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By Albert W. Deurbrouck

This Bureau of Mines report describes the washability characteristics of 13 coalbed samples collected in Colorado. Such data are needed to evaluate the quality of the coals of the West, where most of our low-sulfur-content coal reserves are found. Of the 13 samples included in this report, 11 had a total sulfur content of 1 percent or less. All of the samples contained low percentages of ash or could be readily washed to a desirable ash level with minimal loss of yield. The coals ranged in rank from high-volatile A bituminous to subbituminous B; nine of the samples were high-volatile C bituminous. The coalbeds ranged in thickness from 6 to 26 feet; the average was about 8 feet.

Jan 1, 1970

By Harold F. Yde

Hydraulic tailing fill in the Butte deep-level mines resulted from studies made in 1958 by The Anaconda Co. Mining Research Department. At the time of the study, dry mine tailing was hauled via rail cars from the Anaconda tailing ponds, 25 miles distant, to the tailing fill plants of the underground mines at the Leonard, Anselmo and Mt. Con mines. Presently, tailing from the Weed concentrator in Butte is delivered to the Kelley shaft via pipeline and stope filling has become automated. Tailing at 30% solids is pumped 8000 ft horizontally and upward from the concentrator to the Kelley fill plant, where it is dewatered and deslimed by three Krebs cyclones. These discharge the material into the cased and grouted mine delivery boreholes at desired densities of up to 70% solids. The vertical boreholes and 4-in. rubber-lined Victaulic pipe carry the material downward to horizontal distribution lines, which in turn tap into the 3-in. stope-filling, unlined Victaulic pipelines.

Jan 1, 1970

By R. M. Hudson, P. E. Perry

Weight-gain data obtained by nitriding low-carbon sheet steel in an amrnonia CNH,) atmosphere indicated that the process obeyed a parabolic rate law. The calculated actization energy for nitriding in the range 964" to 1268°F agreed reasonably well with published data. At 1358"F, rate data indicated that the activation energy decreased. Weight-gain data obtained by uszng mixtures of NH3 -Nz at 1268°F containzng jrom 10 to 100 zol pct NH3 also obeyed a parabolic rate law. The rate of 'nitriding increased with an increase in the NH3 content of the gas Mixture. It is well-known that steel heated in gas mixtures containing ammonia (NH3) takes up much larger quantities of nitrogen than steel heated in nitrogen, both gases having a total pressure of 1 atm;' this phenomenon can presumably be attributed to the catalytic decomposition of NH3 on the steel surface to furnish nascent (monatomic) nitrogen. This process was studied bv Brunauer. Jefferson, Emmett, and Hend-ricks at furnace temperatures of 752" and 831°F2 using mixtures of NH3 in Hz. Englehardt and wagner3 reported that, at a furnace temperature of 914°F and under their experimental conditions, both nitriding and denitriding were controlled by the rate of gas-metal reactions at a steel surface rather than by the rate of diffusion of nitrogen in iron. The present study was undertaken to obtain information on the kinetics of nitriding low-carbon steel strip at higher temperatures so that practical rates for short-time strip-annealing treatments could be estimated. Variables studied included time: temperature, and NH, content in the annealing atmosphere. Mechanical and chemical characteristics of steel nitrided in this manner will not be considered in the present article. MATERIALS AND EXPERIMENTAL WORK The samples used were from a commercial low-carbon steel, 0.0244 cm thick, in the cold-reduced condition. The chemical composition of this steel is given in Table I. Panels were cut to 5.1 by 17.8 cm, degreased in toluene, and weighed just before treatment. Four specimens were nitrided under each of the experimental conditions. A study was made of the nitriding rate of steel in a 100 vol pct ammonia atmosphere, 740 mm pressure, at five specific temperatures within the range 964" to 1358°F. The nitriding rates of steel in ammonia-nitrogen gas mixtures containing 10, 18, 26, 50, and 100 vol pct ammonia, 740 mm total pressure, at 1268°F were also determined. All atmospheres used were dried by successively passing them through drying towers packed with soda lime and with Linde Molecular sieve Type 4A. Quoted gas compositions refer to those entering the furnace. Specimens were held in the constant-temperature zone of a vertical annealing tube furnace for times of 14, 3, 5, 10, or 15 min. Gas flow rates were maintained at 3.8 cu ft per hr, which was nineteen volume changes per hour for the system used. The rate of flow was selected to provide a high level of free NH3 for cracking on the steel surface where the ammonia gas is most effectively used as a nitriding agent. The vertical annealing tube furnace consisted of a Hevi-Duty tube furnace with a 2 1/2-in.-ID mullite ceramic high-temperature tube. The constant-temperature zone (controlled within 10°F) was about 10 in. long. After each specimen was degreased, a hole was punched in one end, for attaching the specimen by hook to a chain so that it could be lowered into or raised from the high-temperature portion of the tube by means of a power-driven winch. A stainless-steel access port with O-ring seals was connected by suitable glass-to-metal seals to the cool upper portion of the furnace tube. After the weighed specimen was placed in the access port, the furnace tube was evacuated to approximately 10"3 torr, and then the system was flushed thoroughly with the atmosphere under study. When the gas flow rate and constant-temperature zone of the furnace were established, the specimen was lowered into the constant-temperature zone. The atmosphere flowed from the top to the bottom of the vertical furnace tube and was then vented. For all these runs, during the first 3 min of the time the specimen was in the constant-temperature zone of the furnace the specimen was heating up to the tempera-

Jan 1, 1970

By Jean Bonnemaison

Societe Miniere & Metallurgique de Penarroya Noyelles-Godault works are located in the northern part of France. The complex includes a lead smelter, a zinc smelter, shops for production of manufactured products and all necessary general services. The zinc smelting complex described in this paper was designed in 1959 to replace an old horizontal retort distillation furnace and was first operated in May 1962. It includes: - a sinter plant producing the zinc sinter for the Imperial Smelting furnace : zinc, lead and bulk zinc-lead concentrates are sintered on a Dwight-Lloyd machine with a working area of 80 sq.m. Cadmium sludges are treated by the wet method in a separate plant for recovery of cadmium. Sulphur dioxide contained in gases goes to a gas washing tower and is subsequently made into sulphuric acid in a plant with a capacity of 550 m.t. per day. - a smelting plant where the process developed by Imperial Smelting Processes Ltd. is applied : the blast furnace which was modified in 1967 has an area of 17.5 sq.m. at the tuyeres level and a section of 24 sq.m. at the top of the shaft. It has a theoretical zinc capacity of 100,000 m.t. per annum. Air blast is heated by means of covers up to the theoretical temperature of 950ºC. Zinc produced is either directly cast into slabs for sale as standard 'good ordinary brand' zinc, or sent to a refining plant where the New Jersey process designed to produce 'special high grade' zinc is in application. Mixes of zinc containing various amounts of lead, cadmium or aluminum are prepared to customer specification in a mixing plant.

Jan 1, 1970

By David G. Van Hersett

The single most unique design feature of the Centralia Coal Mine is the public information program. Just what the heck does public information have to do with the development of a coal mine? The utilities of today have had to build larger and larger plants to keep down the costs of power to the consumer. The large plants require huge amounts of capital, take up large areas of real estate, consume unprecedented amounts of coal, and generate large quantities of waste products which have to be reckoned with. Coal mines supplying these plants have also increased in size and production to meet the power plants' unending appetite for coal. This means the disturbance of great areas of land and significant alterations to the landscape. Today's public is greatly concerned about the environment in which he is living. The great size of a power plant with its large stacks, coal piles, and the coal mine with its large earth movers, disturbed acreages and the resulting waste products of both operations appears to present a threat to his environment. Because of this,' many power plants and coal mines are having public acceptance problems. This has resulted in the passage of stringent legislation and in some cases brought upon construction delays for major power plants.

Jan 1, 1970

By S. G. Dixit, A. K. Biswas

The flotation and adsorption behavior of ilmenite, monazite and zircon have been studied with sodium oleate as the collector and pH as the principal variable. The maxima in the flotation and adsorption properties of any of the above minerals fall within similar pH ranges. The bell shaped pH versus adsorption magnitude (r) curve is explained on the basis of collector concentration (Co and the concentration of hydroxyl ion (COH-) acting as the depressant. An equation of the type: 1 =KiCor~K2 Coh-/Coi-is proposed to account for the experimental data. The beach sand deposits along the sea coast in Southern India contain ilmenite, monazite, zircon, rutile and sillimanite as valuable minerals while quartz, garnet, shells and traces of hornblende form the gangue. A typical composition of the deposits is reported to be as follows:' Ilmenite 75%, Zircon 4-6%, Rutile 3-4%, Monazite 2 - 4%, Garnet 2 - 5% and the rest 8 -10%. Selective flotation of beach sand constituents has been reported by many workers.2-4 The fatty acid soaps have been invariably used as collectors. It is seen that all the valuable constituents of the beach sand are efficiently floated by soap collectors such as sodium oleate. In order to selectively float the beach sand constituents, it is necessary to use some depressants such as sodium silicate.3 The physicochemical parameters that govern the flotation of these minerals are yet to be studied in detail. In the present article, the findings on the parallel studies on the flotation and adsorption of the systems — ilmenite-sodium oleate, monazite-sodium oleate and zircon-sodium oleate — are being reported. In these correlative studies on adsorption and flotation of beach sand minerals, ilmenite (FeTiO3), monazite (Ce, Dy, Nd) PO4 and zircon (ZrSiO,) have been selected because they represent three important

Jan 1, 1970

By Gernot Kostorz

In a recent paper, Raffo and itcheell1 compared solid solution hardening of various bcc alloy single crystals at room temperature and concluded that the expression for localized elastic interaction between dislocations and solute atoms2 that gives the critical resolved shear stress (CRSS) 7,: to = Z . µE3/2 C1/2 where c = concentration, e = misfit parameter, (µ = shear modulus, Z = numerical constant Fig. 1—The slope dT0/dc1/2 for niobium alloy single crystals deformed at 570°K plotted against the misfit parameter € = In' I + 1616 I. from Ref. 6, •estimated from Ref. 7. Table I. Plateau Hardening and Alloy Parameters for Niobium Alloys dT0/dc1/2, kg/mm2 Solute Ref. 6 Tantalum 3.7 ± 0.3 1.9 0.73 + 0.06 9 0.0 ± 0.5 15 Vanadium 16.1 ±1.4 - 0.69 i 0.01 9 -7.4 ± 0.5 16 Tungsten 12.5 ? 1.5 20.9 0.92 i 0.05 10 -5.0 t 0.4 17 Rhenium - 25.9 1.24 11.12 -8.5 ± 0.4 I5 Molybdenum - 14.6 1.04 13,14 -4.6 s†±?˜µ?fF?? 0.5 17 Hafnium - 13.9 0.37 12 4.8 ± 0.5 17 Table 11. Solid Solution Hardening and Alloy Parameters for Tantalum Alloys i)' dTo/dc1/2 kg/mm2, dTp/dc1/2 kg/mm2, Ref. 22 1006 Solute ˜570°K Ref. 7 See Text Ref. 25 Rhenium 44.3 32.5 0.65 -8.5 Tungsten 32.1 24.3 0.34 -4.6 Molybdenum 29.3 19.1 -0.19 -5.9 Niobium 5.8 5.5 -0.43 0.I

Jan 1, 1970

By Robley D. Evans, Gerald L. Schroeder

Advanced techniques for control of radon (Rn) daughter product concenrrations (working levels, WL) in the uranium mines are discussed. Understanding the physical laws which govern the flux of radon into a mine, the growth and decay of the radon daughters, and the particulate nature of the daughters when suspended in air allows ventilation personnel to improve the quality of mine air with no increase in ventilation rate. The task of controlling, in a mine atmosphere, the short-lived nuclides produced in the decay chain of radon is a unique problem and as such should be approached with ventilation techniques specific to the problem. For most mines this has not been the case. Rather, procedures for removing these airborne radioactive nuclides have been borrowed directly from ventilation experience in mines where dilution ventilation was the traditionally accepted approach for air purification. With radon daughter products, this has often led to frustrating difficulties and expense. Primary origin of the airborne radioactivity is the a-ray-emitting noble gas, radon (222Rn, Rn), a nuclide formed by the decay of radium (226Ra, Ra). Radon, being a gas, may escape from its parent crystal and diffuse through the parent mineral into the interstices of the rock body. In a sandstone structure, about 20% of all the radon formed may find its way into the interstices of the rock. If a cavity such as a mine is nearby, the radon may diffuse through the rock interstices into the mine. While radium is usually highly concentrated in uranium ores, it is also found in varying concentrations in all minerals. Radon is therefore present in all minerals. In normal glacial till, the equilibrium interstitial radon concentration often equals 5000 pCi (picocurie, also uuCi) Rn per liter of pore volume.' In normal granitic rocks, the interstitial radon concentration often approaches 30,000 pCi per 1. Considering these typical, high-radon concentrations, radioactivity from airborne of daughter products is a potential problem unique not only to the uranium mining industry and should be considered as a potential hazard in all underground environments.

Jan 1, 1970

By Turno De Michelis

The Porto Marghera plant was erected in 1936 for the production of 10,000 tons of electrolytic zinc annually. Since then it has been continuously enlarged until annual production of the metal reached 40,000 tons in 1969. At the same time the processing cycle was modified bringing it up to date with modern techniques, and was completed by installations for the recovery of by-products in the minerals treated and subsequent processing of the base metal. 90% of the zinc produced is of 99.993% purity . At present the plant comprises, first of all, the zinc blende desulphuration department which has a single modern fluid bed furnace capable of processing 220 - 250 tons of dry crude mineral daily; it is connected to the sulphuric acid plant with its three catalysis sections each capable of producing 60-70 tons of sul9huri.c acid monohydrate daily. The roasted blende is conveyed pneumatically to plants for leaching of the zinc and purification of the resulting solution. During recent years this department has been completely transformed from the discontinuous cycle, for which it was built, to the continuous cycle, paying great attention to

Jan 1, 1970

By Dale R. Andrus

Why is there such an increased thrust toward positive multiple use land management and where will it lead? History and purpose of the mining law of 1872. John Marshall discovered gold at Sutter?s mill near Coloma, California, on January 19, 1848, and utter chaos resulted. The great migration of people to the undeveloped western lands had begun. Prior to this discovery, copper, lead, and iron had been the minerals for which the laws were made. With this discovery of gold on the public domain, it became apparent that congressional legislation was necessary. This became even more apparent as each of the numerous mining districts which were springing up in California, and elsewhere in the west adopted local miners' customs to regulate their activities. Although these early miners acted under mining district rules and in some cases state regulations, they were, in reality, appropriating minerals without sanction of federal law.

Jan 1, 1970

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick's law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert's law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick's Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970

By Rex D. Thomas

Concentration of the kerogen (organic material) in oil shale was accomplished by centrifuging after pretreating the oil shale with carbonic acid to remove the carbonates and pretreatment with sodium hydroxide (pH 11.5) to remove the claylike minerals. Analysis of the materials obtained showed that the concentrations of organic sulfur and organic nitrogen compounds were not affected by centrifuging. These compounds are evenly distributed in the kerogen and are not strongly bound to the mineral constituents. Organic oxygen compounds, however, were concentrated in the light fraction. These compounds are more closely associated with the kerogen and are not bound to the mineral constituents. Iron compounds other than pyrite apparently are closely associated with the organic material.

Jan 1, 1970

By J. P. G. Farr, R. Brownsword

THE role of solute segregation in the formation of cellular solidification substructures in tin and its dilute alloys is well-established, see, e.g., Ref. 1. Segregation has been shown to persist during cooling, enabling solidification structures to be studied from sections taken at some distance behind the interface. In the present work, a single crystal of commercial nickel, 99.965 pct, was examined in this way. The crystal was cut from the center of a rod given a single pass in an electron beam floating zone melter. Polished sections of a nickel specimen taken normal to the growth direction showed a very fine precipitate phase, the distribution of which varied over the section. The identification of the phase proved difficult because of the small amount present and the small particle size, about 1 p: but it was shown by probe microanalysis to contain only nickel and oxygen in detectable concentrations and was probably nickel oxide, NiO. Bulk analysis of the material before melting showed there to be only 3 to 4 ppm of oxygen present, thus demonstrating a very considerable segregation concentration effect. In some areas of the section the precipitate formed a discontinuous hexagonal network suggesting decoration of the cellular boundaries known to be present in the sample2 whereas in a restricted region the precipitate formed small clusters. Occasionally it could be seen that the clusters were at the intersections of an hexagonal network of cellular dimension. It was suggested3 that this was the result of enhanced segregation to the cell boundary intersections whereas general cell boundary segregation was insufficient to give a precipitate. Enhanced nodal segregation has since been demonstrated in a number of systems.1, 4-8 The development of a suitable electrolytic etching technique (perchloric acid 20 pct v/v; ethyl alcohol 70 pct; glycerol 10 pct; current below electropolishing plateau; 1 to 2 sec etching) suggested the association of the phase with regions of solute segregation (where ko < 1); in these regions anodic attack produced grooves or depressions. In a study of the variation of solidification substructures with degree of constitutional supercooling, Biloni et a1.&apos; appear to have used standard growth conditions and varied the solute concentration. They were able to produce in a series of individual tin crystals examples of substructure ranging from planar interface through various cellular structures to den- Fig. 1—Electroetched section taken normal to the rod axis; the center of the rod lies to the left and the periphery to the right of the micrograph. The variation of structure across the section is evident. Magnification 60 times. drites. It was possible in the present nickel crystal to observe a continuous range of substructures varying with degree of supercooling across a single section as shown in Fig. 1. Growth rate, 13 mm per min, and temperature gradient were essentially constant; the variation in structure is thought to be due to a radial gradient in solute concentration ahead of the solid interface. The liquid at the interface is likely to have been richer in solute toward the periphery of the zone, the result of curvature of this interface. The type of substructure was seen to vary with increasing constitutional supercooling as follows: a) region free of precipitate. top left, Fig. 1: 6) region of nodal precipitates which became arranged in hexagons on passing from the center of the rod: c) irregular hexagonal cells with incomplete boundary precipitation; d) regular hexagonal cells of decreasing size with complete boundary precipitation. Fig. 2 shows the transition from stage 6 and Fig. 3 shows the structure in stage d. Within stage 0, the range of conditions over which irregularly positioned nodes occur appears to be small and the nodes are soon recognizable as taking up positions at the intersections of an hexagonal network as the supercooling increases.

Jan 1, 1970

By O. M. Bishop

Large reserves of copper are contained in waste dumps which have been created by open-pit mining of porphyry-type copper deposits in the Western United States. Nearly 6 billion tons of copper-bearing material exists in the waste dumps at present, and another billion tons will be added each three to four years as additional material is stripped from the present mines and new open-pit mines are developed. The dumps constitute an enormous resource containing some 7 to 10 billion dollars worth of copper. Increased attention is being given to the recovery of copper by leaching from these dumps as attested by the fact that in 1968 approximately $175 million of copper was recovered by leaching operations. During the leaching process, however, numerous problems exist which prevent complete extraction of the copper from the dumps. Probably the most important problem encountered is the incomplete contact of the copper-bearing materials by the leaching solutions. This problem is mainly created by the formation of physically compacted and chemically cemented layers within the dumps which prevent solution flow to many sections of the interior of the dumps.

Jan 1, 1970

By E. Mcl. Tittmann

Deep-seated human instincts urge us to positively mark the passage of time. We celebrate the passage of each year. Years give way to decades, and decades to half centuries and centuries. At all these mileposts we are inclined to pause, take a look around and catch our breaths before embarking on the next leg. We are at such a point now and this meeting I am sure will give direction to the road ahead into the decade of the seventies. In looking around at this point, 1979, it is obvious to all of us that the environment in which we must mine, mill, smelt and refine lead and zinc has radically changed. These changes have, of course, occurred over a long period of time. They have, however, all been in the same general direction. They have all had the same motivation. The period of greatest contrast is probably the fifteen years just before World War II and the fifteen years following the end of that war. I thought that I might review briefly with you what seems to me to be four of the more important changes that have developed since World War II that profoundly affect our activities in the lead and zinc industry. I mentioned before that all these changes have been in the same direction; that is, they have all tended to restrict our freedom of action in pursuing our objective of producing lead and zinc on a competitive basis at a profit. Consequently, in discussing them you may think that I am merely viewing with alarm. This is not the intent. This is merely supposed to be an objective analysis. I think it appropriate before discussing these trends in detail to examine the position of lead and zinc today.

Jan 1, 1970

By Hans-Jürgen Schaller, Horst A. Brodowsky

Activity coefficients of boron in palladium were determined at concentrations up to PdB0.23 by reducing B2O3 between 870" and 1050°C in a controlled H2-H2stream and measuring the resulting weight gain. The deviations from ideal behavior closely resemble those of the system Pd-H and are interpreted in terms of three principles: 1) The solute atoms occupy octahedral interstitial positions. 2) They donate their valence electrons to the 4 d and 5s bands of palladium, raising its Fermi energy. 3) The lattice strain energy is lower for two nearesl -neighbor interstitial particles than for two farther separate ones. SOLID solutions of hydrogen in palladium are a useful subject for studying thermodynamic aspects of the formation of alloys and of nonstoichiometric systems.1-3 The activity of hydrogen is readily measurable to a high degree of accuracy,4&apos;5 even at low temperatures where the deviations from ideal behavior are more pronounced, and its simple structure facilitates an interpretation of these deviations in terms of a detailed model. Two effects are discussed to account for the non-ideal properties:3 An "electronic" effect, connected with the rise of the Fermi energy, as electrons of the interstitial hydrogen atoms enter the electron gas of the metal, and an "elastic" effect, due to an interaction of the regions of strain around each interstitial atom. The electronic effect is based on the idea that the lowest energy levels of the dissolved hydrogen atoms are higher than the Fermi energy, so that the electron will not occupy a localized state but enter into the electron band of the metal.6 The elastic effect is based on the observation that dissolved hydrogen distorts and expands the palladium lattice. The hypothesis is put forward that the elastic strain energy is lower for two adjacent dilatational centers than for two separate ones; i.e., they attract each other. The resulting pair interaction can be used to calculate an elastic contribution to the thermodynamic excess functions by means of one of the statistical methods. This model permitted a detailed description of the solution properties of hydrogen in palladium3 and in palladium alloys.798 An extension of the approach to describe the excess functions of substitutional palladium alloys is possible.9 In order to further test and refine the model, an investigation of other interstitial alloys was started. Palladium dissolves considerable amounts of boron in homogeneous solid solution.10 The palladium lattice expands linearly up to nB = 0.23 (nB = B/Pd atomic ratio), the highest concentration studied." The expan- sion, extrapolated for 1 mole of interstitial per mole of palladium, is 17 pct of the lattice constant of pure palladium vs 5.7 pct in the case of hydrogen.12 The fact that the lattice expands rather than contracts is a strong indication that interstitial positions are occupied. According to neutron diffraction experiments, hydrogen occupies the octahedral sites of the fcc lattice.13 Unfortunately, this direct evidence is not available for the Pb-B system, mainly because of the high-reaction cross section of boron with thermal neutrons. However, by way of analogy and on the grounds of the rather close similarities between the two systems to be reported here, it seems safe to attribute octahedral positions to the dissolved boron, too. At higher boron contents, compounds of stoichiomet-ric compositions are reported such as Pd3B, which has the structure of cementite,14 so that a close structural relationship seems to exist with the system r Fe-C. In their study of hydrogen absorption in Pb-B alloys, Sieverts and Briining noted that alloys with an atomic ratio of about nB = 0.16 are no longer homogeneous15 This observation was confirmed in an extensive X-ray investigation.11,16 The phase boundaries of two miscibility gaps were established. One two-phase region was stable below a transition temperature of about 315°C and extended from nB = 0.015 to 0.178. The other one extended from nB = 0.021 to 0.114 slightly above the transition temperature and had an apex at nB = 0.065 and 410°C. All phases involved have the fcc structure of pure palladium with lattice expansions proportional to their boron contents. The occurrence of miscibility gaps, i.e., the coexistence of dilute and concentrated phases, points to an energy of attraction between the dissolved particles, in the Pb-B system as well as in the Pd-H system. The filling up of the electron bands seems to be analogous, too, in the two systems, as indicated by the hydrogen absorption capacit15,17,18 and by the suscepti bility of Pd-B alloys.l8 In both types of experiments, boron acts as an electron donor. A chemical method was used to measure the activity of boron in palladium. Boron trioxide was reduced in a moist hydrogen stream: B2O3 + 3H2 = 2B + 3H3O [l] At known activities or partial pressures of boron trioxide, hydrogen, and water, the activity of boron could be calculated from the law of mass action. The equilibrium concentration of boron corresponding to this activity was determined as the weight gain of the sample. EXPERIMENTAL The samples consisted of small pieces of foil of 0.1 mm thickness and about 100 mg weight. The palladium was supplied by DEGUSSA, Germany, and stated to be

Jan 1, 1970

By A. V. Bradshaw, R. I. L. Guthrie

The behavior of large bubbles in the size range 4 to 25 cm3, rising through molten silver, has been studied. It was found that rising velocities were equivalent to those in aqueous systems of low viscosity. Mass transfer coefficients for oxygen bubbles dissolving in silver were found to be 0.036 ± 0.007 cm sec-1, being close to those predicted for transfer through the front surface of the spherical cap bubble only. It is suggested that the surface active nature of oxygen in silver could account for the relatively low coefficients obtained. MANY metallurgical processes involve interactions between gas bubbles and liquids. Examples include the removal of carbon monoxide in Open Hearth Steelmak-ing, the removal of sulfur by blowing air through copper matte during converting, and the removal of hydrogen from steel during vacuum degassing or inert gas flushing. The steps involved in such refining processes include; transport of the dissolved species to the bubble interface, adsorption and chemical reaction of the species at the interface, desorption of product molecules from the interface, and transport of product gas into the bulk gas phase of the bubble. It has been concluded1 that all the interfacial steps involved proceed so rapidly at steelmaking temperatures that transport of the solutes, present in the metal, become the important rate controlling factors provided nucleation phenomena are not restrictive. The O-Ag system was chosen for the investigation into gas bubble-molten metal interactions due to the relatively high solubility of oxygen that enables rates of oxygen transfer to be measured from changes in bubble volume. Other advantages of this system include the absence of a stable oxide phase at an oxygen pressure of 1 atm and the relatively low melting point of the metal which permits the use of a metallic container, providing that it is resistant to oxidation. In those metallurgical processes where bubbles have an important influence, bubble volumes are usually greater than 5 cm3. For this reason the present study relates specifically to single large bubbles of oxygen rising in silver. These bubbles adopt the characteristic spherical cap shape similar to that shown in Fig. 1 for a 30 cc bubble rising in water. After an initial investigation to determine the velocities of inert (nitrogen) bubbles rising in molten silver, experiments were carried out with oxygen and the rates of mass transfer between the oxygen bubbles and the silver were measured. EXPERIMENTAL Apparatus. The apparatus, Fig. 2, for containing molten silver, was constructed from "Nimonic 75" Alloy (75 pet Ni, 20 pet Cr, 5 pet Fe, Mn) and provided for the release of single bubbles from an hemispherical cup, situated at the bottom of the column. The cup was turned by translating the rotation of the drive shaft through 90 deg. This was accomplished by the use of a bevelled gear system, and a smooth drive was provided by the lubricating action of the silver on the gears. Since reliable high temperature seals at 1000°C were found to be impracticable, the filling and drive shaft tubes were extended outside the 3.5 kw resistance wire tube furnace, where connections were made using easily accessible O-ring seals. The apparatus remained gas tight to the atmosphere at pressure differentials far in excess of those used. The filling tube was connected via a small bore tube to the differential pressure transducer. Gas could be bubbled into the inverted cup from two i-in. tubes which passed down the inside of the column to preheat the gas. The temperature of the silver was maintained at 1020°C during all experiments. Measurement of Bubble Volume. In order to calculate mass transfer rates, it was necessary to obtain a continuous record of the bubble&apos;s volume during its passage through the column of molten silver. The method adopted for measuring the bubble volume involved closing off the top gas space to the atmosphere prior to each experiment, and recording the variation in gage pressure of this space during the formation and rise of the bubble. Since any change in bubble volume results in an equal change in top space volume, Boyles Gas Law may be applied (for isothermal con-

Jan 1, 1970

By B. H. Eccleston

The effect upon automobile emissions in changing from leaded to lead-free gasolines was studied in experiments by the Bureau of Mines in cooperation with the American Petroleum Institute. Typical U.S. leaded gasolines and prototype lead-free gasolines of comparable octane quality were used in eight vehicles operated to simulate city driving. The experiments were run at 70° and 95° F. Exhaust and evaporative emissions were measured and the photochemical effect of the emissions was experimentally observed in an artificial smog chamber. Results of the study reveal the manner and degree in which the changes in fuel composition alter the amount and characteristics of both exhaust and evaporative emissions. Briefly, it is shown that the compositional differences between leaded and prototype lead-free fuels resulted in higher photo-chemical pollution potential of the emissions from the lead-free fuels. The effect is attributed to the photochemical characteristics of high-octane fuel components that are used in greater quantity in the lead-free fuels.

Jan 1, 1970

By Fathi Habashi

CLAYS CONTAIN the mineral kaolinite, a hydrated aluminum silicate. It is an important potential raw material for aluminum, especially for those countries possessing no bauxite deposits. Therefore, there is no surprise to find a large volume of research done for the recovery of aluminum from clays. Kaolinite (Al203?2 SiO2?H20) contains 39.8% A1203; 46.3 % SiO2, and 12.9 % H2O. The analysis of a good-quality dried clay of an Eastern Canadian siliceous shale is shown in Table 8-1.

Jan 1, 1970

The effect of temperature, time and SO2 concentration in the atmosphate have been studied for a complex Pb-Zn concentrate, which contained four sulphides and some organic material, in order to determine optimum roasting conditions. Under static roasting conditions virtually complete sulphation was achieved after roasting at 650¦C.2 hours in 10% SO2 in air. Both zinc ferrite and zinc silicate were observed to form early in the roasting, but continued exposure to SO2 -containing gases caused decomposition of these as the roasting time increased. Water and acid solubilities of iron, silica, calcium, magnesium and aluminium in the calcine were determined, as a function of roasting time, temperature and atmosphere composition.

Jan 1, 1970