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By Ellis H. Gates

BENEFICIATION of the manganese oxide ores at Three Kids Mine near Henderson, Nev., has evolved over a period of years. Commercial application of the process is on a secure basis, and an effective working hypothesis has been formulated to help solve the problems encountered in flotation. An outstanding difference between the Manganese Inc. operation and other flotation processes is the necessity for high recovery of slime mineral values. Part of the manganese minerals in the Three Kids ore deposit occurs as primary slime or as minerals that are easily slimed by grinding. High recovery of this slime portion is essential to an economic overall manganese recovery. The aim of much of the research at Manganese Inc. was to recover these slimed and finely ground minerals by flotation. Early Agglomeration Processes: Tunbridge' in 1880, followed by Everson2 in 1886 and Cattermole" in 1904, discovered that under certain pulp conditions precious metals and sulfide minerals could be agglomerated if enough soap or oil were mixed into the pulp slurry. These agglomerated particles, Which under ideal conditions ranged from 1/16 to 1/4 in. diam, were recovered by screening, tabling, and hydraulic classification. Even flotation by air occluded in the agglomkrate particles by vigorous stirring was suggested. Cattermole nearly succeeded in getting his process into commercial operation, but it was finally abandoned, presumably because he could nat compete with the low reagent requirements of the new agitation froth process. Since Cattermole's time Christensen in 1921, Borcherdt4 in 1926, and Chapman and Littleford- in 1934 have attempted to apply the principles of agglomeration. In the light of current research at Manganese Inc. on conditioning of pulp at high energy input levels, it is interesting to note the variety of equipment such as tumbling mills, mixing drums, and shakers described by Borcherdt in his patent to produce the agglomerated particles. Ore Characteristics: Manganese in the Three Kids ore occurs as a 'complex mixture of manganese oxides commonly Known as wad. The manganese minerals have Been identified as psilorflelane, hollandite, coronadite, and pyrolusite with minor amdunts of rhodonite and rhodochrbsite. The ppincipal gangue miherals are quaktz, opal, kaolinite, montmoril-lonite, calcite, gypsum, fcelesitite, and barite. Most of the mangandse ore minerals are either porous and sponge-like in structure or soft clay-like masses composed of fine grained mineral particles approaching the size range of colloids. Consequently the ore minerals from the Three Kids mine have relatively large surface areas and high void content per unit weight. The specific area of various manganese ore samples measured at the California Research Corp. laboratories ranged from 32 to 58 sq m per g. The great surface area and high void content explains in part the unusually high reagent consumption required in the treatment of this ore. Current Milling Practice: At Henderson6 he ore is crushed to —1 in. and ground with rod mills in a closed circuit with spiral rake classifiers and cyclones. Sulfur dioxide solution is added to the pulp as it leaves the grinding circuit, immediately followed by addition of a reagent mixture of soap, oil, and wetting agent in the form of an emulsion. The reagents are initially well mixed into the pulp during their passage through centrifugal pumps to the conditioning equipment. All reagents are added prior to conditioning. The intense conditioning or mechanical stirring of the pulp, in which large amounts of power are consumed, is the principal difference between the flowsheet used at Manganese Inc. and a standard flotation circuit. As much as 38 kw-hr of energy per dry short ton of ore in a pulp containing 18 to 23 pct solids is used for conditioning. After conditioning, the pulp passes to a flotation circuit that consists of one roughing stage, a scav-

Jan 1, 1958

By R. M. Asimow

Both smith1 and wells2 have shown that the dif-fusivity of carbon in austenite increases rapidly with increasing carbon concentration. Smith has shown, in addition, that part but not all of this increase can be attributed to the concentration dependence of the activity coefficient of carbon in austenite. From the work of Eshelby', it is known that, because of the image displacements, there is a uniform dilatation of the material in a body containing random centers of dilatation. It is thus tempting to explain the enhanced diffusivity as resulting from this apparent negative pressure caused by the interstitial carbon atoms.* That is, the activation free energy for diffusion is not directly a function of concentration if we consider that the alloy is subjected to a concentration-dependent pressure. To proceed with a quantitative solution, it is necessary to determine the activation volume AV for the diffusion process. An exact calculation of AV is quite a difficult problem and does not appear to have been solved as yet. A simpler procedure is to use the semiempirical, macroscopic theory of seyes' which relates the activation free energy AG to AV. Keyes has shown that for many types of diffusion processes the following relationship is valid Where p is the Gruneisen constant and x the compressibility. This relationship is based on the assumption that AG can be identified with strain-energy terms. In general there will also be contributions to AG due to a change in the energy of the valence electrons of the metal; thus the relation must be considered largely empirical. Surprisingly, for self-diffusion where it is well-known that the electronic contribution is quite important,' the Keyes relation works quite well for many systems. For interstitial diffusion where it might be expected that the relationship is on a firmer theoretical basis, the limited experimental data available is not in particularly good agreement as can be seen from Table I. However, it must be remembered that besides the uncertain basis of the Keyes formula there is considerable uncertainty in some of the experimental values of AV. The only real justification for using the Keyes formula in the present analysis is that it gives a result which satisfactorily solves the problem at hand and, further, there are no more reliable procedures for calculating AV available. The coefficient 3 in Eq. [I] is determined such that the room-temperature value for x is to be used. The activation entropy AS is estimated as 8.95 x 10"3 kcal per OK mole using the values in Table I1 and the Zener" relation AS = PAHIT, where p is a dimensionless thermal coefficient of Young's modulus which is to be evaluated at low values of T/T,, aH is the activation enthalpy, and T, is the melting temperature of the alloy. The resulting value of AG at 1000°C is 25.6 kcal per mole. The Gruneisen constant (p = 3cup/XC,), where p is the density, is evaluated from the room-temperature data in Table I1 after calculating C, from the relation. A value of p = 8.32 g per cu cm based on the value of a. in Table I is used. The result is C, = 5.0 x lo6 erg per g, H = 2.32, and AV = 3.41 cu cm per mole at 1000°C and infinite carbon dilution. It is assumed that the activation volume is not a function of carbon concentration. The theory could be refined to consider AV a function of concentration, but due to the uncertainties in the parameters there seems little justification for this. Carbon dissolved in austenite forms a nonideal solid solution, so that in writing an equation for. the diffusivity of carbon it is necessary to take into account the change in activity coefficient with concentration. The resulting equation is16

Jan 1, 1964

By George W. Bain

Methods of mining building stone of any sort are planned to produce as few fractures as possible, and present a strong contrast to methods of mining metallic ores, which must be crushed eventually and have fractures produced in as great profusion as possible. Shocks transmitted to a stone invariably make it more porous and more permeable and reduce its effective life, therefore methods of mining building stone involve as This building illustrates the fine detail of workmanship, unprotected sharp corners and thin edges, and tall narrow columns characteristic of marble structures. These features require exceedingly coherent stone, and preservation of these features for decades or centuries demands many special quarrying precautions to keep absorption to 0.14 per cent or less, a detail not essential to stone for coarser architectural types. few shocks as possible. This is singularly true for marble because marble structures are intended to have long life, greater delicacy of line, more gracefulness and fineness of sculpture than those made from any other structural material (Fig. 1). So that delicate lines may remain in almost perfect preservation for decades, or even centuries, it is important

Jan 1, 1938

By George W. Bain

Methods of mining building stone of any sort are planned to produce as few fractures as possible, and present a strong contrast to methods of mining metallic ores, which must be crushed eventually and have fractures produced in as great profusion as possible. Shocks transmitted to a stone invariably make it more porous and more permeable and reduce its effective life, therefore methods of mining building stone involve as This building illustrates the fine detail of workmanship, unprotected sharp corners and thin edges, and tall narrow columns characteristic of marble structures. These features require exceedingly coherent stone, and preservation of these features for decades or centuries demands many special quarrying precautions to keep absorption to 0.14 per cent or less, a detail not essential to stone for coarser architectural types. few shocks as possible. This is singularly true for marble because marble structures are intended to have long life, greater delicacy of line, more gracefulness and fineness of sculpture than those made from any other structural material (Fig. 1). So that delicate lines may remain in almost perfect preservation for decades, or even centuries, it is important

Jan 1, 1938

By Glenn Keep

THIS paper is not an announcement of the successful conclusion of the Cerro de Pasco Copper Corporation's pacos-pyrite problems, but merely a description of the commercial-scale, intermittent-roasting operations conducted by the writer, J. H. Lucas and others of the staff. It was prepared by request, for presentation at the February meeting of the Institute. The results obtained in Peru confirm the 1-ton-a-day experiments completed about three years ago at Kearny, N. J. by C. C. Gordon and Mr. Lucas, where it was first demonstrated that a mixture of about 80 per cent. pacos ore with 10 per cent. pyrite ore and 10 per cent. salt could be roasted intermittently in a small 1-ton-a-day Holt-Dern furnace without extraneous fuel, producing porous calcine that could be leached rapidly. Mr. Keep and his staff, by successfully introducing improvements in the construction of the commercial furnace and in their handling of material, have established beyond doubt a low cost for roasting. The other steps in the process of treating pacos and pyrite ores have not as yet been demonstrated as sufficiently conclusive to warrant their acceptance for a permanent plant.

Jan 1, 1929

By Milton E. Wadsworth, J. Brent Hiskey

INTRODUCTION Fifteen years ago a distinguished electrochemist referred to electrochemistry as an "underdeveloped science " In the article in question, Professor Bockris (1) stated that many areas of.natura1 phenomena and applied technology are not perceived as being electrochemically based At that time, this was especially true for much of non-ferrous extractive metallurgy and was a particularly accurate description of hydrometallurgy During the last decade, there has been considerable advancement in applying the theory of electrochemistry to our know1 edge of hydrometallurgical processes and in understanding the mechanisms of underlying electrode reactions. Impressive as these advances are, there is still a growing need for electrochemical research of mineral systems and electrochemical engineering to apply this work in practical situations In a broad sense electrochemistry is defined as the physical chemistry of ions in solution and of phenomena which occur at the electrified interface. Bockris and Reddy (2) refer to electrochemistry as being divided into two fundamental domains, ionics and electrodics ionics is restricted to the behavior of ions in solutions, examples being many familiar redox processes Electrodics represents the main part of electrochemistry, and is the study of charged interfaces and the conditions governing charge transfer reactions across them. Considering hydrometallurgical applications, electrodics suggests the following relationship for a conducting solid (bulk or surface)

Jan 1, 1981

By C. W. Lawr

THE ores mined by the Santa Gertrudis Co. at Pachuca, Mexico, are mainly silver-bearing; they also yield some gold and carry a little copper. Strong cyanide solutions are used to dissolve the silver and gold, and the mechanical loss of cyanide at the tailings filter has been considerable. Prior to the year 1923, the pulp, after agitation, was given a 35 to 37-min. wash with barren solution in a Butters-type leaf filter; the discharged slime cake was repulped and pumped into eight Merrill self-sluicing slime presses in which the slime was given a further wash with barren solution for 25 to 35 min., followed by a 10-min. water wash. At that time the barren solution titrated around 0.350 per cent. free KCN and 0.500 per cent. total KCN. (Aero brand cyanide is used.) It can readily be seen that a 10-min. water wash would leave considerable cyanide in the filter cake, which of course was a total loss. This averaged 0.522 kg. (1.15 lb.) KCN per ton of solution. As the daily discharge to. the dam was 1600 tons1 of slime of a 2: 1 ratio of liquid to solid, the value of this mechanical loss of cyanide was an important item and its recovery held alluring possibilities.

Jan 1, 1929

By Linn M. Farish

The reported production of petroleum in the Dominion of Canada for 1930 was 1,555,199 bbl., an increase of 455,373 bbl. over 1929. Alberta accounted for nearly all the production with Ontario and New Brunswick, the other two productive provinces, contributing less than 1 per cent, of the total. The completion of about 25 producing wells in Alberta was more than sufficient to offset the decline of the older wells in that province and the small decline in Ontario. The production of about 5000 bbl. in New Brunswick represents a restricted output to meet the market demand. Table 1 shows the production by provinces for the past 10 years. The consumption of natural gas for all purposes in Canada reached a new record of practically 40,000,000,000 cu. ft. in 1930, which was a considerable increase over 1929. The estimated value of the gas output was $10,500,000, against a little over $5,000,000 for the total petroleum production. Gas wells in Alberta accounted for over 75 per cent. of the total, with Ontario second and New Brunswick a poor third. The outlook for 1931 is for very little change in production of either gas or oil in Ontario and New Brunswick but for a substantial increase in both in Alberta.

Jan 1, 1931

By Roy A. Koski

INTRODUCTION Cleveland-Cliffs Iron Company, and its subsidiary companies, operate and manage mining, beneficiation, and pelletizing operations in the Upper Peninsula of Michigan, the province of Ontario, Canada, and the State of Western Australia, Australia. The concentrates and natural ores vary mineralogically, physically and chemically. This paper describes the techniques employed in pelletizing the various concentrates and ore fines. The plant operations described are the Republic, Humboldt, Tilden, Empire and Pioneer in Michigan, the Adams and Sherman in Ontario, and the Robe River in Western Australia. Table 1 contains further details regarding design and operating capacities, commissioning dates, and participant ownerships. Allis-Chalmers grate-kiln systems are utilized in Michigan and Ontario, and Dravo straight-grate systems in Western Australia. Currently, the Empire and Tilden operations are being expanded. At Empire the additional pelletizing unit, identified as Unit IV, will have a design capacity of 8 996 metric tonne/d and is scheduled for startup May 1, 1979. The Tilden operation is being doubled with the additional pelletizing unit, identified as Unit 11, having a de- sign capacity of 12 599 metric tonne/d. Startup is scheduled for January 1, 1980. MINERALOGY OF CONCENTRATES AND NATURAL ORES In the Upper Peninsula of Michigan, the operations process ores from the Negaunee iron formation of the Marquette Range. The

Jan 1, 1977

By A. J. Goss, M. Tanenbaum, W. G. Pfann

THE purification of two metals, antimony and tin, by zone refining is described, and a reciprocating method of passing molten zones through a straight ingot, which effects a considerable economy of time and apparatus, is discussed. Antimony has been used extensively as a doping agent in germanium and silicon. More recently, it has become important in the preparation of new semiconducting compounds such as InSb, GaSb, and AlSb. High purity is especially necessary in this latter use, since the antimony may comprise as much as 80 pct by weight of the compound. Antimony is generally available in a commercial form of about 99.8 pct purity. Column 1 of Table I is a typical emission spectra analysis of commercially available 99.8 pct antimony. Zone refining has been quite successful in increasing the purity of such samples. Columns 2 to 4 of Table I are analyses of an ingot of the antimony of column 1 after the passage of seven molten zones in an atmosphere of nitrogen. The ingot length was 9 1/2 in.; the mean zone length was 2 in.; convection was the only means of stirring. The column headings are sample locations in inches from the leading end of the ingot. The results illustrate both the merit and a limitation of zone refining. It is seen that four of the five impurities—nickel, arsenic, lead,

Jan 1, 1955

By Chauncey L. Berrien

The United Verde Copper Company's mine is at Jerome, Ariz. The orebodies arc of the schist replacement type, the main sulfide mass being a large lens-shaped body approximately 7 acres in cross-sectional area. In general, the mineralization is found along the iron schist contact, with the orebodies extending about 1000 ft. along this contact and varying from a few feet to 250 ft. in width. Three types of ore are mined; schist porphyry and the so-called "heavy" or "massive sulfide" ore. Approximately 50 per cent. of the total tonnage mined at present is of the latter class. A representative analysis of this ore indicates 42 to 46 per cent. sulfur. Because of the high sulfur content, blasting in this ore is an extremely hazardous operation. not only does it endanger the lives of men who may be in the mine at blasting time but it also becomes a potential fire menace when timber is in close proximity to shots being fired in these massive sulfides. The origin of the fires of 38 years ago, embers of which are glowing to this day, may perhaps be attributed to dust explosions due to blasting in the massive sulfides of those early square-set stopes. Dust Explosions Dust explosions in coal mines are a common source of mine disasters. That such explosions may be of common occurrence in metal mines is not generally known, but it is known that metal-mine dust will explode and such explosions have been investigated by the U. S. Bureau of Mines at the Pittsburgh Experiment Station. Samples of "heavy sulfide" ore from the United Verde mine were used in the tests. After studying the results of the tests it was concluded1 that: 1. Dust explosions were initiated in sulfide ore dust in the gallery with a charge of as low as 75 g. of 60 per cent. gelatin dynamite. 2. The exploding dust generated considerable pressure.

Jan 1, 1930

By R. Hoffmann

The Waelz process produces oxides of volatilizable metals from ores, metalliferous products and residues. The process was originally used for recovering zinc and lead, where tailings and residues containing those metals had accumulated at mines or smelters, but it is applicable for obtaining tin, arsenic or other volatilizable metals. It is useful when other methods of obtaining the metals from the ores or residues are too difficult or expensive or show too low a recovery. The Waelz process was developed in 1923 for the treatment of large calamine dumps in Upper Silesia, which showed zinc contents of 8 to 10 per cent. and lead contents up to 3 per cent. The rapid development of the process, from the first trials up to the plants now working or in course of erection, is shown in Fig. 1. The first industrial Waelz plant was started in 1925. Within two years the capacity of the working plants reached 700 tons material per day of 24 hr. During the year 1928 the daily capacity of the plants now at work or in course of erection will rise

Jan 1, 1928

ALABAMA. Anniston.-Noble, A. E., 20th St. and Wilmer Ave. Auburn.-Brown, R. L., Box 0. Belle Ellen.-Hutcheson, W. C. Bessemer.-Abbott, C. E., T. C., I. & R.R. Co Dobbs, G. G., Box 97. Ferguson, V., U. S. C. I. Pipe & Fdy. Co. Williams, E. P., Tenn. C., 1. & R. R. Co. Birmingham.-Aldrich, T. H. Aldrich, T. H., Jr., 406 Woodward Bldg. Allen, A. W., 1616 S. 14th Ave. Bowron, J., 1401 S, 20th St. Burbidge, T. A., Brown-Marx Bldg. Coxe, E. H. Tenn. C., I. & R. R. Co. Crawford, C. G., Tenn. C., I. & R. R. Co. Crockard, F. H., Brown-Marx Bldg. Ellis, E. E.,1515 Brown-Marx Bldg. Fairbairn C. T., Woodward Bldg. Fies, M. H., 2316 Highland Ave. Geismer, H. S., Keiser-Geismer Engrg. Co.

Jan 1, 1917

By N. A. Ziegler

A CERTAIN amount of interest has been indicated recently in the resistance to oxidation at high temperatures of iron-aluminum alloys (rich in iron). Hautman1 published a paper in which some interesting results are given. According to his paper, only alloys containing at least 8 per cent aluminum indicate a marked improvement in their resistance to oxidation. At about this aluminum content, however, alloys become brittle, which considerably reduces their commercial value. About two years ago the author performed a series of experiments, the results of which are presented here. A series of iron-aluminum-carbon alloys was prepared by melting electrolytic iron, aluminum and high-carbon iron alloy in an induction vacuum furnace.2 The list of these alloys is given in Table 1. Each alloy was forged in the ordinary way to

Jan 1, 1932

By C. S. Matthews, H. M. Girner, C. D. Williams, M. J. Edwardson, H. R. Parkison

Quantitative interpretation of electric logs requires knowledge of formation temperature. In this paper, methods are developed for computing changes in formation temperature caused by circulation of mud during drilling operations. The basis of the method is the mathematical solution of the differential equation of heat conduction. The solution of this equation is presented in a series of graphs. These graphs are used to determine formation temperature disturbance at various radii for arbitrary mud circulation histories. Example comparisons with field results show reasonable agreement. It is concluded that, in general, the temperature disturbances caused by circulating mud are small beyond 10 ft from the wellbore but are quite significant near the wellbore. INTRODUCTION Quantitative interpretation of electric logs requires knowledge of the formation temperature in order to establish the resistivity of the formation water with accuracy. To determine the formation temperature, the temperature disturbances produced by circulating drilling mud must be evaluated. -The objective of this investigation was to develop a method for the numerical determination of these temperature disturbances at any distance from the wellbore as a function of time. The first step was to solve the differential equation describing the temperature behavior in the formation during and after mud circulation. This solution was used to calculate a series of curves relating temperature disturbance to shut-in time for various circulating periods. An "exact" method for computing formation temperatures with the use of these temperature-disturbance plots is described, and the results of an application of this method to a well in Montana are presented. Procedures for approximating formation temperatures are also discussed. BASIC EQUATIONS AND ASSUMPTIONS With the assumptions that (1) cylindrical symmetry exists, with the borehole as the axis, (2) heat flow is 1. The formation can be treated as though it is radially infinite and homogeneous in extent, as regards heat flow. 2. The presence of mud cake can be disregarded. 3. The effect of heat generated by bit action is negligible. 4. After mud circulation ceases, the rate of radial heat flow at the wellbore is negligible and is assumed zero for purposes of calculating temperature change with time. These assumptions are believed to be reasonable because of the agreement achieved between calculated and measured borehole temperature in a well, to be discussed later. Further, the agreement at the wellbore indicates that temperatures in the formation were also approximately correct. since it is the formation temperatures that determine wellbore temperature after ceasing circulations SOLUTION OF THE DIFFERENTIAL EQUATION AND ITS APPLICATION The solution of Eq. 2 for the temperature behavior during and after a single period of mud circulation is

By J. W. Spretnak, R. Speiser

IT has been suggested that boron in steel may form a film entirely around the austenite grain and that this film is responsible for the boron hardenability effect. In this connection, it is of interest to examine some of the ramifications of the concentration range of boron usually employed in hardenable steels, namely 0.0005 to 0.003 pct in a grain size range of ASTM grain size No. 1 through No. 10. The ratio of the iron to boron atoms and the number of unit cells of y iron per boron atom are listed in Table I. Even at the highest concentration considered, there are 1600 unit cells of y iron per boron atom, assuming a uniform distribution of boron. To investigate the possibility of the boron film formation, the number of boron atoms required to cover the grain surface completely must be calculated. With some transition elements, boron crystallizes in sheets composed of equilateral hexagons very much like graphite.' The selected value for the length of a side is 1.80Å. A simple calculation shows that two boron atoms cover an area of 8.4x l0 -16 sq cm. Table II lists the number of atoms of boron required for the formation of the monatomic film and Table III lists the number of boron atoms per grain. The hypothetical cases of 100 pct and 10 pct adsorption are calculated (all boron atoms in a grain and 10 pct of all boron atoms in a grain are located at the grain surface respectively). In Table 111, all combinations of grain size and composition below and to the left of the solid line (100 pct adsorption) and the dashed line (10 pct adsorption) are excluded as to the possibility of covering the grain surface with a continuous boron film. Thus, even for 100 pct adsorption, the smaller grains can form the film only at the higher concentrations. For the best case, grain size No. 1 and 0.0030 pct B, the required degree of adsorption is 3.9 pct. The above calculations deal only with the number of boron atoms required to form a monatomic film and do not take into account the mechanism of concentration of boron at the grain surface and the possible limitations to the extent of this concentration at a constant temperature, as for example in the austenitizing process. The question next arises as to how this surface concentration can occur during an isothermal treatment. Such surface enrichment of boron must occur through the phenomenon of surface adsorption, i.e., the concentration of solute atoms in solid solution in the vicinity of the surface without precipitation. A solute atom will tend to concentrate at the grain boundary if it reduces the interfacial tension. The possibility of adsorption effects involving both boron and carbon in iron has been discussed.' In general, the tendency for a sol-

Jan 1, 1954

By Robert L. Marovelli

A recent reorganization placed the health and safety research activities of the Bureau of Mines under a director, Division of Minerals Health and Safety Technology. The new health and safety research organization and its position in the Bureau hierarchy is shown in Table 1.

Jan 11, 1979

By Frederick Laist

Introduction IN a leaching process, having obtained the copper in solution, the choice of the precipitation method is influenced y the following factors: 1. Availability of precipitant. 2. Adaptability to the leaching process. 3. Final product desired. 4. Regeneration of leaching solutions. 5. Fouling of solutions. There are three general classes of precipitation methods: 1. The use of iron, scrap or sponge. 2. Electrolytic deposition. 3. The use of some gas or reagent y which the copper is obtained, usually in the form of an intermediate precipitate which requires further treatment. For example, the precipitation of the copper as Cu2Cl2 from chloride solutions, with SO2 gas. The use of iron is adapted to almost any process. It has the great advantage of extreme simplicity, and the recovery of the copper and any values present in a highly concentrated, easily treatable form. The disadvantages are the cost in isolated places, the uncertainty of the scrap-iron market, and the fouling of the leaching solutions. The latter is a serious factor, When a reagent such as salt is used in them, which makes necessary their re-use. Where applicable, electrolytic deposition is very attractive. The copper is obtained in a form directly marketable, there is a regeneration of acid amid no fouling of solutions. Unfortunately, chloride solutions do not lend themselves to electrolysis. An entirely satisfactory anode material has not yet been discovered, although magnetite, apart from being rather brittle, seems to answer the requirements fairly Well.

Jan 7, 1914

By Wido Tilmann

13.6-1. Importance. In Germany there are large tertiary brown coal reserves, most of which are located close to the surface. Therefore, brown coal has been recovered for many years by means of opencast methods. By utilizing a high degree of technology, a rational operation has been achieved, and as a result, the mining techniques have become renowned all over the world. After the war, all the dredgers and overburden spreaders, as well as the means of conveyance, had to be redeveloped for adapting this equipment to the changing conditions of the deposits. Numerous auxiliary machines were adopted from the American earth moving industry and altered according to the different requirements. As a result of such technical developments, the output per man and per shift was increased remarkably in spite of the deterioration of the geological conditions. In the whole of Germany, the total reserves of brown coal amount to 100 billion metric tons, of which 60 billion tons are situated in the Federal Republic of Germany. In the latter area, 8.5 billion tons will be recover- able by opencast means, of which 3.5 billion tons are already developed. The annual output reached 102 million tons in 1965. This total figure comes from four different mining districts: Rhineland, Helmstedt (town at the border of the Soviet occupied zone), Hesse, and Bavaria. The production figures (1965) are as follows: [ ]

Jan 1, 1968

By N. A. Gokcen, J. Chipman

Aluminum and oxygen dissolved in liquid iron were brought into equilibrium with pure alumina crucibles and atmospheres of known H2O and H2 contents to study the reactions: 1—Al2O3(s) = 2 Al + 3 0; 2—Al2o3(s) + 3H2(g) = 2Al+ 3H2o(g); and 3—H2(9) +O = H2O(g). Aluminum strongly reduces the activity coefficient of oxygen and similarly oxygen reduces that of aluminum. Values of the product [% All" • [% O]3 are much smaller than those found in previous experimental studies and are of the order of magnitude of the calculated values. ALUMINUM is the strongest deoxidizer commonly A used in steelmaking, but the extent to which it removes dissolved oxygen has been debatable. The relationship between aluminum and oxygen has not been determined reliably not only on account of the usual experimental difficulties at high temperatures but also because of uncertainties in the analyses of very small concentrations of oxygen and aluminum. The earliest experimental attempt of Herty and coworkers' was followed by a more systematic study of Wentrup and Hieber.' These authors added aluminum to liquid iron of high oxygen content in an induction furnace and considered that 10 min was sufficient to remove the deoxidation products from the melt. Parts of the melts thus obtained were poured into a copper mold and analyzed for total aluminum and oxygen (soluble plus insoluble forms), assuming that the insoluble parts were in solution at the temperatures from which samples were taken. It is conceivable that the furnace atmosphere in their experiments, consisting of mainly air at 20 mm Hg pressure, was a serious source of continuous oxidation and therefore that their oxygen concentrations were correspondingly high. Scattering of their data was explained to be well within the maximum inaccuracy of 10°C in the temperature measurements and errors of ±0.002 pct each in the oxygen and total aluminum analyses. Maximum and minimum deoxidation values, i.e., values of the product [% All' . [% O] differed by factors of 10 to 15; mean values of 9x10-11 and 7.5x10-9 ere reported at 1600" and 1700°C, respectively. Hilty and Craftsv determined the solubility of oxygen in liquid iron containing aluminum, using a rotating induction furnace. Pure alumina crucibles used in their experiments contained the liquid iron which in turn acted as a container for slags of varying compositions consisting mainly of Al2O3, Fe2O3, and FeO. The furnace was continuously flushed with argon, and additions of aluminum and Fe2O3 were made in the course of each experimental heat. The inner surfaces of their alumina crucibles were covered with a substance other than pure Al2O3, containing both iron oxide and alumina. Although frequent slag additions can change the composition of slag in the liquid iron cup formed by rotation, the inner surface of the crucible must depend upon the transfer of oxygen or aluminum through the liquid iron for any adjustment in composition. It is not clear that their metal was in equilibrium with the crucible wall, but it is clear that it was not in equilibrium with Al2O3. Their deoxidation product, [% A].]" • [% O]3, varied by a factor of more than 50; the average values of 2.8x10- and 1.0x10-7 were selected for temperatures of 1600" and 1700°C, respectively. Aside from the experimental determinations, attempts have been made to calculate the deoxidation constant for aluminum indirectly from thermody-namic data. Schenck4 combined the thermodynamic data for Al2O3 and dissolved oxygen in liquid iron by assuming an ideal solution. His calculated values are 2.0x10-15 and 3.2x10-13 at 1600" and 1700°C, respectively. Later, Chipman5 attempted to correct for the deviation from ideality and derived an expression which led to deoxidation values of 2.0x10-14 and 1.1x10-12 at 1600" and 1700°C, respectively. The errors in these treatments originate mainly from inaccuracies of thermal data and uncertainties regarding the activity coefficients of dissolved oxygen and aluminum. The purpose of this investigation was to study the equilibria represented in the following reactions in the presence of pure alumina: Al2O3(s) = 2Al + 3O K = aAl2.ao3 [1] Al2O3(s) + 3H2(g) = 2Al + 3H2O(g) H2O K2 = aAl2(H2O/H2 ) [2] H2(g) +O = H2O(g) K3 = 1/ao (H2) [3] The experimental method consisted of melting pure electrolytic iron, usually with an initial charge of aluminum, in pure dense alumina crucibles under a controlled atmosphere of H,O and H2 and holding

Jan 1, 1954