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By John L. Miles

John L. Miles (Arthur D. Little, 1nc.)—Pollack and orris" have reported measurements on electron tunneling through A1-A12O3-A1 sandwiches in which the oxide was formed by gaseous oxidation in a glow discharge. From these measurements they deduced the asymmetry of the barrier and, since this is small, conclude that the mechanism suggested by Mott19 for the growth of oxide in thin A12O3 films is inapplicable. In earlier papers20 Pollack and Morris report similar work for oxide films grown thermally. In this case they find a greater asymmetry and conclude that the Mott mechanism is valid. I would like to point out that both these conclusions are quite unjustified. Mott suggests that the growth of the oxide film on aluminum results from the passage of ions through the already present film of oxide under the action of an electric field. This field results from a constant voltage which is in effect a contact potential between metal on one side of the barrier and adsorbed oxygen ions on the other side of the barrier. The theory does not require that the oxide grown is nonuniform either in stoichiometry or structure. It does however specifically assume that the partial layer of ionized oxygen on the surface remains adsorbed on the surface of the growing oxide. In other words, the so-called "built-in field" remains in the oxide only as long as the ionized oxygen is present. When a counter electrode of aluminum is deposited on the oxide, it will react with the adsorbed oxygen on the surface of the oxide, thus forming a small additional amount of oxide. It is clear, then, that there is no requirement in the Mott theory of oxide growth which would necessitate tunneling currents through an Al-A1203-A1 sample to be different when the polarity is reversed. Neither does the theory eliminate the possibility that some additional mechanism could cause the tunneling barrier to be asymmetric and hence tunneling currents to be a function of polarity in such a sandwich. Thus these tunneling-currents measurements are not germane to the question of whether the Mott mechanism is the true method of growth of aluminum oxide films. In fact, it is not surprising that there should be a difference between the oxide properties at the two interfaces (with resulting asymmetry in the tunneling barrier) since the growth conditions and growth rates must have been quite different at these two positions. S. R. Pollack and C. E. Morris (authors' reply)— The point raised by Miles above is one has caused some confusion in the past. The following is an attempt to clarify this point. The built-in field which is responsible for the growth of the thermal oxide at low temperatures arises, according to Mott, because of the passage of electrons from the Fermi surface of the oxidizing metal to surface states introduced by the adsorbed oxygen. It is assumed that the energy of these surface states lies below the Fermi energy of the metal. Electrons therefore continue to flow from the metal to the surface until the built-in electric field raises the potential energy of the surface states to the value of the Fermi energy in the metal, at which time equilibrium is obtained between the surface states and the metal. That is in equilibrium as many excess electrons pass from the metal to the surface per unit time as vice versa. The surface of the oxide prior to deposition of a metallic counterelectrode can then be pictured as follows. The Fermi energy lies in the energy gap of the oxide and is essentially pinned at the energy of the oxygen surface states. The vacuum work function of the oxide is then given by the sum of the electron affinity of the oxide (i.e., the difference in energy between the vacuum and the conduction-band minimum) plus the energy difference between the conduction-band minimum and the Fermi energy. The deposition of a metal onto the surface of the oxide can result in a transfer of electrons across the extremely thin oxide only if there is a contact potential difference between the deposited metal and the parent metal or oxide. That is if the vacuum work function of the deposited metal differs from that of the parent metal, then charge can be redistributed across the oxide in order to equilibriate the Fermi energy across the structure. (It should be

Jan 1, 1965

By M. H. Childs, K. E. Merklin

Blast furnace feed specifications are being revolutionized because of the large increase in iron pellet production from low-grade ores of the Lake Superior region. Recent laboratory findings aimed at a better understanding of factors influencing the physical quality of pellets produced from taconite concentrates are reviewed. Tests for determining better product quality, the effects of additives, and production factors are discussed. The current revolution in specifications for blast furnace feed is typified to a great extent by the recent tremendous growth in iron ore pellet production from low grade ores of the Lake Superior region. Indeed, pellets are responsible, at least in part, for many of the stringent new requirements that are being placed on the suppliers of furnace raw materials. As the tonnage of pellets going to the steel mills increases, more and more attention is being turned to the detailed characteristics that make this product an ideal blast furnace feed. Control of quality in pellets is similar to that of any other product. A basic understanding of the factors that are encountered in their production, from the crude ore through to the finished product, is required, along with careful process supervision and frequent quality checks. Normally, chemical grade is not a problem. This usually can be controlled within the desired specifications by minor operating variations in the con- centrator. While future changes in requirements may result in the need for self-fluxing pellets1 or other chemical changes, today's quality demands center primarily around the physical characteristics of the pellets. It is in this area that many of the recent laboratory studies have proven helpful to the operating plants. A better understanding of the physical factors involved in pelletizing has provided the basis for a continuing program of quality improvement. Tigerschiold and Ilmoni2 and Cooke with various associates are responsible for the development of much of the basic understanding of the pelletiz-ing process. These earlier findings have served as a most useful background for this work. LABORATORY PROCEDURES Magnetite concentrates produced from eastern Mesabi Range magnetic taconites were used for all of the work reported herein. The sizing and chemical analysis of a random sample are shown in Table t Additives usually are mixed with the concentrates in taconite plants before pelletizing to improve the strength characteristics of the unfired balls. Ben-tonite, soda ash, and coal are in common use. The bentonite used in these studies was of the Wyoming sodium type; the soda ash was a standard commercia1 brand. Anthrafines were used where coal was called for. The procedure for making batches of balls at the Hibbing Laboratory is as follows: In an especially designed mulling equipment 2800 g of dry ore are mixed for 10 min with the desired additives. Water is added and mixing continued for 1 1/2 min. The charge is removed from the muller and put through a mechanical shredder to break down any lumps that may have formed. sixty previously formed seed balls are placed in the balling drum, which is in fact a 6 x 16-in. diam airplane tire turning at 53 Wm. Two thousand grams of the shredded concentrate and additive mix are fed by hand into the tire at a con-

Jan 1, 1961

By O. Jay Myers

The war effort has furnished the necessary impetus for better magnesium foundry practice. Four or five years ago, there were but a few formulas in general use for core-sand mixtures for magnesium castings. Certain sands, binders, and inhibitors were specified and the proportions of these materials in each mixture were maintained between very narrow limits. As more and more war industries entered the field, much research was carried out and methods and practices were improved. Magnesium founding is still in a state of flux; therefore it is not uncommon to find one foundry spraying inhibitors on its cores, and another foundry using sand mixtures with incorporated protective agents. The basic core or dry-sand mold mixture for magnesium in use today is compounded with sand, core oil or resin binder, cereal, and moisture. Core oil or resin binder are added for baked strength while the cereal binder and moisture are for green strength. The normal mixtures (based on the weight of the sand) contain from o.5 to 1.5 per cent of both cereal binder and core oil, and the moisture content variesbetween 1.5 and 5 per cent. The ratio of core oil to cereal binder varies from 60:40 to 40:60, while the correct amount of moisture depends upon the method of coremaking. Protective Agents In all magnesium practice, protective agents are used in conjunction with the core and molding sands to prevent oxidation of the metal. The use of these inhibitors is not novel, but publications covering this field are not entirely adequate. Beck1 says: Magnesium alloys decompose water to form magnesium oxide, hydrogen being liberated in the process (Mg + H2O ? H2 ?+ MgO). This reaction results in the blackening of the skin and the appearance of areas of porosity on the casting surface, the cavities of which are filled with a grey oxide powder (these are termed 'burns'). Although sand cores for magnesium castings are thoroughly dried during the baking cycle, burning will take place on the casting5 unless the metal is protected properly. This type of burning is more difficult to define than the "water-magnesium" reaction cited by Beckl A possible explanation may lie in the following equation: 2Mg + O2—> 2MgO Here, the source of the oxygen is not water, but the air in the mold cavity, together with the chemically combined oxygen in the core-binding media. Generally, two methods are used to prevent this reaction from taking place.

Jan 1, 1945

By D. E. Baldwin

A method has been devetoped for predicting the produced concentration profile for a miscible slug in a five-spot pattern. The technique consists of dividing the five-spot into radial etements and applying an approximate radial solution of the dispersion equation to each element. To test the method, laboratory experiments were conducted in five-spot models. The models were 2-ft X 2-ft X 2-in. Berea sandstone slabs simulating one quarter of a five-spot. An aqueous system was used with tritiated water as the tracer fluid. Effiuent concentration profiles were obtained for slug sizes ranging from 0.7 to 10.2 per cent of the pore volume. Agreement between predicted and experimental profiles was excellent. A prediction was also made for a field tracer test. For this case the predictive technique was modified to account for stratification by use of a layer cake model. INTRODUCTION Dispersion in porous media is of growing interest to the petroleum industry because of the increasing importance of secondary recovery operations. One of the controlling factors in the recovery of oil by miscible displacement or by the use of waterflood additives is the degree of mixing between the fluids of interest. Consequently, one of the prerequisites of any recovery prediction is an adequate method of predicting dispersion. Also, any quantitative interpretation of waterflood tracer tests is dependent upon the ability to determine the dispersion of the tracer as it flows through the reservoir. During the past few years there have been reported in the literature the results of a large number of investigations, both theoretical and experimental, concerning dispersion in porous media. (An excellent review of these results has been presented by Perkins and Johnston." Only a few of these investigations, however, deal with non-lin-ear flow systems. Raimondi et al.9 have presented an approximate solution of the dispersion equation for radial, diverging flow. Lau et al. 7 and Bentsen 1 have presented laboratory data for radial systems and have shown that the dispersion can be adequately predicted by Raimondi's solution. Bentsen has also presented a small amount of data for a radial, converging system. Brigham and Smith' have applied Raimondi's solution, with approximating assumptions, to a five-spot pattern to predict the behavior of a field tracer test. The afore-mentioned investigations have been concerned almost entirely with radial diverging flow and have neglected the effect of converging flow. For this reason the present investigation was undertaken to develop a method of predicting dispersion in a five-spot pattern including the effects of both diverging and converging flow. The method which was developed consisted of dividing the five-spot into diverging-converging radial elements and applying an approximate solution of the disperson equation to each element. DEVELOPMENT OF PREDICTION METHOD The development of the prediction method consisted of two phases: construction of a radial model of a five-spot pattern and derivation of equations to describe the dispersion in the radial model. FIVE-SPOT MODEL A radial model which simulated the flow characteristics of a five-spot pattern was constructed by dividing the five-spot into diverging-converging radial elements (Fig. 1). Because of symmetry the model represented only an octant of a complete five-spot. Each element had an included angle of l° (making a total of 45 elements) and a radius r, such that the sum of the individual element areas was equal to the area of the five-spot octant. The normal five-spot fractional flow behavior was determined by averaging the experimental five-spot data of Caudle and Witte,' Dyes, Caudle and Erickson 5 and Fay and Prats. 4 The resulting curve is shown as a solid line in Fig. 2. To match this curve with the radial model it was

Jan 1, 1967

By M. D. Hassialis, C. G. Myer

THE nature of a collector-coated mineral surface has been the subject of some experimentation and much speculation. Various aspects of the problem have been isolated and studied; it is probable, however, that there exist aspects as yet unrecognized, which are needed for a complete description of the system. The recognized elements of the problem are: 1—The nature of the chemical units comprising the film and the nature of the forces holding these chemical units to the mineral surface; 2—The orientation of the chemical units at the surface; and 3—The disposition of the collector units at the mineral surface. This report touches upon all three aspects of the broad problem; it deals, however, with a new and heretofore unrecognized element—the mobility of the collector units in the two dimensions of the solid-liquid interface. Regardless of the viewpoint adopted as to whether the chemical units comprising the collector film are collector ions or molecules, held either by chemical or physical forces, the writers on flotation theory are in apparent agreement as to the orientation of the chemical units at the mineral surface. Wark and Cox' showed that the contact angle at a stable collector-coated surface in a constant chemical environment is independent of the nature of the mineral and of any resurfacing agent; it depends solely upon the collector used. They showed further that the value of the contact angle increases with the number of carbon atoms in a homologous series of compounds. Taggart, Taylor, and Knoll2 postulated that the collector ion is oriented with the chemically reactive, polar end toward the mineral surface and the non-polar, hydrocarbon-like end toward the liquid phase. In support thereof they cited the abstraction of p-p1 dihydroxydiphenylthiourea and of glycol xanthate8 by galena without a concomitant increase in the contact angle above that of clean galena. It was argued that in these cases the water-repellent layer which normally would be presented to the liquid phase owing to the orientation of the collector ions is overlain by a layer of water-avid groups, the hydroxyl groups. Implicit is the analogous orientation exhibited by a monomolecular layer of an insoluble substance at an air-water interface. It should be pointed out that these facts also are consistent with the concept that the collector units be flat on the surface of the mineral and that the response of the surface to an air bubble is determined by the ratio of the area covered by water-avid groups to the area covered by water-repellent groups; the areas being weighted according to the relative watef-avidity or water-repellency of the groups involved. The disposition of the chemical units of the collector film at the mineral surface has not received the attention it merits. Taggart4 concluded from the observed stoichiometry of the ions entering and leaving a surface that the stoichiometry is obeyed in detail at the surface of the mineral. Thus, in the case of xanthate-coated galena, pairs of xanthate ions are attached to surface lead ions. In the case of chemisorption, Gaudin and Preller postulated an agreement between the atoms or ions of the substratum (the mineral surface) with those of the superstratum (collector film); in the case of the physical adsorption their position is not clear. In one place they state "the first type (physical adsorption) does not require any agreement between the atoms or ions of the substratum with that of the superstratum" and in another place that "It seems, in fact, as though some slight influence of the substratum is formed even in physical adsorption." The present work shows that in some cases of chemisorption the chemical units of the collector film are in constant surface-bound motion and may not be assigned to any site of the surface, hence there is no permanent association between the chemical units of the film and the atoms or ions of the solid. The physical property of the collector film that is of paramount importance is its surface energy. Although this property is not susceptible to direct experimental determination, the related contact angle is. Much of the knowledge of the properties of a collector film derives (by deductive and inductive reasoning) from the behavior of an air bubble thereat

Jan 1, 1952

By W. E. Remmers

The defect in wire known as "cuppiness" has appeared and disappeared from time to time but the exact cause of its appearance or disappearance has not heretofore been known definitely. This defect is not limited to one particular metal or alloy but seems to be found at various times in all of the materials that are drawn into wire. Fig. 1 represents cuppy wire made from an aluminum alloy and Fig. 2 illustrates copper wire that became cuppy in drawing without intermediate annealing. Differences of opinion are current among the manufacturers of wire and in the literature (see bibliography at end of paper), some believing that the source of the trouble lies in segregation in the wire rod, oxides, sulfides, slag, etc.; others that the trouble is created by an unevenness of stress distribution across the section of the wire, usually thought of as being a function of die shape. All of the published work is of a qualitative rather than a quantitative nature. With this in mind, it was deemed advisable to make a study of the shape of the wire-drawing dies, as well as the oxygen content of the copper to be drawn. Experimental After several methods were tried, it was found that by studying the contour of the butt-end of the rod after drawing a measure of the "working" across the section of the wire could be made. The butt-end of the annealed rod was not sheared but was sawed off. The end was then smoothed with a fine file so that the plane of filing was perpendicular to the drawing axis. It is to be noted that this method is not an absolute measure of the distribution of cold working but is a very good indicative means of studying comparative values. The method of examining a tension break in wire was found to be the most sensitive in detecting cuppiness. Other methods, such as microscopic examination of longitudinal sections, X-ray radiographic studies, etching away of outer layers with nitric acid, and fracture by bending, can all be used to identify cuppy wire but the tension break will give the fracture characteristic of cuppiness before any of the other methods can

Jan 1, 1930

By E. S. Machlin, Morris Cohen

GRENINGER and Troiano' were the first to establish the fact that the habit planes of mar-tensitic products are usually planes of high indices. In steels containing 0.55 to 1.4 pct C, the habit plane indices are {225}A.* In steels with more than 1.5 pct C and in Fe-Ni alloys, the indices are {259In. The presence of both habits in certain alloy steels has been reported recently." Several investigators"-" have subsequently attempted to provide an understanding of these complex habit relations. Bowles'6 work is the most recent and the most successful. Like Greninger and Troiano, Bowles concluded that the transformation occurs in two steps, the first, a strain (or displacement) that is homogeneous throughout the volume of the martensitic plate, while the second is a strain that is homogeneous only within relatively small portions of the martensitic plate. The first strain yields the measured tilt of the specimen surface, but does not produce the final martensitic structure. This and the correct lattice orientations are achieved by the second strain. Bowles also reasoned that each strain could be described by the motion of a plane of no rotation and no distortion (hereinafter called the invariant plane) in a direction not necessarily contained in the plane.** In applying these considerations to steels with {225}a habits, Bowles found that the habit plane coincided with the invariant plane of the first strain, a result which signified that the atoms move along certain paths during the transformation. Whether this correlation results from the existence of some sort of a plate nucleus6 lying along the invariant plane of the first strain, or whether the invariant plane primarily defines the preferred directions of propagation of the first strain, will be discussed in a later section. There are two obstacles to the general acceptance of Bowles' treatment: 1—it has not been shown that elements of his double-strain analysis are unique, and 2—it is not known whether his treatment applies to transformations yielding the {2591A habit. Unless these two questions are resolved, the correlation between the habit and invariant planes in the {225}A systems might be regarded as coincidental. Experimental Procedure Using a 70 pct Fe-30 pct Ni alloy as an example of a {2591A habit system, preliminary attempts were made to obtain a double-strain solution based on a Nishiyamax** set of orientation relations and on a Greninger-Troianot set, adopting the stereographic technique described by Bowles" who used the Kurd-jumow-Sachstt set in connection with the {225}A habit. These attempts were unsuccessful because the method is essentially one of trial and error and requires either exceedingly good luck or a prior knowledge of the results being sought. Consequently it was decided to measure independently the strain associated with the formation of a martensitic plate as well as the habit-plane indices of the particular plate. By means of matrix algebra, the measured strain was applied to the austenite lattice, whose orientation with respect to the strain was determined, in order to ascertain whether the resultant structure would have the lattice of martensite. This was not found to be the case, and hence it was assumed that the measured strain was the first of two Bowles-type strains, characterized by the motion of an invariant plane. A solution of this displacement was obtained in terms of the invariant-plane indices and the direction of motion of the atoms. Then the second strain

Jan 1, 1952

By G. M. Schwartz, G. A. Thiel

Dimension stone was first quarried in Minnesota in 1820 and a very active industry has grown up over the years. The main basis of the present industry is a wide variety of igneous rocks sold under the general trade name of "granite." Also of considerable importance is the Ordovician dolomite sold under the locality names, Man kato, Kasota and Winona. THE first record of the quarrying of dimension stone in Minnesota dates back to 1820 when limestone was quarried locally for part of old Fort Snel-ling. Limestone quarries were operated at Stillwater, Mankato, and Winona as early as 1854. Granite was quarried first at St. Cloud in 1868, and within a few years thousands of tons were shipped to widespread points. Rough dimension stone for large buildings furnished the first important market, but beginning in 1886 paving blocks were in demand. The largest shipment was in 1888, when 1925 cars were shipped from the St. Cloud area. Quartzite was quarried first at New Ulm in 1859 and somewhat later at Pipe-stone and elsewhere in southwestern Minnesota. The productive dolomite quarries at Kasota were opened first in 1868 and have continued as large producers of a variety of stone to the present time. At present, the industry is controlled by relatively few operators, and for that reason detailed figures on dimension stone are not released for publication. A general idea may be obtained from the data in the Minerals Yearbook for 1948. The figures for total stone produced in Minnesota are 1,804,000 tons valued at $5,090,652. Probably the largest item in the latter figure is received from dimension stone. A better idea of the situation in relation to the country as a whole may be gained by using the data for 1930 when more companies were operating in Minnesota, and complete figures were published. In that year Minnesota produced granite valued at $2,668,119 and ranked third among the states in value. Minnesota's production of granite was almost exclusively for dimension stone. In the same year Minnesota produced 300,000 tons of limestone (dolomite) valued at $840,860, and this likewise was mainly dimension stone. In finished limestone Minnesota ranked second among the states in 1930. Sandstone and minor amounts of quartzite are the only other dimension stones that have been produced in Minnesota, but the quarries are now inactive. The commercial stones of Minnesota have been described in two reports by Bowlesl and by Thiel and Dutton. The early history of quarrying in Minnesota and extensive notes on the various rocks are given by N. H. Winchell.8 Small limestone and dolomite quarries were numerous throughout the area of Paleozoic rocks in southeastern Minnesota. Early production was largely dimension stone. With the increased use of Portland cement, most of these ceased production, and today only those at Kasota and Winona remain in operation. In recent years many quarries have reopened and new ones started, but these are devoted to the production of crushed rock and agricultural lime. As the application of modern quarrying and finishing methods increased, small companies in the granite business have dropped out, and the remaining companies have modernized their plants, purchased old quarries, and opened up new ones, thus furnishing a wide variety of granites suitable for most of the customary uses. It is the purpose of this review to present notes on the geology and operations of each of the quarries now operating within the state. Granites and Related Igneous Rocks The term granite as used in this report includes granites, gneisses, diorites, gabbros, and other igneous rocks. The granites of greatest economic importance are found in three widely separated regions, see Fig. 1. 1—Central Minnesota in the region of the city of St. Cloud, 2—the upper Minnesota River valley region, 3—the northeastern portion of the state, commonly referred to as the Arrowhead region. The St. Cloud Region: The rocks of the St. Cloud region are mainly granites and related rock types such as monzonites and quartz diorites. The stones may be grouped into three major types, namely, pink granite, red granite and gray granite. Most of the pink granite occurs in the area to the southwest of St. Cloud. The rock is best described as stone with large pink crystals set in a finer grained black and white background. The minerals of the matrix occur in remarkably uniform sizes, and the pink crystals are sufficiently uniform in their dis-

Jan 1, 1953

By M. E. Nicholson

The effect of boron on the austenitic transformation rate of iron is smaller than on low carbon steels. The influence of austenitizing temperature on B-Fe is the reverse of its influence on steels. THERE have been many studies made of the influence of boron on the hardenability of steel, but apparently none has been made of its influence on the y-a transformation of pure iron. There are several facts suggesting that boron should have a pronounced effect on the transformation rate of iron. First, Simcoe et a1.l indicated that boron reduces the nucleation rate of ferrite and bainite. Second, they showed, along with others,', " that the lower the carbon content of steel the greater the influence of boron on hardenability. If this trend extends to pure iron, the influence on rate of ferrite formation should be considerably greater for iron than for medium carbon steels. According to Rahrer and Armstrong," the multiplying factor for boron in pure iron should be about 2.40, compared with 1.50 in a 0.35 pet C steel. According to an extrapolation made by Grange and Mitchell,' the effect should be even greater, and the multiplying factor should be about 3.5 in iron. Many investigations of the boron influence'.7, 2, 5 indicated that boron is effective only when in solid solution. On the other hand, Chandler and Bredig" suggested that boron increases hardenability by combining with nitrogen, thereby preventing formation of AlN, which catalyzes the decomposition of austenite. If their hypothesis is valid, boron should have no effect on an alloy free from nitrogen. Digges et al." showed that so far as low nitrogen high purity Fe-C alloys are concerned this is not the case. No experiments, however, have been made on low nitrogen iron. To determine whether or not boron has an effect on low nitrogen iron and, if an effect exists, to determine whether it is as large as predicted from the investigations of boron treated steels, the following work was performed. Because of the rapidity with which iron transforms from austenite to ferrite at even a moderate degree of supercooling, it was decided to study the influence of boron on the transformation rate of iron by determining the effect of quenching rate on the temperature of the beginning of transformation. The technique, essentially that used by Greninger' and Duwez,H consisted of heating small specimens, 0.1 in. sq and 0.010 in. thick, in an atmosphere of purified helium with a resistance heater coil, and then quenching the sample in a jet of helium gas. At the time the jet was applied, the heating coil was removed from around the sample. The sample was suspended in the furnace on 30 gage chrome1 and alumel wires, one welded to each side of the specimen, which also served as a thermocouple for measuring the specimen temperature. Specimens were prepared from vacuum-melted iron obtained from the National Research Corp. which was rolled to a thickness of 0.060 in. and then decarburized in wet hydrogen for 51/2 hr at 700°C. This treatment also removed any boron present in the iron. The resulting iron contained 0.001 pet C. 0.0002 pet N, and 0.005 pet 0. One half of the piece was then boronized by surrounding it with 325 mesh boron powder and heating it for about 2 hr at 900°C in H,. The boronized iron was then homogenized at 1100°C for 24 hr. The iron boride case formed by boronizing was removed by grinding 0.010 in. from each side of the plate, and the piece was finally rolled to a thickness of 0.010 in. The resulting alloy contained

Jan 1, 1957

By P. Somasundaran

Flotation of minerals has usually been discussed in terms of solid-liquid interfacial phenomena. This paper discusses the relative importance of phenomena such as collector adsorption at other interfaces formed between the bubble, liquid and solid. Adsorption of collector ions of various chain lengths at liquid-gas and solid-gas interfaces has been obtained. The data have been analyzed under conditions corresponding to those of flotation to show the significant role of collector adsorbed on the bubble surface in determining the bubble-mineral attachment required for flotation, and consequently to suggest consideration of this role in the development of better flotation conditions. Vacuum flotation of quartz with alkyl ammonium acetate reported in the foregoing paper1 showed that the collector chain length has an effect on flotation even at concentrations below those necessary for hemi-micelle association of the hydrocarbon chains at a solid-liquid interface. This chain length effect might be explained by the following arguments: Hydrocarbon chains find it energetically favorable to be in a medium of low dielectric constant. Considering the possibility of an iceberg structure at the solid-liquid interface, such a structure would produce a region of lower dielectric constant at the solid-liquid interface than in the liquid phase, because the dielectric constant of ice is 2 to 3,2 while that of water is 80. Depending on chain length, this difference will certainly cause even individual ions to adsorb in higher quantities at the solid-liquid interface. Another mechanism to consider is the possible formation of dimers, trimers, etc and chain length would influence this formation. But, above all, the chain length effect on flotation at concentrations of low adsorption at the solid-liquid interface could be due to the significant but often-neglected role of the collector adsorption at the bub- ble surface. Collector ions or molecules are adsorbed both at the solid-liquid interface and the liquid-gas interface. Below the concentration for hemi-micelle association at the Stern plane adjacent to the surface, the bulk of the collector ions adsorbed at the solid-liquid interface are in the diffuse part of the double layer. If such systems, where there is a gas bubble coming in contact with the solid surface, are to achieve some degree of electroneutrality, those collector ions would have to migrate from the diffuse part of the double layer to the region directly adjacent to the surface during the induction period when the bubble is making contact with the solid. The time necessary for this migration would contribute to the induction period required for creation of the solid-gas interface. It seems reasonable that the induction period could be reduced sufficiently for flotation to occur if these collector ions were carried to the surface by the bubble. In an attempt to ascertain whether or not the bubble could possibly have sufficient collector ions at its surface to meet the requirement mentioned above, the adsorption density of the collector ions at the liquid-air interface was determined. For this purpose, the surface tension of alkyl ammonium acetate solutions was determined as a function of concentration. Adsorption densities of the collector at the liquid-gas interface were calculated using the Gibbs adsorption equation: where y is the interfacial tension and ri and pi are the adsorption density and the chemical potential, respectively, of the chemical species, i. Using the convention that the adsorption density of water at the interface is zero, the following relationship is obtained for the liquid-gas interface where lg refers to liquid-gas interface and RA+ refers to the alkyl ammonium ions. For dilute solutions, rf^-wri^&rfwW [3] where C is the concentration of the collector ions in solution. l?:: can now be evaluated using Eq. 3 and surface tension measurements.

Jan 1, 1969

By L. G. Huntley

The occurrence of oil or "tar" in Mexico was mentioned as early as the seventeenth century by Friar Sagahun, who gives the Indian name "chapopote," by which these asphalt seepages are still called. This asphalt was apparently used, as it has been used by primitive people in many parts of the world, in religious ceremonies and for medicinal purposes. Travellers also report that the ruins in Yucatan and the pyramids in southern Mexico show traces of the use of "chapopotel' as a building cement.l DeGolyer says that the first attempt to exploit oil or gas in Mexico in a commercial way is shown by the records of the Memoria de Fomento of 1865, when permission was granted to a Senor Ildefonso Lopez to exploit the deposits of petroliferous substances in the San Jose de las Rusias area in the State of Tamaulipas. Other concessions follow, and probably refer to surface seepages which occur in that district. This was several years after the discovery of oil in Pennsylvania. In 1868, a well 125 it. deep was :drilled by a company organized in Mexico City, in what is now known as the,, Furbero district, and a little oil was refined there. In 1873, residents of Tampico denounced seepages along the Tamesi River, and asphalt was mined near Tempoal in the Canton of Tantoyuca. No drilling was attempted. But between 1880 and 1883 several shallow wells were drilled for oil in Mexico, two of them being near the present Potrero de Llano field west of Tuxpam. The wells were drilled by a Boston company with Canadian rigs, and are said to have reached a depth of about 400 ft., while one is reported to have flowed. Several other abortive attempts were made to drill for oil between 1885 and the beginning of the present century, about which time the Mexican Petroleum & Liquid Fuel Co., Ltd., in which Cecil Rhodes was interested drilled 24 wells unsuccessfully, several of them as deep as 1,500 ft., in the State of Vera Cruz. Also Messrs. Doheny and Canfield of California pur-

Jan 1, 1916

By Harry M. Bendler, W. A. Wood

Electron metallography has been applied to the study of the torsional fatigue of polycrystalline OFHC* copper. The development of slip bands, fis- sures, and microcracks has been followed as a function of strain amplitude and number of cycles. Those factors that have been found to be relevant to a geometrical theory of the fatigue process are described. From the point of view of this theory it is important to distinguish between the effects of cycling at large amplitudes and at small amplitudes (true fatigue deformation). EARLY investigations showed metal fatigue cracking is caused by continued reversal of a small plastic strain. Fundamental study of fatigue, therefore, has been largely concerned with the cumulative effects of these plastic reversals on the metal structure. In particular, recent work has shown that the plastic reversals produce slip movements that are finer than the slip movements produced by unidirectional increments of plastic strain; individual slip movements in fatigue, for instance, are too fine to see by optical microscopy.2 It has also been shown that the fine slip movements of fatigue tend to concentrate in bands and that in this way they can build up, after enough cycles, a progressive surface disturbance. It is this disturbance which, in effect, makes the slip movement visible. It is also in this disturbance that the first cracks appear to form. From this point of view, therefore, the problem of fatigue becomes one of finding why the fine slip movements should concentrate in bands and why the. bands should finally open into cracks. Thus far, study of the slip bands has been limited to the changes they produce at the surface only. These studies have given interesting results. Ewing and Humfrey3 many years ago showed that the bands in iron could extrude debris. Forsyth found that bands in aluminum alloys could extrude thin tongues of material. Thompson showed that, after lightly dissolving away the surface of copper specimens, some bands persisted as superficial cracks might, and that the life of a specimen under fatigue deformation might be prolonged by dissolving away the surface at intervals. Thus these and related results have suggested that the metal structure in fatigue bands may disintegrate and that this may happen long before obvious cracking. These surface studies, however, have not shown definitely how cracking may begin, for they do not show sufficiently what is happening in depth. However, some advance in this direction has been made recently by a new approach, summarized later, which reveals slip bands and their surface disturbances in section. In the work done thus far, the sections have been studied by optical microscopy only. In the present work they have also been studied by electron microscopy with extended results. This paper also describes some observations on the surface disturbances prior to sectioning. These observations are relevant to a suggested theory of fatigue cracking. REVERSED SLIP MOVEMENTS Slip movements in fatigue deformation must reverse direction in each cycle. The question arises: DO the "backward" and "forward" movements take

Jan 1, 1962

By Klaus Schwerdtfeger

The rate of formation of silicon monoxide from silica spheres has been measured at 1500°C in H2, H2-H2O, H2-He, H2-Ar, and CO-CO2 gas mixtures. Indications are that in the hydrogen-containing gases the reaction rate is mainly determined by convective diffz~sion. In the CO-CO2 mixtures the rate approches a constant value which is independent of sphere diometer (and gas velocity). This suggests that a surface reaction becomes rate controlling in CO-CO2 gas. WHENEVER silica is exposed at elevated temperature to a strongly reducing atmosphere there occurs, inevitably, a volatilization of silica by the formation of gaseous silicon monoxide. Because of the importance of this reaction in metallurgical processes and laboratory experiments, its kinetics were studied in the present work. EXPERIMENTAL The spheres made of vitreous silica were suspended by a molybdenum wire in the hot zone of a gas-tight high-purity recrystallized alumina furnace tube of 3.1 cm internal diam and 100 cm length. Molybdenum wire resistance heating was used. A purified H2, H2-H2O, H2-He, H2-Ar, or CO-CO2 gas mixture was passed through the tube, from top to bottom. The amount of silicon monoxide formed was determined by weighing the silica balls before and after the experiments. The silica balls were made from commercially available translucent fused quartz glass. In experiments with hydrogen-containing gases the silica stayed vitreous during the experiment, whereas in experiments with CO-CO2 mixtures, which were performed over longer times, the balls were always crystallized to cristobalite (as determined by X-ray examination) at the surface. Constant-pressure head capillary flowmeters were used to control the composition of H2-He, H2-Ar, and CO-CO2 gas mixtures. The oxygen and water vapor were removed from the gases containing hydrogen by passage through columns containing platinized asbestos (450°C) and an-hydrone. The CO was purified from O2 and CO2 by passing it through activated copper (200°C) and through ascarite. The H2-H2O gas mixtures were prepared by passing purified Hz through a mixture of oxalic acid dihydrate and anhydrous oxalic acid held at a constant temperature in a water bath. The equilibrium water vapor pressures of oxalic acid dihydrate-anhydrous oxalic acid mixtures were taken from the available data.1 The furnace system was checked for sufficient gas tightness at regular intervals. As an additional check, the H2O and CO2 contents were measured in the exit gas and were found to agree closely with the metered contents when H2-H2O or CO-CO2 mixtures were used. When purified H2 was used, H2O pressures found in the exit gas were always below 0.1 mm Hg. These contents originate either from an incomplete reoxidation of silicon monoxide in the cold part of the furnace or from small leaks which cannot be avoided. If the latter is the case, such small uncontrolled H2O contents decrease the partial pressure of SiO in equilibrium with SiO2 by less than about 7 pct, which is considered small in comparison to other experimental uncertainties. The temperature of the furnace was controlled automatically in the usual manner. The reported temperature was measured with a Pl-Pt/l0pct Rh thermocouple and was accurate to ± 5°C. TRANSPORT-CONTROL LED RATE OF REDUCTION The gaseous convective diffusion from the surface of a sphere can be predicted from the semiempirical relationship obtained by Ranz and Marshall2 in a study of the evaporation of water and benzene drops in air. The following equation applies:

Jan 1, 1967

By Richard G. Warren, Michael M. Minor, Gayle J. Thomas

INTRODUCTION Los Alamos Scientific Laboratory (LASL) initiated its effort in the Hydrogeochemical and Stream Sediment Reconnaissance (HSSR), a part of the Department of Energy (DOE) National Uranium Resource Evaluation (NURE) program, in late 1975. Since that time, LASL has completed sampling of the Rocky Mountain states of New Mexico, Colorado, Wyoming, and Montana at a density of about one water or waterborne sediment sample per 10 km2 and has sampled about 85% of Alaska at a density of at least one per 25 km2. Analytical results for these samples are reported by National Topographic Map Series (NTMS) quadrangle. All collection and analytical procedures have been standardized from the outset (Sharp, 1977; Sharp and Aamodt, 1978). Until early 1979, only uranium results were reported for these samples; thereafter, results include analyses for at least 42 additional elements in the sediment samples. Each LASL HSSR report also includes a discussion of the relationship of these analytical data to known or possible uranium resources; more recently, these data have been re- examined for their relationship to resources for other metals (Beyth et al., 1980; 1980a). Analytical results for LASL HSSR sediment samples are both comprehensive, including 43 elements, and precise, allowing close inter-comparison of data between quadrangles. A recent HSSR study shows that elemental concentrations in sediment samples from the Dixon Entrance quadrangle in Alaska are insensitive to the choice of sieve size fraction and do not vary significantly between stream locations a few meters apart, except for extremely high elemental concentrations (Warren, et al., 1980). Elements that are particularly reproducible include thorium, hafnium, and the .ram earth elements. Fortunately, sensitivities for these elements, which are often associated with uranium, are excellent by the nondestructive analytical technique of neutron activation analysis that LASL employs. Wet chemical techniques may not always give reliable results for these elements in sediment samples due to the difficulty of dissolving the resistate mineral phases that normally contain these elements. LASL has recently open-filed results for a large number of NTK3 quadrangles; to date analyses have been reported for about 605 of the quadrangles within the states of the Rocky Mountain region. As a result, uranium analyses am now complete for all sediment samples collected from the state of Wyoming. We have chosen to sumnarize the analytical results for Wyoming and portions of adjoining states hereafter termed "the ~ Wyoming regionn (Fig. 1 ) ; nearly 24 000 uranium analyses and nearly 17 000 analyses for 42 additional elements are available for sediment samples collected from this area. The DOE open-file report numbers are shown in Fig. 1 for reports open filed before September 1, 1980. The Wyoming region provides an ideal area for an examination of regional geochemical patterns ex- hibited by sediment samples. It is endowed with a variety of exposed geologic units and with widely distributed uranium districts associated with host units of several ages. However, discussion will focus on rock units of Eocene and Precambrian ages because they are widely exposed and host the majority of the uranium resources within the region (Fig. 2). Miocene units are also widespread and host mineralization in the Brown's Park Formation (Fig. 2). Epigenetic uranium mineralization occurs in sand- stones of lower Eocene age such as the Wasatch, Battle Springs, and Wind River Formations whereas vein type mineralization occurs in Precambrian crystalline rocks. Precambrian rocks within the region consist of a variety of granitic and meta- morphic rocks with l .4-2.8 billion year ages, except within the Uinta Arch, where they consist of a sequence of very low grade metamorphosed or unmetamorphosed 1.0 billion year old sedimentary rocks. Precambrian rocks have served as sources for much of the clastic material comprising the lower Eocene units, and may also have provided the source for the uranium in mineralized Eocene or Miocene sandstones (Stuckless, 1979). The remainder of this paper describes the relationship of elemental concentrations in HSSR sediment samples to exposures of Eocene and Precambrian rocks. The results are used primarily to determine where these Precambrian rocks might provide the most suitable uranium source areas and to infer the direction of transport toward adjacent depositional basins during the Eocene.

Jan 1, 1980

By N. De Nevers

A calculation method has been developed for carbonated water flooding. This method takes into account the effects of oil viscosity reduction and oil swelling, due to carbon dioxide transferred to the reservoir oil from the carbonated flood water. It shows the effect of changes in carbonation pressure and carbonated water slug size. The method is based on a Buckley-Leverett-type linear flow model. The mathematical approach is similar to that developed by Welge, et al, for enriched gas drives. However, it contains a very important advance over the previous papers in its solution to the problem of injection of a "slug" of carbonated water rather than continuous injection of fluid of constant composition. The method also shows the chromatographic nature of the transport of Co 2 in a carbonated water flood. Sample calculations indicate that viscosity reduction is the most important source of incremental oil recovery. Swelling contributes to a lesser extent. Raising the carbonation pressure increases recovery, but this effect diminishes as pressure is increased. increasing the slug size also increases recovery, but again this effect diminishes as slug size is increased. INTRODUCTION In recent years there has been considerable interest in carbonated water flooding as a secondary recovery method. Several carbonated waterflood field tests are now in progress.1'3 Yet there is no published method for predicting the results of a carbonated water flood. This paper presents a method for predicting the oil recovery for ; carbonated water flood. In a carbonated water flood. a carbonated water slug is injected into the reservoir. Then this slug is driven forward by injecting plain water behind it. The field operator must choose the carbonated water slug size and the CO2:water ratio in the slug. The calculation method presented here shows the effects of both slug size and CO2:water ratio on oil recovery. The calculation assumes that the addition of carbon dioxide to flood water increases the oil recovery by two mechanisms: 1. Carbon dioxide transfers from the flood water to the oil, thereby reducing the viscosity of the oil. At the lower viscosity, the oil flows more readily and is more easily swept out by flood water. 2. The carbon dioxide which transfers to the oil phase causes the oil phase to swell. Assume that the residual oil saturation (volume per cent of pore space) is the same whether the oil is carbonated or not. Then the same volume will contain less stock tank oil if it is carbonated, due to oil swelling. The plain water driving the carbonated water slug forward will strip the CO2 out of this residual oil., causing this oil to shrink. This swelling-followed-by-shrinking leaves behind a lower residual oil saturation than would have been left behind by a plain water flood. Since some oils swell to almost twice their original volume at reasonable CO2 pressures, this effect may be large. Two additional benefits sometimes claimed for carbonated water flooding are: 1. Adding CO2 to flood water greatly increases the water injectivity in some cases.1 (Injectivity = BPD of water injected/ft of sand x differential bottom-hole pressure, psi.) CO2 forms a weak acid in water; injecting carbonated water is, therefore, somewhat like acid treating. If a formation responds to acid treating, it will probably have a higher injectivity for carbonated water than for plain water. Although the increased injectivity increases the profitability of a carbonated water flood over a plain water flood, it does not change the production curve based on total fluid injected. Therefore, the method presented here does not show any effect of increased injectivity. 2. It is claimed in one patent4 that carbon dioxide will react with some constituents of the oil to form detergents. These detergents are expected to increase the oil recovery. There is little data available to support this idea. The calculation method presented here takes no credit for extra oil recovery due to the formation of any such detergents.

Jan 1, 1965

By Werner Engelmaier

Constant-strain rotating-bending fatigue tests were conducted on 2024-T3 aluminum alloy constant-strain McAdams-type specimens in ultrahigh vacuum, 10-lo Torr, and in atmospheric air. In the elastic strain range the ratio of vacuum-to-air fatigue life varied from about 10 at a maximum bending stress of 37 ksi to near unity at the endurance limit. After 10 pct of the fatigue life, intergvanular microcracks appeared on the surface which did not appreciably propagate further until the last 5 pct of the fatigue life, where trans-granular cracks propagating first in slip-plane cracking and then in the stress-dominated mode led to failure. No reduction in residual tensile strength resulted from the fatigue of the specimens short of fracture. The mechanism governing the fatigue life operates between the occurrence of the intergranular microcracks and the initiation of the trans granular cracks. MORE than forty years ago, Mc Adam' and Haigh2 published the first systematic studies showing that the fatigue properties of metals were greatly affected by environments. Gough and sopwith3 found in a later study that the fatigue life of metals subject to corrosion can be substantially increased by reducing the atmospheric pressure. This and their later work4'5 was, however, done in a vacuum of only 10~3 Torr. Subsequent studies6-' at a vacuum of 10- Torr showed that water vapor is the primary agent affecting the fatigue properties of aluminum alloys. Only recently was ultrahigh vacuum used for fatigue studied.l Various theories have been put forward to explain this phenomenon. Wadsworth and Hutchings12 postulated that cracks form very early in the test and that the chemical attack by the corrosive components of the atmosphere at the root of the cracks enhances the speed of the crack propagation. They also noted that chemisorbed layers of gas on the fresh crack surfaces prevent cold welding of the crack and make the separation irreversible. Ham and Reichenbach, on the other hand, reported that their specimens showed no cracks after a run in vacuum, even though the runs were long enough to have caused the specimen to fracture in atmospheric air. They also reported that in argon at 0.14 Torr the fatigue life was about 5 times longer than at 7 X lo-' Torr. Jacisinll reported that fatigue tests in dry nitrogen showed results close to those obtained in ultrahigh vacuum. The present experiment was designed to determine the extent to which cumulative fatigue damage, i.e., the accumulation of length of fatigue cracks, reduces the residual static tensile strength of an aluminum alloy in both ultrahigh vacuum and atmospheric air and to obtain fatigue-life data for this aluminum alloy at various strains. It was also hoped that information ex- tracted from these data might support one of the previously mentioned theories. 1) EXPERIMENT Test Specimens. The material tested was commer-cial 2024-T3 aluminum alloy. In addition to aluminum, this alloy contains approximately 4.4 pct Cu, 0.5 pct Fe, 0.5 pct Si, 0.6 pct Mn, 1.5 pct Mg, plus smaller amounts of other elements.13 Some typical mechanical properties of this aluminum alloy are listed in Table I.'~ The material was used in the as-received condition, i.e., solution-treated and cold-worked. Mc Adam-type1' constant-stress specimens and notched fatigue specimens were machined from 4 -in. -diam rods, Fig. 1. The critical section of the McAdam-type samples was polished with a 45-deg spiral motion to a No. 8 microfinish. The notch in the notched specimens was machined on a lathe with a forming

Jan 1, 1969

By O. R. Morris, G. L. Hawkes

A galvanic cell, using as electrolyte a fused salt solution of calcium carbide and as electrodes carbon and a Fe-C alloy of known composition, has been set up to study the thermodynamics of Fe-C alloys in the temperature rmzge 800" to 1000°C. Time independence and reproducibility of the cell electromotive force were taken as evidence of the reversible behavior of the cell. Carbon was believed to be present in the electrolyte as the so-called acetylide ion, C;-. The plots of the cell electromotive force us temperature for a specific alloy composition were straight lines within the limits of experimental error. The average Partial molar enthalpy of carbon in iron relative to pure carbon was found to be +10,610 i 93 cal per g-atom C. Thermodynamic analysis of the data has led to the following equation for the carbon activity, ac, based upon pure carbon as the standard state: In ac = In Zc + 10,560/RT + (10.02 + 77O/T)ZC - 2.350 where ZC is the lattice ratio [nC/(nF, - nc )] and T is the absolute temperature. This equalion gives carbon activity values generally slightly lower than those from gas equilibration studies reported in the literature. METAL LOGRAPHIC examination of a polished cross section of the steel anode used in the electrolysis studies of fused salt solutions of calcium carbide by Morris and Harry revealed extensive carburization of the steel by the electrodeposited carbon. This carburization was reflected in the variability, with time, of the applied potential to the electrolysis cell, necessary to maintain a constant current density at the electrodes. This observation suggested the setting up of a galvanic cell of the "alloy concentration" type to study the thermodynamics of some metal-carbon alloys. Cells of this general type have been widely used for the study of alloy systems.2 In view of the availability of published data in respect of the austenite phase of the Fe-C system, it was decided to carry out measurements upon these alloys before proceeding to studies of less well documented systems. The galvanic cell may be written: where [C] is carbon dissolved in iron. The electrolyte was a fused salt solution of calcium carbide, containing some 5 to 10 mol pct of carbide. The cell reaction is believed to be: C(s)-[CI [I1 Carbon forms an interstitial solid solution in iron, with the atoms located in the octahedral interstices. In the fcc crystal structure of austenite there is one octahedral interstice per iron atom. Thus, the lattice ratio, ZC, shown by Gurney3 to be the fundamental concentration parameter in the context of interstitial solutions, is given by: where nc and nFe are the number of carbon and iron atoms, respectively. chipman4 has recently shown empirically the advantages of using this concentration parameter instead of the more usual atom ratio or atom fraction. The cell electromotive force, E, assuming reversible behavior, is related to the carbon potential or the partial molar free energy of carbon in the solid solution relative to pure carbon at the same temperature and pressure, GP at the composition ZC, by the equation: where z is the carbide ion valency and F is the Faraday constant. An activity of carbon, ac, in the solution relative to the value of unity assigned to pure carbon, and an activity coefficient, qC , are defined such that: where R is the gas constant and T the absolute temperature. GF is further related to the relative partial molar enthalpy Hm, and the temperature coefficient of the cell electromotive force, (aE/aT)Zc, by the equations: Measurement of the cell electromotive force thus enables calculation of the relative partial molar thermodynamic properties of carbon in iron, if z is known. At E = 0, the solid solution is in equilibrium with pure carbon. More convenient for many purposes is the standard state based upon the infinitely dilute solution, Henry's law. The relationship between the activity coefficient of carbon based upon this standard state, and that based upon the pure carbon standard state, qC , may be obtained by considering the free energy of transfer of carbon from the latter standard state to the former. The relationship is: where +:H is the activity coefficient of carbon in the hypothetical standard state based on a reference of

Jan 1, 1969

By Gen-ichi Nakazawa, Masamichi Fujimori, Ichiro Doi

INTRODUCTION The major products of nickel industry in Japan are the electrolytic nickel (E-Ni), the ferro-nickel (Fe-Ni) and the nickel oxide sinter (NOS), totaling in production to 90 - 100 X 103 tons/year in terms of pure nickel content, and sharing approximately 20% for E-Ni, 10% or less for NOS, and the rest for Fe-Ni. The raw materials to be used for these products depend totally upon the imports from abroad; matte, the raw material used in the production of E-Ni, is from Australia and Indonesia; matte for the NOS is from Indonesia and New Caledonia; and garnierite, the raw material for Fe-Ni, is imported in bulk from New Caledonia, Indonesia and the Philippines. This report describes the acquisition of these raw materials, the production processes, trend of supply-demand, problem areas and the measures taken, and so forth, in connection with the nickel industry in Japan. ELECTROLYTIC NICKEL 1. History The nickel industry in Japan began in 1939 by the Sumitomo Metal Mining Co., Ltd. (SMM) with 150 tons E-Ni/month under the blast furnace smelting and the metal anode electrolysis. This was temporarily suspended after the end of last World War II, but resumed in 1952 with garnierite of New Caledonia as a raw material. Since then, the production capacity has been expanded incidentally to the increase of demand. However, since the smelting of garnierite contained about 2% nickel was very costly, the smelting process had been changed to smelt the briquettes of the mixture of garnierite and nickel sulfide concentrate imported from Canada and Australia. In 1975, this smelter was closed, and SMM's nickel refinery used matte from Western Mining Corp. (WMC) of Australia as a raw material. The refining process had been the metal anode one. The crude nickel oxide derived from roasting the high grade nickel matte had been melted and reduced with coke in the electric furnace and cast into anode. In 1970, a new refinery was constructed to produce 1,000 tons Ni/month under the matte anode process, and further, in 1976, the old refinery was converted into the matte anode process, thus resulting in the total production capacity of 1,690 tons Ni/ month today under the matte anode process. Shimura Kako Co., Ltd. began in 1951 to produce a little of E-Ni, and in 1955, they constructed a shaft furnace smelter with New Caledonian garnierite as a raw material to begin the E-Ni production under the matte anode process. Its monthly production reached 400 tons in 1957, but it discontinued its smeltering in 1963 to convert to the matte import from S. Le Nickel, WMC and INCO. In 1979, it changed the source of matte supply from the above to Soroako of Indonesia, discontinued the E-Ni production in 1979, and arranged for a total toll contract with Sumitomo. Meanwhile, SMM has developed a very distingished process for nickel-cobalt separation and refining by a solvent extraction method from nickel and cobalt mixed sulfide generated as a by-product in the nickel recovering process from laterite under the Nicaro process. Nippon Mining Co., Ltd. (NMC) also developed its own process. The plants under these processes were constructed in 1975, with the monthly production capacity of 230 tons of nickel and 130 tons of cobalt by SMM, and 300 tons of nickel and 110 tons of cobalt by NMC. SMM imports the raw material from the Marinduque Mining and Industrial Corp. of the Philippines, while NMC from Queensland Nickel Pty. Ltd. of Australia. 2. Production Status 2.1 Producers and materials Today, SMM holds the monthly E-Ni production capacity of 1,920 tons, of which 1,690 tons are from the matte anode process, and the remaining 230 tons are from the mixed sulfide as a raw material. NMC also uses the mixed sulfide as a raw material for a production of 300 tons/month. [ ] Most of SMM's raw material, nickel matte, is imported from WMC of Australia, partly using the Soroako matte from Indonesia. An example of material analysis is given in Table 1. Matte is a raw material for E-Ni and NOS, and the major sources of matte supply at present are Australian WMC and Indonesian Soroako, occupying ap-

Jan 1, 1982

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 W. O. Philbrook, R. S. Kaplan

Rates of oxidation were studied for levitation-melted samples of Fe-C, Fe-Si, Fe-C-Si, Fe-C-P, Fe-C-Mn, and Fe-C-S alloys oxidized by mixtures of either 5 or 10 pct O2, in helium at several temperatures in the range 1850o to 2050°C. The concentrations of the oxidized elements decreased linearly with time. Mass transport in the gas phase was found to be the rate-controlling step. Ilowever, a mulliple -film model was necessary to account for the flux of iron and manganese vapor counter to the oxygen flow. THE advent of the basic oxygen and spray-refining processes of steelmaking has generated considerable interest in the kinetics of reactions between oxygen-bearing gases and liquid iron alloys. The object of this research was the determination of the role of mass transport in the gas and metal phases and of surface chemical reactions in the overall oxidation process. Of the reactions for elimination of elements dissolved in liquid iron, the oxidation of carbon has been investigated most extensively. Studies by Fuji and Ura,1 Fuji,' and Gunji et a1.,3 done with pilot-scale basic oxygen furnaces, indicated that mass transport of gaseous oxygen was rate controlling when the metal carbon content was greater than 0.15 to 0.30 pct. When the carbon content was less than this critical amount, diffusion of carbon dissolved in the iron was thought to be rate limiting. L. A. Baker et a1.4,5 levitated samples of iron-carbon alloys and oxidized them in CO-CO2, CO-C02-He, and O2-He atmospheres at 1660°C. These investigators found that the metal carbon concentration decreased linearly with time and their samples exploded when the carbon content fell below about 0.8 pct. They concluded that the rate-limiting step was the transfer of oxidant to the gas-metal interface. A model based on this rate-limiting step predicted decarburization rates within a factor of two of those experimentally observed. The explosion of the samples was attributed to a shift in rate-controlling step from gas-phase mass transport to transport of carbon dissolved in the metal. L. A. Baker and R. G. ward6 and R. Baker7 used freely falling droplets to investigate oxidation kinetics. In both papers, the authors speculated that flame fronts may have been partially responsible for the lack of better agreement between experiment and theory. Swisher and Turkdogan8 oxidized liquid iron having an initial carbon content of 0.97 pct with CO-CO2 and CO-C02-Ar mixtures at 1580°C. They concluded that a surface reaction was the rate controlling step. Iron-silicon alloys have been oxidized by R. Baker7 and Filipov and Martynov.9 R. Baker 7 also studied iron-carbon-silicon alloys falling as liquid droplets through oxygen. He found that the rate of both carbon and silicon oxidation varied inversely with the drop radius. When the initial silicon concentration was greater than 6 pct, the samples cooled during their fall. Manganese oxidation has been studied by R. Baker,7 and by Filipov and Martynov.9 ward10 investigated the loss of manganese from liquid iron under vacuum. He found that mass transport of manganese vapor was rate limiting in argon atmospheres of 0.02 torr to 700 torr pressure. Iron-sulfur alloys were desulfurized with H2-He and H2-Ar mixtures by Peters et al.11 A model based on the transport of H2S from the gas-metal interface into the bulk gas gave fair agreement between the predictions of the model and the experimental results. EXPERIMENTAL TECHNIQUE Essentially, the technique consisted of using helium-oxygen gas mixtures to oxidize levitated samples of liquid binary and ternary iron-base alloys. The fused silica reaction tube is shown in Fig. 1. The coil design is similar to that of L. A. Baker et al.4'5 A Tef-lon-sheathed, ferritic stainless steel lifter (B) and an alumina pedestal (C) were used to support the sample in the coil prior to levitation and for the recovery of the sample. Samples were inserted into

Jan 1, 1970