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By W. R. Ingalls

In choosing the unusual title given to this paper, in which the term "cyclic " might be substituted for "intermittent," my idea has been simply in respect of precision. We might say old method vs. new method, but that antithesis implies something of substitution that has not occurred and perhaps is not in sight. We may say horizontal retorts vs. vertical, but none of the older retorts are truly horizontal, and there are three different types of vertical retorts. Other complexities might be suggested. There is, however, a broad distinction between distilling that is accomplished in a periodic cycle, generally daily; and distilling that is accomplished continuously, irrespective of whether it be done in the vertical retorts of the New Jersey process or in the retorts of the Trollhät-tan process. In offering a summary of the present state of the art with the intermittent process, I shall not have any idea of exemplifying it through descriptions of any single plants, but shall rather divide among the main steps of the process and outline what is best developed among them. In pursuing this thought, it will manifestly be impossible to make a composition that will exemplify the acme of good practice, for the latter will always be a function of the cost of labor, fuel, etc., which are widely variable. As of 1929, in respect of labor we might generalize the average plant wage in the Pittsburgh-Wheeling district of the United States at $5 per day; in Oklahoma at $3; in Great Britain at $3; in Germany at $1.75-$2; in Belgium and France at $1. With high labor costs the metallurgist will naturally use means of the nature of mechanization that with low labor would be uneconomical when capital charges are taken into account. Nor may we from records of performance safely make positive deductions in respect of the efficiency of different types of furnaces unless they have been tested comparatively under identical conditions in the same works. We shall find gas-fired regenerative furnaces showing coal consumption from 1.2 tons down to 0.7 per ton of roasted ore, which may be ascribable to difference in the thermal value of the coal that is used or to differences in proportions of the parts of the furnace, which is something quite distinct from the principle of the furnace. Thus, we have

Jan 1, 1937

By Michael A. Devane, Neil Duncan

Inclines and tunnels can extend from ground surface to considerable depths traversing a wide range of lithologies. The strata encountered may be affected by loosening and induced stresses at different locations along the route. It is suggested that Phase I of the pre- driving assessment process should include study of the geology, hydrogeology, rock material and rock mass characteristics. A rock mass disruption factor is used to express the ratio of the unconfined strength of intact rock material to the unconfined strength of in situ rock mass. It is suggested that there is a relationship between in situ (secondary) permeability values and the disruption factor, since the permeability of the rock mass is governed by parameters which influence strength. In Phase I1 of the pre-driving assessment, consideration should be given to the prediction of primary loosening which results largely from disturbances to the rock mass arising from the driving process. Also in Phase 11, preliminary assessments are made of the effects of induced stresses and of the geodurability characteristics of the rocks. In Phase 111, the mechanics of various secondary loosening pro- cesses are considered along with their relevance to estimates of stand up time and support requirements. Yield-line analysis is introduced for the study of plastic and brittle type bending deformations. Stand up time and support characteristics are also assessed. In Phase IV, the effects of induced stresses are analysed. It is suggested that even for broken rock in the Yield Zone, the rock mass disruption factor may not often increase above lo which is equivalent to an in situ permeability of 10-1 m/s.

Jan 1, 1983

By J. E. Johnson

At the Cleveland meeting of the Institute in October, 1912, I had the honor to present a paper outlining the conditions surrounding the charcoal iron industry…

Jan 1, 1915

By Robert Lewis

THE Utah coal field to which the name Book Cliffs is applied runs in a northeast direction from Mt. Hilgarde, in Sevier county, along the escarpment of the Wasatch Plateau to the vicinity of Castle Gate, thence southeast along the Book cliffs, which lie to the north of and generally within sight of the Denver & Rio Grande Railroad,. to the Colorado line. The Book cliffs form the southern escarpment of the West and East Travaputs Plateaus, and vary in height from 2,000 to 6,000 ft. At the base of the Wasatch and Book Cliffs escarpments is a broad plain known as Castle valley. The coal beds outcropping in the escarpments along this valley are worked on the largest scale of any in the State, and this particular area is known locally as the Castle Valley coal field. Geology The Book cliffs are capped by the Tertiary-Eocene-formation, consisting of varicolored shales; buff sandstone, conglomerate, and subordinate thin beds of limestone. Different sections show diverse stratigraphy. This is mainly the Wasatch formation, and lies unconformably upon the rocks of the Upper Cretaceous. Fig. 1 is a generalized section of the rocks of the. Book Cliffs field. The Mesaverde formation contains the cliff-making rocks of the Book cliffs, and is composed of massive sandstone interbedded with sandy shales and beds of coal and carbonaceous shale. The sandstone has greater resistance to erosion and the formation is characterized by escarpment ledges and cliffs. The shale is commonly sandy and is drab in color, but where it is associated with the coal it is usually carbonaceous. The sandstone is generally buff, though occasionally it is white, and in places red. The bedding ranges from thin to massive. In the lower part. of the formation the sandstone is red in

Jan 7, 1914

By Robert Goodrich

EXPERIMENTS ON A PORPHYRY COPPER ORE FROM BISBEE, ARIZ. THIS research was done partly in the non-ferrous laboratory of the Department of Metallurgy of Columbia University, under the direction of Dr. Edward F. Kern, and completed elsewhere. Acknowledgment is due to Prof. Arthur L. Walker, Dr. Edward F. Kern and Dr. William Campbell of the Department of Metallurgy, for their kind advice and for the inspiration derived from their instruction. This report is given under the following heads: Petrographic Description (Microscopic Study); Sampling and Preparing Ore for Treatment; Chemical Analysis; Treatment of Ore. PETROGRAPHIC DESCRIPTION Texture: Variable. Fine to medium mixed aggregate. Original structure: Obscure. Secondary structure: Fractured; healed.

Jan 8, 1915

By R. L. Fleischer, B. Chalmers

In order to observe size effects associated with a grain boundary, aluminum single crystals and bicrystals of various cross-sectional dimensions were deformed in tension. Typical stress-strain curves are presented in conjunction with measurements of the effects of changes in crystal dimensions. Some effects of the growth rate used in preparation of crystals are also described. It is indicated that the macroscopic constraints at a grain boundary are responsible for the most prominent grain-boundary effect, the production of multiple slip. Two measurements of the width of the region of double slip are in agreement. It is concluded that the yield stress of aluminum is affected markedly by the inherent oxide coating. THE general problem to be examined is that of dimensional effects in the plastic deformation of metal crystals. These effects will be termed "size effects" and are here defined as follows: A size effect occurs in a series of crystals if their plastic-deformation properties are a function of crystal dimensions. Clearly then size effects depend on the nature of the boundary conditions imposed on the crystal. Crystal boundaries can be of three types: interphase, inter-crystalline, and free surface. Such deformation effects as are caused by distribution of phases, grain size, lineage structure, and single crystal external geometry are specific types of size effects. This discussion will be confined primarily to grain-boundary and single-crystal size effects, though in practice most "single crystals" not only have a number of small angle boundaries but also have one or more surface phases, so that the boundary conditions appropriate to a free surface do not necessarily apply. Hence, to this extent interphase size effects will be considered. The question of size effects associated with grain boundaries (called here intercrystalline size effects)

Jan 1, 1959

By Ramesh Malhotra, Hubert E. (Deceased) Risser

THE WORLD Coal, as a source of energy and as a source of coke for the smelting of iron ore, has contributed significantly to the development of every major industrial nation of the world A number of other materials-oil, natural gas, wood, waste materials, water, and, in some applications, nuclear materials -can be used satisfactorily for the generation of heat and energy, but no generally acceptable and economic substitute has been found to supplant coke in iron ore smelting in conventional blast furnaces. In the development of many nations, coal provided the initial source of energy for industrialization Although coal provided more than 60% of the world's energy each year between 1902 and 1929, oil and natural gas have surpassed it as a source of energy in more recent years (Ref. 38, pp. 439, 441). Despite the rapid rise in importance of other fuels, a considerable amount of the total energy consumed is still supplied by coal. In 1972, coal supplied 32.1 % of the total world energy (Ref. 49, pp. 2-3). To produce this energy, 2.4 billion metric tons of coal were consumed-a 16.0% increase over the amount consumed in 1962. A further worldwide increase in the amount of coal used to supply energy is projected. According to Dr. Karlheinz Bund (Ref. 37, p 145), by the year 2000 world coal consumption could amount to 5 billion mt. Coal Resources and Production The world's coal resources are estimated to be about 10,872 billion mt. Of this amount, 1,297 billion mt are classified as measured reserves (Ref. 50, p. 57). In Table 13.A.1 the estimates of measured reserves and total resources, recent production, and the ratio of measured reserves to production of major coal-producing countries are shown. About 90% of the world's total coal resources are estimated to be in the USSR, the United States, and China. The United States ranks second in the world in coal resources, but in measured reserves, it ranks first. Because of the difference in rate at which available coal resources are being exploited, the ratio of measured reserves to actual production varies widely among areas and countries. France and East Germany have the lowest reserve to production ratios, 49.5 and 60.1, respectively. In Mexico, where currently less than 5 million mtpy of coal are produced, the ratio is 1257 For all countries producing more than 200 million mtpy of coal (except East Germany), the ratio ranges from 350 to 670. For the United States, the ratio is 669.7. In Table 13.A.2, distribution of the world's coal resources by area is shown. More than 97% of the total resources lie in the northern hemisphere, with Asia, including European USSR, having 63.4%. Only 1.9% of the total coal resources are estimat-

Jan 1, 1976

INTRODUCTION The regional characteristics of porphyry copper deposits in South America southward from Pantanos and Pegadorcito, Columbia, will be summarized. The age of formation of deposits spans the period from the Permian to the present. Where possible, the general characteristics and the individual structural features of the deposits are integrated into the plate tectonic model. Individual deposits cited in this chapter, located in Fig. 1, are the best known and most fully described, and form the Andean copper belt (Peterson, 1958). Smaller porphyry copper deposits fall both east and west of the line of large, high grade deposits (e.g., Chuquicamata and Toquepala) that make up the spine of this belt. Most of those smaller deposits (e.g., Mi Vida [Koukharsky and Mirre, 19761) are omitted from Fig. 1 and Tables 1 and 2, however. Neither the Andean orogen nor the individual deposits within it are as well de- scribed in the literature as are their counter- parts in the Cordilleran orogen of North America. Therefore, generalizations relying on regional geologic mapping, geophysics, and isotopic geochemistry lack details pertinent to this type of deposit in the Cordilleran orogen. The South American porphyry copper province has been described by Hollister ( 1974) to include most of the Andean orogen excepting the tin province of Bolivia. Porphyry copper deposits have not been commonly found within the tin belt, although copper-tin (e.g., San Rafael, Peru) and copper-tungsten (e.g., Llamuco, Chile) de- posits are known. James (1971) shows the depth to the Moho to be appreciably greater where the tin belt exists, but disclaims any genetic significance from the coincident appearance of the tin-tungsten province and the inhibition of porphyry copper development where the sialic crust thickens. Dates on tin mineralization in this belt (Clark and Farrar, 1973) are similar to some dates for porphyry copper mineralization known else- where in the Andean orogen. It seems that some mechanism is needed to explain the geographic separation of porphyry copper- molybdenum and simultaneous tin-tungsten- molybdenum metallization within the same tectonic system and appearing at similar distances from the trench. The thickened crust of the tin belt is one of the few known differences. Tables 1 and 2 list some of the most important porphyry copper deposits explored to date, but do not include Antaminas, Peru. or a number of other large skarn deposits

Jan 1, 1978

By R. B. Mears, E. H. Dix, R. H. Brown

In the Institute of Metals Division Lecture of 1940, E. H. Dix, J~.(I)~ discussed the acceleration of the rate of corrosion by high constant stresses. Experimental data obtained on this subject at the Aluminum Research Laboratories and a theory compatible with these facts were included in that lecture. The present paper contains data and ideas subsequently developed at the Aluminum Research Laboratories. Dix pointed out that in order for acceleration of corrosion by constant stress to occur: (1) There must exist in the alloy a susceptibility to selective corrosion along more or less continuous paths, as for in- stance at grain boundaries, and (2) There must exist a condition of high stress acting in a direction tending to pull the metal apart along these continuous paths. Acceleration of corrosion rate by stress is not confined to any one alloy system. Table I lists some of the metals and alloys and some of the corroding environments in which acceleration of corrosion by stress was sufficient to cause cracking (stress- corrosion cracking). It will be noted that the variety of alloys in which stress-corrosion cracking has occurred is rather large. Also, it will be observed that

Jan 1, 1945

Jan 1, 1896

By H. M. St. John

MAINTAINING a satisfactory structure in brass and bronze castings has always been a foundry problem of great practical importance. While metallurgists and scientific investigators have not entirely ignored this matter, it has received less of their attention than has been given to iron, steel and the wrought copper and aluminum alloys. Investigation in this field has probably been discouraged to some extent by the complicated nature of the alloys involved. Hundreds of alloys are in more or less common use, most of them containing copper, zinc, lead and tin in-widely varying proportions. They also contain appreciable percentages of iron and antimony as impurities, and often phosphorus, which has been added as a deoxidizer and fluidifier. Small amounts of sulfur are usually present. It is not uncommon to find nickel, sometimes in rather substantial quantities. Traces of other metals are frequently present. So complicated and variable a mixture obviously offers difficulties in. any investigation of the various factors that influence the structure and other properties of the casting.

Jan 1, 1930

By F. G. Clapp

Introduction.......................................................... 915 Scope of Discussion................................................... 915 Literature and Acknowledgments....................................... 915 Geographic Distribution of Petroleum in South America................. 916 Geographical Comparison with North America.......................... 917 Geological Inferences Regarding South America......................... 918 Quality of South American Oil........................................ 918 South America's Position in the World's Production.................... 919 Political Conditions in South America................................. 920 Peru.................................................................. 920 Distribution of Peruvian Fields................................ :...... 920 Surface Indications.................................................. 923 Geological Conditions................................................ 925 Quality................................................,............ 927 Production......................................................... 929 Argentina............................................................. 932 Distribution of Argentina Fields...................................... 932 Surface Indications.................................................. 933 Geological Conditions............:................................... 935 Quality .......................................................... 936 Production.......................................................:938 Venezuela................................................. 939 Distribution of Venezuela Fields...................................... 939 Surface Indications................................................. 939 Geology of Venezuela Fields.......................................... 941 Quality........................................................... 942 Production.......................................................... 943 Colombia.............................................................. 944 Distribution of Colombia Fields....................................... 944 Surface Indications.................................................. 945 Geological Conditions............................................... 948 Quality............................................................ 950 Production......................................................... 950

Jan 1, 1918

By Klaus Schwerdtfeger

Activities of lead in Pt-Pb and Pd-Pb melts in the temperature range of 800° to 1200°C have been detev-mined from electromotive-. force measurements 202th the cells Both systems display strong negative deviations from Raoult's law. The data obtained with cell [1] were combined with available data on the activity of PbO in silica-satuvaterl PbO-SbO2 melts to calculate the standard free cnergy of formation 01- liquid PbO. FREE energies of formation of oxides and activities of components in metal and oxide melts can be determined with galvanic cells consisting of a metal phase, an electrolyte containing the oxide of one of the components of the metal phase, and an oxygen electrode. This technique has been used previously to measure the standard free energy of formation of solid sio2, 1 and activities in Fe-si, CO-si,2 Ni-Si,2 and CaO-P2O5 3 melts. The present paper reports activities in Pt-Pb and Pd-Pb melts as measured with the same experimental technique. EXPERIMENTAL METHOD General Considerations. The following cells were used: Pbl (PbO-SiO2)liquid, SiO2 Pt-Pb 1 (PbO-SiOz)liquid, SiO2solidO2 [2] Pd-Pb (PbO-SiOz)liquid, SiO2solid O2 [3] Liquid alloy and' oxide melt were contained together in a silica glass crucible of essentially the same design as described previously.1'2 The PbO-SiO2 melts are ionic conductors.' During the experiment, the silica glass crystalizes in a layer adjacent to the electrolyte. The electrolyte equilibrates with solid silica and hence attains the composition of the Si02-liquidus curve in the system PbO-SiO2 at any particular temperature. Molybdenum wires were used to establish contact with the liquid metal. The oxygen electrode, which reaches the surface of the PbO-SiO, electrolyte from above, consists of a platinum wire inserted into a ceramic tube and provided with a 2-mm-diam platinum bead at its end. Gas of known oxygen partial pressure (pure oxygen of 1 atm: air, or N2 with 1.04 pct 0,) is blown through the ceramic tube onto the surface of the electrolyte. The cell reaction is Pb (metal) + 1/2O2 (gas) = PbO (electrolyte) [4] No oxidation of platinum or palladium ("displacement reaction") occurs. This is to be expected from the noble character of platinum and palladium, but was also shown experimentally, as described in the next section. The galvanic electromotive force of the cell is given by where AG is the change in free energy for Reaction [4], E(=2) is the number of electrical equivalents necessary to form 1 mole of PbO, and F is the Faraday constant. Formula [5] is valid only if no junction potential exists within the electrolyte. Junction potentials occur only when the compositions of the electrolyte are markedly different at the electrodes. Such differences are negligible in the PbO-SiO, electrolyte, as shown in the next section. Since molybdenum contact leads are used, appropriate corrections were made on the measured electromotive forces to account for the thermoelectric effect of the Mo-Pt couple. The thermoelec-tromotive forces were measured separately with a Mo-Pt couple, and were found to vary linearly from 19 mv at 740°C to 40 mv at 1310°C with molybdenum being positive and platinum negative (cold junction at 25°C). Extrapolation of these values to higher temperatures yields values which are in satisfactory agreement with those obtained previously in the temperature range 1440° to 1630°c.1,2 The change in free energy for Reaction [4] is expressed as where chemical potentials of the species. The value of constant for a given temperature because the slag composition is fixed. Inserting [6] into [5] and using appropriate expressions for upb and uO2 the relation

Jan 1, 1967

By Alden Greninger

METALLURGISTS have long believed that martensite in steel forms as plates along the octahedral {111} planes of austenite. Much has been written about mechanisms whereby units of the austenite lattice are pictured as transforming to martensite by shearing movements initiated along the octahedral planes of austenite, supposedly resulting in plates of martensite lying parallel to these planes of shear. A critical inspection of two or three photomicrographs of quenched hypereutectoid steel led us to the conclusion that the orientation habit of martensite, at least in hypereutectoid austenite, could not possibly be octahedral. Inasmuch as recent studies30,31 of the martensite-type reaction in nonferrous alloy systems have established the irrational orientation habit as characteristic of this type of lattice transformation, the need for a thorough restudy of the crystallography of martensite formation in steel was evident. The present paper reports the results of such a study, extended to include both cementite and some of the products of constant-temperature decomposition of austenite. Also reported are a few of the results obtained from a microscopic and X-ray study of the austempering process in very high-carbon steel.

Jan 1, 1940

By Carls Benedicks

It is well known by every one who has had to deal with boiler tubes that these are often seriously affected by a sort of corrosion, occurring as a local pitting, that frequently causes a perforation of the tube in a rather short time. The characteristic appearance of this corrosion is shown in Fig. 1. A very similar corrosion occurs in condenser tubes (Fig. 2).l A study of the microstructure or local chemical composition of the metal (iron 70:30 brass) fails to reveal any cause for this pitting. Of course one might possibly assume the starting point to be some oxide particle, causing an electrolytic local action, but this in no way explains the continued corrosion, progressing even when the assumed oxide particle must have disappeared. By the excellent work done by the Corrosion Research Committee of the Institute of Metals, and communicated, in October, 1923, to the Institution of Engineers and Shipbuilders in Newcastle-on-tyne, stress was laid on the faot that a content of entangled air has a very obnoxious effect. In the following correspondence, Sir George Goodwin stated that "engineers have, for a long time past, regarded air as the big enemy to be fought against in all questions of corrosion'72 and Kenneth Fraser pointed out that the most vital point is "the avoidance or removal of possibly the chief cause of present day corrosion, i. e. entrapped air and gases brought out of solution."3 In their reply, however, the authors state that they had "never for a moment believed that entangled air was responsible for the beginnings of corrosion, and express the opinion that the gradual liberation of air could not account for localized corro~ion."~ On consulting the many textbooks on corrosion, as that

Jan 1, 1925

By Edgar T. Wherry

EDGAR .T. WHERRY,* Washington, D. C. (communication to the Secretary ?).-Dr. Pogue's presentation of the facts concerning the emerald deposits is very clear and convincing, and the only addition that I can suggest is a summary of previous theories of origin. He makes it evident that the pegmatite theory is the only one capable of explaining the existing relations, but upon certain details there may be some difference of opinion. If I understand the term pneumatolytic, it does not imply that all the elements concerned in a given deposit were transported as gases, but rather that the crystallization of these elements into the various minerals was favored by the presence of certain gaseous substances, notably H20, C02 and HF. It is highly improbable that the oxides of glucinum, aluminum, chromium, and silicon, which enter into the composition of the mineral emerald could have been transported in the gaseous form. The same is true of the metallic constituents of the parisite and other associated minerals. The explanation suggested, that solutions separated into liquid and gaseous portions, the latter ascending and forming the emerald in the upper portions of the rock only, therefore, seems to me untenable. When two formations exist side by side and one, A, is mineralized while the other, B, is barren, the possible explanations may he classed as (1) chemical, and (2) physical. 1. Some chemical feature of A not found in B might have caused crystallization of certain minerals in the former, which did not appear in the latter. In the present instance both rocks appear to be so similar chemically that no such effect can be looked for. Pogue mentions carbon as a possible precipitating agent, but describes both formations as carbonaceous, so that the difference in the minerals of the two can not be thus explained.

Jan 10, 1916

By E. A. Gulbransen, W. S. Wysong

THE behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a metal or as an important component in alloys in high temperature oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a microbalance study1,2 of the following problems: (I) the oxidation behavior in the temperature range of 25 to 550°C (2) the reduction with pure hydrogen of thin oxide films formed on tungsten, and (3) the volatility of thin oxide films on tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the oxide to metal volume ratio is greater than one, the oxide is not considered protective, (2) the metal readily oxidizes at temperatures from 300° to 550°C (3) the oxides W02 and WO3 are reduced at temperatures as low as 500°C. by hydrogen, and (4) the oxide W02 is volatile at temperatures from 800 to 1100°C. LITERATURE The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°C. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides. Scheil4 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bedworth5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.7 They have reported that W03 is the stable oxide in contact with the metallic substrate up to approximately 600°C while W02 forms first at 700°C. Hägg and Magneli8 have recently reported a study of the lattice structures observed in the tungsten oxides using the X-ray diffraction method. In addition to an a-phase W03 and a d-phase W02, they reported the existence of two new phases. A ß' phase, homogeneous between

Jan 1, 1947

By Luiz C. Correa da Silva, Robert F. Mehl

An experimental study of the movement of markers in the systems Cu/a-brass, Cu/Sna-solid solution, Cu/Ala-solid solution, Cu/Ni, Cu/Au, Ag/Au, employing many types of markers and a variety of temperatures. Marker movement is confirmed and undoubtedly associated with the manner in which atoms move during diffusion. EVERAL years ago Smigelskas and Kirkendall' •S reported measurements on the interdiffusion of copper and a-brass and on the movement of inert markers placed at the original join. These markers were observed to move toward the a-brass side of the join, and from this it was inferred that zinc diffuses in a-brass more rapidly than copper. Similar results were reported a little earlier for the diffusion of solvents into high polymer solids.' This has attracted much attention, particularly from those interested in the mechanism and the theory of diffusion: Seitz3 has employed it in supporting the vacancy theory of diffusion; from the data Darken4 has calculated separate diffusion coefficients for copper and zinc, developing a "phenomenological" theory of diffusion; and Bardeen5 has employed it in constructing a general theory, including therein the work of Seitz and Darken, as has Le Claire. These matters have recently been reconsidered in a sympo~ium.7 Some reason has existed for questioning the work of Smigelskas and Kirkendall.' Their technique consisted in electroplating copper on a-brass, upon the surface of which Mo-wires had been secured, and then diffusing, measuring the extent of diffusion along the normal to the join, and measuring the marker displacement in the same direction by a comparator determination of the distance between Mo-wires on opposite sides of the electroplated brass sample. It has been suspected that the copper plate might have been porous, and that the original interface might have been an imperfect join, both contributing to the transfer of the volatile zinc by vapor transfer;' it has also been questioned whether the marker movement might not in a measure be a property of the marker itself; etc. These legitimate questions require experimental answers; the present paper offers such answers. Moreover, Smigelskas and Kirkendall studied the effect only in the Cu-Zn system and at one temperature; the attention which the work of Smigelskas and Kirkendall has commanded recommends similar

Jan 1, 1952

By Michel Elle, John Chipman

The equilibrium of gaseous H20-H2 mixtures with liquid iron-columbium alloys in the range 0.2 to 2.4 pct Cb shows that the activity coefficient of oxygen is strongly diminished by Cb. The oxide in equilibvium with the melt is identified as CbO2. The equi-librium constant at 1600 deg C is [%Cb][fo. % 0]2 = 2.9 x 10-4 where log fo= —0.14 [%Cb]. The deoxidizing power is comparable to that of vanadium, COLUMBIUM (niobium) is finding increasing use as an alloying element in steel. It forms several stable oxides and is removed from the steel bath by oxidizing slags. The specific oxide formed in steel-making is not known although Sazanov snd Shvarts-man,' in their study of its partition between slag and metal, have assumed this to be Cb2O5 It is the purpose of this study to determine its deoxidation equilibrium at 1600°c, the nature of the oxide formed and the interaction between columbium and oxygen in the melt. The investigation was based on the reaction H2 + O=H2O; Kl=ph2o/(pH2[%O]) [1] in which 0 signifies oxygen dissolved in the liquid Fe-Cb alloy. The method and equipment of recent studies2,3 were utilized. In brief, the molten alloy, contained in a small crucible, is held in a controlled mixture of steam, hydrogen, and argon until equilibrium is reached. It is then cooled quickly in a stream of helium and analyzed for columbium and oxygen, the latter by vacuum fusion.4 The solubility of the oxide in liquid iron is determined by visual observation of scum formation on the surface of the melt. Crucibles of MgO proved unsatisfactory because of partial reduction at the metal interface. Pure A12O3 crucibles were heavily blackened by the melt and could not be used at high concentrations of columbium. Silica crucibles were more satisfactory but these introduced some silicon into the melt thus necessitating an uncertain but small correction for its effect on the activities of the other solutes. In silica it was possible to observe the scum formation when the melt became saturated and there was no apparent reaction between scum and crucible. The procedure for saturated melts was as follows. The alloy charge composed of electrolytic iron and columbium grain was melted and held at constant temperature. The gas ratio H2O:H2 was progressively increased by raising the saturator temperature until a point was reached at which a bright film appeared on the surface and covered it completely. This film could be dissolved by raising the temperature of the melt and it reappeared when the temperature was lowered. Under a partial film covering, utilizing bare areas for temperature measurement, the melt was brought to equilibrium with the atmosphere by holding at temperature for about 1 hr as suggested by Dastur.5 INTERACTION IN THE MELT Several experiments were made without columbium to establish a base in silica crucibles. The results are shown in Table I. Except for one run, they agreed well with Floridis1 comparable results in other crucibles. The value of log K1 is taken from Table I as 0.58. This is slightly larger than Floridis' result, probably because of less elaborate safeguards against thermal diffusion. Results obtained in the Fe-Cb-0 series in which no scum formed are shown in Table 11. The equilibrium ratio Kl is defined as ph2o/(ph2[%O]). It is related to the equilibrium constant K1 as follows:

Jan 1, 1962

Jan 1, 1899