. instead of from a lower temperature of I7OO°F., it is impor-TaiiT to ascertain The relative cooling rates for various distances along the bar. It is a question as to whether the cooling occurs at the same rate or whether there is any significant difference from the standard cooling-rate curve published by Jominy and confirmed by others.4,5 This paper reports experimental evidence concerning the effect of quenching temperature on the cooling rates in the end-quench hardenability test. The effect of quenching temperatures on cooling rates has been studied by a number of investigators.6'7 French has considered this effect from both theoretical and experimental aspects. In French's studies on complete quenching of spheres and rounds, an increase in the quenching temperature caused an increase in the cooling rate at 720°C. at the center of the specimen. The center cooling velocity also has been shown to be dependent upon the surface per unit volume for the type of specimens studied; the velocity of cooling increases with an increase in the surface per unit volume. Three methods of indicating the rapidity of cooling of a body of metal during a quenching operation have been propped: I. The time it takes for the metal to cool from the quenching temperature to a temperature halfway between the quenching temperature and the temperature of the quenching medium (half-temperature time): Grossmann, Asimow and Urban7 justify the use of this criterion by the fact that the half-temperature time includes the temperature and time of incubation as well as the zone of formation of pearlite and, further, the data so derived accord very closely with experimental values. 2. The time interval the metal remains in a given temperature range; for example,

Jan 1, 1944

By R. K. Waring, E. C. Truesdale

The Research Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kinds of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein1 some years ago: ZnO+ CO = Zn + CO2 [1] C + CO2 = 2 CO [2] Each of these reactions is dependent upon the other for the supply of CO and CO2 , respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + H2 = Zn + H2 O [31 C + H2O = CO + Ha [4] While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction I is still the faster. He also says (p. 48), "At temperatures . . . between IIOO° and I3oo°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates." In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier's statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented. *

Jan 1, 1943

By C. Ernest Birchenall

AS a basis for further progress in several branches of metallurgy, particularly the study of physical properties of solid solutions and the kinetics of solid-solid reactions, a more complete understanding of the structure of solid solutions and the nature of the metallic bond is- necessary. Any investigation contributing to this understanding should be of primary interest to the metallurgist. Since the metallic bond is characteristic of an assemblage of atoms, it can be studied only where this assemblage exists. One of the most promising approaches to this study of the interactions in metals is through the general problem of binary metallic solutions. Although crystal structures of many solid metallic solutions have been determined and solubility limits for many systems are given in phase diagram studies, progress beyond this is irregular. Electromotive force and vapor pressure determinations have provided thermodynamic activity data for small concentration and temperature ranges in the amalgams and a few other systems.' In two systems, however, copper-zinc and iron-carbon, data are available for the calculation of activities over wide ranges of temperature and concentration. This activity data for the brass system is summarized in the preceding paper.= A detailed study of the solubility and distribution of carbon in iron is given by Smith and Darken.3 Their treatment of interaction energies is applicable only to dilute interstitial solutions. The objectives here will be to derive from activity gats given in the previous paper for the brasses and structural considerations as much new and detailed information as possible about the interactions between copper and zinc in metallic solid solution and the effect of these interactions in determining the short range structure of the equilibrium phases; that is, we shall investigate the energy of interaction between pairs of atoms of the same and different kinds, the deviations of the distribution of nearest neighbors from complete randomness, and show that the conclusions found are consistent with the observed behavior of the brass system. The method of treatment is fairly general for substitutional metallic solid solutions and will be applied to other systems. The determination of vapor pressures of the components of alloy systems is being undertaken in this laboratory to supply more data for this purpose. The information obtained from solid solutions may be extended by careful analogy to liquids as long as the metallic type of bonding is preserved. Since it will be necessary to employ the language of thermodynamics, a brief summary defining the terms used extensively in solution theory is given below. Solution Theory4 An ideal solution is one in which the vapor pressure of the constituent molecules

Jan 1, 1947

By M. Schussler, J. S. Brunhouse

Arc-melted and electron-beam melted tantalum in the cold-worked and the recrystallized conditions showed high strength, good tensile ductility, and excellent notch toughness down to 321°F. Arc-melted material, containing moderate amounts of interstitials, possessed better short-time strength than higher purity electron-beam melted material up to 2000°F. Cold-working substantially strengthened arc-melted tantalum, whereas electron-beam melted material exhibited a low work-hardening rate and possessed better formability characteristics. With identical compositions and microstructures, the mechanical properties of melted tantalum and uacuum-sintered tantalum should be similar. TANTALUM metal usage is increasing rapidly in a number of applications. The outstanding chemical corrosion resistance of tantalum accounts for its applications in chemical processing equipment for severe service conditions and for surgical uses in the medical field. The largest present requirements for tantalum are in the electronics industry, where its special properties are useful in capacitors. The high melting point (5425°F) and inherent ductility of tantalum also suggest that tantalum and tantalum-base alloys might offer an excellent combination of high strength at very high temperatures and good fabri-cability. Pure tantalum has been used in significant amounts in parts requiring high-temperature strength, such as heating elements, reflectors, and heat shields in high-vacuum high-temperature furnaces and in electronic tubes. A few very promising tantalum-base alloys have been developed and are being investigated extensively. The possibilities for tantalum as a high-temperature structural material, either unalloyed or alloyed, will become better defined when more extensive mechanical property data are known. pughl measured the tensile properties of vacuum-sintered tantalum in sheet form for the temperature range of 78" to 1500°K (-321' to 2240°F), and Bechtold reported data obtained at low temperatures.' Drennen3 determined creep and stress-rupture properties of both vacuum-sintered and arc-melted tantalum sheet at 1200 °F. Some additional data on the mechanical properties of tantalum at temperatures up to 5000 °F have been summarized elsewhere.4'5 It is probable that large structural shapes of tantalum, either unalloyed or alloyed, can most readily be produced from ingots prepared by melting. Consequently, the present investigation was undertaken to determine more extensive short-time mechanical properties of tantalum metal consolidated by melting. EXPERIMENTAL PROCEDURE Melting and Fabrication—Two tantalum ingots were utilized in this study to obtain information on the effect of interstitial elements on mechanical properties. Both ingots were melted from Union Carbide Metals Co. tantalum dendrites.

Jan 1, 1961

By E. C. Truesdale, R. K. Waring

The Research Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kinds of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein1 some years ago: ZnO+ CO = Zn + CO2 [1] C + CO2 = 2 CO [2] Each of these reactions is dependent upon the other for the supply of CO and CO2 , respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + H2 = Zn + H2 O [31 C + H2O = CO + Ha [4] While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction I is still the faster. He also says (p. 48), "At temperatures . . . between IIOO° and I3oo°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates." In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier's statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented. *

Jan 1, 1943

By John Brown

As a part of a symposium on the relations of structure to ore deposi-tion, in February 1938, the writer presented some tentative opinions derived from his experience with a number of important lead-zinc replace-ment deposits. These ideas were set forth, as a basis for discussion and a stimulus to further inquiry, in a mimeographed leaflet that read as follows: Intimate acquaintance with a number of lead and zinc deposits in metamorphosed limestones seems to indicate the existence of certain common features from which can be established some general principles governing the localization of ore in this type of formation. It is suspected that these principles can be applied, with modifica-tions, to mineralization in unmetamorphosed limestone. In metamorphosed forma-tions, some observed rules are as follows: 1. Bands or masses of pure limestone are very resistant to replacement by ore solutions, and are likely either to contain no ore or to resist replacement until near the end of mineralization. The reason for this apparently is physical, not chemical, since microscopic data indicate that when ore is deposited by far the greater part of it substitutes for carbonate. The chief factor is believed to be a lack of porosity in massive limestone that has undergone flowage and recrystallization. 2. Masses of intensely siliceous or silicated rock are likewise unfavorable ore receptacles. This seems to be accounted for by two factors: (a) chemical unsuit-ability or resistance to replacement, and (b) physical resistance to small-scale brecci-ation, which might facilitate the opening of effective channelways for solutions. Some low-grade ore may occur, however, and also sporadic fracture fillings. 3. The optimum condition for ore reception appears to be found in bands or areas containing carbonate and silicates (or quartz) intimately mingled in something like equal proportions. In this situation movement is likely to result in mixed flowage and fracture, producing a fine-textured porosity that admits solutions freely and provides access to an abundance of replaceable carbonate. Cleavage cracks in some minerals such as diopside are believed to facilitate the penetration of solutions. 4. Certain minerals or assemblages are regarded as favorable impurities in a lime-stone and others as unfavorable. Original quartz, and subsequently developed diopside, and perhaps garnet, are typical favorable pre-ore gangue; in general rather equidimensional, brittle minerals. Tremolite, biotite, and probably wollastonite, are typical unfavorable pre-ore gangue; in general highly elongated and somewhat flexible minerals likely to develop under strong shearing stresses. 5. Tentative opinion is that the ratio of lime and magnesia in a limestone-is of little or no importance.

Jan 1, 1940

By Carl F. Floe, John Chipman

The system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or CO2 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modern metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100" to 1500ºC., and pressures from about 20 mm. of mercury to somewhat above atmospheric. Review of Previous Work The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as O2, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: 2M+G2=2MG K=(MG)2 /M2 X PG2 [I] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: MG = K1 vPG2 [2 Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: 6Cu + SO2 = Cu2S + 2Cu2O [3] K= Cu2S X (Cu2O)2 i - (Cu)6(Pso2) [4] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: K1 =V3SO2 /Pso2 or

Jan 1, 1941

By John S. Brown

As a part of a symposium on the relations of structure to ore deposition, in February 1938, the writer presented some tentative opinions derived from his experience with a number of important lead-zinc replacement deposits. These ideas were set forth, as a basis for discussion and a stimulus to further inquiry, in a mimeographed leaflet that read as follows: Intimate acquaintance with a number of lead and zinc deposits in metamorphosed limestones seems to indicate the existence of certain common features from which can be established some general principles governing the localization of ore in this type of formation. It is suspected that these principles can be applied, with modifications, to mineralization in unmetamorphosed limestone. In metamorphosed formations, some observed rules are as follows: 1. Bands or masses of pure limestone are very resistant to replacement by ore solutions, and are likely either to contain no ore or to resist replacement until near the end of mineralization. The reason for this apparently is physical, not chemical, since microscopic data indicate that when ore is deposited by far the greater part of it substitutes for carbonate. The chief factor is believed to be a lack of porosity in massive limestone that has undergone flowage and recrystallization. 2. Masses of intensely siliceous or silicated rock are likewise unfavorable ore receptacles. This seems to be accounted for by two factors: (a) chemical unsuit-ability or resistance to replacement, and (b) physical resistance to small-scale brecci-ation, which might faeilitate the opening of effective channelways for solutions. Some low-grade ore may occur, however, and also sporadic fracture fillings. 3. The optimum condition for ore reception appears to be found in bands or areas containing carbonate and silicates (or quartz) intimately mingled in something like equal proportions. In this situation movement is likely to result in mixed flowage and fracture, producing a finc-textured porosity that admits solutions freely and provides access to an abundance of replaceable carbonate. Cleavage cracks in some minerals such as diopside are believed to facilitate the penetration of solutions. 4. Certain minerals or assemblages are regarded as favorable impurities in a limestone and others as unfavorable. Original quartz, and subsequently developed diopside, and perhaps garnet, are typical favorable pre-ore gangue; in general rather equidimensional, brittle minerals. Tremolite, biotite, and probably wollastonite, are typical unfavorable pre-ore gangue; in general highly elongated and somewhat flexible minerals likely to develop under strong shearing stresses. 5. Tentative opinion is that the ratio of lime and magnesia in a limestone is of little or no importance.

Jan 1, 1941

By Arthur L. Christenson, Clarence E. Jackson

In the establishment of the relationship between weldability and hardenability, two methods have been employed in correcting for the grain growth produced in the heat-affected zone: first, the hardenability calculated from chemical composition* may be corrected to the grain size observed in an actual weld? or, second, a hardenability test may be made on the steel quenched from a temperature high enough to produce a grain size comparable to that found in the heat-affected zone.8 In order to obtain grain sizes in the end-quench hardenability bar comparable to those resulting in the base metal from the welding cycle, a quenching temperature of 2Ioo°F. has been used. In studies of the end-quench hardenability specimen quenched from 2Ioo°F. instead of from a lower temperature of I7OO°F., it is impor-TaiiT to ascertain The relative cooling rates for various distances along the bar. It is a question as to whether the cooling occurs at the same rate or whether there is any significant difference from the standard cooling-rate curve published by Jominy and confirmed by others.4,5 This paper reports experimental evidence concerning the effect of quenching temperature on the cooling rates in the end-quench hardenability test. The effect of quenching temperatures on cooling rates has been studied by a number of investigators.6'7 French has considered this effect from both theoretical and experimental aspects. In French's studies on complete quenching of spheres and rounds, an increase in the quenching temperature caused an increase in the cooling rate at 720°C. at the center of the specimen. The center cooling velocity also has been shown to be dependent upon the surface per unit volume for the type of specimens studied; the velocity of cooling increases with an increase in the surface per unit volume. Three methods of indicating the rapidity of cooling of a body of metal during a quenching operation have been propped: I. The time it takes for the metal to cool from the quenching temperature to a temperature halfway between the quenching temperature and the temperature of the quenching medium (half-temperature time): Grossmann, Asimow and Urban7 justify the use of this criterion by the fact that the half-temperature time includes the temperature and time of incubation as well as the zone of formation of pearlite and, further, the data so derived accord very closely with experimental values. 2. The time interval the metal remains in a given temperature range; for example,

Jan 1, 1944

By C. G. Dunn, J. L. Walter

The c/laracterzstics of cube-oriented nuclei ard other matrix grains that are associated with secondary, recrystallization to the cube texture in high-purity silicon iron were investigated by me-tallographic and X-ray methods. The results show that the structure consists of relatively perfect grains of average diameter between one and two times the sheet thickness ad that the texture has a moderately strong (110) [001] component and a weak (100) [001] component. The results also indicate that matrix stability results from the two-dimensional nuture of the graitzs and that cube-orzented nuclei are neither more Perfect nor larger grains than other matrix grains but have a preferred [001] direction in the rolling direction and have a more effective driving force for growth than other grains because of a low (100) surface energy. THE structures and textures of fine-grained rnatrices determine to a large extent the kinds of secondary recrystallization textures that form on annealing. The understanding of secondary recrystallization processes therefore depends on adequate information about the initial matrices. Matrices usually have three characteristics: 1) they consist of fine-grained primary recrystallization structures, 2) the fine-grained structures are stable toward normal grain growth, and 3) they contain secondary recrystallization nuclei. Stability toward normal grain growth may be due to either a strong single orientation texture (texture inhibition)' or a dispersed second phase (dispersed phase inhibition).2"4 If normal grain growth is not inhibited by either of these two factors, it nevertheless stops when the average grain size is between one and two times the sheet thick- ness.5 This thickness effect satisfies one of the characteristics of a matrix for secondary recrystallization. Its importance in the development of the cube texture in high-purity silicon iron by secondary recrystallization was pointed out by the authors in a recent paper on tertiary recrystallization7 and will be discussed further in the present paper. Assmus, Detert, and he8 have provided some information on a matrix for secondary recrystallization to the cube texture in silicon iron. They found a (110)[001] or Goss texture with enough spread about the rolling direction to include a small amount of the (100)[00l] orientation. The distribution of the [00l] directions was strongest parallel to the rolling direction for both (100) primaries and cube secondaries. These authors found no correlation between size of a matrix grain and orientation and concluded that some property other than size must be the distinguishing characteristic of the cube-oriented nucleus. No consideration was given, it

Jan 1, 1961