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References are in all cases to the earliest known editions. In the few cases where the first edition has been unavailable for consultation, the particular one studied is indicated. English translations are included when known, but not others. [ ]

Jan 1, 1942

By J. L. Bray

LEAD has often been suggested as a protective coating for iron and steel. Such a protective coating should possess: (1) good adhesion, (2) durability, (3) ease of application, (4) freedom from pinholes, (5) good appearance and (6) low cost, but, unfortunately, lead coatings so far produced do not have all of these characteristics. Because of the necessity of carrying out the coating process cheaply, and because lead solutions have poor plating characteristics, most of the efforts have been directed toward the hot-dipping process rather than electroplating. The hot-clipping processes using lead have not been successful chiefly because of the lack of adherence between iron and lead. In any coating process involving iron a bond can be obtained only by the formation of an intermetallic compound, the formation of a solid solution, or mechanical means. Lead forms with iron two immiscible liquid solu-tions, and in the solid state no intermetallic compounds or solutions. It is necessary, therefore, to employ some other element or elements as a binding agent. Tin may be used as in terneplate, or copper in the form of a thin film of electrolytically deposited metal to which the lead will adhere. Because of its physical and chemical properties, lead as a coating medium would undoubtedly be limited in its use to sheet and wire and then only when the article is not subject to abrasion or wear. A very large tonnage of these products are being used under such conditions and a successful lead-coating process should be a valuable contribution to the science. Two other difficulties stand in the way of successful lead coating-that of poor appearance of the weathered surface and the tendency of the lead to form pinholes during solidification. Since lead is commonly accepted as cathodic to iron, these exposed areas are ones of accelerated corrosion.

Jan 1, 1937

By J. D. Raulerson, J. M. Williams

This paper presents a comparative evaluation of several system currently being used or proposed for the transport of matrix from an open-pit mine to a large fixed plant. The matrix is a sticky, wet clay to be carried from 8-16 km (3-10 miles) at 910 t/h to 1.8 kt /h (1,008-2,000 stph). The system is complicated by frequent moves of the open-pit mine site and other factors, such as use of the clay component in land reclamation.

Jan 1, 1984

By J. Avraamides

Many of the current methods for producing metallic silver particles having specific characteristics involve several steps, are time consuming and subject to contamination. The novel non-aqueous chemistry of silver and copper is used in a simple two step process capable of producing high purity silver powders of specific size and shape. The chemical basis of the process involves the manipulation of the equilibrium -- Cu(I1) + Ag [=]Cu(1) + Ag(1). The addition of at least 50% (V/V) acetonitrile (CH3CN) stabilizes both Cu(1) and Ag(1) ions in aqueous sulphate medium, and the metallic silver dissolves. Removal of the volatile nitrile by distillation reverses the equilibrium and silver powder is precipitated. The nature of the powder depends on the presence of additives such as gelatin, thiourea and polyacrylamide.

Jan 1, 1984

By Edgar L. Collis

NO industry or group of industries is more deeply interested in the influence exerted by atmospheric dust than that concerned with the getting of coal and of metalliferous ores. The coal miner in the past has mainly been interested on account of the part played by coal dust in the occurrence of explosions; but investigation is revealing that coal miners experience, at least on certain coal fields, unduly high mortality ascribed to lung diseases, some part of which may reasonably be attributed to dust inhalation, and that a small group of men employed in sinking shafts and driving roads through sandstone rocks experience troubles identical with those that afflict many metalliferous miners. Coal Mining The Registrar General for England and Wales issues information every 10 years concerning the mortality experienced in various industries. The records dealing with coal mining are of particular interest, since they are given separately for each of the largest fields. When examined they exhibit the coal miner with a favorable death rate on the whole when compared with all other occupied males; but they reveal great differences on the different fields; thus the Lancashire miner in 1900-2 had a comparative mortality from all causes of 1006 as against a figure of 675 for the Nottinghamshire and Derbyshire miners, and in 1910-12 of 941 as against 570 for Nottinghamshire. When mortalities due to four only of the great causes of death are subtracted from the total the differences are greatly reduced; these four causes are phthisis, pneumonia, bronchitis and accidents. Thus for 1910-12 more than one-half of the mortality in Lancashire, 478 out of 941, is so accounted for, but less than one-third of the mortality in Nottinghamshire, 184 out of 570; the latter fraction compares with that for all males, 293 out of 790. Exactly why the accident mortality varies thus with those for the lung diseases has not been determined; the fact, however, points to an interesting association between health and so-called "accidental" occurrences.

Jan 1, 1927

By P. D. Merica

ALUMINUM and its alloys have been the subject of much investigation, during recent years, in the course of which the principal features of the constitution of most of the binary alloy systems with aluminum have been determined. Except in the case of a few metals-silicon, bismuth, cadmium, lead, zinc, and tin-an aluminum-rich compound is formed in each binary system, which forms a eutectic with the aluminum or its solid solution with this compound. Thus such compounds as FeAl3, CuAl2, Mg4Al3, and NiAl3 are formed, which are found in aluminum-rich alloys of their respective series as eutectics with the aluminum solid solution. These compounds are, in all cases, hard and brittle and their presence affects profoundly the physical properties of the alloys in which they occur. Within the zinc-aluminum system a compound, Al2Zn3, is formed that decomposes at lower temperatures. Silicon and tin each form a simple eutectiferous series with aluminum; bismuth, lead, and cadmium are only partly miscible in the liquid state with it. The extent of the solubility in aluminum, in solid solution, of these compounds or of the elements themselves, in the case of those series

Jan 7, 1919

By Robert Maddin, Neng-Kuan Chen

THE (001) planes have been reported as the cleavage planes in body-centered cubic metals such as alpha-iron and tungsten.' However, in molybdenum, which is also body-centered cubic, experimental X-ray evidence indicating a similar cleavage plane still seems lacking. Tsien and Chow" observed microscopically in the extension at around 1000°C of molybdenum single crystalline wires 0.25 mm in diam that the fracture plane seemed to be parallel to the operative slip plane, which appeared to be (110) at that temperature. Zapffe' pointed out from fractographic study of polycrystalline molybdenum that "although the transgranular pattern is characteristically non-crystallographic, patterns occasionally reveal {100} cleavage." This has been generally assumed to be the case at ordinary temperatures. In the present experiments, a single crystal of Fansteel molybdenum, Vs in. diam x 2 in. long, prepared by the methods described by Chen, Maddin, and Pond" was fractured at room temperature by bending. The fracture surface appeared to be quite similar to the cleavage surface of zinc and was crys-tallographic. A back-reflection Laue photogram was made using 35 kv copper white radiation; the X-ray

Jan 1, 1952

By L. A. Panek

Using an approach based on the theory of similitude, the author develops a general equation and related concepts that provide new insights to an old problem. The load-bearing capacity (strength) of a square, rectangular, or cylindrical prism of a brittle material such as rock, coal, or concrete is expressed as the mathematical product of a size effect, a shape effect, and a function of the mechanical properties (deformability, cleat/joint spacing, and friction) of the pillar, roof, and floor materials. Through an application of multivariate statistical analysis, the results of assorted tests (laboratory and in situ) and observations of failed pillars can be combined into a fundamental scaling equation, which provides a unified, consistent approach to the estimation of mine pillar strength. The form of the equation is sufficiently general to be able to incorporate refinements in the characterization of the structural parameters, as they become available through future analysis and experimentation. Analysis of the published test data suggests that pillar compressive strength (per unit of area) is proportional to the cube root of the pillar width, and that the height effect can be described as the superimposing of a variable size effect (characteristic of the material) on the constant width effect.

Jan 1, 1981

By John A. Mathews

It is twenty years since the writer made his first molybdenum steels and others were making them commercially five years earlier but the prevailing opinion seems to be that molybdenum steels are new; from time to time the daily press speaks of important discoveries in Europe and intimates that American steel makers have much to learn in regard to alloy steels. The earlier experiments were largely confined to the use of relatively high percentages of molybdenum in tool steels and permanent magnet steels. Recent developments deal with the types of alloy structural steels used for airplane, automobile, and other engineering requirements; in these, the molybdenum content is usually less than 1 per cent. The earlier types generally have been unsuccessful commercially, but the newer types of steels are becoming of increasing importance. The war showed our dependence on foreign sources for alloying metals; molybdenum alone is widely distributed in the United States and seemingly abundant. Many deposits are not now of commercial interest, owing to location and relatively small amount of ore available, but other deposits are being developed and a stable source of supply seems well assured. In tool and magnet steels, it was early found that 1 part of molybdenum was equivalent to from 2 to 2.5 parts of tungsten. The permanent magnet steels investigated by Madame Curie,' in 1898, contained from 3.36 to 4.05 per cent. molybdenum; in 1902, Dr. E. L. French and the writer thoroughly tested steels containing from 2.0 to 4.0 per cent. These steels gave satisfactory tests for permanence, but were low in residual density and much more sensitive to hardening than the corresponding tungsten products. We discontinued work with them, therefore, and have no advice that such steels have been used commercially here or abroad. Prior to the development of the Taylor-White process and the modern high-speed steels, air-hardening steels were in general use. These were

Jan 1, 1922

By John A. Mathews

It is twenty years since the writer made his first molybdenum steels and others were making them commercially five years earlier but the prevailing opinion seems to be that molybdenum steels are new; from time to time the daily press speaks of important discoveries in Europe and intimates that American steel makers have much to learn in regard to alloy steels. The earlier experiments were largely confined to the use of relatively high percentages of molybdenum in tool steels and permanent magnet steels. Recent developments deal with the types of alloy structural steels used for airplane, automobile, and other engineering requirements; in these, the molybdenum content is usually less than 1 per cent. The earlier types generally have been unsuccessful commercially, but the newer types of steels are becoming of increasing importance. The war showed our dependence on foreign sources for alloying metals; molybdenum alone is widely distributed in the United States and seemingly abundant. Many deposits are not now of commercial interest, owing to location and relatively small amount of ore available, but other deposits are being developed and a stable source of supply seems well assured. In tool and magnet steels, it was early found that 1 part of molybdenum was equivalent to from 2 to 2.5 parts of tungsten. The permanent magnet steels investigated by Madame Curie,' in 1898, contained from 3.36 to 4.05 per cent. molybdenum; in 1902, Dr. E. L. French and the writer thoroughly tested steels containing from 2.0 to 4.0 per cent. These steels gave satisfactory tests for permanence, but were low in residual density and much more sensitive to hardening than the corresponding tungsten products. We discontinued work with them, therefore, and have no advice that such steels have been used commercially here or abroad. Prior to the development of the Taylor-White process and the modern high-speed steels, air-hardening steels were in general use. These were

Jan 1, 1922

By C. F. Allen, G. B. Walker

The sink-float methods designated by heavy-media separation processes were pioneered by C. Erb Weunsch for the treatment of base metal ores as an improvement over jigs. The work of Weunsch was further developed by Victor Rakowsky and The American Zinc, Lead and Smelting Co. Early in the development of the processes, the inherent unsuitability of galena as the solid constituent of the medium was recognized and ferrous media amenable to magnetic recovery and control were developed. The high efficiency and low cost of magnetic recovery and cleaning of ferrous media regardless of particle size, slime contamination, or surfacial oxidation had led to the adoption of ferrous media by all of the sink-float plants operating under the heavy-media separation processes patents controlled by American Zinc, Lead and Smelting Co. Approximately 2,000,000 tons of base metal and nonmetallic minerals are treated each month by these methods. Heavy-media separation processes are a modern practical and economical adaptation of the well-known laboratory procedure for separating a mixture of two solids by immersing the mixture in a liquid having a specific gravity intermediate the specific gravities of two solids. The lighter solid floats while the heavier sinks. This method of separation has been attempted on a commercial scale, but the high loss and high cost of the organic liquids halted the development of the process. Many attempts have been made to simulate a heavy liquid by using a suspension of a finely divided solid in water. If the solid phase of the suspension is ground fine enough, the suspension can be made stable or so slow settling that a substantially uniform specific gravity can be maintained from top to bottom of the bath. However, any material separated by such methods will inevitably be contaminated by some slime which will eventually accumulate in the bath and cause a viscous medium at the expense of separating efficiency. Therefore, it is necessary to provide means for continually cleaning a portion of the medium to eliminate slime at the same rate at which it is introduced to the medium. The problem of efficiently cleaning the medium limits the minimum grain size of the solid of the suspension in the case of the Chance sand process for cleaning coal, because de-cantation is the only cleaning method available. If the sand is too fine, it will be lost along with the slime. Therefore, coarse sand must be used, and to maintain a semblance of a uniform suspension, it is necessary to use strong rising water currents. The combination results in a separation based more on hindered settling classification than on sink-float principles. As previously mentioned, galena was used as the solid constituent of the medium during the early stages of the development work. The high specific gravity of galena made it suitable for the preparation of medium for high specific gravity separations. Galena can be cleaned by either decantation or by froth flotation. As with sand, de-cantation limits the minimum particle size of the media that can be cleaned without excessive loss. Froth flotation for cleaning galena medium has been used, but the problem of floating fine galena that has been exposed to extensive oxidation is well known to be a most difficult one. Last year the largest heavy-media plant m the world, and the second plant to be installed, converted from galena medium to ferrous medium despite the fact that the ore contains galena which can be used as medium. The change to ferrous medium has been beneficial in many ways. Today all the heavy-media plants have been converted from galena to ferrous media. Unquestionably, ferrous media have the widest application of any media developed, for the following reasons: 1. Ease of recovery and cleaning by magnetic means. Particle size or surface condition not a factor. 2. Low consumption per ton of ore treated. 3. Resistance to abrasion. 4. Widest range of media densities, including higher workable densities (1.25 to 3.4) than have been found possible with nonferrous media. 5. Space required for recovery and cleaning of ferrous media is considerably less than that for nonferrous media. 6. Ferrous media require lower capital investment and operating costs for media recovery and cleaning. Advantages of Heavy-media Separation Processes Heavy-media separation processes offer the following positive advantages, amply demonstrated on a wide variety

Jan 1, 1950

By C. K. Eilerts, J. D. Ham

Laboratory research has been conducted to evaluate the characteristic effects of condensate saturation on the mobility of gas in typical reservoir rocks. A pump with two pistons provided phases in equilibrium at controlled flow rates and constant liquid-vapor volume ratios. Core samples were tested in a holder that permitted sealing steady-state phases in the pore spaces under flow test pressures for weighing with sufficient precision to give an accurate measure of the attained saturations. Parameters of the study were pressure, apparent velocity, flowing liquid-vapor volume ratio, fluid composition, core material and length-to-diameter ratio. Tests were conducted at 515 and 1,515 psia to determine the effect of pressure on the mobility-saturation relationship. Influence of the apparent velocities 0.30, 0.15 and 0.07 cm/sec and of five liquid-vapor volume ratios from 0.0001 to 0.01 was determined at 515 psia The principal fluid system was nitrogen and and separator liquid from a Gulf Coast condensate, but the effect of a condensate of different viscosity was also determined. The significance of a possible concentration of liquid near the outlet end of the test cores was investigated. Core materials included a consolidated sandstone and a low-permeability limestone. Relative mobility and liquid-vapor volume ratio relationships are concluded to be dependent on pressure, saturation and, to a lesser extent, on velocity. For each porous medium and fluid there is a minimum saturation essential to two-phase flow, and high velocities of flow have only limited effect on saturations in this range. INTRODUCTION It is now recognized that knowledge of the availability of a reservoir gas — the period that gas may be recovered from a reservoir at a given rate — is as important as the estimate of gas in place. When reservoir conditions are such that pressure decline owing to production will result in retrograde condensation, liquid saturation can increase in the structure around the production well in a way that may restrict flow capacity, and hence future availability. l Based on a numerical solution of transient radial flow of single-phase gas-condensate fluids, 2 a program for computing the accumulation of condensate in a reservoir and the effect of this condensate on deliverability has been developed. During this development a need evolved for data that described the influence of pressure, velocity of flow and condensed liquid on mobility as recovery progressed. This paper presents the results of experimental investigation to obtain insight into the mobility relationship at reservoir pressures of gas-condensate fluids. A core holder for flow tests at reservoir pressure was developed to weigh the core and its fluid contents under pressure to determine saturation. A specially constructed pump was used to drive a two-phase fluid through the core until a steady state prevailed. The core was used as a differential device, and properties measured were intensive rather than extensive. APPARATUS Fig. 1 shows a schematic representation of the major pieces of equipment used in the mobility determination. The weighable core holder is connected to a two-piston, constant-displacement pump. Attainment of steady-state flow is indicated by stability of the flow differential read from the high-pressure manometer. WEIGHABLE CORE HOLDER An important part of the data needed was the mobility-saturation relationship. This required that mobilities and saturations be measured at pressures, flow velocities and liquid-vapor volume ratios characteristic of condensate reservoirs.

By H. A. Bedworth

ALLOYS of copper and silicon have been known for one hundred years or more but the commercial development of this type of alloy has taken place during the past few years. In 1905, Sperry1 proposed the use of copper-silicon alloys for springs and other purposes for which copper-tin bronzes were used. Some attention was given to this proposal at the time but no one succeeded in producing a practical alloy containing more than a fraction of a per cent. of silicon. The equilibrium relations of the copper-silicon system were studied first by Rudolfi2 and later by Sanfourche3 and Corson.4 The constitution of the system has also been recently investigated by Matuyama,5 and in the laboratories of the American Brass Co. by Smith.6 Some of the physical properties of the copper-silicon alloys have been investigated by Norbury7 and by Geiss and Van Liempt.8 Summarizing the results of various investigators of, the constitution of copper-silicon alloys, the solubility reaches its maximum value, 6.7 per cent. silicon, between 721° and 782° C. At 852° C. the solubility is 5.25 per cent., while at 400° C. it is only 4.1 percent. silicon. The copper-silicon alloy begins to get so hard at about 3 per cent. silicon that it is difficult to manage. It was found by Jacobs that the addition of manganese to this alloy considerably improved the working

Jan 1, 1929

By Richard P. Rothwell

A REFERENCE to the geological map of Alabama shows the coal- measures of that State to form three distinct fields. The Coosu, or most easterly, contains about one hundred square miles ; the Cahaba, or middle field, which is also the most southern true coal in the United States, contains about 230 square miles ; and the Warrior field, which contains in the State of Alabama some 5000 square miles, is the southern extremity of the great carboniferous deposit, which extends through Pennsylvania, West Virginia, Kentucky, Tennessee, and Georgia. But very little has yet been done towards developing those coal- fields, partly owing to the absence of all commercial manufacturing enterprise in the South under slavery, and partly owing to the want of capital and the disturbed condition of the South since the war. During the past three or four years I have devoted a large part of my time to the examination of the coal and iron ores of this range,

Jan 1, 1874

By R. P. Rothwell

A Reference to the geological map of Alabama shows the Goalmeasures of that State to form three distinct fields. The Coosu, or most easterly, contains about one hundred square miles ; the Cahaba, or middle field, which is also the most southern true coal in the United States, contains about 230 square miles ; and the Warrior field, which contains in the State of Alabama some 5000 square miles, is the southern extremity of the great carboniferous deposit, which extends through Pennsylvania, West Virginia, Kentucky, Tennessee, and Georgia. But very little has yet been done towards developing those coalfields, partly owing to the absence of all commercial manufacturing enterprise in the South under slavery, and partly owing to the want of capital and the disturbed condition of the South since the war. During the past three or four years I have devoted a large part of my time to the examination of the coal and iron ores of this range,

By W. R. Shimer, F. O. Kichline

The investigation herein described was carried out for the purpose of studying, both by chemical and metallographical means, the extent of over-oxidation of steel that can be accomplished by excessive overblowing in a Bessemer converter. 111 addition there are appended some results of basic open-hearth and crucible steels. Remarks on Chemical Methods. The test block used was hemispherical in shape, 4.5 in. in diameter and 2 in. thick. Drillings for analysis were obtained by drilling through the entire solid part of the block, carefully avoiding all cracks and blow-holes and mixing these drillings thoroughly. Drillinga were carefully examined for scale and the finest were gone over with a microscope to be sure all scale from whatever source had been removed. Oxygen was determined by the well-known method of Ledebur, modified according to Cushman,1 with, however, the removal of the preheating tube, which was found unnecessary. This method has been found to give concordant results. Blanks run from 0.0003 to 0.0006 g. Duplicate determinations varied not more than 0.001 to 0.003 per cent. It seems to be generally supposed that the hydrogen method gives only that oxygen which is combined with iron. Whether this be true or not, the content of oxygen existing as iron oxide no doubt predominates sufficiently, so that the result obtained is sufficient to indicate whether the steel is over-oxidized or not. We are well aware that the oxides of manganese and chromium, when existing alone, are not reduced by hydrogen at a red heat. To learn of their action in steel the following work was carried out: A sample of ferro-manganese and of ferro-chrome were each exposed

Jan 1, 1914

By F. M. Doyle-Garner, A. J. Monhemius

Hydrolytic stripping is the process whereby metal ions in a loaded solvent extractant are hydrolyzed by water, typically at 130°C to 200°C (265°F to 392°F). Equilibrium hydrolytic stripping tests were done on Versatic 10 solutions containing various metals, singly and in mixtures. Single solutions of Fe, Ni, Cu, Mg, and Mn precipitated [a]Fe2O3 Ni(OH)2 Cu2O + CuO, Mg(OH)2 and [?]Mn203 respectively, during hydrolytic stripping. Several mixtures containing iron precipitated magnetic spinel ferrites, MFe204. No other combinations formed mixed oxides. It is proposed that the mechanisms for hydrolysis and precipitation of iron in loaded Versatic solutions are similar to those for iron hydrolysis in aqueous solutions. Magnetic interactions between mixed carboxylate complexes are thought to be responsible for the homogenous nucleation of magnetic mixed oxides in preference to single oxides.

Jan 1, 1986

By K. A. Gschneidner, O. D. McMasters

DgIel-ential thermal, nretallographic, and X-ray paramzetric methods were used to establish the Yb-Pb phase dingram. The terminal solid solubilities in the system are less than 0.2 at. pct. Lead additions lower the 792°C transformation tewzperature of pure ytterbiun~ at 787°C by means of an inverted peritectic veaction. Ytterbium additions raise the 327oC melting point of lead to 329°C by means of a perilectic reaction. Three intermetallic compounds Yb2Pb, YbPb, and YbPb, melt congruerttly at 1246", 1116o, and 740°C. respectively. YbsPb3 forms by a peritectic reacliorz at 1250°C. YbzPb crystallizes in the PbCh (C23) type structure and the orthorhombic latliceo constants are a, = 7.478. bo = 5.225, aud C0 = 9.549A. YbsPbs crystallizes in the hfnsSi3 (D8a) type structure. The hexa~nal lattice constants for this phase are a, = 9.325 and co = 6.92d. YbPbl crystallizes in the cubic AuCU3 (Ll2) type structure with a: = 4.8628 + 0.0008A. YbPb is diwrorphic with the structure change occurring al 507°C upon healing. The crystal structures of the two forttzs were not determined. Eulectic reactions occur at 5.1 at. pct Pb and 769oC, 41.5 at. pct Pb and 1086oC, and G8.0 at. pct Ph and 717°C: RELIABLE information concerning the alloying behavior of most of the rare-earth metals is scarce. A systematic study of the rare earth-lead alloy systems now in progress is an effort to supply such information. Determination of the phase diagram of the Yb-Pb alloys is the first step of this study. Variations in the valence of normally divalent ytterbium may be studied by comparing the characteristics of the Yb-Pb alloys to those of the trivalent rare earth-lead and of the divalent alkaline-earth-lead systems. Of particular interest are the melting temperatures of the intermetal-lic compounds since these are known to be high relative to the melting points of the constituent metals. Crys-tallographic and magnetic susceptibility data for the rare earth-lead alloys are to be included in the comparative study. Results from this and subsequent investigations should provide a better understanding of alloy formation. EXPERIMENTAL PROCEDURE Materials. The major impurities in the ytterbium and lead used in this investigation are listed in Table I. The lead was obtained from Cominco Products, Inc., and was specified to be 99.99 pct pure. The ytterbium was prepared in this laboratory by the lanthanum reduction of the oxide followed by a distillation of the ytterbium. Alloy Preparation. The alloys were prepared by

Jan 1, 1968

Conservationists have launched an attack on the mining law of 1872, accusing it of permitting the min- ing industry to rob the public and despoil the environment while doing it. Michael McCloskey, executive director of the Sierra Club, and one who has made known his opposition to the law said, "environmentalists are unified in their agreement that repeal . . . is one of conservation's most urgent tasks . . . ." Charles H. Callahan, executive vice president of the National Audubon Society, paralleled McCloskey's sentiments, calling the law a "disgrace" and a "give-away." In his opening statement before the Senate Interior Committee, Chairman Henry M. Jackson (D-Wash.) said that legislation pending before the committee would put the hard rock minerals under a leasing system as is the case with oil and gas.

Jan 1, 1971

By Takeyasu Ito, Mayumi Someno, Kazuhiro Goto

SINCE the pioneering work by Kiukkola and Wagner,1 many experiments have been reported on solid electrochemistry at elevated temperatures. However, the studies have been confined to experiments under isothermal conditions. One may conceive many situations under nonisothermal conditions. With two different temperatures T1, and T2 at the two electrodes, the electromotive force, E of a Galvanic cell will be expressed by the following equation under a steady state heat transfer in solid electrolytes of zirconia-lime and thoria-lime. E = ^ $ l&-dGO2+a(T2-Ti) [1] where tO2- is the transference number of oxygen ions in the electrolyte, Go, is the chemical potential of oxygen, and a is the coefficient of the thermoelec-tromotive force due to the temperature difference. The objective of the present study was to evaluate the coefficient of the thermoelectromotive force for zirconia-lime and thoria-lime under isobaric condition. The physical meaning of this coefficient is out of the scope of the present communication. The experimental cell assembly is schematically shown in Fig. 1. The zirconia-lime electrolyte tube and thoria-lime electrolyte tube were 8.0 mm OD and 5.0 ID, from commercial sources with chemical analyses of 94.8 wt pct ZrO2, 3.85 pct CaO, 0.83 pct SiO2, 0.25 pct TiO2, and 0.05 pct Fe2O3; and 95.0 pct ThO2, 4.0 pct CaO and rare earth metal oxides, respectively. The specific gravity was 5.5 g per cu cm for zirconia-lime and 9.8 g per cu cm for thoria-lime. Original powder size before shaping and sintering the tube was several microns for both electrolytes. The distance separating the two electrodes was 4.0 or 5.0 cm. Platinum wire of 0.5 mm diam was used for the electrodes. The temperature gradient was controlled by heating one electrode with a small heating coil of nichrome wire. The temperatures at the two electrodes were measured with two calibrated Pt-13 pct Rh:Pt thermocouples, directly contacting the two platinum electrodes. The atmosphere was either air or pure oxygen. The partial pressure of oxygen in air was considered equal at the vicinities of the two electrodes, with negligibly small thermal segregation in the gas phase. The difference of the chemical potential of oxygen was controlled only by the temperature difference at the two electrodes and not by the oxygen pressure difference. The temperature ranges were 600" to 1200°C for zirconia-lime and 850" to 1200°C for thoria-lime electrolytes. Fig. 2 shows the relation of the measured electromotive force and the difference of the oxygen chemical potential at the two electrodes for zirconia-lime and thoria-lime electrolytes. The electromotive forces in the figure were measured by a *0.05 mv potentiometer. The chemical potential difference was calculated by the following equations.'

Jan 1, 1970