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By W. A. Tiller, D. H. Lane

A simple zone melting technique for investigating the effect of ultrasonic irradiation upon ingot solidification is described. The effect of i) ultrasonic power level, ii) freezing velocity, iii) constant or variable frequency, iv) direction of irradiation, and v) transducer-cozlpling bar joint upon the grain size of type 316 stainless steel have been investigated. The results of this study support the postulate that the ultrasonic vibrations increase the nucleation probability in the layer of liquid adjacent to the freezing interface. In the first paper of this series,l the possible mechanisms whereby ingot structure may be altered by irradiating a solidifying melt with ultrasonic vibrations have been discussed. A new technique for efficiently introducing the ultrasonic energy into the solid-liquid interface region was presented and applied to ingot preparation by the consumable-electrode arc-melting technique. The experimental results support the postulate that the ultrasonic vibrations may refine the ingot structure by increasing the nucleation probability in the zone of liquid adjacent to the solid-liquid interface. The present paper describes the application of the same technique to a relatively simple laboratory-scale zone-melting apparatus. This apparatus is found to be well suited to the detailed study of ultrasonic technology in this area and allows one to determine, in particular, the minimum ultrasonic power level needed to produce a certain grain size in a particular material. The results of this study support the nucleation mechanism for grain refinement, but do not provide any deeper insight into the specific nucleation mechanism responsible for the effect. EXPERIMENT The apparatus used in these experiments is shown in Fig. 1 and illustrated schematically in Fig. 2. The material to be studied, type 316 stainless steel, was in the form of a 3/4-in. sq bar 30 in. long. This bar was placed in a square open-topped mold with open ends made from high-purity graphite coated with a flame-sprayed Al2O3, skin. Surrounding the crucible was a molybdenum susceptor with 3/8-in. diam holes spaced at 1-in. intervals along its length to serve as sight ports. A tapered transducer horn was brazed to one end of the specimen. The entire assemblage was enclosed in a quartz tube, the transducer itself projecting out one end and resting in a cooling tank. A vacuum seal between the coupling bar and the end plate enclosed one end. A similar plate and seal enclosed the other end. The system is gas tight and can be operated under vacuum or an inert atmosphere. For these experiments, flowing argon at 15 in. of Hg pressure was used. The heat source for melting the stainless steel specimen was a 2-in. long 3-kc induction coil placed around the quartz tube; this source heated the susceptor, inductively melting about a 3-in. zone of the sample by radiation. To move the molten zone at a specified rate, the induction coil was moved down the tube at this rate with the aid of a simple pulling device. Thus, the sample could be irradiated at varying ultrasonic frequencies and power levels and could be solidified at varying rates. The power input to the transducer was measured using a "John Fluke Model 120 VAW-Meter." 1 The power delivered to the interface region is probably only about 50 pct of that measured on the VAW-meter. In a typical run, when the ultrasonic power was turned on, the interface of the molten zone closest

Jan 1, 1961

By Michael J. Virnig, Murdoch W. MacKenzie, Michael R. Davis

The objective of this paper is to present preliminary capital and operating cost estimates (±25%) comparing conventional carbon-in-solution (CIS) with resin-in­solution (RIS) using AuRIX® 100 for the recovery of gold and silver from typical heap leach solutions. Preliminary testwork was carried out with AuRIX® 100 using real and synthetic leach solutions to determine the technical viability of the resin for gold/silver recovery and to provide process design parameters for the preliminary RIS circuit. The scope of the resin testwork was sufficient to support the level of accuracy applied in the capital and operating cost estimates. No parallel testwork was carried out with activated carbon. Industry standard design data and operating data from existing CIS operations were used as a basis for the comparison. Both the capital and operating cost comparisons indicate a substantial savings for a RIS circuit using AuRIX® 100 (- 14 to 18% in terms of capital and 25 to 35% in terms of operating costs) over a conventional CIS circuit depending upon solution flows and grade.

Jan 1, 1999

By Donald T. Hawkins, Ralph Hultgren

The lorsion effusion method has been used to measure the vapor pressure of lead over pure lead and eight Pb-Sn alloys ranging from 9.1 to 87.9 at. pct Pb in the temperature range 950° to 1125°K. The resulting ?H°y 298 = 46,630 ± 200 cal per g-atow for pure lead is in excellent agreement with previous work. Deriued ?Gph values for the alloys were smoothed and correlated with previous heat of formation data to obtain entropies for the liquid alloys. values for the tin component were calculated by Gibbs-Duhem integmtion. Surfhce depletion of these liquid alloys was found to be absent, as shown by the fact that the measured pressure remained substantially constant with time in contrast with previous measurements on iron-rich solid Fe-Mn alloys. The activities and Gibbs (free) energies of the liquid Pb-Sn system are not well known although the heats of formation have been accurately determined by K1eppa.l Vapor pressure determinations of the activity of lead by Voronin and Evseev2 disagree with those of Predel.3 Elliott and chipman4 measured activities by the electromotive -force technique in the ternary Pb-Sn-Cd system. From the resulting values of the activity of cadmium, they were able to calculate the activities of lead and tin for the binary Pb-Sn system at the compositions xsn = 0.33 and 0.67. Atarashiya, Uta, Shimoji, and Niwa5 determined the activity of tin from Hz-H2O equilibrium measurements, but their results are subject to question due to uncertainty in the final state of their samples. To resolve these differences, measurements of the activity of lead were made using a torsion-effusion apparatus. Among other advantages, this apparatus rapidly detects errors caused by surface depletion, which tends to reduce the apparent vapor pressure of the more volatile component. If the measured torques remain nearly constant with time, only bulk depletion is occurring. This contrasts with the rapid decrease in torque found in solid Fe-Mn alloys at high temperatures and low manganese contents.6 EXPERIMENTAL 99.999+ pct Pb was obtained from the American Smelting and Refining Co. and 99.999 pct Sn from Vulcan Detinning Co. Eight Pb-Sn alloys were prepared by melting together weighed amounts of the pure metals in evacuated Pyrex tubes and quenching the melts in water. Loss of weight in preparation was less than 0.02 pct in all cases. The effusion cells were made from high-purity, nonporous graphite. Graphite was chosen because of its resistance to reaction with lead and tin and because it can be accurately machined with precision orifices. Two cells were used with overall dimensions as shown in Fig. 1. The orifices of cells 1 and 2 were, respectively, 1 and 1.5 mm in diam.

Jan 1, 1968

Use controlled blasting techniques to reduce blast-produced overbreak damage to underground mine ribs and back for both safer working conditions and improvements in productivity. The Problem Blasting is used in metal and non-metal underground mine slopes, drifts and crosscuts to fracture rock to be excavated and further processed. Standard blasting also produces fractures in the rock beyond the desired excavation area. This is sometimes evident by rough surfaces, undercutting and other signs of excessive damage. This damage contributes to rockfalls in the mines, a major cause of injuries and fatalities, and equipment damage. A variety of controlled blasting techniques has been developed for civil engineering projects where long-term stability is essential. For several reasons, these methods arc not widely used in mining. For example, these methods incur additional costs and time; there is little need to maintain stable openings over long periods of lime; and there is the perception (hat corrective remedial techniques, such as rock bolting, are more practical. Basically the benefits of these methods are not demonstrably clear for application in underground mines.

Jan 1, 1991

By Heinrich Möller

The electro-oxidation of 0.1 M ethylene glycol at gold, platinum and gold-platinum alloy electrodes in different heat treatment conditions has been studied in 0.5 M NaOH, at room temperature. Poisoning of all the electrodes occurs. However, the alloy electrodes poison at a faster rate than the pure gold and platinum electrodes. This indicates that the initially higher activity of these electrodes cannot be the result of decreased poisoning through a "third-body" effect.

Oct 1, 2003

By J. D. Zhu, T. Ohmichi, H. Yasuda, S. Kashiwai, I. Ohnaka

"Since the casting process affects the properties of castings, its computer simulation has been greatly developed in the last decades. This paper presents our recent works, especially on mold filling simulation, because most casting defects such as porosities and inclusions that greatly affect the properties originate during mold filling. The first topic is the mold filling simulation with consideration of cavity pressure change during mold filling, including direct observation of flow phenomena with X-ray and pressure measurement. The second .one is the mold filling simulation in the lost foam process, in which gasification of polystyrene pattern and gas outflow through the coating and mold have been considered. The simulation can predict not only the mold filling sequences but also periodical vibration of the gas layer between the melt and pattern. The third one is the comparison of simulation of Al melt flow in a metallic runner and direct observation through a transparent mold, showing that the entrapped gas or inclusions is expelled ahead through the melt and its simulation needs very fine meshes. These examples show that the comparison of simulation and observation is very important to develop the numerical simulation further.IntroductionThe mechanical properties of castings are greatly affected by casting defects such as porosities and inclusions, and solidification structure. Although recently the structure simulation has greatly progressed [1-4 ], the application in plants is very limited, because the structure is mostly determined by chemical compositions and cooling rate, enabling us to estimate it from the structure of past similar castings without simulation.On the other hand, the casting defects often vary with each casting or time. Among the defects, porosities and inclusions are main causes to deteriorate the properties and mostly originate during mold filling. Therefore, a lot of efforts to simulate the mold filling and estimate those defects have been made in the last decades [l,5,6]. These efforts have been mostly to develop numerical techniques to solve the Navier-Stokes equation. However, the flow phenomena in molds have not been well understood, because the direct observation of the flow phenomena in mold is not easy. This means the accuracy of the simulation is still not clear."

Jan 1, 2000

By Zhonglin Ye, Yifeng Shi

"This paper has outlined forms of Au & Ag losses in copper smelting process and methods for increasing Au & Ag recovery, analyzed factors influencing Au & Ag recovery in copper converting process, presented Au & Ag behavior in copper electrorefining process, and reviewed effect of current density/electrolyte circulation rate during electrolysis and surface finish of cathode on Au & Ag losses. Measures and research direction for decreasing Au & Ag losses in electrolysis have also been introduced. Based on Au & Ag behavior in copper electrorefining process and previous studies by others, new approach for increasing Au & Ag recovery in copper smelter has been discussed. And brief comparison has made between continued multiplication method and equilibrium method application in the case of calculation of Au & Ag recovery in copper smelter.IntroductionAs gold and silver are the major by-products from copper smelting process, efficient Au & Ag recovery has become one of the key approaches for copper producers to increase economic efficiency. With similar physicochemical properties, Cu, Au and Ag belong to the first subgroup of elements in the same periodic table. Au and Ag will be enriched into Cu phase firstly when both matte-slag phase and copper-matte phase appear in copper smelting process. However, great changes have taken place in Au & Ag proportions into individual phase due to changes of physicochemical conditions in each smelting process. Metallurgists at home and abroad have carried out a great deal of pilot plant tests and laboratory tests in order to increase Au & Ag the former Soviet Union with regard to Au & Ag losses in copper smelting process in the 1970s and 1980s, and he proposed solutions to increase Au & Ag recovery in copper metallurgical plants. As more than 20 years passed, Jingchun Lu's paper, Discussion on Increasing Au & Ag Recovery in Copper Smelting System, remains as a literature of the most comprehensive study. Based on Jingchun Lu's literature, the authors of this paper discussed new approaches to increase Au & Ag recovery in copper metallurgical plants with combination of many researches done by other researchers for over 20 years."

Jan 1, 2013

By Kwang K. Koh, Nicholas C. Nahas, Richard C. Neavel

Sodium, a relatively abundant element in Illinois coal, is reported to cause fouling of utility boiler heat exchange surfaces. Distilled water extraction of 22 Illinois coal samples resulted in average removal of more than 50% of their included sodium. Chlorine was the dominant anion. Extraction rate conformed to Fick's law of diffusion. Extraction with hot water increased both the rate and maximum amount removed. A commercial-scale countercurrent staged process can be envisioned as technically feasible.

Jan 1, 1978

By Alfred E. Hunt

Professor EGGERTZ first published a method based upon the fact that, when steel is dissolved in dilute nitric acid, and heated until the separated flocculent carbonaceous matter goes into the solution, the liquid assomed a brown color proportionate in intensity to the amount of the combined carbon in the steel. This method has been so variously modified that at present but few chemists use exactly the same procedure. It is the object of this paper to present

Jan 1, 1884

By Fathi Habashi

New technology first introduced by Nippon Steel Corporation at Kitakyushu in Japan in 1976 now used at a number of plants in other countries, known as dry quenching of coke, uses nitrogen in a closed circuit to avoid environmental emissions. In addition, heat is recovered in the form of steam, from the red-hot coke. In steel plants oxygen is used extensively and therefore by-product nitrogen from air liquefaction can be effectively utilized in this way.

Jan 1, 2014

By J. E. Murphy

The high-purity thorium metal was prepared by the Bureau of Mines from electrolytically produced thorium alloys. The thorium-chromium and thorium-manganese alloys were separated into the component elements by vacuum distillation. Chromium and manganese impurities remaining in the thorium metal after distillation at 1,850° C were <0.005 weight-percent. Removal of volatile impurities such as aluminum, calcium, magnesium, and lead was also accomplished.

Jan 1, 1969

By A. Poitras

The Cummings Complex consists of three superposed sills, exhibiting a differentiation pattern: the lowest sill being the most basic and the highest sill, the most acid. Each sill is also characterized by an internal petrographic and geochemical variation which is evidence of differentiation due to fractional crystallization. The REE concentrations in the different units of the complex indicates that the three sills are comagmatic. The interpretation of these results permits the formulation of an emplacement model not previously proposed for this complex.

Jan 1, 1984

By José Murilo Mourão

A pelotização de minério de ferro hematítico demanda grande quantidade de calor para a produção de pelotas de boa qualidade. Avalia-se, neste trabalho, a quantidade teórica de calor, necessária para a queima de três tipos característicos de pelotas, e destacam-se pontos importantes do processamento de queima nos fornos de pelotização, no sentido de otimizar o consumo de calor..

Oct 30, 2017

By Felipe Darabas Rzatki

Polyether ether ketone (PEEK) is a high performance thermoplastic often selected for high temperature tribological applications under chemically aggressive environments. The present work evaluate the tribological behavior of a high performance PEEK composite under ambient and high temperature (30 and 80°C, respectively). The atmosphere was also varied (air or tetrafluorethane). An AMTI tribometer equipped with a hermetic chamber and a heating system was used to carry out sliding tests of PEEK cylinders on 304 stainless steel polished discs (Sq < 10 nm) with reciprocating movement and 175 N normal force. Surfaces roughness analyses were performed with a white light interferometer. As expected, there was a strong influence of temperature on the tribological behavior of the samples tested in ambient atmosphere (25% decrease in friction coefficient associated with a 100% increase in wear rate). On the other hand, samples tested in tetrafluorethane atmosphere showed no significant friction temperature dependence.

Jul 31, 2018

By L. Hacini

The start-up is the most critical phase of the cell life, as an uncontrolled start-up could lead to early infiltrations, instabilities, and in some cases to the cell death. Lots of efforts are put to increase the lifespan of cells, as it has a major impact on both the operating costs and the environmental footprint of the aluminum industry. Obviously, a true size test on a cell is a resources- and time-consuming approach that could be used only to validate mature concepts. Moreover, numerical modelling is a low-cost and versatile tool capable to test a wide range of potential ideas and concepts. In the present article, a thermal electrical mechanical slice model is presented. This model describes the preheating and bath periods of a P155 aluminum cell start-up, as used at the Grande Baie smelter. The impact of sodium diffusion and expansion is also included in the model. This model will be useful to study different problematical issues such as the global behaviour of lining materials, shell and cradle deformations during start-up and several start-up scenarios. Such a model will also be able to answer some interrogations regarding early infiltrations and their impact on the lifespan of the electrolysis cell.

Jan 1, 2011

By K. L. Komarek, P. F. J. Landler

Synthetic polycrystals of wustite were reduced ilz H2-H2O mixtures over limited roncentration ranges wiltun the wustite. field and the weight changes were continuously followed with a McBain quartz spiral balance. The reduction was. found to be controlled by a combined surface plus solid-state diffusion reaction. The solid-state diffusion had an activation energy of 38 kcal. Self--diflusioities of iron decreased with itzcreasing vacancy concentration. The activation energy of. the surface reaction runs different tor- different samples. The surface reaction-rate constan increased with increasirzg vacancy concentration. THE reduction of the oxides of iron has been studied for many years. Edstroem&apos; has summarized the early work and has provided much information on the reduction of magnetite and hematite by hydrogen and carbon monoxide. More recent summaries are those by smeltzer2 and Themelis and Gauvin.3 Most investigators have reported that the iron metal which forms the outer layer during gaseous reduction is rather porous. According to Kohl and Engel14 the formation of such a porous iron layer depends on the properties of the underlying wiistite layer, on the reaction of the gas with the wustite surface, and on the transport of matter through the wustite layer. McKewan, Quets, Wadsworth, and Lewis, and Knacke 10 have found that, if a porous iron layer is formed, a surface reaction between gas and wustite at the bottom of the pores controls the rate of reaction. Seth and ROSS 11 and Warner 12 have pointed out that the influence of the gaseous pore diffusion through the porous iron layer cannot be neglected. It has further been shown that the wiistite layer formed during reduction is dense and that transport of matter across the layer occurs only by solid-state diffusion of iron ions.13,14 The solid-state diffusion rates observed by Edstroem and Bitsianis 14 and the surface reaction rates observed by Quets eta1.&apos; show that an interaction of the two steps in controlling the reaction rate has to be considered. In this investigation the reduction of wustite was studied with respect to the interaction of the two steps, isolated from any other effects, by reducing wustite within the wustite field from higher to lower oxygen concentrations with H2-H2O gas mixtures. A similar study with CO-CO2 mixtures has been performed by Levin and wagner.15 Fused synthetic wustite polycrystals were reduced in steps of 0.4 wt pct from 24.4 to 23.2 wt pct 0 and over a temperature range from 700" to 1050°C. A few tests were also conducted with reduction steps from 24.4 to 23.6 wt pct 0 and 24.5 to 23.2 wtpct0. The Fe-O phase diagram is shown in Fig. 1 where the composition of the gas phase in equilibrium with the condensed phases is plotted as pct H2 vs the temperature. A careful study of the literature led to the conclusion that the fully drawn equicomposition curves (in wt pct O) in the wustite field used by Edstroem 1,16 and other authors needed some correction. Based on results by Darken and Gurry17 (shown as open circles) and on some of our own data, four corrected curves for 23.2, 23.6, 24.0, and 24.4 wt pct O were calculated (drawn as dashed lines in Fig. 1) which should replace the fully drawn equicomposition curves. MATERIALS AND APPARATUS Materials and Specimen Preparation. Wustite was prepared from iron sulfate (Fisher Scientific Co., New York) which had a purity of over 99.92 pct, with small amounts of manganese, copper, and zinc adding up to 0.03 pct. From the aqueous solution iron oxalate was precipitated and decomposed to magnetite according to Economos. 18 The magnetite powder was pressed into cylinders and sintered in vacuum at 900°C for several hours. The sintered compacts were placed in a platinum crucible of 2.5 cm diam which was fitted into a high-purity alumina crucible and then inserted into the center of the graphite heating element of an electric resistance furnace.lg The furnace was evacuated to below 1 p Hg and the magnetite sample was slowly heated. The evolution of gases during heating deter-

Jan 1, 1967

By Marco Olper

Zinc bearing materials containing chlorides and fluorides of alkali metals, such as EAF dust, Waelz oxides, galvanizing ashes, zinc & brass foundry fumes and converter fumes are little attractive, both technically and economically for processing in ISF plant or in a conventional zinc sulphate electrolysis works. The Ezinexm Process allows for the recovery of high purity zinc in cathode form, from these materials, regenerating the leaching liquor. The process is based on a new electrochemical system which depolarizes the anode reaction with reduction of the cell voltage, compared with the traditional sulphate electrolysis method. The electrolyte, based on a chloroamrnino complex, allows for the recovery of other valued metals present in the zinc bearing materials such as lead, copper and silver, these being recovered as a metallic cement consequently improving the economics of the process.

Jan 1, 1994

By John D. Janak

Thank you for inviting me to come here and be your keynote speaker. Texas also thanks you for being included as part of the Rocky Mountain Coal Mining Institute. We&apos;ll kind of think of Texas as Baja Rocky Mountains. I&apos;ve always wondered why coal miners were the only people to go to the mountains in the summer time-and now I know why. The program committee should be given a big hand for selecting this RESORT. And the golf course is stimulating to say the least. This is a very beautiful location. I was asked to talk about CHALLENGES, OPPORTUNITIES and INNOVATIONS as they affect the coal industry. I am going to do that from a Texas perspective. But first, since Texas is the newest state to belong to the Institute, I would like to give you a little background on how our coal industry got started and where we are at today. The vast majority of our coal is called lignite-it has a little lower heating value than most other coals and ranks somewhere between buffalo chips and sub- bituminous. Lignite is found In three geological formations running Northeast to Southwest through South and East Texas. In-place reserves lying within 200 ft. of the surface total 14 billion tons. This slide shows the lignite formations with cur- rent mine operations colored in RED. Mines that are planned to be built in the next 10 years are shown in BLUE. Lignite was used mostly by settlers in Texas during the 1800s. It was used as a fuel to fire locomotives during the Civil War. Between 1900-1930, about 100 mines, mostly underground, were operating in Texas producing lignite for home heating and as a boiler fuel. Here are some slides showing underground access, [lie tipple used to process the lignite, and the underground workings. This is the "BIG LUMP COAL COMPANY" as shown here. The typical underground mine was 100-150 ft. deep and each miner produced 7-10 tons per day-all by hand. In 1926, the Texas Power & Light Company built the Trinidad Power Plant and began using lignite as a boiler fuel. The lignite was mined by the McAlester Fuel Company at the nearby Malakoff Mine. Here are some slides showing a stripping shovel at Malakoff uncovering lignite. The lignite was loaded into railcars in the pit for transport to the power plant. This is a picture of the Trinidad Plant which had two 20 MW units and one 32 MW unit. At the time, Trinidad was the largest power plant in the United States using lignite exclusively as a fuel. Trinidad operated until 1942 when it was converted to natural gas that was sold to the plant for 3 ½ ¢ per MMBT&apos;U. The mine closed after having produced 7 million tons. Lignite was mostly forgotten about until 1953 when Alcoa started an aluminum smelter. Our Company formed a subsidiary called Industrial Generating Company to operate the power plant that furnished electricity to the smelter. We also operated the nearby Sandow Mine that supplied lignite as a fuel to the power plant

Jan 1, 1989

By D. R. Uhlmann, T. P. Seward, K. A. Jackson, J. D. Hunt

microscopic ohservations on alloys of organic trzaterials show that dendrite arms can melt off under normal conditiorzs of growth. This occurs because of the interactiorz of&apos; heat and matter fluxes during dendritic growth. The re melting occurs where the den-drite arms are joined onto the main deizclrite sterrz. Many detached crystals can be produced in this fashion. It is postulated that this remelting phenornenon occurs in metal alloys, giving rise to the equi-axed region in castings. Experiments peyformed orr castings of transparent materials support remelting as a primary source of detached crystals. Ob~ervations an equiaxed tones in metal castings are discussed in terms of this and other mechanisms. It is concluded that the partial remelting of dendrites is on important mechanisnl for producing the equiaxed regions in castings. THE freezing of a casting can be divided into three regions: a chill zone formed near the mold wall, a columnar region, and a third region, at the center of the casting, which is called the equiaxed zone. The origin of the grains that comprise the equiaxed region is the subject of this paper. We will first outline the mechanisms which have been proposed to account for the origin of the equiaxed region and discuss some recent experiments which cannot be explained by these theories. We will then present some microscopic observations of dendritic growth which have led us to conclude that the equiaxed zone in castings can arise from partial remelting of dendrites. This proposal is supported by observations on transparent castings. Finally, we will discuss several observations on metal castings which could not be explained previously, and which can be accounted for by the present proposal. Previous Mechanisms. Winegard and Chalmers3 pointed out that the molten central region of an ingot could be constitutionally supercooled, because of the solute layer at the growing interface. In this supercooled region, nucleation on particles could occur, giving rise to the equiaxed crystals. Another mechanism has also been suggested,4y5 that the nuclei originate in the chill zone then float or are carried by convection to the center of the casting, where they grow to produce equiaxed crystals. In this case, all the crystals nucleate immediately on casting, so this mechanism will be termed "big-bang" nucleation. Walker&apos;s Experiments. J. L. Walker has made observations on the solidification of nickel and Ni-Cu alloys which cannot be accounted for by either of the above mechanisms. In studying the grain size resulting from freezing of nickel at various undercoolings, walker6 found that at large undercoolings the grain size was small, due to mechanical nucleation, as discussed by walker7 and Horvay.&apos; At small undercoolings, the grain size was large, and the growth dendritic. In Ni-Cu alloys, however, for initial undercoolings starting from just below the melting point and extending for a hundred or so degrees of undercooling, fine grains were also observed. Samples were undercooled 200 Centigrade degrees without nucleating, and were then heated 130 Centigrade degrees so that the undercooling was 70 Centigrade degrees, and nucleated. The samples had a small grain size, indicating multiple nucleation. There were no heterogeneous nuclei in the liquid which could operate at the temperature of growth. Constitutional supercooling could not have been greater than the supercooling of the initial melt, since the temperature rose as the freezing continued. walker -as also shown that a Ni-Cu alloy which can be undercooled to below its solidus will produce typical columnar and equiaxed regions when cast into a cold mold. This alloy could not reach a temperature below its solidus by constitutional supercooling. It could not, therefore, have nucleated heterogeneously. Neither the big-bang mechanism nor the Winegard-Chalmers mechanism can account for the fine grain

Jan 1, 1967

By E. W. Dewing

The nature of solid solutions of sodium in non-paphitic carbon at temperatures near 1000°C has been investigated by an electrolytic technique. The activity coefficient is found to vary strongly with the heat-treatment temperature of the carbon, and an analysis of the energy terms involved suggests that this is due to variations in the Fermi level. The diffusion coefficient for sodium is in the range implying that the sodium atoms (or ions) are not bound to specific sites on the carbon, in agreement with lack of evidence for specific compounds in the activity -composition curves. In the light of These results phenomena occurring in aluminum reduction cell linings are dis-cussed. It is concluded that sodium migrates by diffusion through the carbon lallice and not the pores, and that A14C9 is formed within the lining hy The excess of NaF invariably found in used linings is formed by this reaction and by air oxidation: There has recently been much interest in the swelling of carbon which occurs when it is made cathodic in an aluminum electrolysis cell, and there is general agreement that the phenomenon is due to the penetration of sodium atoms, derived from the reaction on the carbon lattice. (NaF and AlF3 are constituents of the fused-salt electrolyte.) The low-temperature lamellar compounds of potassium with graphite are well-known, and one compound between sodium and graphite has been reported.4 There is, however, virtually no information on the basic chemistry of the interaction of sodium with nongraphitic carbon at high temperatures, although Dell3 has made some fundamental studies of rates of penetration. At the time the present work was carried out these were not available. Rapoport and samoilenkol had measured rates of physical expansion in a dilatometer, using the fractional increase in length of a carbon specimen after electrolysis in a cryolite bath for 2 hr as an index of susceptibility to cathodic swelling. Work here with a similar apparatus showed that expansion (of a 1.5-in.-diam cylindrical specimen) ceased in less than 20 hr, and that the final expansion was much more reproducible than the value at some intermediate time. This suggested that an equilibrium was being set up, and that a thermodynamic approach was required. The results obtained are not as accurate as had been hoped, but they are the only ones of their type available and have enabled useful conclusions to be drawn. The experimental work was divided into two parts: an investigation of the activity-concentration diagram for sodium in carbon, and a rough determination of the diffusion rate. For the former, most of the experiments were made with petroleum coke even though this is not a form of carbon used in cell linings. It has the advantages, however, that it is a homogeneous material, that it is low in ash, and that its structure is reasonably well understood. Anthracites and coal cokes gave results of the same type as obtained with petroleum coke, but the reprodu-cibility from specimen to specimen was extremely poor. EXPERIMENTAL 1) The Activity-Composition Diagram for Sodium in Carbon. The petroleum coke was ground, pressed at 40,000 psi into plates 19 by 9 by 2 mm without added binder, and heat-treated. The sodium activities were established by an electrolytic technique. The carbon was made anodic in a cryolite bath with an aluminum cathode, and a controlled potential, E, applied so that the sodium activity at the anode was given by ln Na = 1n asa - EF/RT [21 where as, is the sodium activity generated by Reaction [I]. The relative activity is sufficient for many purposes and is simply given by The value of Na not at present known, but when the thermodynamics of the Na-A1 system have been worked out it can be derived from the equilibrium

Jan 1, 1963