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By John A. Church

The Lake Superior blast-furnaces probably represent the maximum economy of fuel possible in this country. They smelt an ore which is very rich and easily reducible, and as the small amount of gangue present is not all silica, but in part a silicate, the amount of limestone required is a minimum. The average yield of the ore treated at six furnaces was 63 per cent., and the average quantity of limestone 179 pounds per ton of pig. The fuel used is charcoal, so burned as to retain most of the combustible volatile part, which, before the utilization of furnace-gas, was burned away. With these conditions it is not surprising that the Lake Superior charcoal practice is extraordinary in almost every respect. In any scientific discussion of American furnace work, the establishments there will be found at the head of the list, and they work under conditions which are extremely favorable for careful study. The Bay Furnace, near Marquette, has the honor of carrying "the broom" for the largest daily make. With a capacity of 1908 cubic feet it has, for months together, produced 29 tons of pig, graded at

By Garland R. Dever, Preston McGrain, George W. Ellsworth

Limestone resources for industrial, constructional, and agricultural uses occur on the surface and at minable depths in several areas along the Ohio River and its navigable tributaries in Kentucky. High calcium and high carbonate limestones suitable for use in cement and lime production, steel manufacture, environmental control measures, and other special uses are present in the High Bridge Group (Ordovician) and Warsaw and Ste. Genevieve Limestones (Mississippian). Deposits with thicknesses of 7.3 to 20.7 m,(24 to 68 feet) have been documented by the analysis of samples taken at 0.3-m (1ft) intervals. Active and potential mine and quarry sites afford access to water transporation and proximity to a number of industrial and metropolitan centers. Geologic factors affecting the distribution of deposits include the Cincinnati arch, regional dip into the Appalachian and Eastern Interior basins, complex faulting in and near the western Kentucky fluorspar mining district, and late Paleozoic erosional unconformities in northeastern Kentucky.

Jan 1, 1979

Professor Somasundaran has given an excellent presentation of the numerous problems which remain to be solved before the selective aggregation of fine particulates is likely to see broad commercial application in the beneficiation of mineral fines. However it is useful, I think, to reiterate some of the major problem areas. The over-riding factor which has limited the development of selective aggregation techniques is that processes such as coagulation and flocculation tend to be inherently non-selective. Conditions which favor the aggregation of one kind of fine particles usually favor the aggregation of all kinds of particles. As Professor Somasundaran has pointed out, the state of aggregation of a fine-particle dispersion is primarily determined by the forces of interaction between the individual particles. In most systems, the dominant forces are: 1. van der Waals - London Dispersion forces between the particles themselves 2. electrical double layer forces 3. steric forces between adsorbed layers on the surfaces of the particles. The London Dispersion forces between like particles are always attractive, but for dissimilar particles dispersed in a fluid medium can, in some cases, lead to a net repulsion. Electrical double layer forces always lead to repulsion between like particles but can, again, cause either attraction or repulsion for dissimilar materials. The steric forces, which are by far the least understood of the three types, can also lead to attraction or repulsion depending on condi-

Jan 1, 1979

The following letter has been received from the Chairman of the United States Shipping Board. August 1, 1918. American Institute of Mining Engineers, New York, N. Y. GENTLEMEN: I am going to call upon your organization for some teamwork. The time has come for Americans everywhere to put themselves solidly behind American ships. Our railroads must no longer stop at the ocean. We are building an American merchant fleet of twenty-five million tons-three thousand ships. We are backing modern ships with modern port facilities, establishing our bunkering stations all over the globe and will operate with American railroad efficiency. We will carry American cargoes at rates corresponding to our railroad rates-the cheapest in the world. Fast American passenger-and-cargo liners will run regularly to every port in Latin America, the Orient, Africa, Australia. Are you taking steps to use these ships to increase your own prosperity? Do you realize that American products of factory, farm and mine can be delivered to customers in foreign countries on terms which will build lasting trade? Do you realize the possibilities for bringing hack raw materials to extend your products and trade? We must all take off our coats and work to bring these American ships home to the people of every American interest and community. The manufacturer must think of customers in Latin America as being as accessible as those in the next state. The farmer must visualize ships carrying his wheat, cotton, breeding animals, dairy products and fruit to new world markets. The American boy must think of ships and foreign countries when he chooses a calling.

Jan 9, 1918

By Francis B. Foley

THE casting of steel in large molds brings into play all of the undesirable effects that result inevitably from slow cooling. The origin of the molten metal, whether basic or acid open hearth or electric furnace, has little if anything to do with the phenomena involved. If the quantity of molten metal to be cast in a single mold is large enough, there is very little one can do about it-the metal will cool so slowly that 'nothing one can do, other than to provide as good feeding as practicable from an adequate reservoir of metal in the sink head, will be of any avail. Recently we have had occasion to cast a 108-in. octagon ingot weighing 545,700 lb, necessitating the combining of metal from three 100-ton open-hearth heats. This is one of the largest ingots ever made. The body of the ingot weighed 448,800 lb, which includes a bottom pool of about 7500 lb of metal, and the sink-head weight was 96,900 lb, or about 18 pct of the total weight.

Jan 1, 1947

By W. N. Logan

THE petroleum industry in Indiana made no extraordinary progress during the year 1924. The surplus stock of crude, brought about by the production of 732,407,000 bbl. in the United States in 1923, as against a production of 557,531,000 bbl. in 1922, had its effect on prices though there were slight advances. These advances were more than offset by the continued high prices of labor and materials. TRENTON OIL DEVELOPMENT The principal development of the year occurred in the Hotmire pool of the Ridgeville district in northeastern Indiana. This pool lies partly in the southern part of Jay County and partly in the northern part of Randolph County. The oil is obtained from the upper horizon of the Trenton. During the past year, about 30 wells were drilled, 21 of which were productive. An attempt to extend the Hotmire pool to the northeast resulted in the discovery of a gas-producing area near the center of Pike township in Jay County; 10 wells have been drilled 4 of which produced oil. The Harvey Orr No. 1 produced 900,000 cu. ft. of gas per day.

Jan 3, 1925

By D. A. Kinneberg, J. W. Donaldson, N. J. Themelis

In the Kennecott Converter Smelting process (KCS), copper concentrate pellets are smelted and converted to high-grade matte in a modified Peirce-Smith converter using oxygen-enriched air and fuel. A high-grade matte bath is produced and maintained in the converter. Periodically, the slag layer is skimmed, slowly cooled, and its copper content is recovered by milling. Ladles of matte are transferred and finished to blister copper in another converter. The gases from the Kennecott Converter contain the SO2 products of the smelting and converting processes and can be treated in an acid plant, eliminating the problem of low-concentration gases associated with the operation of the reverberatory furnace. Pilot tests at Utah Copper Division were followed by a full-scale prototype converter test at the Chino Mines Division of Kennecott Copper Corporation. The concepts of the process and the results of this campaign are presented.

Jan 1, 1976

By Wen H. Su

Multiple seam mining and its associated problems are very serious in Southern West Virginia where poor planning or lack of knowledge in seam interaction often results in complete loss of coal properties. Several measures have been proposed to alleviate the interaction problems under various multiple seam conditions, but few of them are specific in terms of mining plan. Two parallel approaches are adopted for this paper. One is field investigation which consists mainly of mine site visits and gathering of data. The other is the two-dimensional finite element simulation of mine workings using the data gathered as input. Two typical cases which represent the past and present multiple seam mining practice in West Virginia were investigated. Much attention is focused on the interaction problems experienced and the important parameters controlling interaction. Several key parameters controlling interaction in multiple seam mining were analyzed. Proper mining plans, by which the interaction problems can be minimized, are proposed for the individual cases after a better understanding of the interaction mechanism was realized through finite element analyses.

Jan 1, 1984

By Eli Sani

Investment in the mineral industries-particularly in the mining industry-differs from investment in nonminera1 industries in that the latter have an indeterminate life, assumed to be perpetual, and are not called upon to replace the firm's original investment. In mining ventures, on the other hand, once the ore bodies are depleted the mine has no economic value; the original capital investment must be returned to the investor by the time the ore is exhausted. A mining venture is also characterized by the significant cost and time associated with the exploration phase. A myriad of samples must be taken, geological features investigated, and ore grade assured. In addition, most mining ventures require substantial capital expenditures aggregating several hundred million dollars for a number of years before the project begins producing any revenue. Any theoretical model employed in evaluating a mining venture, as well as similar mineral ventures, must take all these factors into consideration.

Jan 5, 1977

By B. L. Thane

Within the past few years, the mining industry has taken a new impetus in all its branches. New mines are being opened every day, while old ones, which have been either working at a loss, or have been compelled to shut down, are now gradually being reopened and placed on a paying basis. This growth and new life is due, in a measure, to the discovery of new mining districts, but the most important cause of the progress is the wonderful advance that has been made in all branches of mine-engineering. By means of the important inventions and discoveries that have been made in mechanics, chemistry, and electricity, we are now able to work ores which, only a short time ago, would have been regarded as worthless. We find, for instance, the electrician eliminating two of our greatest difficulties, those of distance and superior elevation, while the mechanic has brought to the highest degree of perfection, not only ore-crushing and hoisting machinery, but all such devices as pertain to the mechanical handling of ores, and, at the same time, the metallurgist, with his combined chemical and mechanical skill, has helped us to extract the precious metals from the most refractory of ores. But when we turn to examine methods in actual use for

Jan 1, 1900

By Richard D. Snouffer

Prime topics of conversation these days are the new concepts of rail haulage for bulk items such as iron ore, potash and coal. We have heard such ideas as the "integral train" and the "unit train" discussed frequently during the past two years at various AIME meetings, and progress reports have kept up a steady appearance in the technical press and in local newspapers. While no railroad has a complete "unit train" in service at this moment, one has 50 fast-discharge cars under construction and the Pennsylvania Railroad has experimented with radio-controlled motive power distributed at intervals throughout the train. To a great extent, however, the promise for greater efficiency and lower costs held out to industry by these new haulage methods is dependent not on greater speed or larger cars or more dedicated equipment alone but, rather, on the utilization of modern practices in the loading and unloading of rail cars. It is the purpose here to examine these two key steps and the up-to-date procedures and equipment they entail.

Jan 7, 1963

By K. V. S. Sastry

This paper summarizes recent research on the kinetic aspects and process behavior of agglomeration in balling circuits. The physical concepts underlying agglomeration, the mechanisms responsible for size changes during agglomeration, and a generalized population balance model for agglomeration systems are summarized. Experimental techniques for investigating the batch balling behavior and for simulating the balling- circuit operations are reviewed. Further, the effect of such operating variables as feed moisture, bentonite content, and the rate of feed addition are discussed. An approach to the computer simulation of the agglomerating circuits is shown and the importance of such models in process engineering is discussed.

Jan 1, 1977

By Bennett Bates

NOWHERE in the world has cone classification in closed-circuit grinding with tube mills reached as high a state of development as on the Witwatersrand. In the development of the Far East section the necessity of fine grinding to obtain. satisfactory residues gave rise to a situation with which the cone could cope only at a great sacrifice in efficiency of tube-mill grinding. H., A. White1 recognized the limitation of the cone in his study of the theory of tube milling as early as 1915, but it was not until Ewing, Davis and. Willey2 carried out their tests at Springs Mines during 1920 that the advantages of mechanical classifiers' were demonstrated. During the fall of 1924 the writer supervised a series of tests with Dorr classifiers undertaken by Mr. White, Consulting Metallurgist, at the mill of the Geduld Proprietary Mines, Ltd., Dersley, Transvaal (Far East Rand). The importance of classification to obtain efficient tube-mill grinding was thoroughly demonstrated. The installation of classifiers of the above type that followed the test, confirmed the results of the experimental work.

Jan 2, 1926

By Benjamin B. Lawrence

Arthur Launcelot Collins was born at Truro in Cornmall, England, July 8, 1868. His father, J. H. Collins, is well kuown as an engineer, and his books have been widely read in this country: Arthur was the third son. Three of his brothers are engaged, as is his father, in the profession of mining engineering. His education, gained partly at St. Austell, partly at Falmouth, and partly at Nuttall's Collegiate School in Truro, England, was supervised by his father, who was then Lecturer on the Mining Sciences to the Miners' Association of Cornwall and Devon. In 1881, J. H. Collins went to Rio Tinto, in Spain, as chief chemist and metallurgist, and it was there that Arthur began his practical work in the laboratory and continued his studies in chenlistry and mineralogy. To the latter science he was deeply attached; and he never lost an opportunity of adding to his cabinet of minerals, of which he was an ardent collector. In 1883, he became assayer and general assistant to Mr. Nicol, Manager of the Peña del Hierro copper-mines, ncar Rio Tinto. Until 1885 he was associated with his father in the study of the geology of the Rio Tinto belt. In 1885 he retuined

Jan 1, 1904

By I. Stapf

Systematic investigations on silver-rare earth metal systems have been extended on the Ag-Ce system in order to clarify the discrepancies reported in literature. The phase diagram has been reinvestigated on the base of thermal analyses and of microstructure examination on cast and annealed specimen. All intermetallic phases Ag4Ce, Ag3Ce, Ag2Ce and AgCe show no extended range of homogeneity, they melt congruently fm), or decompose peritectically (d) at 815 °C (d), 1030 °C (m), 855 °C (d) and 855 °C (m), respectively. The system shows eutectics at 793 °C/10 at.%, 780 °C/42 at.%, and about 505 °C/81 at.% Ce. d-Ce dissolves up to 2 at .% Ag and decomposes metatectically at 710 °C. Furthermore, the phase transformation of the intermetallics would be clarified. The phases Ag5Ce and Ag51Ce14 reported in literature could not be verified.

Jan 1, 1984

By S. T. Wlodek

The surface and subscale oxidation reactions were followed by means of continuous weight-gain and metallographic techniques over the range 1600" to 2200°F (871° to 1204 °C) for up to 400 hr. Full identification of all scale and subscale reaction products was obtained by electron and X-ray diffraction. At or below 1800°F (982°C) a linear rate of reaction (QL = 46.0 kcal per mole) governed the oxidation process, extending for up to 100 hr at 1600°F (871 "C). During linear oxidation the surface scale consisted of an amorphous SiO2 film overgrown with Cr 2O 3 and NiCr204. This initial linear process was followed, and above 1800°F completely replaced, by two successive parabolic rate laws (Qp = 60 and 57 kcal per mole). This parabolic reaction involved the formation of a complex scale consisting of Cr2 O3 and smaller amounts of NiCr2O4. Parabolic oxidation appeared to coincide with the disruplion of the silica film present during linear oxidation and was followed by subscale (internal) oxidation of crystobalite and NiCr2O4. The balance between the subscale and surface oxidation reactions controls the oxidation of this commercial alloy. The amorphous silica film appears to result in the linear rate and diffusion through Cr2O3 is the more likely rate-limiting step during parabolic oxidation. THE oxidation of a multicomponent composition is a complex phenomenon not presently amenable to a rigorous classical interpretation. Nevertheless, even a qualitative understanding of the scaling and subscale reactions that occur in a commercial composition can illuminate the reactions that limit its high-temperature stability in an oxidizing environment. This study of the oxidation of Hastelloy Alloy X presents the first of a series of studies with the above approach in mind. Hastelloy X exhibits one of the best combinations of strength and oxidation resistance available in a wrought, solution-strengthened, nickel-base alloy. Although during long time exposure some precipitation of M6C and M23C8 carbides as well as a complex Laves phase occurs, the amounts are probably small enough to have no appreciable effect on the chemistry of the matrix. Radavich has identified the oxidation products on Hastelloy X oxidized for 5 min to 10 hr at 1115°F as NiO and the NiCr2O4 spinel. Oxidation for 5 to 15 min at 1500°F produced a scale of spinel, NiO, and a rhombohedra1 phase, probably Cr2Os. Sannier et 2. have reported continuous weight-gain data for Hastelloy X at 1650" and 2010°F and internal-oxidation measurements after 150 hr at 2010°F. In addition, much of the data on binary Ni-Cr alloys recently reviewed by Kubaschewski and okins' and Ignatov and Shamgunova4 as well as studies of binary Ni-Mo alloys5 are also pertinent to the oxidation of this composition. EXPERIMENTAL Continuous weight-gain measurements and metallographic measurements of subscale reactions were the main experimental techniques used in this study. X-ray and electron diffraction backed up by a limited amount of electron-microprobe analysis served to characterize the nature of the scale- and subscale-reaction products. Two heats of commercial sheet of the composition given in Table I and identified as A and B were used in the bulk of this study. Internal-oxidation measurements were made on a third heat of material in the form of a 0.5-in.-diam bar. In order to assure homogeneity, all heats were reannealed 4 hr at 2175°F prior to sample preparation. weight-Gain Measurement. All specimens (1.5 by 0.4 by 0.03 in.) were abraded through 600 paper, electropolished, and lightly etched in an alcohol-10 pct HCl solution. An electrolyte of 150 cu cm H,O, 500 cu cm HsPO4 (85 pct conc), and 3 g CrO3 at a current density of 0.9 amp per sq cm or a solution of 10 pct HaW4 in alcohol used at 4 v and 0.3 amp per sq cm was used for electropolishing. The resultant surface exhibited a finish of 3 ± 1 p rms. Continuous weight-gain tests were made at 1600°, 1700°, 1800°, 1900°, 2000", and 2200°F on auer' type balances capable of recording a total weight change of 110 mg with an accuracy of k0.1 mg. All tests were made in air dried to a dew point of -70°F and metered into the 2-in.-diam reaction

Jan 1, 1964

By E. Martinez

Samples of chrysocolla, a hydrated copper silicate, from several sources were submitted to differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). Pure samples of chrysocolla are difficult to obtain, but comparison of the thermograms revealed that certain reactions occurred in all the samples and it is believed that these are due to chrysocolla. Endothermic reactions occurred at 50' to 175°C, 350° to 650°C, and 980° to 1100°C each of which caused a weight loss. The first was due to loss of absorbed water, the second to a dehydroxyla-tion, and the last to conversion of cupric oxide to cuprous oxide. In addition, two exotherms were detected at 685° to 695°C and 935° to 950°C. Infrared spectra of heated samples indicated the exotherms were due to changes in the Si-O bonds leading to the formation of cristobalite. The results suggest that thermoanalysis may be a more sensitive and reliable method for detection and identification of chrysocolla than X-ray diffraction, infrared spectroscopy, or optical techniques. The recovery of copper from oxide ores has been the subject of much research in recent years. One of the principal oxide copper minerals is chrysocolla, a hydrated copper silicate. The information available indicates that it has widely varying properties depending on the origin of the sample. Chrysocolla usually is found associated with cuprite, malachite, azurite, and native copper. Most of these other minerals are recoverable by present day flotation practice, but chrysocolla is lost in the tailings.1,2 Reagent combinations that are successful in laboratory chrysocolla flotation with ore from one source have been found to be ineffective with another. 3 The copper segregation process offers an altemative to beneficiation of oxide copper ores.4'5 The process is of particular interest in processing ores that cannot be treated by conventional hydrometal-lurgical methods because of high acid consumption.6 Fuller understanding of the properties of chryso- colla may prove of value in the search for improvements in both the flotation and segregation processes. Chrysocolla samples from Arizona, Nevada, Chile, Australia, and South Africa were studied by differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). In addition, a sample from Miami, Ariz., was submitted to X-ray diffraction, infrared spectrophotometry, and surface area determination. EQUlPMENT Differential thermal analysis (DTA) detects, amplifies, and records exothermic-endothermic reactions occurring in a sample as its temperature is raised at a constant rate, usually 10°C per minute. A unit made by the Robert L. Stone Co. was used in this study. The tests can be run if desired with a gas streaming through the sample. A thermobalance records weight losses or gains in a sample as its temperature is raised at a uniform rate. The gravimetric analyses (TGA) were run on a Chevenard thermobalance converted electronically for graphic recording. A heating rate of 5°C per minute up to 1100°C was used in these tests. A Perkin Elmer Infrared Spectrophotometer, Model 221, was used with sodium chloride optics obtaining IR spectra in the 2 to 15 region. A pressed pellet technique with potassium bromide was used in preparing the samples. DESCRIPTION OF SAMPLES Chrysocolla is found in the oxidation zones of copper deposits commonly associated with malachite, azurite, and limonite. It is described as varying in composition and in color from bluish green to brown or black. Inclusions of other minerals are usual so chemical analysis of chrysocolla samples may be suspect. However, it is considered by many to be a solid solution of CuO, SiO2 and H2O with a general formula of CuO.SiO2.2H2O or 2CuO.2SiO2. 3H20. Chukhrov7 has described a sample from the Urals as CU3,5(OH)2 (A1Si3) O10.nH2O and stated that chrysocolla is a montmorillonite-type mineral. On the basis of X-ray analyses, DTA, and infrared spectra of chrysocolla from the Inspiration Mine, Ariz., Sun8 concluded that there was no substantial evidence to classify it as a montmorillonite mineral. Chrysocolla samples from many sources throughout the world were used in this investigation. The following is a brief description of each:

Jan 1, 1963

By D. Y. F. Lai, R. J. Borg

Tracer diffusion of Fe59 has been measured in the a-stabilized Fe-1.8 at. pet V alloy from 700° to 1500°C. The activation energies are obtained in both the presence and absence of magnetic order. Furthermore, it is established that diffusion in the alloy is identical to that in pure iron and consequently the values of Do and Q accurately represent the temperature dependence for self-diffusion. The purpose of this investigation is to obtain an accurate estimate of the temperature dependence for self-diffusion in bee iron in both the presence and absence of magnetic order, and, in so doing, to establish the temperature range of the magnetic effect.&apos;" As the temperature interval suitable for diffusion measurements is severely limited in both bee phases of pure iron because of the intervening fee ? phase, the experiments were performed on an a-stabilized alloy containing 1.8 at. pet V. This alloy is bee over the entire range from room temperature to the melting point. Although there have been several independent investigations of self-diffusion of iron in a, iron,1, 3-6 there still exists considerable disagreement regarding the values of Do and Q for the paramagnetic region. The two systematic studies of diffusion in 6 iron6, 7 previously reported are also only in fair agreement; but in view of the extremely small temperature range available for diffusion studies, i.e., 1390o to 1535oC, this is not surprising. It is comparatively easy to obtain accurate values of Do and Q for the a-stabilized alloy inasmuch as measurements can be made over the entire temperature range -700o to 1500°C. However, in order to assume that these same values apply to pure iron requires careful comparison of the data in the a, and 6 regions in both the alloy and pure iron. We have made several measurements in the appropriate temperature ranges and are unable to establish any systematic difference between the diffusion coefficients of iron in pure iron and in the alloy. We therefore conclude that the values obtained for the alloy are truly applicable to pure iron; the complete evidence favoring this conclusion will be discussed later in this paper. EXPERIMENTAL The experimental methods will be given here only in barest detail since they have been thoroughly de- scribed elsewhere.l, 7 The alloy was prepared by induction melting and chill casting under argon. Diffusion samples were machined from the ingot and annealed in hydrogen for several days at 900°C to give an average grain diameter of 1 to 2 mm. The penetration profiles of the tracer were established by a sectioning technique, the residual activity being counted after the removal of each section. The tracer used is Fe59 which emits two high-energy ? rays of 1.098 and 1.289 Mev, respectively; these were detected by a ? scintillation counter equipped with a pulse-height analyzer. For the measurements in the temperature range -700o to 1130°C the samples were vapor-plated with Fe59, encapsulated in quartz under vacuo, and annealed in resistance-heated furnaces which are controlled to ±1°C. The specimens diffused at higher temperatures are prepared as edge-welded couples, the two halves being separated by a thin washer of the alloy to prevent sintering. The diffusion anneal is then carried out by inductive heating under a dynamic vacuum. The temperature is monitored pyrometrically. RESULTS The diffusion coefficients are obtained from the penetration profiles in the usual way using the error-function complement relationship. The results over the entire temperature range are shown in Fig. 1. In the linear region, 900o < t > 1500°C the least mean squares (lms) values of the diffusion coefficients are given by D = 1.39 exp[-(56.5 ± 1) x 103/Rt] cm2/sec [l] The average departure of the measured diffusion coefficients from the values given by Eq. [1]In order to determine whether or not the slope is truly constant over the entire range from 900" to 1500°C, the data are arbitrarily divided into two groups, the first containing values between -900" and 1133°C and the second between -1133o and 1500°C. The lms values for the two groups are given by Eqs. [2] and [3]: D = 0.519 exp[-55.7 x 103 /RT](900° to 1133°C) cm2/sec [2] D = 1.45 exp[-56.7x103/RT] (1133° to 1500=C) cm2/sec [3] Thus, there is no significant difference between the high- and low-temperature segments of the linear region. This not only assures us of the consistency of the values obtained by induction heating as compared to those obtained from the resistance-heated

Jan 1, 1965

By L. S. Darken

A quadratic formalism is developed lor the representation of the excess free energy, and of the activity coefficients of each component of a ternary system in the vicinity of a single component selected as solvent. This formalism, in contrast to the e formalism, is thermodynamically consistent at .finite concentrations. Numerous specific systems are used as illustrations, with cross checks where possible; these systems are Fe-C-X systems in the vicinity of 1600°C and include practically all those for which reliable data are available. It is shown that this formalism is usually quite adequate to rebresent available data up to a solute concentration of 20 to 30 at. pet. It is hoped that the formalism here presented may prove useful for the treatment and tabulation of data on ternary and multi-component solutions. SINCE, as discussed in a prior paper,&apos; we do not as yet have an adequate basic understanding of the nature of binary metallic solutions, we cannot hope to be in better position for ternary and multicomponent systems. However, the accumulation of thermodynamic data on ternary and multicomponent metallic solutions has led to an urgent need for a rational formalism for the presentation and use of such data. Notable attempts to represent the isothermal isobaric thermodynamics of ternary solutions were made by Benedict et 01.&apos; and by Wohl.3 These attempts were directed toward developing an analytic expression adequate to encompass the entire ternary triangle, primarily for organic systems; they generally involve the power-series approach, which has been shown&apos; to be inappropriate, in general, even for binary metallic systems. On the other hand, interest in the thermodynamics of ternary and multicomponent metallic solutions has tended to focus either on general thermodynamic relations4-10 over wide compositional ranges, or on cases where one or more components have been at rather low concentration. This latter approach has been followed by Wagner,= by chipman,11 and by Alcock and Richardson,12 and more recently in many publications by the same and other authors. It has already been shown&apos; that the thermodynamic behavior of binary metallic systems is, in general, relatively simple only in the terminal regions. Hence, it would appear that any approach, at this time, to a simple formalism for ternary and multicomponent systems must, a fortiori, be limited to the vicinity of the major component or solvent. The present treatment is aimed to be useful for a given solvent with moderate solute concentrations ranging up to 20 or 25 at. pet and in exceptional cases to considerably higher concentrations. In order to achieve even this modest objective, it is necessary that any appropriate formalism have built into it 1) a thermodynamic consistency (at least within the desired degree of approximation), and 2) an approach at infinite dilution to Raoult&apos;s law for the solvent and to Henry&apos;s law for each solute. Let us first formulate the condition of thermodynamic consistency for a ternary system. Under isothermal isobaric conditions, we may write for the molal value G of any extensive function dG - C1 dN1 + G2 dN2 + G3 dN3 [l] where the G&apos;s are the corresponding partial molal quantities and the N&apos;s are the atom fractions. Taking component 1 as the solvent, this relation may be rewritten in terms of the independent variables N2 and N3

Jan 1, 1968

By C. W. Covington, H. C. Cook, J. F. Libsch

Sputtered aluminum thin films were prepared in each of two conventional bell-jar vacuum systems. One system utilized an inner "getter sputtering" enclosure; the second system was a standard diode sputterirlg arrangement. Consistent and repeatable film properties were obtained in both systems provided sufficient cleanup and presputter time was allowed. The various problems associated with aluminum sputtering are discussed, with pavticular attention to the vzinimization of film contamination by outgassing and oxidation. The growth and structure of the aluminum thin films were studied with the aid of electron wzicroscopy and related to deposition rate, substrate temperature, and film thickness. The resistivity of the films was correlated to film structure and surface roughness. Resistiuities as low as 3.5 microhm-cm (2.3 x bulk resistiuity) were measured for relatively thick films (20,000). THIS investigation was undertaken to explore the problems and film characteristics associated with the sputtering of aluminum. Earlier work reported on aluminum sputtering has stressed the contamination of both the cathode and film as well as abnormally low deposition rates.&apos; Data on sputtering yields,3 however, indicate that aluminum sputtering could be practical. Recently, it was shown by Theuerer and Hauser3 that aluminum sputtering was feasible in a conventional oil-diffusion pumped vacuum system provided an inner "getter sputtering" enclosure was employed to minimize gaseous contamination. This technique employs the getter action of aluminum to produce extremely low reactive gas partial pressures in the deposition zone. Aluminum films have already found use in solid-state electronic devices such as transistors and integrated microcircuits. To the present time, most aluminum films have been prepared by evaporation due to the ease with which this metal can be evaporated. Controlled sputtering of aluminum offers a number of advantages over evaporation, however, such as 1) manufacturing compatibility with other metals which must be sputtered, 2) better control of process variables resulting in more repeatable and uniform films, 3) generally better adhesion resulting from higher-energy metal atoms, 4) built-in material supply for continuous operation, and 5) the ability to deposit alloys. The data presented in this paper are the result of two separate studies. One study utilized a small "getter sputtering" enclosure (System A) and was concerned with the structure and properties of thin aluminum films up to about 1600A thick. In this thickness range, study of the film structure was possible with transmission electron microscopy. The second study was conducted with a conventional diode sputtering apparatus (System B) and covered $ much wider range of film thickness up to about 34,000A. Emphasis was placed on developing techniques which would extend aluminum sputtering to an existing in-line continuous deposition process.4 I) EQUIPMENT AND PROCEDURE System A. Fig. 1 shows a schematic of the "getter sputtering" inner chamber used and Fig. 2 is a photograph of this chamber mounted on an 18-in. access ring of a standard liquid-nitrogen trapped bell-jar vacuum system. This chamber was designed after a similar system used by Theuerer and auser.3 The configuration allowed the glow to emanate in all directions from the cathode. Argon (99.99&apos;) was allowed to enter only at the top of the chamber such that most of the reactive gases entering with the argon were reacted with the aluminum vapor and deposited on the chilled walls of the chamber before reaching the deposition zone. Provision was also made as shown, Fig. 1, for heating and cooling the substrate from about 20" to 400°C. Two substrate materials were used: Corning 7059 glass (12 by 12 by 0.048 in.) and carbon films about

Jan 1, 1967