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By B. E. Sundquist

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

Jan 1, 1967

By C. A. Stetefeldt

In May and June, 1885, I was engaged in examining the goldores of Las Minas, in the State of Vera Cruz, Mexico, with a view of finding a cheap and efficient method for extracting the gold. The following minerals could be plainly seen in the ore : magnetite, pyrites of iron, pyrites of' copper, quartz, and garnet. Neither galena nor zinc-hlende mere visible, but the ore contained a trace of lead, and in some samples of ore from the Muertos mine, 1.19 per cent. of zinc mas found. Antimony and arsenic were not present. Native gold could scarcely be seen in specimens of' the ore, and it only appeared—mainly in extremely fine particles—after pulverizing and washing. Magnetite was in every instance the most prominent mineral, its quantity varying between 43 and 67 per cent. Determinations of copper and sulphur showed that from 3.5 to 7 per cent. pyrites of copper, and from 3 to 22 per cent. pyrites of iron were present. The gold-value of the ore varied between 0.3 oz. and 0.8 oz. per ton. I do not speak of specimens, but of average samples of large quantities of ore put through the battery. In ore that had been crushed through a No. 40 screen, the gold appeared, in part, as free gold, the rest being thoroughly mixed with the magnetite and pyrites, both minerals containing about the same percentage of gold. If this free gold was brought in contact with pure quicksilver it (lid not amalgamate readily, even if the quicksilver was charged with sodium amalgam.

Jan 1, 1886

By John Wulff, David A. Stevenson

The rates of solution of copper, nickel, and three copper-nickel alloys in liquid lead were studied at 527° and 727°C under dynamic conditions. The relative velocity at the solid-liquid interface was varied from 8.65 to 125 cm per sec. Analysis of the data for the pure metals indicates that the solution rate is transport corztrolled at lower velocities, but a transition to mixed control occurs at higher velocities, higher temperatures, and higher percent saturation. 1 HE present work concerns the effect of relative velocity at a solid-liquid interface on the dissolution kinetics of pure solid materials in liquid metals. This general problem is of interest in electrode kinetics, in electrolytic processes, and more recently in the field of liquid metal corrosion. Considerable work has been done on dissolution kinetics in aqueous environments because of the obvious importance to electrolytic processes.1,2 In purely metallic systems investigation has been more limited. There are, of course, extensive data from loop tests which are used in an engineering evaluation of liq- uid metal corrosion. Here, however, the dissolution process is complicated by several interdependent processes. In general, one of two factors is considered to be rate limiting in the dissolution process: the transport of material from the solid-liquid interface into the bulk liquid, or an activation process directly at the interface. A number of studies of the dissolution rates of solid metals in liquid metals under static conditions have been published.3- Since the attendant hydrodynamic conditions imposed by thermal gradient convection and concentration gradient convection are difficult to analyze, it is doubtful if a clear interpretation of the experimental findings of these papers in terms of the mechanism involved in the dissolution process can be made. A clearer picture of the dissolution process is provided by

Jan 1, 1962

By M. A. El-Aouar

Drilling muds are complex colloidal systems. In an effort to analyze the physical properties that affect their performance at high temperature, an investigation was made of the hydrothermal stability of the monoionic hydrogen, calcium and magnesium forms of montmorillonite and attapulgite. Samples were heated to 400°1F in a simple autoclave and analyzed for cation exchange capacity, c-axis X-ray diffraction spacing and pH factor us sodium hydroxide titration dependence. Out of the six monoionic clay minerals tested, calcium montmorillonite and magnesium attapulgite showed the least base exchange capacities and were relatively unaffected to heat. It is concluded that, of the six clays studied, these two clays were the most suitable forms for use in drilling fluids. INTRODUCTION The drilling of deep wells is dependent upon the drilling mud, and problems frequently arise concerning the effect of mud temperature and prolonged heating. Drilling muds are complex colloidal systems. In an effort to analyze their behavior in deep, hot boreholes, it was thought desirable in this investigation to study suspension of pure, monoionic montmorillonite and attapulgite clays before and after hydrothermal heating. Chemically, clays are hydrated aluminum silicates, such as montmorillonites and attapulgites. The structure of montmorillonite is composed of units made up of two silica tetrahedral sheets with a central alumina octahedral sheet. Attapulgite consists of double silica chains running parallel to the c-axis with the chains linked together at their longitudinal edges. The apexes of the tetrahedrons in successive chains point in opposite direc-tions.4,7,10 One of the most important characteristics of clay minerals is their property of sorbing certain anions and cations and retaining them in exchangeable state. The property of exchange capacity is measured in terms of milliequivalents (meq) per 100 gm of clay. The cation-exchange capacities are taken at pH 7 from titration curves which show the relation between pH and milliequivalents of added NaoH.9,11 The following are causes of cation exchange: (1) broken bonds around the edges of the silica alumina units would give rise to unsatisfied charges, which would be balanced by adsorbed cations; (2) substitution within the lattice structure of trivalent aluminum for quadrivalent silicon in the tetrahedral sheet and of ions of lower valence; and (3) the hydrogen of exposed hydroxyls may be replaced by a cation which would be exchangeable. The primary techniques employed to study the effects of hydrothermal treatment were titration curves and X-ray diffraction analyses. Titration curves were useful in characterizing the nature of the clay mineral surface and the stability of the various samples to attack by acid or alkali before and after hydrothermal treatment. X-ray diffraction analyses were used to determine changes in the nature and crystal structure of the minerals present and to determine the cations in exchange positions on the montmorillonite samples. EXPERMENTAL PROCEDURE PREPARATION OF SAMPLES Selected samples of Wyoming bentonite and attapulgite clay from mines along the Georgia and Florida border were purified by centrifugation to remove all particles larger than 2 microns. In preparing magnesium attapulgite, first a 1.00-normal solution of magnesium acetate was prepared. The pH of the solution was adjusted to 7.0 by adding magnesium oxide. One hundred grams of attapulgite clay were mixed in a blender for 30 minutes with the magnesium acetate solution. The attapulgite solution was left overnight, and then filtered in a Buchner funnel. The suspension was leached with further quantity of magnesium acetate solution and then washed with distilled water for 20 days, after which the filtrate was free from magnesium ions. The concentration of magnesium attapulgite in the clay slurry was adjusted and determined quantita-

By John A. Putnam, Morrough P. O’Brien

DATA on the physical and thermodynamic properties of hydrocarbons have been made available in recent years but the formal method of applying these data to flow in porous media appears not to have been fully developed. By making usual thermodynamic assumptions and employing existing data on permeability to two-phase flow, Darcy's law may be applied to obtain the flow characteristics for representative combinations of flowing medium and geometry. The numerical examples presented herein are based on hydrocarbons for which complete physical and thermodynamic data are available under equilibrium conditions. INTRODUCTION Thermodynamic data are obtained in the laboratory under equilibrium conditions and their application requires the assumption that equilibrium also exists during flow. This assumption is at least usual in engineering analyses, though not easily justified in many instances, and will be followed here. In regard to hydrocarbons, laboratory experience in determining the pressure-volume-temperature relationships indicates that gas-liquid mixtures must often be stirred vigorously for periods of 15 to 20 min. before reaching equilibrium. On the other hand, boiling and condensation are known to occur on solid surfaces and the large surface exposed to the flowing substance by a porous medium may bring about rapid approach to equilibrium. For the purpose of providing at least a guide to experimentation and a standard for later comparison with experimental results, it will be assumed that the phases present in cross sections perpendicular to the direction of flow are in thermodynamic equilibrium. Another assumption usually made in the solution of problems of flow in porous media is that the fluid remains at a constant temperature; i.e., isothermal flow. This assumption is arrived at by considering the porous medium and surroundings to be an infinite heat source and the rate of heat flow to be infinite at a boiling front. Its validity depends in large measure upon the character of flow, the number of components, and the physical and thermodynamic properties of the fluid. However, the assumption of isothermal flow represents a limiting case. The other limit can be represented by the assumption that the fluid is thermally isolated; i.e., irreversible adiabatic. The thermodynamic process characterizing the actual flow of a given fluid system probably lies somewhere between these two limiting cases and might be thought of as a flow system in which the confining walls are maintained at a constant temperature. For isothermal flow the solid material of the porous media is considered as the infinite heat source capable, without loss in temperature, of giving up heat to the fluid as the latter tends to cool by expansion. For the thermally isolated system, the solid material is considered to give up no heat to the fluid. In the intermediate case the impervious walls confining the porous media are at constant temperature from which heat is transferred along various paths, solid and fluid, throughout the porous media. It would appear that an actual petroleum-

Jan 1, 1941

By Richard H. Terhune

The use of water-cooled breast-jackets or cinder-tap blocks is a great convenience in lead-smelting, even when siliceous slags are made. If the charges are at all basic it is almost imperative. Jackets of riveted wrought-iron or steel are expensive; those of cast-iron are liable to crack; those of bronze are costly and not durable, being easily penetrated by tapping-bars or destroyed by streams of matte impinging against them. To overcome these objections I introduced at the Hanauer works, in April, 1886, castjackets of steel, which have been in constant use since that time and are to-day as good as new. These jackets were made for us by the Chester Steel Castings Company, of Chester, Pa., at a cost of ten cents a pound at the works of that company. The metal is 5/8-inch thick, and the jackets were cored and tapped for l1/2-inch bushings, affording two large holes for the removal of dirt and incrustations. The same holes are used for feed- and discharge-water through 3/4-inch pipe. I hope the successful introduction here of cast-jackets of steel will lead to their more extended use in all branches of metallurgy where water-cooled surfaces are severely taxed, and where the size and thickness of the castings are not unfavorable to the production of a sound article, impervious to water and of high tensile strength.

Jan 1, 1889

SECTION I PAGE PAGE President's Western Trip v Presentation of the' John Fritz Hoover Makes Plea to. Stop Food Medal to Henry M. Howe.... xv Waste v International Mining Convention. xxxv. American Committee of Engineers Personal xl in London vii Employment xlii Proceedings, Meeting of Board of Local Section News xliii Directors : vii Forthcoming Meetings of Societies xlvii St. Louis Meeting V... Library xlviii The Woman's Auxiliary. xi Membership liv Members of the Institute in Mili- Biographical Notice of H. T. Chen. lxxiv tary Service xiv Institute Committees lxxv Officers and Directors lxxxii

Jan 7, 1917

By W. A. Barrows

Mesabi ores differ from all other soft hematite-ores of the Lake Superior region in having but little or 110 binder. When exposed to heat, instead of baking into lumpy masses as do the Gogebic, Menominee or Marquette fine ores, they are changed to a sandy powder; and the finer particles, having little or no tendency to adhere together in the furnace, are carried by the ascending gas-currents into the down-comers and gas-mains forming flue-dust of a fine gritty nature. The term " finer particles " is used in this paper to mean ore fine enough to pass through a sieve with 80 meshes to the linear inch. Ore coarser than this is not likely to be carried over except in case of a slip, or an explosion in the furnace. The higher the percentage of fine particles in an ore from this range, therefore, the greater the amount of dust likely to result from its use. This statement, however, does not hold good in case of fine ores from the other ranges, and ores from the older ranges, carrying as high as 20 per cent. of material fine enough to pass through a 100-mesh sieve, have been in successful use for years, and have left no records of their causing trouble in furnace-practice by dust, slips, or explosions, so common since the introduction of Mesabi ores. Mesabi ores containing less than 12 per cent. of material which will pass through an 80-mesh sieve are considered of good structure; from 12 to 18 per cent., fair structure; and more than 18 per cent., poor structure. It was at first supposed that all these fine particles were carried over when the charge was lowered into the furnace, or during a slip, but the presence of partly reduced iron oxides in the flue-dust, even when no slip has occurred, proves that a part of the dust at least must have been low enough in the

Jan 1, 1905

By S. Ramachandran, R. A. Walsh

Many investigations have shown that the manganese enhances the deoxidation power of silicon. Here it is suggested that this phenomenon could be explained in terms of the formation of impure silica. Data of Hilty and Crafts on the Fe-Mn-Si-O System has been evaluated on the basis of the reaction S_i + 20 = (SiO2) where (SiO2) denotes silica of variable activity. The activity of silica in this system is a function of aMn/aSi and the temperature, and can be described by the equation 12700 l°gaSiOz = -6.85+ - - 0.5 log aMn /asi PRACTICAL melting experience has shown that it is helpful to maintain a certain range of Mn/Si ratio in deoxidizing quality alloy steels. Herty,1 as early as 1932, reported a strong association between manganese and silicon as did schenck2 and Korber and Oelsen3 in later work. More recently, Hilty and crafts4 have studied the solubility of oxygen in the Fe-Si-O system, both with and without manganese. Their study confirmed the marked ability of manganese to increase the deoxidizing power of silicon. This phenomenon has remained unexplained in the liter,ature5 since it has been shown that manganese has virtually no influence on the activity coefficients of silicon or oxygen.= In this paper, an explanation for the role of manganese is suggested and equations are devised for quantitatively describing this influence. DISCUSSION Hilty and crafts4 equilibrated their melts under an argon atmosphere and the system established equilibrium with a self-generated slag which was not always the oxide of lowest free energy. Drawing on the early work of Korber and Oelsen,3 it was reasoned that the formation of complex Fe-Mn-silicates

Jan 1, 1963

By Christopher W. Schram, Allan B. Tanner, Frank E. Senftle, George R. Boynton, Philip W. Philbin

A borehole sonde using a 252Cf neutron source and a Ge(Li) gamma-ray detector was field tested in a coal bed in Belmont County, Ohio, to ascertain whether such a device could be useful as a coal-exploration tool. As the sonde was lowered into the borehole, successive spectra were accumulated over short time intervals. The intensities of the capture gamma rays from hydrogen and of decay gamma rays from aluminum were determined simultaneously in each spectrum. A log of the intensities versus depth shows the depth and thickness of the coal bed. With the sonde stationary at points above, in, and below the coal bed, capture gamma rays were measured to show the variation in concentration of certain elements. From the spectrum recorded in the bed, a complete ultimate analysis, the percent ash content, and the heat content were determined without recourse to an external standard. Delayed gamma-ray analyses of the core were also made on the surface in the vicinity of the borehole in a fixed-geometry irradiation facility wing the detector in the borehole sonde. The concentrations of 10 elements were determined by this method on a coal split from the drill core. These experiments show that it is feasible to use a 252Cf- Ge(Li) borehole sonde as an aid in coal exploration.

Jan 1, 1979

By Sherwin F. Kelly

Twenty five years of exploration has shown that the "geophysical dollar" is worth $1780 in the Orange Free State, $1488 on the Witwatersrand, $85 in Sweden, $28,000 in the Transvaal and $3500 or more in the U.S.

Jan 6, 1951

By R. W. Raymond

The sudden death of Captain Jones, September 28,1889, became known to his fellow-members on the eve of the Ottawa meeting of the Institute; and at that meeting, Mr. Charles Albert Ashburner, of Pittsburgh, expressed with unaffected feeling and unpremeditated eloquence the sorrow of all. Mr. Ashburner subsequently undertook to revise and extend, for in in the Transactions, the remarks he had made at Ottawa; but death surprised him also, in the midst of his labors; and it has become my duty and privilege to prepare from the memoranda he left behind, the present brief and inadequate notice. To me, who knew and loved them both, this task of double sorrow recalls them both, with a peculiar sense of presence and of absence. They seem to speak from another land, not far away, yet not with human voices—like an echo and its echo. William Richard Jones was born in Luzerne county, Pennsylvania, February 23, 1839. His father was Rev. John G. Jones, a Welsh minister, who had immigrated to the United States in 1832. William was the eldest son, and his father's failing health made it necessary for him to begin early the work of self-support. At the age of ten, he was apprenticed to the Crane Iron company, of Catasauqua, and in this humble capacity entered upon the profession in which he was to become famous. Unquestionably, the thorough acquaintance with all details, acquired by working his way from the bottom to the top, was one secret of the conspicuous executive ability which characterized him in the height of his career. According to a letter from Mr. J. H. Geer, Assistant Chief Engineer of the Cambria Iron Company, Mr. Jones entered the service of that company in 1858 or 1859 as a machinist, and continued to work in that capacity until July, 1862, when he enlisted as a private in the 133d Regiment of Pennsylvania Volunteers, in which he afterwards commanded a company. The regiment was mustered out of service in 1863, and Captain Jones re-enlisted in the 194th

Jan 1, 1890

By E. S. Bardwell, Roy H. Miller

During the period extending from May, 1922, to September, 1923, the copper-refining furnaces of the Great Falls Reduction Department of the Anaconda Copper Mining Co. at Great Falls, Mont., were operated exclusively with pulverized coal as fuel. The installation was made first as an experiment. It proved successful from the start and was abandoned solely because fuel oil from the Sunburst field became available at a price sufficiently low to be more desirable from an economic standpoint. The equipment required for pulverized coal has, however, been kept intact and is available for immediate use should the oil supply fail. Inasmuch as pulverized coal had been used on two large reverbera-tory smelting furnaces and was, at the time we were considering its application-to the copper-refining furnaces, being used on the Wedge furnaces roasting zinc concentrate for the electrolytic zinc plant, we were equipped with a coal-pulverizing plant of ample capacity to supply pulverized coal for the furnace refinery. The only problem was to devise suitable means for transporting pulverized coal from the pulverizer plant, located in the smelter building, to the refinery about 3000 ft. distant and about 150 ft. above the level of the pulverizer plant. When studying this installation, it should be borne in mind that the layout represents an adaptation suited to the existing conditions at this particular plant. The installation was entirely satisfactory and uniformly dependable but might be modified to advantage from an operating point of view if an entirely new installation were being planned. Fuel Supply The use of the local coals, high in ash and sulfur, was abandoned some time before coal-dust firing was attempted. Local coals from the Great Falls field carrying an average of 4 per cent. sulfur and 22 per cent, ash were used with fair success in the small furnaces in use prior to 1916. In the 250-ton furnaces, however, the time lost in grating and removing clinker from the fireboxes, as well as the difficulties incident to the high-sulfur content of the fuel, became serious and recourse was had to the

Jan 1, 1927

POSITIONS VACANT (Under this heading will be published notes sent to the Secretary of the Institute by members or other persons.) A copper company in Arizona desires a young engineer to assist the superintendent and take charge of the surveying, sampling and assaying. A graduate mining engineer with a few years' experience in mine surveying and sampling preferred. Salary, $125 to start. No. 10. A company in Quebec desires a metallurgist familiar with copper smelting to remodel an old plant and carry on experimental work to determine whether its ore can be smelted profitably in the district. No. 11. A foundry making a specialty of medium and light weight. steel castings of high grade waists a competent man as assistant manager capable of taking complete charge of production in the absence of the general manager. No. 12.

Jan 3, 1914

By J. S. Marsh

AN incomplete statistical analysis performed wearily on the morning after Thursday, Feb. 12, indicates that the unavoidable items of conversation among steelmen were the current shortage of sleeping time and the "Normandie." No analysis is needed, however, to be certain that many thousands of valuable words were uttered, both in and out of technical sessions, concerning matters of deep interest to members of the Iron and Steel Division. The opening session consisted mostly of papers that have appeared, or will appear shortly, in Metals Technology. One, however, that was not finished in time to be printed in any form, but that aroused great interest, was by E. L. Ramsey and L. G. Graper (Wisconsin Steel Works). Its subject was the production of high-sulphur steel by treatment with sulphur dioxide derived from anhydrous sodium sulphite or bisulphite added to the ladle or to the mold. The sulphide distribution in the finished steel is such that increased machinability and longer tool life result. Both items are of obvious importance in these days of mighty production.

Jan 1, 1942

By R. C. Ruder, C. E. Birchenall

The method of decrease in surface activity was used to determine the rates of diffusion of Co" into cobalt and into nickel. Since the absorption curves for cobalt radiation were quite complex under the conditions of these experiments, the effects of geometry and surface preparation on the diffusion results were investigated. The cobalt self-diffusion coefficients obey the equation DCoco = e-61100/RT cm2 per sec. For dilute cobalt diffusing in nickel, DConi, == 1.46 e-/R' cm2 er sec. AS part of the general program to measure the self-diffusion and dilute-solution diffusion rates of the iron-group metals, the diffusion coefficients of cobalt into cobalt and nickel have been measured using the radioactive isotope Co"'. Self-diffusion studies in iron have been previously reported by Birchenall and Mehl.' The technique of measurement used was the decrease in surface activity method described by Steigman, Shockley, and Nix.' It has been determined that scattering of the measured beta radiation by the specimen matrix is significantly influenced by the condition of the surface and the counting geometry. Accurate diffusion coefficients can be calculated from the activity data provided that the specimens have plane diffusion surfaces and that the absorption properties of the emitted radiation are determined under geometrical conditions duplicating with external absorbers the absorption and scattering in a thin film at the specimen surface as nearly as possible. The cobalt used in this research was originally in the form of hydrogen reduced rondels 99.9+ pct pure. The nickel had been prepared by the carbonyl process and was found by spectrographic analysis to contain 0.03 pct Fe, 0.04 pct Co and smaller traces of other metallic elements for a balance purity of 99.9+ pet Ni. Both materials were vacuum melted and cast in rectangular ingots. Specimens 7/8x7/8x1/4 in. were machined from these ingots. The specimens were then ground to 4-0 emery paper and annealed in hydrogen for at least a day at 1200°C. Some of the specimens were used in preliminary experimentation after which their diffusion faces were machined to remove the radioactive material from the previous diffusion experiments. After grinding, the specimens were polished using an electrolytic lapping technique described by Mazia." This lapping was continued until at least 0.005 in. was removed from the diffusion surface. The final surfaces were metallographically smooth except for a few fine scratches caused by the glass cloth. A large percentage of the area was undisturbed as determined by microscopic examination. The grain diameters of the diffusion specimens varied from 0.1 to 5 mm. There were no effects due to grain boundary diffusion in the experiments

Jan 1, 1952

By G. R. Belton, Y. K. Rao

A galvanic cell, using liquid MgCl2 or MgC12-CaC12 mixtures as the electrolyte, has been used to determine activities in Mg-A1 liquid alloys between 700' and 880°C. The incovporation of a chlorine electrode in the cell also allowed measurements to be made of the standard free energy of formation of MgCl2(l). The results are shown to be in good agreement with thermo-chetrlical values from the literature, and this is taken as evidence that the small, known solubility of magnesium in iMgCl2 introduces no significant error in galcanic cell measurements. Within experimental error, the activity coefficients and relative partial molar enthalpies at 800°C are shown to be represented by the following "subregular" solution equations: logy~~ =-0.68(1 -xMgj3 log yAL =-1.02(1 - XMf + 0.68(1 - XMf H.M = -4400(1 - %)3 / cal Mg 7Ag' HZ =-6600(1 - xA1)' + 4400(1 - XMf cal SCHNEIDER and toll' have used a transpiration technique to measure the vapor pressures of magnesium over Mg-A1 alloys between 544" and 594°C. amsstad,' however, has since suggested that the extrapolation to zero flow rate, used by these authors in interpreting their apparent pressure vs flow rate data, gives unreliable results. Rogers, Tomlinson, and Richardson,3 in interpreting the results of solution equilibria between Mg-A1 alloys and liquid MgC12, also considered the measurements of Schneider and Stoll to be unreliable and preferred to derive activities for the alloys from the earlier boiling point determinations of ~eit~ebel~ and the partial molar heats recommended by Kubaschewski and ~atterall.~ These latter heats were based substantially on the early calorimetric work of Kawa-kami but, unfortunately, his work on other systems has sometimes been found to be inaccurate.7 Rogers et al., in the above-mentioned paper,3 tentatively concluded that the most likely species responsible for the limited solubility (0.3 mole pct at 800°C) of magnesium in MgC12 were Mg° (neutral) and Mg2++. Two more recent studies8,9 have supported Mg2++ as the soluble species. In the present study, activities in Mg-A1 alloys have been determined by means of a galvanic cell involving liquid MgCl2 or MgC12CaCl, mixtures as the electrolyte. Since the reactive nature of magnesium precluded simple Faraday yield experiments, a chlorine electrode was incorporated in the cell in order that the performance of the cell could be checked by measurements of the heat and free energy of formation of MgC12. This procedure was considered necessary since it has been suggested1' that the solubility of a metal in a molten salt might introduce electronic conductivity; also, previous determinations of the standard electrode potential for MgC12 differed by as much as 70 mv11-13 EXPERIMENTAL Materials. Analyses of the materials used in preparing the alloys and the electrolyte mixtures are presented in Table I. The alloys were prepared by induction melting weighed amounts of the metals in a graphite crucible held under an argon atmosphere. Pure anhydrous magnesium chloride was prepared by heating the mixture MgCl, . 6H20 +NH4C1(1:1) to 650°C, followed by melting under dry argon. The melting point of the dry MgC12 was found by differential thermal analysis to be 714.8oC, which compares well with the accepted value of 714C.14 This agreement was taken to be an indication of the high purity of the dried salt. Table I. Compositions of Materials, wt pn Impurity Mg Al MgCI2 CaCI, Ba - - 0.005 Ca - - 0.010 Cu 0.02 0.02 Fe - 0.10 0.001 0.010 Pb 0.01 - 0.001 0.005 Mn 0.15 0.001 Si - 0.10 Sr - - 0.005 MBSO* - 0.040 ARGON TUNGSTEN CHLORINE LEAD—411 11 II ALUMINA 'A I / ave GRAPHITE on irA~_ ( ^"l ROD MAGNESIUM S>ILICA~^ /, OR ALLOY-. I /A] ___________ -«^- _ ELECTROLYTE I y FRITTED DISCS Fig. l—Arrangement of chlorine and metal electrodes in electrolytic cell.

Jan 1, 1970

By C. S. Finney, John Mitchell

There is no field of human thought or endeavor which does not owe much to the past. Yet, surrounded by the prodigious scientific and technological achievements of our day, it is all too easy to forget the extent to which we have stood on the shoulders of giants. The coking industry of the United States is now a little more than one hundred years old. As with the American nation itself, the earliest beginnings of the industry owe a great deal to British influences, and its development owes much to those influences of continental Europe. No serious contribution to the history of coking in the United States can be written, therefore, which does not mention the work of the pioneers of the Old World. It is believed that the use of metallurgical coke dates back to antiquity. The fact that certain coals would soften under the influence of heat to yield a porous solid was known to the ancients of China and India, where a very crude coking operation was carried out by simply setting fire to piles of coal. After active combustion had started, turf or wet straw was used to seal off the pile. The coke obtained was used to forge iron and steel implements and weapons. Perhaps the earliest reference to the coking phenomenon is to be found in the writings of Theophrastus, pupil of Aristotle. In his History of Stones, which was written in or about the year 371 B.C., there appears the following observation. "But the Lipara stone empties itself, as it were, in burning and becomes like the pumice, changing at once both its colour and density; for before burning it is black, smooth and compact.... Certain stones there are about Tetras, in Sicily, which is over against Lipara, which empty themselves in the same manner in the fire." The first comparatively modern reference to coke is to be found in a recommendation for carbonization made in 1584 by Julius, Duke of Braunschweig-Luneberg, owner of the Hohenbuchen mine in the Harz district of Germany. In 1587, Sir Francis Willoughby of. Wollaton, England wrote: "There are twenty rooks broughte into charcoal and laid up in store." A rook of coal was equivalent to some 25 tons, and the coking would probably have been carried out in a manner similar, to that used for the production of charcoal. In 1589, Thomas Proctor attempted to carbonize coal, and in the year 1590 an English patent was granted to John Thornborough, Dean of York, in order that he might "purify pit coal and free it of its offensive smell". Sir Robert Cecil (1595), Robert Chantrell (1607), Simon Sturtevant (1611) and John Rovenzon (1613) were all granted patents for the use of coal or coke

Jan 1, 1961

By J. S. Ll. Leach, J. B. Cohen, M. B. Bever

IN the work reported here, the heats of formation of a copper-rich Cu-Sn (a) solid solution and of the Cu.Sn (0 phase were measured by tin solution calorimetry. An approximate determination of the heat effect attending the precipitation of 6 from a supersaturated a solid solution was also made.

Jan 1, 1955

By R. D. Schoone, J. T. Michalak

Recovery, recrystallization, and texture development of a cold-rolled aluminum-killed steel have been studied during simulated box annealing. Two different initial conditions existed prior to cold rolling: 1) essentially all of the nitrogen in solid solution and 2) most of the nitrogen precipitated as AlN. The combined effect of nitrogen and aluminum in solid solution before annealing was to inhibit recovery and sub-grain growth at temperatures above about 1000°F and to raise the recrystallization temperature range on continuous heating at 40°F per hr from 1000"-1050°F to 1065"-1085°F. For the material with nitrogen and aluminum initially in solution there was an inhibition in the nucleation of the (001) [110] texture component and an enhancement of the (111) [110] texture component. The differences in annealing behavior mzd texture development are attributed to preprecipitation clustering of aluminum and nitrogen at subboundary sites developed by prior cold working. THE annealing of cold-worked aluminum-killed steels has been the subject of numerous investigations.'-'2 These studies have been concerned with kinetics of recrystallization, with microstructure and texture development, and with the individual and combined effects of composition, thermal history prior to cold rolling, and heating rates during subsequent annealing. It has been shown that the inhibition of recrystallization, and the development of the pancake-shaped grain and recrystallization texture characteristic of aluminum-killed steels, can be associated with the precipitation of A1N particles during a recrystallization anneal involving heating rates in the range 20" to 80°F per hr. If the AIN is precipitated before cold rolling or if more rapid heating rates are employed, the cold-rolled steels recrystallize more rapidly to an equiaxed grain structure and texture comparable to that of rimmed low-carbon steel. The retardation of recrystallization, the development of the elongated grain structure, and the pronounced (111) texture have been attributed to: 1) precipitation of A1N at prior cold-worked grain boundaries to form a mechanical barrier to grain boundary migration;' 2) precipitation on the boundaries of the growing recrystal-lizing grains as well as on cold-worked grain boundaries;'" and 3) preprecipitation clustering or precipitation on subboundaries to retard recovery, nucleation, and growth. The present study was undertaken to study in more detail recrystallization and texture development during commercial box annealing of cold-rolled aluminum-killed steels. Comparison of the annealing be- havior after cold rolling, for two different conditions prior to cold rolling, was made in an attempt to define more clearly the role of aluminum and nitrogen in forming the recrystallization texture. A) MATERIAL AND PROCEDURE The material used in this investigation was a commercial low-carbon aluminum-killed steel which was hot-rolled with a finishing temperature of about 1565"F, then coiled at about 1020°F. The composition, in wt pct, was: 0.050 C, 0.30 Mn, 0.007 P, 0.019 Si, 0.03 Cu, 0.02 Ni, 0.02 Cr, 0.045 Al, and 0.004 N. Two 4.5 by 13 by 0.078 in. sections were cut from the center section of a hot-rolled panel and one of these was reheated to provide two different conditions prior to cold rolling: low AlN: as commercially hot-rolled, with aluminum and nitrogen in solid solution; and high AlN: as commercially hot-rolled, then reheated at 1300°F for 3.5 hr to precipitate most of the nitrogen as AlN. ~etallc&a~hic examination indicated that the reheating did not change grain size nor carbide distribution (some spheroidization of pearlite was noted). Texture analysis at half-thickness level showed that both sections had the same substantially random as-hot-rolled texture. The results of check chemical analysis of each sample are given in Table I. Both sections were cold-reduced 65 pct on a laboratory rolling mill to a final thickness of 0.027 in. Cold rolling, in one direction only, was in the direction of the prior hot rolling. Specimens 1.0 by 1.25 in. were cut from the cold-rolled sheets and given a simulated box anneal in an atmosphere of 2 pct HZ-98 pct He. Specimens were heated at a constant rate of 40°F per hr from room temperature to various temperatures in the range 750" to 1300°F and cooled immediately by withdrawal to the water-cooled end of a tube furnace. The temperature in the 6-in. uniform hot zone of the furnace was controlled within 3"F. Selection of the individual specimens was made to give a random distribution of annealing temperatures with respect to location in the cold-rolled sheet. At least two specimens of each condition were annealed to the same temperature and smaller specimens for light microscopy, transmission electron microscopy, and X-ray studies were prepared from each of these. Rolling-plane sections for each of these studies were taken at half thickness. Light microscopy and transmission electron micro-

Jan 1, 1969