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By T. D. McKinley

Theory, operational characteristics, and indicated precision and accuracy of analytical methods based on vacuum extraction, equilibrium pressure, and combustion approaches are reviewed. At the present time vacuum extraction at 1400°C and the equilibrium pressure method are recommended for determination of hydrogen in titanium and titanium-rich alloys. UNTIL a few years ago the role of hydrogen in titanium was an unknown factor with regard to its effect on the physical and mechanical properties of the metal. However, following the work of Jaffee and othersa-" it is now generally acknowledged that hydrogen has a degrading effect on titanium and its alloys. The chief manifestations are a decrease in impact strength in -systems and delayed cracking in a-ß systems. Since hydrogen does have a de- grading effect on titanium it is essential to control it within tolerable limits. It then follows that procedures for quantitative estimation of hydrogen are a primary requirement for the industry. For greatest benefit these methods should be simple, rapid, and precise. In addition to having these virtues, methods must be easy to duplicate in both equipment and technique to gain widespread use. After inherent accuracy has been established, the, required precision to make a method acceptable is dependent largely on the nature of the work at hand. Ability to obtain a representative sample has a pro-

Jan 1, 1959

By Christopher G. Atwater

The object of this paper is to describe and discuss the progress that has been made, up to the present date, in the development of the modern by-product coke-oven. There are few members of the Institute who have not heard more or less of the by-product oven-installation, and there are many whose acquaintance with it is intimate and practical. Since the general opinion on the subject has hardly become crystallized as yet, it is hoped that this paper will at least furnish matter for discussion. In order to obtain an idea of the present status of the industry in the principal iron-producing countries, the following table has been prepared : Table Showing Proportion of Coke Made in By-Product Ovens in Various Countries. United Kingdom (1898, Mr. George Beilby). Short Tons. Per Cent. Coal coked in by-product ovens,. .. 1,400,000 7.9 Coal coked in blast-furnaces with by-product recovery,.......2,240,000 12.7 Coal coked in non-by-product ovens,. . 14,000,000 79.4

Jan 1, 1903

By Benjamin Miller

FROM earliest recorded times, limestone has been employed in the industrial life of peoples of all sections of the world where it exists. It is widely distributed and therefore has been available in almost every country and has been employed for a variety of purposes. Its earliest use was for buildings, since it is more easily quarried and dressed than most other kinds of rocks and so could be utilized by early inhabitants, poorly equipped, with tools. The next use was in the manufacture of lime, which was employed by the ancients in mortar. These two uses of limestone are still all important, but they have been overshadowed in scores of regions by literally hundreds of new applications for raw lime-stone or products made from it. Anyone familiar with modern manu-facturing processes can quickly call to mind many industries in which limestones are essential, and new uses are continually coming to notice. Any enumeration would probably be incomplete and soon out of date.

Jan 1, 1935

By W. A. Mudge, Paul D. Merica

One of the most prominent features of our present-day industrial development is the ever-increasing demand put upon materials of construction. Engineering ingenuity, within the past 25 years, has been unusually active, and in some fields at least engineers frankly say that engineering design has progressed as far as the limitations imposed by the properties of the present materials of construction will permit. Consequently, they are today demanding improvement in their working materials and seeking new ones, through the aid of which the present limitations of design may be overcome. The activity of this search is evident in all fields, but it is particularly so in that of structural materials required to be resistant to corrosion. The corrosion resistance of metals and alloys is never absolute and all-inclusive; a particular alloy will withstand some corrosive conditions well and fail utterly under others. Furthermore, other properties, physical and mechanical, required in conjunction with corrosion resistance vary considerably for different commercial applications. One wants a soft, ductile sheet metal resistant to atmospheric corrosion; another, a high-strength alloy resistant to sulfuric acid. The last decade has witnessed active and definite progress in the development of high-strength, corrosion-resisting alloys. In June, 1924, a symposium by the American Society for Testing Materials, on Corrosion-resistant, Heat-resistant and Electrical-resistance Alloys, disclosed no less than 60 commercial alloys the properties of which were described as being suitable for industrial service where corrosion resistance was a feature. Today the number of these alloys has been doubled, at least. In addition, economy in design and construction through decreased weight has given considerable impetus to the improvement of alloys of which the mechanical propprties may be improved by heat-treatment.

Jan 1, 1935

By Paul D. Merica, W. A. Mudge

One of the most prominent features of our present-day industrial development is the ever-increasing demand put upon materials of construction. Engineering ingenuity, within the past 25 years, has been unusually active, and in some fields at least engineers frankly say that engineering design has progressed as far as the limitations imposed by the properties of the present materials of construction will permit. Consequently, they are today demanding improvement in their working materials and seeking new ones, through the aid of which the present limitations of design may be overcome. The activity of this search is evident in all fields, but it is particularly so in that of structural materials required to be resistant to corrosion. The corrosion resistance of metals and alloys is never absolute and all-inclusive; a particular alloy will withstand some corrosive conditions well and fail utterly under others. Furthermore, other properties, physical and mechanical, required in conjunction with corrosion resistance vary considerably for different commercial applications. One wants a soft, ductile sheet metal resistant to atmospheric corrosion; another, a high-strength alloy resistant to sulfuric acid. The last decade has witnessed active and definite progress in the development of high-strength, corrosion-resisting alloys. In June, 1924, a symposium by the American Society for Testing Materials, on Corrosion-resistant, Heat-resistant and Electrical-resistance Alloys, disclosed no less than 60 commercial alloys the properties of which were described as being suitable for industrial service where corrosion resistance was a feature. Today the number of these alloys has been doubled, at least. In addition, economy in design and construction through decreased weight has given considerable impetus to the improvement of alloys of which the mechanical propprties may be improved by heat-treatment.

Jan 1, 1935

By R. G. Bowman

DISCUSSIONS of processes for the manufacture of white lead generally open with the statement that white lead is the oldest chemical pigment known to man. This fact is of more than historical interest; in the light of the present extensive use of white lead, ii indicates that the .compound possesses characteristics that make it unique among white pigments, and superior to all ;in its particular field. A greater variety of processes have been proposed for manufacturing white lead than for any other one chemical compound. Only a few of these processes have come into commercial use, however, and a large part of the present production here and abroad is made by the process used in ancient times. The outstanding disadvantages of the old process are that it is slow and laborious, affords no control of the product, and yields at best an impure material lacking in uniformity. Improved processes, sometimes classed all together as "quick processes," have had as their main object the shortening of the time required. Most of them accomplish this and some have yielded a superior product as well, but only two or three are now in use commercially. For centuries the manufacture and mixing of paints has been treated as an art, and the practice has been much influenced by tradition and precedent. There is a reluctance to abandon old materials for this purpose, and as few new uses for white lead have been developed, the adoption of the quick processes has been slow. The electrolytic production of white lead is not-new, a large number of processes and forms of apparatus have been proposed and patented within the past 25 years, all directed toward the, production of white lead, wholly or in part, by electrolysis. One or two of these processes were tried commercially but proved unsuccessful.

Jan 9, 1925

By D. J. Jr. McAdam

RESULTS of a general survey of corrosion-fatigue phenomena at the Naval Engineering Experiment Station were presented in five previous papers.1-5 In these papers references were given to the work of Haigh in 1917.6 The five papers mentioned gave a general survey of the behavior of metals when tested to failure under simultaneous corrosion and cyclic stress. As a result of this survey the fourth paper gave a tentative analysis of the corrosion-fatigue process. According to this analysis, if the initial stress is below the endurance limit but above the corrosion-fatigue limit, the corrosion-fatigue process is divided into two periods. The first period is the formation of pits. As the initial stress is below the endurance limit, the pitting is assumed to be due to corrosion, not to fatigue. The corrosion pitting, however, is not the ordinary pitting of stressless corrosion, but is an accelerated pitting due to the effect of the cyclic stress on the corrosion. As the pit progresses, both the actual stress and the effective solution pressure increase. The increase of actual stress is due to increasing stress concentration at the bottoms of the pits. The increase of effective solution pressure is due to the increase of actual stress. The mutual intensification of stress and solution pressure continues until the actual stress at the bottoms of the pits surpasses the endurance limit. The second period of corrosion-fatigue then begins. In this period the process is merely fatigue accelerated by the corrosion. The cracks advance at a continually accelerated rate until the specimen breaks.

Jan 1, 1930

By D. D. Pollock, D. I. Finch

Relationships between the compositions of specially prepared manganin-type alloys and some of their electrical properties have been established. Empirical equations, based upon the electronic configurations of the alloying elements, are given which describe the resistivity, temperature coefficient, peak temperature, and thermoelectric power of Cu-Mn-Ni-Fe alloys at approximately room temperature. Calculations based upon these relationships are correlated with experimental data. SECURING suitable alloys for the construction of stable resistors, for use in precise electrical measuring devices, has been important ever since the art of electrical measurement was begun. German silver, Pt-Ag, and Platinoid are examples of some of the alloys in early use. These early alloys were un- satisfactory for one or more of the following reasons: l—insufficient stability of electrical properties with time, 2—poor reproducibility of electrical characteristics from melt to melt, 3—excessive temperature coefficients of resistance, and 4—excessive cost. Weston introduced the Cu-Mn-Fe and Cu-Mn-Ni-Fe alloys of the type now generally known as manganins. His patents are believed to represent the first disclosure of any alloy with a negative temperature coefficient of resistance. After this work, the German company, Isabellenhutte, in conjunction with Feussner and St. Lindeck, produced alloys of

Jan 1, 1957

By Hermann Wedding

It is now fourteen years since we German ironmasters, in considerable number, visited the United States on the occasion of the Philadelphia Exposition, and found the iron metallurgy of this country, as must be frankly confessed, in an advanced stage of development not previously suspected by us. At that time the United States already occupied, as now, the second rank, with Germany in the third, the product of pig-iron for that year being, in Great Britain, 6550, in this country, 2093, and in Germany, 1850 kilotons.* This relative position has not been changed. The present annual product of the three countries is, in round numbers, Great Britain, 8380, the United States, 7790, and Germany, 4530 kilotons. But the proportion of the United States, which was, in 1876, but 15 per cent. of the world's product, has now advanced to 30 per cent. When we left America in 1876, it was not only with gratitude for cordial hospitality and for the liberality with which our professional colleagues here had opened to our inspection whatever was worthy of notice in our special field, but also with the conviction that we had collected a great treasure of new and interesting information which we could utilize for the benefit of our German Fatherland. Particularly the achievements of the never-to-be-forgotten Holley in the field of Bessemer practice, set us an inspiring example for imitation in our own country. As an expression of our thanks in more practical fashion, I attempt in this paper to sketch what we have done in Germany since

Jan 1, 1891

By John S. Johnson, Thomas Fraser

SIZING is the process of separating mixed particles into groups of particles all of the same size, or into groups in which all particles range between certain definite maximum and minimum sizes. In coal preparation, sizing is generally accomplished by passing the coal over screens. Separation by differential settling in air or water currents has been adapted to the special field of separating very fine sizes, and these processes are in commercial use to a relatively small extent in the coal industry. Separation with screens is a very old industrial practice. Agricola described the use of screens for ore treatment in the middle ages. In the literature of the British coal industry references were made to the screening of coal as early as 1589, but the practice of extensive sizing for the market did not become general until the last half of the nineteenth century. In America, the practice of sizing developed first in the Pennsylvania anthracite region, beginning with the use of rakes' in the mine working places to recover coarse coal. This mining procedure left the fines in the mine. Preparation outside the mine started with the installation of station¬ary cast-iron plates with 4 to 6-in. square holes. The run-of-mine coal was dumped upon the platforms, the large pieces of rock were picked out by hand, and the large lumps of coal were broken with hammers. The term "breaker," which still applies to the anthracite-preparation plant, originated with this practice, but the term is no longer descriptive of the entire function of the plant. In 1884, the first power-operated anthracite coal breaker' was erected by Gideon Bart at his colliery at Wolf Creek near Minersville, Pa. This plant utilized a system of rolls for breaking the coal and revolving screens for sizing. The plant was driven by a steam engine. It 'could handle

Jan 1, 1943

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10'a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann' in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5'6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1'-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1' ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968

By John V. Hamme

ONE of Tungsten Mining Corp.'s Vance County, N. C., mill near Henderson was the installation of a new crushing plant with a capacity of 45 to 50 tph. During 1953 the milling rate was jumped from 650 tons to 800 tpd simply by expanding existing facilities, eliminating bottlenecks, and making changes in the existing and new circuits. Previous expansions in 1951 and 1952 raised mill capacity from 300 tons to 650 tpd. In its latest move, Tungsten Mining decided that expansion of existing facilities would be more economical than building that normal production was uninterrupted. For the engineering and design of the new crushing plant and mill expansion the services of the Southwestern Engineering Co., Los Angeles, were obtained. The Southeastern Construction Co., Charlotte, N. C., carried out construction, alterations to existing facilities, and the installation of equipment

Jan 10, 1954

By Wido Tilmann

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

Jan 1, 1968

By Edward Jeffrey

THE use of coke in metallurgy, to any important degree, dates from the middle of the 18th century. Its utilization came most opportunely for European civilization. The forests of Europe, except in the most remote and inaccessible regions, had been largely fed, in the form of charcoal, into the smelting furnaces. For a hundred years-the middle of the 17th to the middle of the 18th century-there was a stationary condition of population corresponding to the exhaustion of European forests. This situation, which was particularly evident in Great Britain, was due to the fact that the forests had been depleted and the practical utilization of coke had not begun. The coking industry is essential for our metallurgical industries, which in turn are basal to healthy economic progress. But coke is of great importance, not only on its own account, but for its byproducts, which enter fundamentally into all the arts of peace and war. The dyestuff industry and the manufacture of explosives are intimately connected with one another, as was shown by the recent war. The subject of coking coal, therefore, is well worthy the serious attention both of practical industry and the scientific investigator. The most valuable coking coals, from the metallurgical standpoint, are derived from the coals of highest ranks. Coals, for example, that have a carbon ratio of from 70 to 80 per cent. yield the most valuable coke for the blast furnace. The difficulty of investigating these coals, however, is great, for they are rather friable and delicate and possess a high carbon content, which makes them difficult to manipulate. They present, on account of their high carbon content, a considerable degree of opacity when examined, in thin sections, under the microscope. The tenderness of structure and blackness of such high-grade coking coals as those of Connellsville and the Pocahontas region make them extremely difficult to investigate.

Jan 1, 1925

By Henry W. Edwards

Concrete is not a new, nor even a modern substance. Important structures built by the old Romans before the commencement of the Christian Era are to-day sound and solid— for example, the dome of the Pantheon in Rome, 142 ft. in diameter. I do not propose, therefore, to discuss the durability of the material, as in the mining and metallurgical business, structures, as a rule, are not calculated to endure for two thousand years. I do wish to urge, however, that much of the stone masonry around mines and smelters would have given better results if concrete had been used in place of stone. Concrete looks better; is stronger, cheaper, more durable, more quickly built, and above all requires no skilled labor, except that of the carpenter, who, like the poor, is always with us. Well proportioned concrete, that is to say, having well proportioned ingredients, may be safely relied upon to withstand a compressive or crushing strength of 50 tons per square foot. In most American cities, however, the building laws limit it to the absurdly low figure of 16 tons. This restriction is probably due to the political influence of the building-trades unions, which object strongly to its too free use, undoubtedly owing to its not requiring the services of skilled workmen. I hope to show that quite important construction work may be' undertaken without the aid of the gentleman with the trowel. In some of the isolated districts of the West and Southwest this is no mean advantage. The weight of good concrete, dry, is from 130 to 160 lb. per cubic foot. Ingredients of Concrete. Concrete is composed of four ingredients; viz., 1. Crushed Stone; 2. Sand; 3. Cement; and 4. Water.

Jan 1, 1905

By William G. Kegel

Apart from a usable product and good mining conditions, the greatest asset for a profitable coal mining organization is an effective mine maintenance program. The first step in achieving this is to have good mechanics-or men who want to be mechanics and are interested in knowing, more about the design and control of the machines in their charge. A good mechanic's knowledge and ability result from ambition, curiosity, and determination. Starting with these qualities, the aspiring mechanic can launch his career by learning all he can about mechanics, electricity, and hydraulics. Though the path is rough, the end result is rewarding. Mining machinery probably receives as much, if not more, abuse as any other heavy equipment in use today. Considering the conditions under which much of the repair work must be done, it is essential that the mine operator has the best men and tools to perform the work. Mining machines, from their inception, have utilized the electric motor; and down through the years of mechanization, this power source has undergone many changes to better adapt it to the job. The first motors used were direct-current (d-c) motors since d-c power was the most economical power source for mining at the time of early mechanization. These motors were large open-type machines which are seldom used in modern mining. Because of the mine environment, the d-c motor has been reduced in size to better suit the application in mining machines and is now manufactured with dust-tight or explosion-proof enclosures. The d-c motor is constructed with either (or both) series and shunt fields located on the stationary part of the motor (stator) and an armature coil wound on the rotating part of the motor (rotor). Power is supplied to the armature by brushes which are held stationary and make sliding contact with the armature. The brushes requires regular and careful maintenance because worn or defective brushes will cause heat or arcing which can destroy the motor. D-c motors can be used as d-c generators when mechanical power is supplied to them by the rotating

Jan 1, 1981

By F. W. Willard

VIEWING with alarm is a preoccupation not exclusively the habit of the political spellbinder. In good faith many of our mineral technologists have been and are genuinely alarmed over the prodigal consumption of our mineral reserves. Most competent observers are cautiously pessimistic. There are sound technical reasons for such caution. It is the purpose of this paper to discuss some of those reasons without benefit of a gift of prophecy. Perhaps the outstanding reason for caution is ignorance of accessible but undiscovered mineral reserves. The petroleum technologists have an edge on their metallurgical brothers for they have better tools for exploration. This is not to say that the mining geologist has to depend on hunches or the divining rod. The outstanding work on orogenesis by Lindgren and others has provided the mining geologist with some sound scientific knowledge as to where accessible metallic minerals are most likely to be found, As Clinton H. Crane has recently observed, most of the accessible areas of the earth have been combed for easily identified outcrops, and those have been or are being actively exploited. To find ore bodies hidden below the surface is still a costly speculation.

Jan 1, 1946

By Robert Keeney

Before the outbreak of the war in 1914, the only electric-furnace smelting plant operating on a commercial basis west of the Mississippi River was an electric pig-iron plant in California; rare metal ores were not smelted, concentrates of molybdenum, tungsten, uranium, and vanadium ores being shipped east for reduction. Practically no- chrome ore was being mined, and only comparatively small amounts of manganese ore. Today there are two electric smelting plants in California, one in Washington, one in Iowa, and four in Colorado; two plants are under construction in California, and one in Montana. Ores of manganese, chromium, molybdenum and tungsten are now smelted in the West, and although uranium and vanadium concentrates are still shipped to the East, they will probably be treated in western plants in a short time. The four electric-furnace plants in Colorado are listed in Table 1. TABLE 1.-Electric Smelting Plants in Colorado Capacity, Company, Location Kilowatts Products . Tungsten Products Co Boulder 800 Ferrotungsten, ferromolybdentun. Boulder Tungsten Production Co. . Boulder 400 Ferrotungsten. Ferro Alloy Co Utah Junction 1200 Ferrochrome, ferrotung-sten. Iron Mountain Alloy Co Utah Junction 3000 Ferromanganese. Power for all of these plants is supplied by the Colorado Power Co.

Jan 8, 1918

By R. L. Fleischer, B. Chalmers

In order to observe size effects associated with a grain boundary, aluminum single crystals and bicrystals of various cross-sectional dimensions were deformed in tension. Typical stress-strain curves are presented in conjunction with measurements of the effects of changes in crystal dimensions. Some effects of the growth rate used in preparation of crystals are also described. It is indicated that the macroscopic constraints at a grain boundary are responsible for the most prominent grain-boundary effect, the production of multiple slip. Two measurements of the width of the region of double slip are in agreement. It is concluded that the yield stress of aluminum is affected markedly by the inherent oxide coating. THE general problem to be examined is that of dimensional effects in the plastic deformation of metal crystals. These effects will be termed "size effects" and are here defined as follows: A size effect occurs in a series of crystals if their plastic-deformation properties are a function of crystal dimensions. Clearly then size effects depend on the nature of the boundary conditions imposed on the crystal. Crystal boundaries can be of three types: interphase, inter-crystalline, and free surface. Such deformation effects as are caused by distribution of phases, grain size, lineage structure, and single crystal external geometry are specific types of size effects. This discussion will be confined primarily to grain-boundary and single-crystal size effects, though in practice most "single crystals" not only have a number of small angle boundaries but also have one or more surface phases, so that the boundary conditions appropriate to a free surface do not necessarily apply. Hence, to this extent interphase size effects will be considered. The question of size effects associated with grain boundaries (called here intercrystalline size effects)

Jan 1, 1959

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.' The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of ' However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-' have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h') formed by the reaction where, accorhng to the notation of Kroger and Vink,6'7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i' and Fe3' ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.'-' A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i' and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970