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By Cyril Smith

IN the study of the structure or the properties of a series of alloys or nonmetallic compounds, it is often advantageous to express the com-position not as percentage by weight, according to which the material is always made up and analyzed, but as the atomic percentage of the two constituents. The conversion from the one to the other is repre-sented by the formulas: 100A 100x or 1 x/A+100-x/B B(100-x) _ 100yA 100y [2] X. yA + (100 - y)B or y (100 - y) where x and y are the weight and atomic percentages respectively of the element of atomic weight A, and (100 - x) and (100 - y) are the per-centages by weight and by atoms respectively of the element of atomic weight B. While calculations according to these formulas are simple, they are time consuming if several conversions have to be made. In 1931 Water-man1 constructed a nomograph for performing the conversion, but this did not permit an accuracy greater than about 1 per cent to be obtained in the neighborhood of 50 per cent. Ölander2 has proposed a graphic method simpler than Waterman's and one that gives a uniform precision throughout the entire scale. The possible accuracy is about 0.5 per cent of the whole, depending on the size and accuracy of the coordinate paper used. Recently, Hermann3 has described a slide rule for making the calculations. These devices make use of the simple rearranged equation

Jan 1, 1933

A. K. McCosh, Coatbridge, Scotland (written discussion*).-It is well known in Great Britain that oven operators in the United States have been able to reduce the coking time much below European standards by the employment of higher temperatures. Our linings have always been the factor that has prevented our doing the same, and it would be of much interest to coke-oven operators here if Mr. Blauvelt would give a typical analysis of the bricks his company uses for the linings of its ovens, and if he could see his way to send me a sample so that I could have the texture examined, I should personally be very much obliged. The lining brick which my company has found most successful is of a ganister variety, and has the following analysis: Silica, 80.8 per cent.; alumina and iron oxide, .17.8 per cent.; lime, 0.8 per cent.; magnesia, 0.07 per cent.; but with this brick the least carelessness on the gas regulator's part may destroy the lining. It would also be of interest if Mr. Blauvelt could give the temperatures of the air leaving these generators and also of the oven flues.

Jan 10, 1918

The following is an incomplete list of members and guests who called at Institute headquarters during the period July 11, 1918 to August 11, 1918. John Carter Anderson, Tucson, Ariz. Edson S. Pettis, San Francisco, Cal. Lieut. Frank A. Ayer, Tyrone, N. M. Wm. H. Rettie, Yonkers, N. Y. W. R. Canton, McGill, Nev. J. T. Robertson, Port Richmond, S. I. Alden Crankshaw, Palmerton, Pa. Harry O. Robinson, Margarita, John Davenport, W. Norfolk, Va. Venezuela. A. Faison Dickson. C. K. Seng, Gilbert, Minn. F. A. Fahrenwald, Cleveland, C). E. S. Sheffield. L. Hall Goodwin, New York. H. G. Smith. W. H. W. Hamilton, Baker, Ore. Harry M. Spoor. Floyd D. James, St. Louis, Mo. H. H. Stoek, Urbana, Ill. George A. Laird. Arthur L. Tuttle, Copperhill, Tenn. J. W. McBride, Spokane, Wash. Thor Warner, Phoenix, Ariz. Arthur Notman, Bisbee, Ariz. Christopher G. Atwater, Manager Agricultural Dept., The Barrett Co., is in Washington serving the U. S. Navy Bureau of ordnance in connection with the Navy nitrate plant recently authorized by Congress. Edward Ludlam Blossom announces his marriage to Mabel Townsend, daughter of Mr. and Mrs. George Comings Mills, on Wednesday, July 17, 1918, at New York City.

Jan 9, 1918

By W. E. Keck

THERE is a considerable tonnage of iron ore in the Menominee Range Michigan that is unsalable only because it has too large a content of sulphur. Beneficiation of such ore is economically desirable, as a rela-tively large quantity of finished concentrate would be obtained (deleteri-ous sulphur mineral content being generally less than 5 per cent) and because large blocks of such ore have been developed incidentally during search for low-sulphur ore. Research on the flotation beneficiation of these high-sulphur ores consisted of: (1) a study of the flotative properties of the principal min-erals in a nearly puree state, (2) flotation of synthetic mixtures of these pure minerals and (3) application of this experimental information to samples of the ores. Gypsum in iron ores is extremely deleterious; but when sufficiently free from impurities it is a valuable commodity. In 1934, the United States produced 1,500,000 tons of calcined and uncalcined gypsum valued at $13,700,000'. Of this quantity and value, Michigan produced approxi-mately 19 per cent4. Thus this investigation may also prove to be of interest in connection with the gypsum industry if minerals separation, such as flotation, becomes necessary in the future processing of gypsum. Data on the flotative properties of gypsum would also be of interest to the science of flotation because such information has been extremely limited. The technical literature reveals one reference to the flotation of gypsum, in which was discussed the use of the mineral, with several others, to determine the relation between the floatability of minerals and the pH of the flotation solution2. This investigation necessarily was not comprehensive in regard to gypsum, but it did show that the mineral could be floated with oleic acid under varying pH conditions.

Jan 1, 1937

By L. A. Weakly

The Viburnum ore trend is the largest, single known ore body of lead in the world. Four well-known mining companies operate in the trend, which is approximately 64 km (40 miles) long and up to 610 m (2,000 ft) wide, located some 121 km (75 miles) southwest of St. Louis, MO. Total production from the mines for 1979 was 33 kt/d (36,000 tons) of ore or 472 kt/a (520,350 tons) of lead and coproduct metal. The district is the number one producer of lead, providing 90% of the United States' output with its coproducts, zinc ranking second, and copper and silver both ranking sixth in total US output. Mining is done in a stratiform deposit approximately 305 m (1,000 ft) in depth with the host rock principally dolomite. Ore is mined in large open stopes by the method commonly referred to as room-and-pillar mining. Mining methods and equipment are fairly similar, with the mines classified as trackless, all mining equipment operates on rubber tires. This paper will present a description of the different methods and equipment used to move ore from the active heading underground to the ore shaft for hoisting to the surface. Basically, three methods are incorporated: front-end loader and truck haulage combination; front-end loader and truck, with main line track haulage combination; and front-end loader and truck, with conveyor haulage combination. The logistics of each system, such as method of use, equipment specifications, ore handling rate, and those cost figures that could be made public, will be included.

Jan 1, 1983

In high-volume mining operations, preventive maintenance programs that include standardized replacement wear parts can boost equipment availability and lower unit costs. Meeting the daily production targets depends heavily on keeping equipment working as close to full time as possible. This is the case at one medium-sized western surface coal operation producing approximately 2.7 million t/y (3 million stpy). The mine, located in western Wyoming, removes in excess of 8 million m3 (10.5 million cu yd) of highly abrasive overburden each year. According to the mine superintendent, "Abrasion at this mine is some of the worst I've ever seen. Shovel points can wear out in little more than one shift. Dozer blades some- times last two weeks, but can wear out sooner. And ripper points really take a beating. If we can replace this fast-wearing iron with small pieces that go on quickly, we think that's the way to go."

Jan 3, 1978

By W. W. Eckles

This paper is presented as a suniniary report of the use of well gas composition correlations obtained from mass spectrometer recordings as a means of identification and determination of reservoir continuity. Conventional methods for detecting composition differences are en-pensive, elaborate, and difficult to obtain. This excludes the use of extensive composition data for most applications. During recent years the mass spec-trometer has come into general use as an analytical tool in petroleum refineries. The use of mass spectrometer composition patterns ir~ characterizing or "finger-printing" the produced gas from a reservoir, presents a novel method for correlatitlg gas samples from well to well. The mass spectrometer provides a trace similar to an electric log. having peaks which represent the abuntlnnce of certaitz hydrocarbons in the well gas sample. Without going further into the detailed analysis the idea has been advanced that these traces or patterns could be used as a means of identifying a particular natural gas. This theory has proven to be essentially correct. The mass spectrometer pattern method is simple and cheap as COi?7pared to other standard methods. It greatly facilitates the solution of reservoir and geological problems in which correlation of well gas Com-positions is a factor. Specific field applications have been made. This paper concerns the results obtained in 465 individual gas analyses from 35 fields and 77 res- ervoirs. In a number of cases it has been found that such data have been extremely valuable in the determination of reservoir continuity. In at least one case, the method was a valuable contribution in tracing a reservoir from sand to sand in a coinplex fnulted field involving n11rnerous gas reservoirs. Field applications are presented to illustrate the possibilities of the method at the present stage of developnient and to stimulate the ernployrnent of this new approach by geologists and petroleum engineers in the industry. INTRODUCTION Identification of producing horizons and the determination of reservoir continuity are often a problem in those areas where dome structures and highly faulted sands are encountered. To complicate the picture further, there may be numerous sands, one on top of the other which dip and diverge in different directions. Even though it may be possible to develop some solutions to the preceding problems on the basis of the geological and reservoir data on hand. it is readily recognized that substantiating data based on independent methods would he extremely valuable. It has been found through field studies that correiation of well gas composition can be used to advantage in the geological and engineering study of a complex reservoir identification problem. METHOD FOR COMPARISON AND CORRELATION OF WELL GAS SAMPLES Since a large number of well gas samples are required in a gas identification or reservoir con- tinuity problem, it is necessary that a method of analysis be employed which can detect differences in composition readily and inexpensively. Although detection would be possible by means of low temperature fractional distillation (POD) analpsis, the method requires a relatively large sample and is comparatively slow and expensive to run. The mass spectrometer affords an inexpensive and precise analysis of small well gas samples taken at the surface which are about 1/300 as large as a POD sample. These samples can be obtained by regular field personnei and shipped to the spectrometer for analysis. It is, therefore, a practical approach to the problem. A typical record from the mass spectrometer is illustrated in Fig. I. The peaks on the record represent the abundance of ions produced from the different hydrocarbon molecules making up the gas sam-ple. In well gas comparisons only five peaks are employed, since the other peaks are formed from the same gas molecules and furnish no additional information. The five peaks used represent the abundance of methane, propane, ethane, butane and heavier, and oxygen. They are referred to respectively as the 16, 29, 30, 43, and 32 peaks. The oxygen peak is used to correct for air content in

Jan 1, 1958

By Walter R. Hibbard

ALTHOUGH extensive pole figure studies have been reported by Brick1 and others2,3 showing preferred orientations in rolled and annealed 70-30 alpha brass, and by Hermann and Sachs4 in 70-30 alpha brass cups, comparatively little information has been published on textures in drawn 70-30 alpha brass tubes. Crampton5 reported a (110), [III] texture in drawn brass tubes based on selected individual X ray photograms following the method of Norton and Hiller,6 but the extent and ease of developing this texture and the annealing texture have not been reported and pole figures of these structures were not found in the literature. The present investigation was further stimulated by the possible influence of textures on the mercury stress-corrosion cracking of brass tubes. According to Snoek,7 iron-nickel alloy sheet with a strong cubic texture was more resistant to corrosion than a randomly oriented sheet. Crampon5 reported that single crystals of 70-30 alpha brass drawn into tubes did not crack after 24 hr s in a standard mercurous nitrate test. Edmunds 12 found that single crystals of 70-30 alpha brass did not crack in a standard mercurous nitrate test but did crack when subjected to ammoniacal vapor. Wassermann reported a similar failure of a single crystal of brass in ammonia. A tube with a strong texture might approach single crystal behavior and tend to resist mercury cracking if the differences in orientation between adjacent grains were sufficiently slight. PREPARATION OF SPECIMENS Crampton's5 tubes drawn 28 pct reduction in area developed a slight degree of preferred orientation while in tubes drawn 48 pct it was more marked. Based on this information, in order to obtain specimens with markedly different degrees of preferred orientation but with the same final draw, two sets of 70-30 alpha brass tubes were made following the mill schedules shown in Table I. The final draw involved a large reduction in outside diameter, and a ratio of reduction in area to reduction in outside diameter similar to that reported by Crampton,5,10 to cause mercury cracking of brass tubes. The brass contained 71.31 pct copper, 0.01 pct lead, 0.01 pct iron and zinc by difference. DETERMINATION OF POLE FIGURES A 6-in. length from each tube was rotated rapidly by an electric stirrer in 25 pct nitric acid until the gauge was reduced to 0.003-0.005 in. The tubes were carefully cut longitudinally and the walls gently flattened. They were further etched in 25 pct nitric acid to 0.0015 in. thickness and (III) pole figures were determined using copper K-alpha radiation in the manner described by Brick.1 The three general types of pole figures

Jan 1, 1947

By J. F. Ednie

SCRAP metals to the value of more than a billion and a half dollars were recovered in the United States in 1939 for further use in industry. Few people have any true conception of the magnitude of the secondary-metal industry as related to that engaged in the production of the primary, or virgin, metals; of its importance, particularly when a shortage of primary metals exists, as at present; or of the advance that has been made in standardizing and improving the quality of its products. Of the iron and steel produced in the United States in 1939 (the data used in this article are largely taken from Bureau of Mines reports for that year) just over 50 per cent came from scrap and slightly less than 50 per cent from ore. Of the principal nonferrous metals-aluminum, anti-mony, copper, lead, nickel, tin, and zinc-63 per cent came from domestic ores and 37 per cent from scrap. Fig. 1 presents graphically the relative tonnage and value of primary and secondary production of ferrous and nonferrous metals. In this chart only purchased secondary metals are considered, the figures being exclusive of "home" or "plant" scrap which amounts to rather large figures in the iron and steel industry. Incidentally, the chart shows that from the tonnage standpoint the iron and steel industry is some twenty times larger than the nonferrous industry, though with regard to the value of the product the ratio drops to about two to one.

Jan 1, 1941

A. Bement, Chicago,Ill. (communication to the Secretary*):— Formerly it was the general practice of engineers to designate coal that is free from moisture and ash as " combustible," notwithstandirig that it contains oxygen and nitrogen. The origin of this practice was more particularly due to the requirements in connection with boiler-testing, which demanded a consideration of that portion of the fuel which took part in the combuition-process because results based on a unit of either moist or dry coal were not comparable, since both moisture and ash were recognized as variable quantities. Thus, a pound of " combustible " became a standard of value, and was treated as a constant before employing measurements of heating-power and calculating therefrom the percentage of efficiency. The recognition of this term " combustible " was an advance to be credited to the engineer rather than to the chemist, because the latter, not having to do with the interpretation of analyses in practice outside the laboratory, usually saw no reason for reporting results in terms other than those of the moist-coal composition. Some years ago I needed a table of fuel-composition in terms of moist, dry, moisture-free and ash-free coal, and of the combustible components. This table required the use of the word combustible in its proper sense, for the purpose of designating carbon, hydrogen, and sulphur, instead of including these three elements with oxygen and nitrogen, to which aggregate the term combustible was formerly applied. To make such a tabulation involved either the use of the inconvenient and cumbersome term, "ash- and moisture-free coal," or of some other representative term, and for this purpose I adopted the expression pure coal, which is short, simple, convenient, and technically correct. It is also harmonious, because it agrees

Jan 1, 1909

By Harry Udin

IN 1948, the writer and his associates determined the surface tension of solid copper by balancing the force of surface tension in a very fine wire against an external load.' At that time we, in common with other early workers, assumed that grain boundary energy in a pure metal is very small in comparison to the energy of an external surface. Accordingly, we neglected the internal surface energy of the coarse-grained specimens. Since that time, experimental evidence has accumulated showing that grain boundary energy, far from being small, is generally about one-third of the energy of an external surface.2-4 This is sufficient to introduce a significant error into our determination. The differential equation governing equilibrium is: wdl - yds, + y*ds2 [I] rather than wdl = yds as originally written. w is the balancing force in dynes, 1 the length of the specimen, sl the external and s2, the internal surface area, y the copper/ copper vapor surface tension, and y* the grain boundary tension. Fortunately, we had made for another purpose a careful study of the size and shape of the grains, and found that the boundaries, with rare exceptions, traversed the specimens and were perpendicular to the wire axis. For this case, eq 1 leads to w = rry -(n) r2y* [2] where r is the wire radius and (n is the number of grains per unit length. A count of some twenty 5-mil wires indicated that - n became 80 & 10 after a short anneal near the melting point, and remained nearly constant for as long as 96 hr at temperature. An assumption of y* = 1/3y leads to a defining eauation for r: [31 The term in the brackets may be considered a correction factor applied to eq 11 of ref. 1. Upon applying this factor, the surface tension of solid copper at its melting point is found to be 1650 & 100 dynes per cm, rather than 1370 as previously reported.' The new temperature coefficient is —0.55 dynes per cm per "C. Grain boundary energy is more significant than surface energy to the physical metallurgist. It is evident from eq 2 that a series of experiments with wires of different grain size can lead to an evaluation of y*. The details of such an experiment are being worked out now. References 1 H. Udin, A. J. Shaler, and J. Wulff: The Surface Tension of Solid Copper. Trans. AIME, 185, 186-190; Journal of Metals (Feb. 1949) TP 25303. 2 G. L. C. Bailey and H. C. Watkins: Surface Energies in the System Solid Copper-Molten Lead. Proceedings Physical Society. (London) (1950) 36B, 350. 3 L. H. VanVlack: Inter granular Energy of Iron and Some Iron Alloys. Ph.D. Dissertation, Univ. of Chicago, Sept. 1950. 4 . P. Greenough: Grain Boundary Energies in Silver. R.A.E. Report, No. Met. 52. (May 1950) Fan-borough, Hants, England.

Jan 1, 1952

Meeting; May 23, 1913.-On the petition of 25 or more members residing in the different localities, the following Local Sections were established: St. Louis Local Section. Southern California Local Section; Denver Local Section. It was voted to publish a statement in regard to tours in connection with the Butte meeting, which-is published on p. i of this Bulletin. Mr. Edward Caldwell was appointed as expert advisor. on printing. The report of the Committee on Printing advising certain changes in methods of printing. was accepted.

Jan 6, 1913

By E. W. Engelmann

RAPID progress has been made during the past year in the copper mills throughout the country. Particular efforts have been made to increase the fine-grinding efficiency by the installation of larger classifying units operating in closed circuit with ball mills, such as the 78-in. high-weir Akins installation at the Phelps Dodge plant at Ajo, Ariz.; also the Type "FX" Dorr classifiers of Nevada Consolidated at McGill. Nev. and the "FX" Dorr bowl classifier of the Braden Copper Co. in Chile. Some of the copper milling plants in the Southwest, such as Chino in New Mexico and Ray Con. in Arizona, have replaced rolls operating wet in their fine-grinding circuit by rod mills. At Hollinger primary rod mills were formerly used in open circuit followed by pebble mills in closed circuit with classifiers. They now have primary ball mills in closed circuit with large extra heavy classifiers and no secondary mills. This new installation is producing the same grinding on 5000 tons per day with a reduction in cost of nearly 4c. per ton. At the Braden plant, in Chile, short-head Symons crushers have replaced 54-in. rolls, thereby in- creasing crushing capacity with some saving in maintenance cost.

Jan 1, 1939

By H. E. Montgomery

H. L. Burghoff.*—I have a question, Dr. Smith. A number of the alloys you mentioned contain lead, which, of course, is present as discrcte particles. At what level of concentration does lead begin to play an important part in determining these elevated-temperature characteristics ? A. J. Smith.—That is a difficult question to answer because of the complicating features of the alloys that arc lead free. I do not know of any work done on the subject. But for comparison, 85-5-5-5 has about the same characteristics at, say 450°F. as 88-10-2, which is lead free or contains at most 0.30 per cent. Both 85-5-5-5 and 88-10-2 precipitate delta. The specification limit of usage is 406°F., temperature of saturated steam at

Jan 1, 1945

By A. B. Kinzel

MUCH work has been done recently in an attempt to analyze the physicochemical mechanism involved in the production of steel by the open-hearth process. . This has resulted in reducing the process to a series of interrelated phenomena obeying the usual laws of mass action and diffusion. Of these, the reaction of the iron oxide and carbon in the molten steel is of most interest from a technical point of view as it con-stitutes the main action in the usual steelmaking processes. A. L. Feild1 has formulated a basic differential equation expressing the open-hearth reactions and Hefty has done considerable experimental work on the determination of a number of constants involved in the basic open-hearth reaction. In considering the application of the law of mass action. to the reaction FeO +C ?? CO +Fe, the iron will be taken as constant, as is the case in the open hearth and the carbon monoxide pressure will be assumed' constant at one atmosphere. From this xy = m at equilibrium, where x is the percentage weight of carbon, y percentage weight of iron oxide and m the weight-concentration equilibrium constant. While it is customary for physical chemists to express equilibrium constants in terms of molar concentrations, the constant is here expressed as the product of the percentage-weight concentrations for ease of comparison with the constants quoted by Herty and by Feild, and for more ready applicability to the open-hearth reactions. Herty and his associates have attempted to calculate the value of this constant from data on open-hearth heats. So many variables affect these results that an adequate calculation presents very great difficulties. A value of 4 X 10-2 was first arrived at, but this was later changed to 1.6 X 10-2. Feild, in order to illustrate the operation of the differential equation of the open hearth, has assumed a value considerably lower than Herty's, namely, 1.0 X 10-2, the largest value consistent with certain theoretical

Jan 1, 1929

By Raymond B. Ladoo

NONMETALLIC minerals (excluding fuels) arid their primary products produced annual in the United States have a value in excess of one billion dollars, or more than that of the metals, yet the lack of expert knowledge of some of the fundamental technical and economic aspects of this most important and complicated business is astonishing. This paper will deal with the economics of this non- metallic mineral field-the business of making money from producing these minerals. The incentive behind all business activity in a capitalistic economy is to make money-to plan so that each dollar invested in property, plant, equipment, services, and so on will return more than a dollar plus simple interest. Of course, business has social, civic, and national duties and responsibilities, but the fulfillment of these is largely dependent upon financial success.

Jan 1, 1939

By John M. Loveioy

EVERY producer of crude oil knows what is meant by the Rule or Law of Capture. It means that the ultimate ownership of a migratory substance such as oil is not determined until that substance is reduced to physical possession. Unless, therefore, the producer moves quickly to capture his share from the common pool, he may lose to any neighbor who is drilling and producing more rapidly than he a portion of the oil originally underlying his property. And there is no recourse open to him if his property is so drained. Under this rule it is obvious that the owner of an oil property, if he is to protect his' ownership, must be governed in his development and production policies by the activities of his neighbor rather than by his own business requirements. He must drill as densely and as fast as the other operators in the field or lose part of the oil to which he should be entitled.

Jan 1, 1936

Member ship L P MATHEWSON, Chairman GEORGE D BARRON LOUIS D HUNTOON JOHN A CHURCH, JR H N SPICER Alternates LEWIS W FRANCIS WILBER JUDSON F T RUBIDGE Increase of Membership JOHN A CHURCH, JR, Chairman Other members to be appointed

Jan 1, 1923

By B. J. Kochanowsky

To improve blasting methods it is necessary to know how the explosive force acts and how rock resists this force. Because of the tremendous power developed within milliseconds and the great number of other factors directly affecting the technical and economic results, an analysis of the fundamentals of blasting theory is difficult. But since the rules used for layout design and for calculations of size of explosive charges are based on theoretical assumptions, complete knowledge of blasting theory has great practical importance in mining. Analysis of Blasting Theory: It is interesting to note the opinion of blasting experts with respect to contemporary blasting theories. F. Stussi,' Professor of the University of Zurich, stated: "We do not have enough experience yet to change our army engineering regulations in blasting and base it on new fundamentals. It is our duty to collect more practical data and to do more research in blasting to close this gap." K. H. Fraenkel,' editor of the Manual on Rock Blasting published in 1953 in Sweden and written by well-known Swedish, German, Swiss, and French blasting and explosive experts, said: "To the best of our knowledge no suitable formulas for civil blasting work are to be found in the American, French or German literature."

Sep 1, 1955

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain' and magnesia.' Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann'" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965