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By William B. Phillips

It would be hard to find a mineral region that has been more beset with " processes" for the extraction of gold from auriferous sulphides than North Carolina. And it would be hard to find a mineral region less sought by capital. So many promising mines have come to grief here (perhaps because they were too "promising"), SO many "processes" have been tried and abandoned, so much expensive machinery has been bought and thrown aside, that to invite money here for investing in gold mines is almost sure to cause a smile of incredulity, or a sigh of disappointed hopes. Within the writer's personal knowledge, at least five disastrous failures have followed the introduction of as many processes. It would seem as

Jan 1, 1889

By Barton, Donald C.

THE elastic, earthwaves produced naturally by earthquakes -have been used for a long time as evidence from' which to draw conclusions in regard to the constitution of the interior and crust of the earth. The elastic earthwaves produced artificially by occasional explosions and recorded by seismological .observatories were used to draw conclusions regarding the-geology of the intervening area. Intentionally produced elastic earthwaves in the past five years have come to be used extensively in the investigation of very local geologic structure. The seismic method of working geologic structure, which makes use of artificially controlled explosions and the resulting earthwaves, has developed almost `clairvoyant power in handling certain geologic situations, and in the discovery of salt domes in the Gulf Coastal: Plain region of Texas and Louisiana has 'scored the, most brilliant success.

Sep 1, 1928

By J. B. Novak

The program describes preventive maintenance practices and controls applicable in situations where maintenance actions are triggered primarily by breakdown or part failure and specification and documentation of detailed maintenance practices are minimal or nonexistent. The presentation describes requirements of organization structure, program administration, implementation and operation, type of benefits expected, and actual benefits derived in selected areas. The principle objectives of the program are to provide quick, inexpensive, and effective controls over maintenance practices and requirements and to establish a nucleus of controls that subsequently can be expanded to cover all maintenance activities.

Jan 1, 1973

By N. D. Policow, J. S. Orphanos

Dewatering fine clean coal fractions, -595µm (-28 mesh), represents one of the most difficult and costly separations in typical plant circuits. Since 1969, the screen bowl centrifuge has offered an economical alternative to filtration/thermal dyer combinations. The performance of screen bowl centrifuges has been continuously modified and improved to dewater not only coarser coals, but also today's variety of ultrafine material. Test comparisons with alternative methods show the screen bowl centrifuge to be most cost effective and efficient when all factors are considered.

Jan 1, 1984

By A. M. Gaudin

THE large increase in the use of selective flotation as contrasted with the collective flotation of a few years ago has focussed attention on the desirability of achieving accurate control of the pH of mill circuits. Although it is well-known that alkaline circuits result in dropping pyrite and that acid circuits conversely float it, but drop the gangue, there is little that is known, beyond question, ass to the action of the acidity or alkalinity of the circuits. A complete answer is not available at present but experiments -are now in progress at the University of Utah, whose aim is to find out what the effect is on recovery of a change in hydrogen-ion concentration and how this change is brought about. Broadly speaking, a change in hydrogen-ion concen¬tration seems to affect either the mineral surface, as was suggested by A. W. Fahrenwald in his paper "Surface Reactions in Flotation"1 (TRANS. 70, 647) or the attachment of the collecting agent on the mineral surface.

Jan 1, 1929

By Y. L. Su, R. Stefanko, Y. J. Wang

This chapter describes a new approach to the solution of stress distribution around underground openings utilizing the finite element method and employing stochastically simulated rock properties. It is well-known from extensive laboratory tests that the properties of rocks, e.g., Young's modulus and Poisson's ratio, are not single-valued but form some distribution. If the scatter of test data is attributed to the variability of the rock itself rather than due to an inadequacy in test procedure, then stress solutions have to consider these variations. Utilizing this basic philosophy, the present study was initiated. A long circular opening subjected to plane strain in a hydrostatic stress field was chosen as a specific example to illustrate this approach. The technique adopted in solving stress distributions was based on the finite element method. This method is essentially a generalization of standard structural analysis procedures in which the continuum is idealized as an assemblage of "elements," interconnected at a finite number of nodal points. It is capable therefore of handling different material properties for individual elements in the model, if desired. In this study, each individual element was assumed to be isotropic, homogeneous, and elastic. However, values for Young's modulus and Poisson's ratio were randomly varied from element to element according to an assumed frequency distribution.

Jan 1, 1970

By Robert C. Meaders, Arthur R. MacPherson

Many attempts have been made to eliminate most of the crushing plant and all the grinding plant in the process of ore beneficiation by substituting a combined crushing and grinding unit which could take coarsely crushed ore and reduce it to a fine size in one unit. This unit normally would have no other grinding media than the ore itself. This is true autogenous grinding, as we understand it today, and should be clearly distinguished from pebble mill grinding, where pebbles are substituted for steel balls to grind a ball mill size feed. To compete in efficiency with normal methods of crushing and grinding, the autogenous mill must use less labor and steel to produce an equivalent product at equal or lower power consumption. In general terms, a unit to perform these functions must have means to crush the ore to fine sizes and to then further reduce the crushed pieces by grinding. In other words, to do efficient autogenous grinding, there must be a proper balance established between crushing and grinding rates. There is not much point in crushing at too fast a rate if the grinding means are not present to reduce the small particles to the required product size. The crushing means used in an autogenous mill are impact forces of two kinds, namely, (1) the rock travelling at high speeds striking the shell, and (2) the lifters travelling at high speeds striking the rock. Grinding is probably effected in a manner equivalent to pebble milling.

Jan 9, 1964

By S. Lipson, H. W. Antes, H. Rosenthal

A study was made of the effect of ingot structure on the strength and ductility of high-strength wrought-aluminum alloys. It was found that a fine-cast structure facilitated complete homogenization which, in turn, resulted in significant increases in ductility and strength. A completely homogenized 7075-T6 alloy developed tensile properties of 85,000 psi UTS, 75,000 psi YS, with 40 pct RA. Completely homogenized 7001-T6 alloy tensile properties were 102,000 psi UTS, 99,000 psi YS, with 19 pct Ra. A method was devised for making small ingots having secondary dendrite arm spacing of less than 10 u. This method involved multiple-pass arc melting of commercial rolled plate with a tungsten electvode. This material could be completely homogenized after 3 hr at 900°F; homogenization of the original plate material was not complete after 120 hv at 900°F. Degree of homogeneity was determined by use of metallographic and electron-microprobe analyses. The electron-micro-probe study also showed the preferential segregation of solutes in the microstructure. HIGH-strength aluminum alloys, such as those of the 7000 series, usually freeze by the formation and growth of dendrites. The dendrite arm spacing (DAS) depends on the rate of solidification.' Commercial ingots are usually direct chill-cast to promote more rapid solidification, but, due to the large mass of the ingot, localized solidification times are long and a large DAS results. During solidification, solute elements are rejected by the solid as it forms, causing enrichment of the liquid and ultimately solute-rich interdendritic regions. In order to attain a homogeneous ingot, the segregated solutes must diffuse across the dendrite arms. The larger the DM, the longer the time for complete homogenization. In the case of commercial ingots, the DAS is so large that the time for complete homogenization is prohibitively long and, therefore, second phases or compounds are always present. These un-dissolved phases are carried over to the wrought material during processing, resulting in an impairment of strength and ductility. In addition, the mechanical fibering of the undissolved second phases or compounds during working results in mechanical property anisotropy. If complete homogenization could be attained, higher ductility could be expected. The realization of higher ductility at current strength levels is a desirable objective; however, if higher-strength alloys were wanted, it might be possible to sacrifice some of this ductility by adding more solute elements and produce even higher-strength alloys than are currently available. Further, if complete homogenization leads to more efficient utilization of solute elements, then more dilute alloys should have relatively high strengths with very high ductility. In all instances, it would be expected that the degree of mechanical property anisotropy due to mechanical fibering would be reduced. Therefore, it was the purpose of this investigation to produce cast structures that would facilitate homogenization and to determine the effect of homogenization on the properties of high-strength, wrought-aluminum alloys. MATERIAL CLASSIFICATION Commercial Alloys. In order to illustrate the non-homogeneous condition that exists in commercial high-strength, wrought-aluminum alloys, typical micro-structures of 7001, 7075, and 7178 are shown in Fig. 1. The chemical compositional specifications of these alloys are given in Table I. It can be seen in Fig. 1 that a considerable amount of undissolved second-phase material is present in each of these alloys. The solute elements associated with the undissolved phases were identified by electron microanalyses. Back-scattered electron images and characteristic X-ray images of the three commercial alloys are shown in Figs. 2, 3, and 4. These data indicate that the second phases are regions of high copper and high iron-copper concentrations. The second-phase material also was analyzed for magnesium, zinc, manganese, chromium, and silicon, but no significant enrichment above that of the matrix was found. Therefore, the problem of homogenization resolved itself into one of dissolving the copper-rich and the iron-copper-rich second phases. In order to accomplish this objective, two approaches were made. The first was to reduce the iron as low as possible since this element has a maximum solid solubility of 0.03 pct in aluminum. The second was to produce cast structures with finer DAS to facilitate dissolving the second phases. Commercially Produced High-Purity Alloys. A special high-purity, 2000-lb ingot of 7075 alloy was made by a commercial producer. This alloy contained the following weight percentages of solutes: 5.63 Zn, 2.48 Mg, 1.49 Cu, and 0.21 Cr. All other elements combined were less than 0.02 pct by wt including iron and silicon at less than 0.01 pct each. The ingot was cast and processed into rolled plate using standard commercial techniques. Microstructures of standard commercial 7075 and the special high-purity 7075 are shown in Fig. 5. It can be seen from this figure that the high-purity alloy has less undissolved second-phase material, but a significant amount was still present. The second phase in the high-purity material did not contain iron but it was found to be enriched with copper. The slight effects of the increased purity and de-

Jan 1, 1968

By AIME AIME

BBENJAMIN LEROY MILLER, of geology at Lehigh since 1907, is known the world around, for his former students are on every continent. He knows the earth is round for he has encircled it twice, once in 1927, and the other way around in 1937 to regain the day he lost on the first trip. An early trip was to Great Britain and Ireland, another to central Europe, a third to Spain for the International Geological Congress, a fourth to Scandinavia. His trip to the Southern Hemisphere is recorded in "Mineral Deposits of South America." In 1940 he was booked for Australia but because of the war went instead to Alaska. He spent the summer of 1941 in Central America. Thus he has gained a broad. world knowledge of mineral deposits, both metallic and nonmetallic.

Jan 1, 1942

By W. F. Chiao

With the application of dislocation damping theory an attempt was made to determine whether the generation and extension of dislocations is inherently more difficult in a brittle steel than in a ductile steel. A ductile steel was compared with a brittle stee1 by simultaneously measuring the ultrasonic attenuation and velocity during tensile test, and the density of free dislocations and their mean loop length were then calculated as a function of strain. The results showed that in the ductile steel there was always a large generation of dislocations and great extension of loop length occurring at some stage within the early plastic region. In contrast, the brittle steel showed very little or no such sudden changes in dislocation dynamic states after the onset of plastic deformation. Furthermore, a strong temperature dependence of dislocation dynamic states was also observed in the ductile steel and a hypothesis was suggested that a thermally activated process of dislocation rearrangement could occur at higher deformation temperatures. The activation energy of dislocation rearrangement at room temperature was estimated as about 2030 cal per mole.C. DUCTILITY is an indispensible property in the application of engineering materials, especially steel. During the past two decades the theoretical and experimental approach to the understanding of flow and fracture of metals has been constantly undergoing changes and progress." while the fracture behavior of metals can be influenced by many factors such as chemical Composition,3 second-phase particle mor-phology,4 and dislocation arrangement,5 it is now a general belief that the fundamental understanding of the ductile-brittle fracture phenomena of solid materials must stem from the study of dislocation dv-namics developed under stress conditions.6,7 Most of the traditional ductility tests, such as Charpy impact test, slow bend test, and tensile fracture test, cannot by themselves reveal directly the mechanisms of ductile to brittle transition of materials. In the experimental investigation of tensile ductility it would be ideal to be able to study directly the dynamics of dis-locations in a bulk specimen during the process of deformation. Since the ultrasonic pulse technique is the only satisfactory method for studying dislocations and the fine details of deformation characteristics in metals in the course of a tensile test, it would appear that a comparative study of ultrasonic attenuation changes during tensile tests of metallic materials exhibiting different ductility might be very informative. So far no work comparable to this study has appeared in the literature. Recent progress in both theory and experiment has indicated the feasibility of studying the dislocation mechanisms of ductility behaviors by ultrasonic measurements during tensile test. Granato and Lucke8 have developed a quantitative theory that enables the calculation of dislocation density and their average loop length from the measurements of ultrasonic attenuation and velocity, and several investigators, including Chiao and Gordon,9'10 have shown that simultaneous ultrasonic measurements can be successfully made during a tensile test. Furthermore, many investigators11-13 have repeatedly proposed in the past several decades that deformation and fracture are mutually self-exclusive, and that the ability or inability of a material to deform plastically, i.e., to generate dislocations, is a major factor in determining whether the material will be ductile or brittle. Thus, in the present work an attempt was made to determine whether the generation and extension of dislocations is inherently more difficult in a brittle steel than in a ductile steel. This article is principally concerned with the study of the relation between the propagation of ultrasonic waves and tensile deformation in a steel series which displays quite different toughness at room tempera-turk. changes in attenuation and velocity of ultrasonic waves have been measured as a function of strain during the deformation process. The results have been interpreted in terms of the vibrating string model for dislocation damping as developed by Granato and Lucke, and it has been found that some of the more subtle predications of the model are in good agreement with the experiments. This would be especially meaningful because most of the previous experiments in testfying the model were carried out with single crystals of high-purity materials and little work has been done with polycrystalline steel alloys. EXPERIMENTAL PROCEDURES AND RESULTS Specimen Materials. The tensile specimens used throughout this experiment were of two compositions selected from a series of Fe-Mo-0.77 pct Mn-0.22 pct C steels prepared for a ductile-brittle fracture transition study. One steel contains 0.21 pct Mo and the other 1.03 pct Mo. These two compositions were chosen for the present study because they possess quite different toughness properties at room temperature. The 0.21 pct Mo steel is quite ductile while the 1.03 pct Mo steel is rather brittle, as measured by the standard Charpy impact test. The alloys had been prepared by vacuum induction melting and chill casting in steel molds. The ingots were hammer-forged into 1/2-in.-sq bars from which tensile specimen blanks were cut. These blanks were first normalized under argon atmosphere at 1700°F and then reaus-tenitized and isothermally transformed at 1050°F to a bainitic microstructure. The chemical compositions, heat treatments, hardness measurements, and Charpy transition temperatures of the two steels are listed in Table I.

Jan 1, 1970

By William A. Hustrulid

INTRODUCTION Prior to the mid-1970's, the U.S. Radioactive Waste Disposal Program was focused on salt deposits as the geologic medium of choice, almost to the exclusion of other rock types. These efforts are illustrated by the Project Salt Vault experiment in a salt mine at Lyons, Kansas, in 1965-1967 followed by attempts to locate a repository site in central Kansas. Preliminary evaluation of other geologic media led, in 1978, to the GAIN (Geotechnical Assessment and Instrumentation Needs for Nuclear Waste Isolation in Crystalline and Argillaceous Rocks) Symposium held at the University of California (Berkeley), for the purpose of preparing a state-of-the-art document together with research needs for some of the other possible rock types. Because possible sites had not been selected, nor would they be for some time, the primary emphasis was for research and development focused on generic rocks and generic sites. A basic ground rule at that time was that the host rock formation should provide the primary containment for the waste. Also, the U.S. Nuclear Regulatory Commission (NRC) was just drafting the proposed rules regarding site suitability so that this input was not available. The collection of baseline data, conduction of some critical experiments both in the laboratory and field, and the performance of scoping studies were deemed needed. Such work was indeed undertaken; and to date, a great deal of information has been compiled and much has been learned regarding the characteristics of rock masses, rock behavior

Jan 1, 1984

By J. I. Budnick, W. B. Ittner III, D. P. Seraphim

A reliable technique has been developed for producing single crystals of tantalum in the form of small diameter wires. By suitably heat treating these and polycrystal samples, first in an oxygen atmosphere and finally in vacuum, it has been found possible to reduce residual resistivities to 10-3 microhm-cm. The purity of these samples is thus comparable to the purities obtained in zone-refined silver, copper, and aluminum. THE growth and purification of pure single crystals of the transition metals is, in general, difficult. The high melting and annealing temperatures of these metals make it necessary to employ rather special techniques in any crystallization process. In addition, the transition metals show a great affinity for and are easily contaminated by nitrogen, oxygen, and carbon. Recently, however. a number of investigators have been successful in growing,

Jan 1, 1961

By Roland W. Rammler

With oil consumption increasing more rapidly than known reserves in industrial countries, there has been a growing interest in the production of synthetic crude oil. The main starting materials for such production are coal, oil shale and tar sand, all of which occur in enormous quantities in North America. A process sequence suitable for all three of these starting materials incorporates a preliminary retorting step to produce oils for subsequent hydrotreating. For this retorting step, a technique known as the Lurgi-Ruhrgas process has proven highly efficient. The process has been commercially used for the flash carbonization of coal and has also been tested in pilot- plant experiments with oil shale and tar sand.

Jan 1, 1970

By R. J. Jones, L. D. Clark, R. C. Howell

This research provides an empirical approach toward further analysist10 of the variables in rock breakage under direct, hydroimpact (impacting on fluid) and explosive impulse loading. That the strain on the face of a block of rock, below an impact pin or explosive charge, is directly proportionate to the rupturing force F and inversely proportionate to the product of the burden W and the hole periphery S, is borne out in the laboratory using electrical resistance strain gages to measure a peak strain during rupture by small explosive charges detonated in boreholes. Furthermore, such findings established the validity of the expression F = Ss • Wy • R as a useful relationship from which, it is believed, can be derived practical applications in commercial rock blast design.

Jan 1, 1972

By Edward Hyde

THE HIGH-TEMPERATURE SCALE IN OPTICAL PYROMETRY AT the basis of optical pyrometry lie the theoretical and experimental data of the so-called blackbody. The black body is essentially a theoretical conception, with certain simple properties attributed to it -fundamentally, the property that its radiation at any temperature is a unique function of the temperature and does not involve any other variables. As a theoretical conception, an equation has been developed by Boltzmann connecting the total radiant power with the temperature, and another equation by Planck connecting the distribution of radiant power throughout the spectrum with the temperature. The integral of the latter with respect to wave-length conduces to the former and permits the evaluation of the constant c1 of the Planck equation, ass given in the form. J-= cl?-5 c2 (1) e ? T ? 1 assuming that the constant Q of the Stefan-Boltzmann law E=a(T4-T40) is known. The other constant c2 is arrived at by other methods, which will be discussed later. This equation for the black body lies at the foundation of optical pyrometry. To make the discussion complete, it should be stated that the theoretical black body is quite closely realized by a hollow enclosure with walls at a uniform temperature and radiating through a small orifice. The electrically heated black body, first introduced by Lummer and Kurlbaum, is an essential part of the equipment of a pyrometric research or testing laboratory. Numerous investigations have shown that its radiation conforms to that of the theoretical black body within experimental errors. Hence by operating the electrically heated black body at the melting point of some pure metal for which the temperature of melting has been determined on the vas scale. a standard is obtained for comparison with

Jan 9, 1919

By J. W. Edington

THE Hopkinson bar has become a popular technique for the measurement of the mechanical properties of materials deformed at high strain rate. Maximum use of the equipment is made in the arrangement first used by Kolskyl in which a short compression specimen is sandwiched between two pressure bars and is loaded by a single pulse travelling through the system. The pressure bars are used both to apply the load to the specimen and as transducers to obtain continuous strain-time histories of three pulses, incident on, reflected, and transmitted by the specimen. The data measured by the pressure bars can be analyzed in terms of the stress/strain behavior of the specimen.2'3 However, one of the assumptions of the analysis of the observed pulses is that the total stress and total strain do not vary significantly from point to point within the specimen at any given instant during the deformation process. Although this assumption is generally justified for very short disc-like specimens2 the situation is uncertain for larger specimens. For example, at small plastic strains (-0.01) Hauser et al.2 have some evidence of small flucations in the total stress within the crystal during deformation, even in relatively short aluminum specimens. In addition, Karnes4 has shown that the plastic strain, and by inference strain rate, is different at each end of a compression specimen tested in a Hopkinson bar, although the length of the specimen was not specified. Recently, the mechanical properties and the dislocation substructure have been investigated in single crystals of columbium5 (length 0.25 in., diam 0.19 in.), and copper6 (length 0.5 in., diam 0.5 in.) deformed at high strain rates. As part of this research program the assumption that the plastic strain is constant throughout the specimen has been checked by measuring the total dislocation density as a function of position in the specimen. Compression specimens of the same orientations and dimensions were tested as described previously5,6 sing a split Hopkinson bar. Since any discontinuity in strain distribution is most likely to arise during the initial stages of deformation the investigation was performed on specimens deformed to plastic shear strains of 0.054 (copper) at a strain rate 1.2 x l03 sec-1, and 0.06 (columbium) at a strain rate 1.5 X l03 sec-1. The orientation of the single crystals is shown in Figs. 1 and 3. Thin foils were taken parallel to the most highly stressed slip plane, i.e., (111) in copper and (011) in columbium, using conventional disc techniques. The dislocation densities were measured using first order reflections with compensation for invisible dislocations.5'6 In the copper single crystals the discs were randomly distributed throughout the cross section of the specimen. However, the dislocation density obtained from each disc was plotted vs the disc positions relative to the ends of the specimen. The results for the copper specimens are shown in Fig. 1. Clearly the dislocation density is constant throughout the main portion of specimen within the experimental error. The error bars on the dislocation densities correspond to a shear strain variation of 0.015 on the basis of previous measurements% ± of the rate of increase of dislocation density with strain in copper single crystals of the same geometry. Thus within this experimental error the plastic strain can be concluded to be constant within the specimen and the assumptions used in the analysis of the stress/time curves are therefore reasonably valid. The higher measured dslocation density near the impact end and the lower dislocation density at the bar end of the copper specimen is in agreement with the results of Karnes4 who showed that this strain/time curve rose to a maximum more rapidly at the impact end compared with the bar end. Hauser et al.2 have also pointed out that at small plastic strains (-0.01) the strain at the impact end of the specimen may be greater than that at the bar end. Thin foils taken from different points within the columbium single crystals demonstrated that the dislocation density could vary significantly within the specimen, see Fig. 2. Large areas of some thin foils up to 30 µ sq contained very few dislocations, see Fig. 2(a). However, in other parts of the compression specimen dislocation configurations like those shown in Fig. 2(b) existed over large areas (-30 µ sq). As a result, when the average dislocation density in a thin foil is plotted as a function of the position of the thin foil relative to the ends of the specimen, considerable scatter is observed, see Fig. 3. In this material then, the local dislocation density, and consequently the

Jan 1, 1970

By Russell Paul

THE Wisconsin zinc district, also known as the Upper Mississippi lead and zinc district, is an area of about 2500 sq. mi. in the southwestern portion of Wisconsin and adjacent parts of Illinois and Iowa. It includes Iowa, Grant and Lafayette counties in Wisconsin, Jo Davies County in Illinois, and an irregular strip of Clayton and Dubuque counties in Iowa, parallel to the Mississippi River. During periods of high metal prices mining has been quite active in this district, but recently the lower metal prices have caused many companies to suspend, so that at the present time there are only a small number of mines operating. The short life of these mines and the low mineral content of the zinc deposits limit the investment in development and equipment, and necessitates the operation of this equipment at maximum running time and maximum capacity. The tonnage of rock handled (locally termed dirt) is large in comparison with the tonnage of concentrate produced. Moreover, the zinc content of the concentrate is low, varying from 25 to 40 per cent zinc, and the value per ton is correspondingly low. The life of the mines varies greatly. An exception-ally good deposit may produce 2,000,000 tons of rock during a period of ten years, market value permitting, from which will be obtained 100,000 to 150,000 tons of concentrate. One property which might be con-sidered as fulfilling the requirements of a profitable operation was developed and equipped in 1925, oper-ated continuously for a period of two and a half years, produced 484,292 tons of rock, from which was obtained 37,659 tons of zinc concentrate, 34.4 per cent Zn, and 1155 tons of lead concentrate, 67 per cent Pb. During the war period prices of ore permitted the mining of lower grade ores than has been possible in the past few years. The maintaining of a higher grade mill-feed has resulted in reducing the size of stopes formerly carried in the old mines and confining the workings within narrower limits.

Jan 7, 1928

By J. E. Dorn

A STUDY of the increase in density of copper powder as as a function of the time and temperature of sintering has been previously reported.' The present note will describe the results of a series of experiments under conditions similar in all respects to those of the first series, except that

Jan 1, 1951

COUNCIL OF SECTION DELEGATES E H Stevens, Chairman James W Halley, Vice-Chairman George J Donaldson, Secretary The Peoples Natural Gas Co 140 Stanwix St Pittsburgh 22, Pa EXECUTIVE COMMITTEE H R Wardwell, J G Evans, H R Bianco, Harry Campbell

Jan 1, 1955

By L. S. Darken

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968