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To the members of the A. I. M. E., who have given much and risked all to fight "Over There" with pick, or gun, or brain, and to the members who have chosen the sometimes more self-denying duty of remaining at home to help produce metals for fighters: Your experience in foreign lands has bred in you that spirit of internationalism which will soon be infused into every corner of our country by virile lads thrilling from a great experience in an old, yet new, land over the seas. To them the East will not seem as far from the West as it was, nor the North from the South. Sectional jealousies will seen despicable to one who has fought for a great ideal shoulder to shoulder with real men of other nations. And they who have willingly sacrificed much on the altar of service will have little patience with an egotist, be he laborer, tradesman, capitalist or engineer. The problems which peace brings to us are more difficult than those of war and their solution requires not only cool heads, tolerance, and wise judgment, but the "getting together" of sections and classes and individuals. The triumph of justice over individualism, represented by the draft law, must be repeated, for there are "slackers" in peace Is well as in war, and the spirit of self-denial expressed in response to Liberty Loans, Red Cross, and Welfare drives and Food Administration appeals must live. We have only just begun to learn how to serve. It is often claimed by our members that the engineer is not given, in the community at large, the recognition which his training should merit; that his reward is not as great nor his service as welcome as it should be. Public service is generally assumed to be a logical activity for a lawyer,

Jan 12, 1918

By A. E. Nehrenberg

IN an earlier publication' it was shown that the.. shape assumed by a volume of growing austenite is inherited from the prior structure. The matrix grains of pearlitic microstructures are equiaxed, and austenite grows in an equiaxed manner in these prior structures. Martensite and bainite, on the other hand, have an acicular grain structure, and the austenite produced in such structures grows in an acicular manner. In the discussion of this paper' it was pointed out that in cold-rolled tempered martensite, austenite grows in an equiaxed, rather than an acicular manner. The results of an experiment carried out to arrive at an understanding of this behavior are illustrated by the micrographs. Fig. 1 shows the acicular microstructure produced by heating tempered martensite to a temperature within the Ac1-Ac3 range, 1350°F. When tempered martensite is cold rolled, then heated to the same temperature, the equiaxed structure shown in Fig. 2 is produced. A sample of cold-rolled tempered martensite heated at 1350°F just long enough for the formation of a small amount of austenite is shown by Fig. 3 to have an equiaxed (recrystallized) ferrite grain structure. The small particles of. austenite which formed at 1350°F in the equiaxed ferrite matrix are likewise equiaxed. Thus, the equiaxed growth of austenite in cold-worked tempered martensite is not a contradiction of the principles described in the previous paper, for the growth pattern reflects the matrix grain structure existing at the time of austenite formation. References A. E. Nehrenberg: The Growth of Austenite as Related to Prior structure. Trans. AIME (1950) 188, pp. 162-174; Journal of Metals (January 1950). 2 J. R. Vilella and R. A. Grange: Discussion of ref. 1. Trans. AIME (1950) 188, pp. 1378-1381; Journal of Metals (November 1950).

Jan 1, 1953

By C. M. Warner

In both the Flat River district of southeast Missouri and the Joplin district of southwest Missouri the lead concentrates are of very high grade, free of arsenic, antimony and bismuth, and contain no gold and very little silver. The general practice in both districts is to smelt the concentrates containing 70 to 85 per cent lead on Scotch hearths, to recover 70 to 85 per cent of the lead, and then smelt in a blast furnace the slag formed in the Scotch hearths to bring the total recovery of lead from lead concentrates to over 97.5 per cent. At the lead smelter of the St. Joseph Lead Co. at Herculaneum, Mo., no Scotch hearths are used. In the other smelters in the district the blast furnace plays a minor role to the Scotch hearth . The concentrates produced from the Flat River district are either table concentrates or flotation concentrates containing: Both types of concentrates are received at Herculaneum in box cars after being sampled. Great care is taken in weighing and sampling of cars of concentrates and in the determination of moisture and lead contents. The concentrates are unloaded into bins by an adaptation of scoop grain unloader. Four men unload and sweep a 40 to 45-ton box car of concentrates in 30 minutes. The same grade of concentrates is received each day and no metal-bearing fluxes are available. The problem is to get as high a recovery as possible as cheaply as possible from the high-grade lead concentrates produced by the company's concentrating mills. Sintering The bulk of the sulphur is removed from the concentrates and the fine concentrate particles are agglomerated by double roasting on typical Dwight and Lloyd sintering machines.

Jan 1, 1937

By V. Sobitsky

In open cast mining of coal, the cost per ton of output is four to five times less and labor productivity five to six times higher than in under- ground mining. This is why the coal industry of the USSR is oriented toward giving priority to the development of open cast coal mining. Deposits of coal which lend themselves to open cast mining in the USSR are enormous, with 90% of them located in the eastern part of the country. The technique is by no means limited to the eastern part, however-despite wide variations in climate, other parts of the Soviet Union also use open cast mining. The occurrence and type of coal deposits in the USSR vary greatly. Some of them are flat coal seams 2 to 40 m thick, and a few are even thicker. There are also deposits having a complex mode of occurrence, such as a series of seams of different thicknesses with angles of dip varying from slightly inclined to steep, often with dislocations. Overburden materials are quite diverse with regard to physical and mechanical properties. There are three kinds encountered-loose or unconsolidated overburden, medium-hard material, and hard rock. The stripping ratio, i.e., the amount of cover per ton of mined coal, varies from 1 to 12 cu m per ton. SYSTEMS OF MINING The great diversity of natural conditions has brought forth a variety of technologies and techniques in the open cast mining of coal. In open cast practice, the following systems of mining are used : (1) a transportation system in which the overburden is transported to spoil banks by rail or by truck; (2) a system with direct disposal of overburden, the rocks being dumped on spoil banks with a stripping excavator; and

Jan 1, 1969

By J. Jolly, R. V. Wheeler

This short note on the probable character of the organic sulfur compounds in coal can do no more than indicate lines of research. We have no new experimental work to describe, nothing comparable in value with the careful studies of American coals by Powell and Parrl and Yancey and Frazer. A study of the manner in which sulfur compounds exist in British coals (and their behavior on heat treatment) is rendered increasingly necessary by the fact that the British reserves of good coking coals of reasonably low sulfur content are fast being depleted. We believe that it is essentially by a study of the modes of formation, occurrence, and decomposition of the various types of inorganic and organic sulfur compounds in coal that it will be possible, with hope of success, to attack the problem of purifying coals, otherwise eminently suitable for coking, from these objectionable ingredients. Sulfur, so far as is at present known, does not normally occur in the free state in the coal conglomerate, but is chiefly distributed, irregularly, in three forms : 1. As primary constituents of the coal conglomerate, organic in nature and probably associated with those molecular complexes that have resulted from the degradation of the proteins of the plant tissues responsible for the formation of the coal mass. These constituents can be classed as "organic sulfur." 2. As metallic sulfides, e.g., iron pyrites. 3. As metallic sulfates, e.g., calcium sulfate and ferrous sulfate. (The occurrence of these compounds varies with the occurrence and degree of degradation of class 2.) It is usually found that sulfur compounds of class 3, the metallic sulfates, are present in coal in small proportions only, amounting to about 1 or 1.5 per cent. of the total sulfur. The compounds in classes 1 and 2 are therefore of more importance. Class 1 alone will receive considera-

Jan 1, 1925

By J. M. Morkowitr

A. Sawatzky (Atomic Energy of Canada, Ltd.)—The detailed criticism by Markowitz of my simple treatment of the thermal diffusion of hydrogen in Zircaloy-2 indicates that my paper was not as lucidly written as it could have been. I would therefore like to reiterate several of the main points of my proposed mechanism and describe in more detail some of the features only implied in the original paper. The distribution equation derived in my paper was stated to hold only for the case where the volume taken up by the hydride was small compared to the volume taken up by the solid solution phase, subsequent work, mentioned below, having shown it to be out by only a few percent up to a hydrogen concentration of about 3000 ppm. Of course, hydrogen in the two-phase region alone is not conserved in my treatment as pointed out by Markowitz. On the contrary, one of the important features of my proposed mechanism is that in the presence of a temperature gradient a two-phase region cannot exist over the whole specimen. For example, if the specimen is entirely a + 6 initially, then on application of a temperature gradient, a single phase (a) region at the hot surface develops from time t = 0 onwards. As mentioned in my original paper, the interface between the a and a+d regions moves toward the colder surface of the specimen with a discontinuity in hydrogen concen- tration developing at the interface and increasing with time. This interface moves at such a rate that hydrogen in the specimen as a whole is conserved. It must be pointed out that my distribution equation (Eq. [5] in Markowitz's paper) holds only for linear geometry. It is easy to show that for the cylindrical geometry of Markowitz the assumptions used in my treatment lead to

Jan 1, 1962

By G. W. Tuffnell, S. Floreen

Three Fe-18 pet Ni-base ternary alloys cortaining carbon, molybdenum, or cobalt were aged to pgroduce hardening by carbides, Ni3Mo, or ordering, respectively. Each alloy was tested in rotating-beam fatigue tests after hardening to 195 ksi ultim.ate tensile strength. The fatigue properties of three alloys soere essentially identical. The results suggest that tlze fatigae strength of an igron-base alloy should depend primarily upon the tensile strength, and not iipon the hardening mecaanisrn. THE fatigue strengths of many steels have been found to be directly related to their ultimate tensile strengths. For ultimate strengths below 200 ksi, the fatigue endurance limit at 107 to 10' cycles is approximately half the ultimate strength. Essen- tially all of the steels that have been tested, however, have been hardened by carbon. Thus it is not certain whether the relationship between fatigue and ultimate strengths is a general one that applies for other types of hardening in steels, or whether it applies only for the particular method of hardening by carbon. The recent developments of the martensitic precipitation-hardened stainless steels and the marag-ing steels have shown that it is possible to achieve high strengths in iron-base alloys by other hardening mechanisms than that due to carbon. Therefore, it is now possible to compare the fatigue properties of several iron alloys having the same ultimate strengths but hardened by different mechanisms. For the present study a binary Fe-18 pct Ni martensite was selected as a base material. This particular matrix composition has been found to have deformation characteristics very similar to pure iron.' Three ternary alloys were prepared by adding either 0.23 wt pct C, 5 wt pct Mo, or 20 wt pct Co to this base composition. After suitable heat

Jan 1, 1965

By Clyde E. Williams

The purpose of this report is to supply the Coal Classification Committee' with information for use in the formulation of a system of classification of coals according to their uses. Consideration is given here only to the nonferrous metallurgical operations that consume relatively large amounts of coal or coke; i. e., the smelting of copper, lead, zinc and aluminum. For all of these uses, coal of certain definite qualities is desired. Geographical location, however, often determines whether these qualities can be specified. In some instances the preferred qualities must be specified, regardless of cost. In others, quality may be sacrificed for lower cost, although the best quality consistent with cost is usually the determining factor. These considerations will be outlined in the following discussion under the various uses, which, however, will illustrate the impracticability of preparing definite specifications for coal used in the majority of the nonferrous industries. Coal and Coke in Copper Metallurgy From the standpoint of coal consumption, copper smelting and refining operations are the most important of the nonferrous metallurgical uses of coal. As nickel ores treated in the United States and Canada are associated with copper, the first step in their recovery is really a copper-smelting operation; accordingly, the following considerations under copper smelting apply equally to nickel. Copper Smelting in Reverberatory Furnaces.—For a long time, rever-beratory copper-smelting furnaces were fired with lump coal burned on grates in a fire box. Later, lump coal was displaced by pulverized coal or oil burned directly in the smelting chamber. Recently, natural gas has been used in several plants, although producer gas was used for this purpose at Great Falls as early as 1903.2 Requirements for coal used in

Jan 1, 1932

By Charles H. White

+1HARVARD UNIVERSITY, CAMBRIDGE, MASS. The equipment of a laboratory in which students are to be trained for practical work in metallurgical chemistry presents many difficulties not encountered in the fitting up of a commercial or works laboratory. At an industrial plant the chemical work required usually demands the frequent repetition of a comparatively limited number of methods. In a steel-works laboratory, for instance, by far the larger part of the work consists in making determinations of the usual impurities found in iron and steel; at a smelter the great bulk of the work is confined to the analysis of ores, slags, mattes, and fuels, which involve the frequent application of perhaps not more than a dozen different methods. In a laboratory of this character, therefore, those operations most frequently applied may each have a certain section set apart and fitted permanently with such apparatus as best facilitates the carrying out of this one operation. The work of a commercial or custom laboratory is perhaps more varied than that of a works laboratory, but the couditions are similar in these respects, that there is usually no great need for economy of space, and that a few skilled workmen are employed to carry the determinations through from beginning to end without interruption. On the other hand, the laboratory of a technical school should be planned on such a scale that a comparatively large number of students may work at the same time, and each desk should be equipped for general metallurgical analysis. In most institutions for technical education the student's program is so arranged that his day is divided among several subjects in the course of study; only a few consecutive hours being devoted to one subject, or spent in one laboratory. Therefore, those appliances should be provided that render possible the safe continuation of such processes as

Jan 1, 1905

By J. S. Kirkaldy, G. R. Purdy

THE formation of ferrite in supersaturated aus-tenite has been the subject of considerable speculation and investigation. Aaronson has recently reviewed the data pertinent to this reaction.' Since these data in all cases refer to ternary or high-order alloys it is not possible to put them to the test of simple binary diffusion formalism. It has not, therefore, been possible to make a certain statement as to the controlling mechanisms in the process. An assessment of the difficulties inherent in the conventional statistical metallographic approach suggested that a study of the problem by means of a macroscopic two-phase diffusion couple might contribute useful information. Accordingly, such a couple was synthesized, and the rate of motion of a ferrite-austenite phase boundary (the growth of an austenite layer at the expense of a ferrite layer) was determined. Wagner originally produced a diffusion solution applicable to the motion of a planar phase interface in a binary diffusion couple, assuming local equilibrium throughout the diffusion zone. This solution, which is stated free of typographical error* in Ref. where a is the position of the interface in A space (A = x/fi), C; and CL1 are the equilibrium inter-facial concentrations in phases I and 11, C: and C*1 are the initial bulk concentrations in phases I and 11, and & and are diffusion coefficients (assumed constant). If a diffusion couple consisting of homogeneous layers of ferrite and austenite in equilibrium is raised to a higher temperature, the austenite layer will grow at the expense of the ferrite. Provided that the thickness of the ferrite layer is much less than the diffusion length of carbon in ferrite, we can set , so that Wagner's solution reduces to

Jan 1, 1963

By H. C. Heard

INTRODUCTION As the world's population expands and nations struggle to better their relative position and standard of living, increased emphasis is being directed to the exploration and production of mineral resources, to the mitigation of natural hazards such as earthquakes and volcanic eruptions, and to geotechnical engineering projects such as high-level nuclear waste disposal, underground military facilities, and transportation tunnels. Several topics are common to all of these endeavors. One is the characterization of the rock mass in situ, including the definition of the initial environment (e.g., temperature, stress, etc.). A second is, depending upon the use of the underground or the desired result, the manner in which the boundary conditions or the environment are to be changed by man. Next, the physicochemical behavior of the rock mass must be measured, or inferred with uncertainty limits placed on this behavior, over the appropriate range of environmental conditions (e.g., temperature, chemistry, etc.) for the application proposed. And last, an appropriate, validated predictive model must be applied to estimate the rock mass response to the perturbation. In the period preceding about 1955, only relatively simple testing of soils and rocks was commonplace, partly because the environment (depth) to which these data were applied was not so extreme as it is at present and partly because less precise predictions of material response were acceptable. Only limited and relatively simple test data seemed to be needed to guide the engineering. At the present time and certainly in the future, as we extend our interaction with the earth's crust to greater depths and impose more extreme perturbations on it, we need a larger body of data, deter- mined under much more complex conditions, in order to make the required predictions. The present societal problem of high-level radioactive waste disposal is a case in point. We in the rock

Jan 1, 1982

By T. B. Crowe

MucH has been written upon the precipitation of metals from cyanide Solution by zinc. We often read of the many factors that influence precipitation, such as zinc surface, purity of zinc, percentage of lead, temperature of solutions, strength of solutions in cyanide or alkali, etc. -Little do, we hear, however, of the part that oxygen plays in precipitation. Caldecottl says: "As the dissolving of gold is essentially an oxidation process, so its precipitation is one of reduction." All who have studied or worked with cyanide solutions will agree that Caldecott's statement is true.' . In the cyanide work in the mills of the Portland Gold Mining Co., we have always found oxygen to be the greatest enemy to precipitation. Oxygen Antagonistic to Good Precipitation A few years ago, while making some experiments on the effect of pressure upon the dissolving rate of gold from our ores, to prove a point, I made some bottle tests under vacuum. The results were surprising, and showed that under vacuum practically no gold dissolved, which confirmed my belief that Elsner's equation was true and also led me to investigate the amount of dissolved air carried by solutions at atmospheric pressure. The experiment consisted in partly filling an acid-bottle with mill-solution and connecting it by a rubber hose to a vacuum pump. When the vacuum was suddenly applied, a cloud composed of thousands of small air bubbles rose out of the solution, showing qualitatvcily' the amount of dissolved air that was contained in the solution, and also proving that the relief of atmospheric pressure on the solution permitted this dissolved air to escape. In studying literature on the subject, we find Henry's law—"The amount of gas dissolved by a liquid is proportional to the pressure to which the gas is subjected."

Jan 1, 1919

By James R. Cudworth, Joseph C. Mead

The Birmingham district of Alabama has utilized the slag from its blast furnaces consistently since the earliest development of the slag industry. Today there are producers of slag cement who started business in 1900, and who have, under a progressive policy, expanded the number of their products to meet present demands. There are producers of slag aggregates and other crushed slag products who have been successful for periods of over thirty years. There are at the present two companies, Cheney Lime and Cement Co. and the Southern Cement Co., manufacturing puzzolan cement; two companies, Birmingham Slag Co. and Woodstock Slag Co., making slag aggregates and by-products; one company, Tennessee Coal, Iron and Railway Co., a subsidiary of the U. S. Steel Corporation, producing ground open-hearth basic slag for soil conditioning. Two companies, the Sloss Sheffield Steel and Iron Co. and the Woodstock Slag Co., make slag concrete in ready-mix plants and one company, the Superock Company, manufactures fine and coarse slag aggregates under a new granulation process. NO Portland cement is made with slag as an ingredient, because dolomite is used so extensively as a blast-furnace flux that the magnesium content of the slag is excessive. Sources of Slag In the Birmingham district there are 22 blast furnaces, of which the majority are in blast. The present production is 165,000 tons of pig iron monthly; the production in 1935 was 1,297,960 gross tons1. There arc also two blast furnaces at Gadsden and one ferroalloy electric furnaee at Anniston. From these two sources is obtained slag to approximately 1.1 tons per ton of pig iron. History of Development of the Industry The history of the local utilization of slag as an industry probably starts with the Birmingharii Slag Cement Co. This company was

Jan 1, 1938

GEORGE F. KUNZ, New York, N. Y. (written discussion*).-We have been informed that the nickeliferous ores of Sudbury could furnish more palladium than the whole of the present world supply, together with a large amount of platinum. As the quantity of ore melted in Sudbury in 1916 totaled 1,521,689 tons, giving 80,010 tons of matte, and as the average of 3 years, up to 1915, are stated to show an average of 0.10 oz. of platinum and 0.15 oz. of palladium per ton of matte, this would indicate the presence of 12,000 oz. of palladium and 8000 oz. of platinum in the ore mined in 1916.1 Interest in the platinum situation is now more intense than it has ever been, and the great importance of this metal for many special uses is being increasingly appreciated. For munition manufacture, for chemical apparatus, in dentistry, and for jewelry, it has been and continues to be in great demand in spite of the phenomenal rise in its value. It is true that this has necessarily led to a search for substitutes, especially for dentistry and chemical uses, but while some of these have been found to answer the needs fairly well, for many 'other purposes platinum is still employed in spite of its great cost. As to the jewelry industry, the most public-spirited efforts have been made to restrict its use, and its employment in the manufacture of watchcases, purses, bracelets, and catches has been abandoned, gold being used in its place. The prime cause of the present shortage is, of course, the elimination of 'the Russian supply which, in normal times, constituted probably more than 90 per cent. of the world's production. This makes an intensive

Jan 4, 1918

By W. M. Weigel

THE rapid advance, during recent years, in the manufacture of articles that have been in common use for generations and the development of new materials entering into appliances and devices unheard of fifty years ago, have created a demand for some of the more common non-metallic minerals. To supply this demand there has quietly developed a branch of the mining industry of which little is known by most mining engineers the mineral-filler industry. In this paper, and generally in the trade, the term mineral filler is applied to a mineral used, in its natural state after mechanical preparation only (such as. grinding, milling and washing), without undergoing any chemical change and without exerting any chemical action on the substance with which it is incorporated. The consumption of mineral fillers is confined chiefly to large manufacturing centers in the eastern and northern states. Where available, materials originating near the place of consumption are used, as most fillers bring a comparatively low price and, frequently, the freight may equal the cost of the finished filler at the mine. The southern states have abundant deposits of non-metallic minerals suitable for fillers, which supply the manufacturing industries in adjacent states. Many of these deposits are equal to, or superior, in quality to those mined in the north, but they can not compete with them because of the freight rates. The mineral-filler industry has felt the present depression, but it has suffered less than most mining industries for as a rule the mills are simple, the overhead expenses are low, and the labor is entirely local and can revert to farm work when the plant closes down. Many other deposits in the southern district will undoubtedly be developed when business. revives and freight rates are adjusted.

Jan 2, 1922

By Joseph C. Mead, James R. Cudworth

The Birmingham district of Alabama has utilized the slag from its blast furnaces consistently since the earliest development of the slag industry. Today there are producers of slag cement who started business in 1900, and who have, under a progressive policy, expanded the number of their products to meet present demands. There are producers of slag aggregates and other crushed slag products who have been successful for periods of over thirty years. There are at the present two companies, Cheney Lime and Cement Co. and the Southern Cement Co., manufacturing puzzolan cement; two companies, Birmingham Slag Co. and Woodstock Slag Co., making slag aggregates and by-products; one company, Tennessee Coal, Iron and Railway Co., a subsidiary of the U. S. Steel Corporation, producing ground open-hearth basic slag for soil conditioning. Two companies, the Sloss Sheffield Steel and Iron Co. and the Woodstock Slag Co., make slag concrete in ready-mix plants and one company, the Superock Company, manufactures fine and coarse slag aggregates under a new granulation process. NO Portland cement is made with slag as an ingredient, because dolomite is used so extensively as a blast-furnace flux that the magnesium content of the slag is excessive. Sources of Slag In the Birmingham district there are 22 blast furnaces, of which the majority are in blast. The present production is 165,000 tons of pig iron monthly; the production in 1935 was 1,297,960 gross tons1. There arc also two blast furnaces at Gadsden and one ferroalloy electric furnaee at Anniston. From these two sources is obtained slag to approximately 1.1 tons per ton of pig iron. History of Development of the Industry The history of the local utilization of slag as an industry probably starts with the Birmingharii Slag Cement Co. This company was

Jan 1, 1938

By GEORGE D. RAMSAY

ABOUT three miles west of Fontana San Bernardino County, California, and fifty miles east of Los Angeles, the Kaiser Co., Inc., has built an integrated steel plant. By integrated, I mean that from its wholly owned iron ore and coal supply, the Kaiser Co. is producing in its own mills iron and steel products. Pig iron to meet the West Coast needs has been produced at Fontana since Jan. 1, 1943; steel ingots were first poured there May 14, 1943; and steel plate for ships was first rolled Aug. 15, just sixteen months after ground was broken. Briefly, the plant consists of: (I) Two batteries of by-product coke ovens, totalling ninety ovens, carbonizing about 1740 tons of coal per day at capacity; with by-product facilities for the production of tar, ammonia, and ammonium suIphate, light oil distillates, and tar distillates. (2) One blast furnace producing at

Jan 1, 1944

By Raymond L. Orr

Calorimetric measurements have been made of the heats of solution of gold axd indium in a number of liquid tin-rich alloys at a temperature of 705°K. Relative partial molar enthalpies of gold were determined as a function of dilute solute concentrations in the binary Au-Sn system and in the ternary Ag-Au-Sn and Au-In-Sn systems. Relative partial molar enthalpies of indium were determined for dilute solute concentrations in the In-Sn, Ag-In-Sn, and Au-In-Sn systems. Through application of the interaction coefficient concept introduced by Wagner and more recently extended by Lupis and Elliott, ualues have been obtained for the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. The results are inte@reted in terms of solute atom distributions through comparisons with the predictions of dilute solution models. INTEREST in the thermodynamic behavior of dilute liquid alloys stems from two primary sources. From a practical viewpoint, it is often of importance to know or to be able to predict the effect that one solute will have on the thermodynamic properties of the other solutes in a multicomponent system. Studies of dilute solutions may also be rewarding from the theoretical point of view. Some of the difficulties arising from the more complex interactions possible in concentrated solutions are avoided, leading to easier interpretations in terms of solutibn models and bonding energies. For example, in a binary alloy the limiting values of the partial molar properties of the solute represent the case for which each solute atom is completely surrounded by atoms of the solvent, and no other interactions are possible. Solute - solute interactions in dilute solutions are conveniently treated by the interaction coefficient concept of ~agner.' Using a Taylor series expansion for the logarithm of the activity coefficient, In yi, of a component, i, in a solution consisting of dilute solutes with atomic fractions xi, xj, xk, and so forth, in a solvent, s, and neglecting the second- and higher-order terms, Wagner obtained the expression: Where Wheyz is the limiting value of yi in the pure solvent, s. The interaction coefficients, e:, e:, and so forth, are defined by: Since yi is related to the excess partial molar Gibbs energy of component i by GfS = RT In yi, E: is re- ferred to as the "Gibbs energy interaction coefficient". Lupis and Elliott~ extended Wagner's treatment to the relative partial molar enthalpy, aHi, and the excess partial molar entropy, qS. They defined the enthalpy interaction coefficient as: and the excess entropy interaction coefficient as: leading to expressions similar to Eq. [I]: The three interaction coefficients are related by? The self-interaction coefficients, E:,qf,and at, represent the effects of interactions between atoms of component i in solvent s; €3, q{, and 03 represent the effects of interactions between i and j atoms in solvent s; and so forth. From the Maxwell-type relationships between partial molar quantities, it may be shown1'2 that e{ = ej, r}\ =tj), and ai - crj. Experimental determination of the interaction coefficients requires extremely precise measurements of the appropriate properties as functions of solute concentrations in very dilute regions. Few such data exist for intermetallic alloys, even for binary systems, because of experimental difficulties. This is especially true with respect to enthalpy data for dilute alloys. Examination of the compilation of data for binary alloys by Hultgren, Orr, Anderson, and ~elle~~ reveals that determination of limiting values of &fii(Xi =0) often requires extrapolations to infinite dilution from xi = 0.05 to 0.10. Direct measurements of the enthalpy interaction coefficient, qi, for multicomponent systems are virtually nonexistent. This quantity is of course subject to direct calorimetric measurement, but its determination must be limited to cases where high experimental precision is possible. The heats of solution of gold and indium in liquid tin can be measured with relatively high precision, which makes determinations of 73 involving these metals as the measured solutes experimentally attractive. This paper presents the results of such determinations of the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. MODELS FOR DILUTE-SOLUTION BEHAVIOR Random-Solution Behavior. In the quasi-chemical treatment of solutions, only nearest-neighbor bonds are considered, and a composition independent value

Jan 1, 1967

By N. A. D. Parlee

The diffusion rate of hydrogen in liquid iron has been measured by a gas-liquid metal diffusion cell technique. The diffusion cell was formed by immersing an alumina tube containing hydrogen gas at 1 atm in a bath of stagnant liquid iron. The change in the composition of the melt in the cell was determined by measuring the rate of absorption of the gas in the cell. The appropriate solution to Fick's second law was used to examine the data and calculate diffusivi-ties. The absorption of hydrogen in stagnant pure liquid iron has been found to be diffusion-controlled. The results show that the chemical diffusion coefficient, D, of hydrogen in pure iron in the range of 1547" to 1726°C can be represented by the following Arrhenius relation: D(sq cnz per sec) = 3.2 x X exp(- 3300 i 1800/RT) where the uncertainty in the activation energy corresponds to the YO pct confidence level. Oxygen in the melt (above 0.015 pct 2) increased the apparent rate of absorption of hydrogen. The importance of diffusion data on liquid metals for predicting the rates of certain metallurgical processes has been recognized for a long time. Moreover, these data are much needed to test and develop theory for diffusion in liquid metals. Despite this practical and theoretical interest, however, relatively little reliable information about diffusion in liquid metals is available in the literature. This is particularly true for gas components such as hydrogen, oxygen, and nitrogen in liquid metals, where almost no data on chemical diffusion coefficients are to be found. This is probably due to a multitude of experimental difficulties particularly associated with high-temperature melts. In an effort to fill this gap in information, a research program was undertaken to study the diffusivities and rates of solution of gases in liquid metals. This paper presents the results of a study of the diffusion of hydrogen in liquid iron. EXPERIMENTAL METHOD Two methods for the study of the kinetics of dissolution of gases in liquid metals are being employed in this laboratory. Both involve the measurement of the volume of gas absorbed by the melt as a function of time and as such both avoid the uncertainties involved in chemical analyses of quenched samples for relatively small amounts of gas. In the first method, the gas dissolves in an inductively stirred melt and, in the absence of a slow surface reaction, the results are often interpreted in terms of mass transport across a liquid "boundary layer" between the homogeneous gas phase and well-stirred part of the melt. Other interpretations of the results of such experiments have also been described in the literature.1'5 In the second method a gas-liquid metal diffusion cell is used.' The gas dissolves in a cylindrical column of stagnant liquid metal and, in the absence of a slow surface reaction, the results are interpreted in terms of a non-steady-state diffusion solution to Fick's second law. The weakness of the first method is that while it gives information on the mechanism of absorption by stirred melts it yields an overall rate constant which even in the simplest cases depends on the nature and the thickness of the "mass transport layer" or "boundary layer". It yields no values of diffusion coefficients. The second method was used in this research because in many cases it is possible to determine the diffusion coefficient of the gas component in the liquid metal. In this research it has been utilized to measure diffusion coefficients of hydrogen in liquid iron. The apparatus used was essentially the same as that described by Mizikar, Grace, and par lee but certain modifications have been introduced to meet the elevated temperatures and special conditions of this research. Fig. 1 is a schematic drawing of the apparatus and Table I gives the identification of various parts in this figure. The diffusion cell, shown in detail in Fig. 2, was formed by immersing an impervious alumina tube (hereafter called absorption tube) in a bath of pure liquid iron contained in an alumina crucible. Two types of tubes were used, Morganite triangle RR and McDanel AP35. The crucible was contained in a vertical impervious alumina combustion tube (32 mm ID by 914 mm long) which was closed at both ends by water-cooled brass heads employing O-ring compression seals, Fig. 1. A protection tube enclosing a Pt, 5 pct Rh-Pt, 20 pct Rh thermocouple was introduced through the lower end of the combustion tube

Jan 1, 1968

By G. S. Cole

The temperature has been measured ahead of stationary solid-liquid interfaces under conditions approximating luzidirectional heat flow and therefore unidirectional solidification. Natural convection flow patterns may be deduced from the temperature distributions , temperature fluctuations, and shape of the interface. Fluid flow increases with the height and the rate of heat transfev through the interface and this is further manifested by a deviation of the interface from aflat vertical plane. The influence of fluid flow on solute inhomogeneity during alloy crystal growth can be inferred from the observed temperature distributions. A buoyancy force exists in the liquid ahead of a vertical solid-liquid interface, caused by a difference in density between cold fluid near the interface and warmer fluid in the bulk liquid. When the viscous and inertia forces in the melt exceed this buoyancy force, a flow of fluid takes place, termed natural or free thermal convection. Natural convection in purely liquid systems has been extensively studied for many years. 1"u On the other hand, fluid flow during horizontal crystal growth has oniy recently been the subject of experimental investigation."-25 The requirements for horizontal crystal growth differ from other heat flow systems. The small aspect ratio (ratio of height of cold wall to length of fluid) has never been considered. The uniform furnace gradient which supplies heat radially (and not necessarily symmetrically) differs from previous boundary conditions of uniform heat flux at the cold and hot ends. And most important of all an isothermal s/l interface is present which can adjust its shape and position to conform to heat and fluid flow. All of these boundary conditions involve complexities which cannot be readily solved analytically. Preliminary observation has demonstrated the penera1 shape of the natural convective flow pattern in transparent media.20'24'25 The flow is circulatory, directed toward the interface at the surface of the liquid, down and away from the interface at the bottom, and then up at the hot end of the melt. During crystal growth such a flow may interact with the solute boundary layer at the s/l interface to affect solute incorporation.M'1B|28'i!T Evidence has also been presented recently to show that thermal convective flow will affect the structure of ca~tin~s.~~-~~ The rate of heat transfer (conduction plus convection) in a given fluid system is a function of the temperature difference between the hot end of the liquid and the s/l interface and the height of the interface. At the lowest values of these variables* all heat is *It has been shown' that adverse temperature gradients as low as O.OOS°C oer cm are sufficient to cause convection. transferred by conduction. When the temperature difference or interface height are increased, laminar fluid flow commences and heat transport takes place by laminar convection as well as by conduction; turbulent heat transfer takes place at higher values of these variables. In the transition region between laminar and turbulent flow, boundary layer separation takes place; fluctuations in temperature are also noted and increase in amplitude and frequency as turbulence becomes dominant. In this paper, fluid flow patterns in the melt ahead of a stationary interface are deduced from observations of temperature distribution and fluctuations, heat flow rate, and interface shape. The fluid flow ahead of advancing interfaces and the effect of such flow on solute incorporation may be inferred from these measurements on stationary interfaces. Observations during enforced fluid motion will also be considered. EXPERIMENTAL PROCEDURE The metal was contained in a lava boat 10 cm in length, 1+ cm in width, and 2 cm in height, as shown in Fig. 1. A water-cooled, molybdenum block heat-sink is at one end of the boat; surrounding this assembly is a slotted stainless-steel tube noninductively wound with a nichrome heating element. Temperature was measured by 38-gage Chrome1 vs Alumel thermocouples sheathed in 0.05-cm-diam graphite-coated stainless-steel tubing, which were moved longitudinally and vertically through the melt by means of a two-dimensional motorized micrometer stage. In some experiments the thermocouple junction was exposed, but in the majority of experiments the junction was welded to the sheath tip; no significant difference

Jan 1, 1968