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Jan 1, 1967

By Roshan B. Bhappu

This is the Centennial year of AIME and many of us reading this issue of ' will be getting ready to attend the Centennial Celebration in New York from February 26 through March 4. The officers of the Division sincerely hope that a large number of our members will attend the fine technical sessions and social functions arranged for this really big meeting. The year 1971 will be a crucial one for MBD. This SME Division is a working group organized "to furnish a medium of cooperation among those interested in the basic unit processes and unit operations of minerals beneficiation; and to promote the advancement of this branch of mineral technology through meetings for professional intercourse, and to stimulate the preparation, reading discussion and circulation of papers connected therewith." No one can deny the worthiness of these objectives or minimize the efforts that Division officers and members have made to attain them. Much has been done over the past several years to achieve a smooth-running and effective MBD organization. However, there is still room for improvement and much more needs to be done in order to provide the best possible services for the membership and the profession.

Jan 1, 1971

By G. C. Stone

AS the term "hardness" is used with many different meanings, it should be understood that it here means resistance to deformation by compression. It was determined by measuring the pressure, in pounds per square inch, necessary to reduce by 20 per cent., the length of cylinders 1 in. (25 mm.) in diameter by 2.6 in. (66 mm.) long. The tests were made at Columbia University on an Olsen 400,000-lb. machine, the load being applied at a constant rate of speed 0.0319 in. per min. The results were obtained by Messrs. Rigg and Williams, and some of them were given in a paper read at the Sixteenth Annual Meeting of the American Society for Testing Materials, in June, 1913. The remainder of the results were obtained in subsequent experiments by the same authors. In all cases, the results given are the averages of three or more closely concordant tests. All of the spelters tested were of standard commercial grades and all were of compositions making them good deliveries. The accompanying table gives the results arranged in the order of increasing hardness:

Jan 1, 1919

The new Ceramic Engineering Building of the University of Illinois is to be formally dedicated on Nov. 20 and 21. The occasion will be made one of great interest to the clay-workers of the country. It is expected that the exercises will be attended by many representatives of the architectural, structural, mining, geological, chemical, and manufacturing interests. In connection with the dedication exercises, an industrial conference will be -held, in which a number of topics of current interest to the ceramic engineer, the clay-worker and the manufacturer will be discussed by well-known experts. : The number of students registered in the College of Engineering of the University of Illinois eleven days after the beginning of registration - for the new year, is as follows: Architecture, 116; Architectural Engineering, 167; Ceramic Engineering, 46; Civil Engineering, 190; Electrical Engineering, 266; Mechanical Engineering, 273; Mining Engineering, 25; Municipal and Sanitary Engineering, 26; Railway Engineering, 34; total, 1,143. The enrollment of students in the whole University, not including the College of Medicine, the College of Dentistry and the School of Pharmacy, which are located in Chicago, is 5,21.4.

Jan 10, 1916

By G. Sachs, C. C. Chow, L. J. Klingler

Most structural parts which are heat treated are designed using strength properties which have been determined in the principal direction of the wrought material. For example, for rolled or drawn materials, properties are given for the rolling or drawing direction. The structures, however, may be loaded so that the critical stress is in some direction other than that for which the properties of the material are known. Investigations of forged products,123 have shown that while the yield strength and tensile strength of carbon steel billets and bars vary little with the direction of the test specimen in relation to the fiber, the contraction in area in tension tests and the impact strength in notched bar impact tests decrease in the transverse direction. The contraction in area and, consequently, the fracture stress of hard aluminum and magnesium alloy forg-ings have also been found to be lower in the transverse direction. An investigation on aluminum alloy plate4 likewise has shown the dependence of the fracturing characteristics upon the direction* of the test specimens, the longitudinal direction being considerably stronger than the transverse direction and the normal direction, with the normal direction being the least strong. The variation of properties with direction has been explained by a type of anisotropy called mechanical anisot-ropy. This anisotropy results from the elongation, in the direction of the principal strain, of certain phases, inclusions, and/or cavities in the metal during working. A mechanical fibering is thus produced which seems to persist through annealing and heat treatment. This investigation was initiated to determine the flow stress and fracture stress, at high hardness levels, at 90° to the rolling direction in a round steel bar. It is this direction which receives the critical stress in drawing dies machined from round bars. Preliminary tests showed a large difference in properties between the 0° and 90° directions. Consequently, it was felt that a more complete investigation, utilizing several types of tests, was warranted to determine the flow and fracture characteristics of a steel at various orientations, for a number of hardness levels. This investigation was conducted on an air hardening nondeform-ing die steel. Material and Procedure The distribution of properties was made on a 3-in. round bar of annealed high-carbon, high chromium steel of the following analysis: Pct Carbon................... 1.53 Manganese................ 0.39 Silicon.................... 0.27 Chromium................ 11.76 Vanadium................. 0.25 Molybdenum.............. 0.81 The 3-in. bar was produced from an 8-in. ingot, which was annealed and forged to a 4-in. square billet. The billet was annealed and rolled to a 3-in. round which was then annealed and straightened. This steel is an air hardening die steel which has very good dimensional stability on hardening; therefore, the residual stresses resulting from hardening would be expected to be low. A hardness survey across the diameter of the annealed bar showed no difference in hardness from the center to the outside. However, the test sections of all the specimens were taken approximately half way between the center of the bar and the surface to avoid any surface effect or possible porosity at the center. Tension, compression and bend tests were made on specimens hardened and tempered at six different temperatures. The tension test specimens, Fig 1, were machined from the bar at orientations of 0, 22.5, 45, 67.5 and 90° from the axis of the steel bar. The specimens were rough machined, heat treated and then ground to size. The test section on each specimen was lapped in a direction parallel to the axis of the specimen to remove any transverse scratches which might act as stress raisers. The specimens were tested in fixtures which insured concentricity of loading of less than 0.001 in.5 The transverse strains were measured with a radial strain gauge,5 the least count of which was 0.0001 in. change in diam. The compression specimens, Fig 1, were machined from the bar at ori-

Jan 1, 1950

By C. T. Young, J. L. Lytton

In recent investigations,1,2 the strength and thermal stability of dislocation substructures prepared by 5 to 25 pct room temperature tensile straining and recovery annealing at 120°, 160°, and 200°C have been studied in randomly oriented polycrystalline high purity aluminum. The techniques of transmission electron microscopy revealed that a major source of the strength and stability of dislocation substructures was the formation, during room temperature straining, of well-defined cells bounded by dislocation tangles which rearranged into nearly perfect dislocation networks during recovery, forming the boundaries of subgrains. The strength of such substructures increases with decreasing cell or subgrain size,2"6 and the formation of fine subgrain structures can provide thermally metastable strength at low temperatures and can favorably alter the course of primary creep at elevated temperatures.7'8 For maximum benefit, however, sub-grain growth should be reduced or eliminated. It was, therefore, decided to investigate the use of heterogeneous precipitation on dislocation networks as a means of imparting increased strength and thermal stability to subgrain structures through effective pinning. C.T. YOUNG, STUDENT MEMBER AIME, and J. L. LYTTON, Member

Jan 1, 1970

By John D. Morgan, Sylvain J. Pirson

An instantaneous and continuous analysis of a mineral suspension should be of great value in controlling various mineral preparation processes. Described herein is a method of analysis based on the use of high-frequency alternating current, which, under certain restrictive conditions, could be of use. Theoretical Considerations In a suspension of conductive minerals, the electrical effect primarily responsible for the variations in electric conductivity is the capacitance. In Fig Ia, let an alternating voltage E be applied across two electrodes F and F', between which are two rows (S and T) of mineral particles, all of approximately the same size, immersed in a fluid. Let the number of rows of particles between the electrodes be R and the number of particles in each row be N. If A is the area of a particle, D is the distance separating two particles, and k is a constant depending on the fluid, the capacity, CO, of the particle system will be given by: KRA C°= ND Referring now to Fig Ib, let R, the number of rows, be held constant, but let N, the number of particles in each row (S and T), be increased X-fold. The capacity, C1, of

Jan 1, 1949

Meeting of June 26, 1914.-The President was authorized to appoint Advisory Committees to co operate with the United States Bureau of Mines. The President announced the appointment of Edward H. Benjamin and W. C. Ralston as additional members of the Committee on Arrangements for the San Francisco meeting, 1915. H. T. Van Ells and Judd Stewart were appointed to represent the Institute on a joint committee of several technical societies to consider the standardization of graphical methods for the presentation of statistics. The President announced the appointment of H. Foster Bain to succeed Edward H. Benjamin, resigned, on the Committee of Management of the International Engineering Congress, 1915. The Secretary was authorized to issue a new circular advertising the sale of back Transactions and to sell back Transactions, bound in cloth, at a price of $35 for 46 volumes, provided sufficient orders were received to warrant the special binding. The sum of $177.50 was contributed to the San Francisco Local Section. Upon recommendation of the Committee on Membership, 70 Members, 4 Associate Members and 7 Junior Members were elected to their respective classes; there was also one change of status from Junior Member to Member.

Jan 8, 1914

By H. W. Maynor, C. J. McHargue

DURING the course of an investigation of materials suitable for use as thermocouples at elevated temperatures by one of the authors, several nlolybdenum-rhenium alloys were prepared. Micrographs of an annealed alloy containing 25 pct Re (intended concentration; analysis not obtained) showed a number of twins, Fig. 1, suggesting a face-centered cubic structure. This note reports the structure and recrystallized wire texture of an alloy containing 25 wt pct Re. Alloys were prepared from 99.9 pct Mo (Fansteel Metallurgical Corp.) and rhenium obtained from the University of Tennessee (purity unreported). Powders were combined and briquetted at 56,000 psi and sintering was carried out at 2400°C for 5 hr in vacuum. Ingots so prepared were swaged at 982.2" to 1037.8oC into wires 0.036 in. diameter, a reduction in diameter of 85.6 pct. These wires were vacuum-annealed 1 hr at 2000°C. A North American Philips 114.59 mm powder camera and nickel-filtered copper radiation were used for structure determination. For the texture determination a Laue-type camera was used with zirconium-filtered molybdenum radiation and, because of the high background, aluminum foil was mounted next to the film. Exposures were taken with the wire perpendicular to the X-ray beam and tilted by 10". It was found that the X-ray pattern could be indexed on the basis of a face-centered cubic structure. Because of difficulties associated with obtaining a good X-ray pattern for this material, accurate parameter determinations were not made. An indicated parameter value of 3.70A was obtained. The X-ray data are given in Table I. The annealed wire texture was observed to be a sharp [111] texture. The spread about this fiber axis was k8" at the surface of the 0.036 in. wire. The annealed wire textures of aluminum have been reported as retention of the [Ill] deformation texture for anneals below 500°C and a new [1121 texture for anneals above 600°C.1 In copper wires, with a [Ill] plus [loo] deformation texture, results indicate a retention of this texture for annealing at lower temperatures and new components or the disappearance of components for annealing at higher temperatures.' The presence of the strong [I111 texture in the molybdenum-rhenium alloy after a 2000 °C anneal suggests that the deformation texture was the same. Acknowledgment The wires used in this study were prepared and heat-treated at the Institute for Atomic Research, and Ames Laboratory, Iowa State College, and the authors wish to express their thanks to the Institute for allowing the use of the material and permission to publish the results.

Jan 1, 1954

By F. R. Morral

INDUSTRY has yet to find a universal solution to the problem of engineer personnel selection. Today, the choice of the right man for the right job is even more pressing than ever before. The age of the hard apprenticeship seems to have passed. In its place one finds the interviewer who must determine through personal contact and evaluation of college grades whether a graduate engineer will fit into his company's scheme. The problem, as it is constituted today, may be broken into four parts: Need for better use of human resources (there is a shortage of engineers, scientists, and skilled workers), productivity with higher efficiency, encouragement of personal pride in work performed, and employee's happiness on the job and away from it.

Jan 4, 1953

By Maurice Grieves

The great majority of shafts constructed today are still excavated by drilling and blasting, a method which changed very little in over 100 years until the introduction of the mechanical lashing unit and cactus grab by the South Africans, which enabled muck to be removed as fast as massive hoisting systems could handle it and resulted in very rapid rates of sinking. Record breaking month's performances were achieved at -Hartebeestfontein No. 4 shaft, October 1960-337.1 m; Western Reefs No. 4 shaft, October 1961-340.7 m; and Buffelsfontein eastern twin shaft, March 1962-381.2m. The method was very labor-intensive, requiring a crew of over 60 workers at the shaft bottom during the drill cycle. Safety precautions were strict, but in the drive to achieve rapid advance, cases of personal injury were still somewhat high because of the large number of people engaged in this potentially hostile environment. The South African method, as it came to be referred to throughout the rest of the world, was adopted in the United Kingdom in the late 1950s in a modified form with greatly reduced manpower and nonsimultaneous sinking and lining, which was insisted on by the British Mines Inspectorate. In that instance, it was successfully used to sink the 7.3-m-diam concrete-lined shafts at Kellingley to 770 m depth, with rates of advance of over 90 m/month achieved, a British record at that time. During the sinking of the 1.15-km-deep twin shafts at Boulby potash mine in the UK in 1970, the method was again used, but for the first time ever in Britain exemptions from the mining code permitted the use of crash beams, crash doors, jack catches, and semi-simultaneous sinking and lining techniques. New British shaft sinking records of over 120 m/month were achieved in both shafts. Similar equipment and techniques were used in the early 1970s to sink several deep shafts in Canada, notably Creighton #7 and the Con zinc mine at Yellowknife in the NW Territories. Today, this equipment is standard for deep shafts in the US and the rest of the world. However, with the tremendous escalation in mining labor costs, the impact of health and safety legislation, and environmental regulations, coupled with a very real shortage of miners willing to work in this exposed situation it was apparent that an alternative to the labor-intensive conventional method of shaft construction had to be found. Recognizing the trend is inevitable, one or two major German shaft sinking contracting firms began to take a fresh look at full face boring techniques applied to tunnels and raise bored shafts. The results were most encouraging. Tunnel drivage techniques using moles had developed considerably from Colonel Beaumont's original channel tunnel machine circa 1880 to the superbly engineered Priestley machine selected to cut the British side in 1975 and the double shielded Robbins Grandori borer on the French side of the English Channel. Full face tunnel machines were being successfully used to drive uphill in inclined shafts in Austria and Switzerland. At Mapprag in Switzerland, the Demag mole drove the first (intentional) vertical transition and curve, and then went on to successfully complete the 730-m-long penstock shaft at an inclination of 35°. In Austria, the Wirth mole drove the Kaprun Glacier ski-lift railcar tunnel at record breaking rates of 457 m/MONTH (best 30 m/d) through green schist at an inclination of 29° for a distance of 3.35 km while the Hydro tunnel at Sarrelli in Switzerland was being driven by the Robbin's mole at an inclination of 35°. Simultaneously, extremely promising results were obtained using large assemblies of cutter discs on raise borer heads, such as the 4.87-m-diam X 460-m-deep shaft raised by Teton for Jim Walter Resources Inc. Bearing in mind that most mine shafts in the future (unless in exceptionally competent rock) will require some form of lining, and the trend will be toward deeper shafts as the more easily accessible mineral deposits become exhausted, it was seen that normal raise boring had definite limitations in vertical accuracy, in the limitation imposed by the drill string on the available torque that could be applied to the cutter head, and in the risk of collapse of the unsupported shaft rock wall in friable or jointed and fissured ground, since it is not possible to apply any form of temporary support until the permanent lining is being installed. A further problem was the economics of installing a subsequent lining, necessitating setting up a headgear and hoisting arrangement approaching in size that required for conventional drill and blast sinking and lining. Because of the economics, German contractors opted for a phased transition from drill and blast to the full face, rodless, out of the solid shaft mole, by starting off with a down-the-hole shaft boring machine -without a drillstring-but using a pilot hole to get rid of the muck.

Jan 1, 1982

By H. E. Strauss

The time-to-fracture test has been applied to pure platinum and to two alloys of platinum under the special conditions of small cross-sectional area of the specimens and of a test temperature above the annealing temperature. While the results are similar in character to those secured with large specimens of steel at temperatures below the annealing temperatures, two differences are noted: (I) an upward inflection in the curves for log stress vs. log time for the alloys, and (2) a sharp break in the curve for log stress vs. log time for pure platinum when single crystals filled the wire. The experiments showed that: (I) platinum and 10 per cent rhodium-platinum maintained their strengths at IIOO°C. better than did to per cent iridium-platinum, and (2) the rhodium-platinum after a time exceeded the iridium-platinum in strength at IIOO°C. Platinum alloys in their service at high temperatures encounter conditions somewhat similar to those that exist in the usual form of the "time-to-fracture"l test with steel. This paper is intended primarily to present results obtained by a "time-to-fracture" test under conditions approximating actual service for platinum (at the temperature IIOO°C. under oxidizing conditions) with three materials, pure platinum (99.99 per cent), a platinum alloy with 10 per cent iridium, and a platinum alloy with 10 per cent rhodium. The experimental procedure differed from that previously used in this type of measurement in that the samples were of small diameter (0.010 in.), were fully annealed, and were tested at a temperature definitely above their annealing points (600°C., IOOO°C. and 1050°C., respectively, for 60 per cent cold reduction and 15 min. heating time2,3). The experimental arrangement was similar to that previously described,' using as heating unit a small, horizontal, platinum-wound furnace, ½ by 12 in., maintained at constant temperature by an automatic controller. The samples were 0.010-in. wires, which had been annealed at 1200°C. by drawing them slowly through the furnace. The time-to-fracture was measured electrically. Elongation was not determined because of the difficulties inherent in the experimental arrangement. Life—that is, the time-to-fracture—was considered the important property in these first tests. No attempt was made to measure the reduction in area, but the types of fracture were noted qualitatively; in the text they are referred to as (I) the normal, plastic, or necked fracture, (2) the knife-edge fracture, and (3) the brittle or intercrystalline fratture with small reduction of area. Results for different constant applied stresses are plotted in Fig. I. In all cases at least two trials were made for each stress, although they cannot always be indicated separately on the curves. The breaking Stresses drop very rapidly to a small frat-286

Jan 1, 1943

By H. E. Strauss

The time-to-fracture test has been applied to pure platinum and to two alloys of platinum under the special conditions of small cross-sectional area of the specimens and of a test temperature above the annealing temperature. While the results are similar in character to those secured with large specimens of steel at temperatures below the annealing temperatures, two differences are noted: (I) an upward inflection in the curves for log stress vs. log time for the alloys, and (2) a sharp break in the curve for log stress vs. log time for pure platinum when single crystals filled the wire. The experiments showed that: (I) platinum and 10 per cent rhodium-platinum maintained their strengths at IIOO°C. better than did to per cent iridium-platinum, and (2) the rhodium-platinum after a time exceeded the iridium-platinum in strength at IIOO°C. Platinum alloys in their service at high temperatures encounter conditions somewhat similar to those that exist in the usual form of the "time-to-fracture"l test with steel. This paper is intended primarily to present results obtained by a "time-to-fracture" test under conditions approximating actual service for platinum (at the temperature IIOO°C. under oxidizing conditions) with three materials, pure platinum (99.99 per cent), a platinum alloy with 10 per cent iridium, and a platinum alloy with 10 per cent rhodium. The experimental procedure differed from that previously used in this type of measurement in that the samples were of small diameter (0.010 in.), were fully annealed, and were tested at a temperature definitely above their annealing points (600°C., IOOO°C. and 1050°C., respectively, for 60 per cent cold reduction and 15 min. heating time2,3). The experimental arrangement was similar to that previously described,' using as heating unit a small, horizontal, platinum-wound furnace, ½ by 12 in., maintained at constant temperature by an automatic controller. The samples were 0.010-in. wires, which had been annealed at 1200°C. by drawing them slowly through the furnace. The time-to-fracture was measured electrically. Elongation was not determined because of the difficulties inherent in the experimental arrangement. Life—that is, the time-to-fracture—was considered the important property in these first tests. No attempt was made to measure the reduction in area, but the types of fracture were noted qualitatively; in the text they are referred to as (I) the normal, plastic, or necked fracture, (2) the knife-edge fracture, and (3) the brittle or intercrystalline fratture with small reduction of area. Results for different constant applied stresses are plotted in Fig. I. In all cases at least two trials were made for each stress, although they cannot always be indicated separately on the curves. The breaking Stresses drop very rapidly to a small frat-286

Jan 1, 1943

By Charles A. Morgan

The proms of mire drawing depends upon the property which certain metals possess, termed ductility, which is defined in Brande's Dictionary of Science as a property inconhequcnce of which metals may be drawn out at length wilhotit interrupting the continuity of their constituent parts. As ticfincd thy M. Tresca, it is the property of flowing when subjected to pressure, and ie termed by him the "flow of solids," in his paper, read before the AcaiXemy of Sciences in Paris, November, 1866 * In the simple language of the wire shop, it is that quality in certain metals that thcm to be drawn (or etretched) out througl~ a tapering hole in a metal block or die, the die being more dense and harder than the metal to be redud. It is a fact well known to tllose slrillet1 in the ai*, that to eu~xeed in drawing iron or steel wire, it is of' the utmost, importance to have tborough lubritatiun, as a lack of it woullii udu-se abrasion of the wire, or of the walls of the tapering hole in the dia or plate, and quickly put an end to the operation. In drawing coarse or large sizes of pire, say & inoh diameter, the pressure upon the sides of the tay~dng hole, where the wire comes i.u contact with the die, so great that an ordina,y labricaot is equeezed out when the nsoal rc~luctions iu size are matie, and abrasion takea place. In order to meet this diffic:ulty, and emure proper lubrication, it has been a ccmmon prtictice for yazrs to apply a paste made of rye or wheaten flour, or lime, to the surface of the wire to be drawn, and when the pnstc is dry, to smwr tl~e wire with tallow or grease; the wire is then ready to be draw, the dried pa serving fo prevent the lubricant from being presetf out in the prows. Some years since, when Bessemer metal came iargely into use material for wire, 'the writer fourid that its dmwing requid so much more power than iron wire, that he was led to institute a. series of trials to ascertain the difference in power required. It was fotind that Bessemer wire requircd from 100 to 200 per cent. more power to makc the same reduction in sizes than soft iron wire, the difference depending npou the amount of carbon and other chemical constitu-

Jan 1, 1881

By D. J. Cox, J. P. Conway, A. E. Gooch

A two-year test conducted by the USBM's Spokane Mining Research Center (SMRC) has proven the feasibility of the yielding rockbolt, a concept which may prove very useful to the mining industry by providing ground support under a variety of conditions. The yielding rockbolt was originally developed in South Africa3 to overcome the limitations of conventional bolting in rock subjected to high-stress or rock burst conditions. The yielding effect is obtained by fitting the bolt prior to thread rolling with a smooth-bore die of internal diameter slightly larger than the shank diameter but smaller than the rolled thread diameter.

Jan 4, 1977

Jan 1, 1961

By E. N. Aqua, C. M. Owens

The microstructure in cold-rolled Zircaloy-4 sheet has been characterized by transmission electron microscopy and X-ray diffraction line-broadening techniques. The rate of work hardening is measured in terms of microstrains, particle sizes, micro hardness, the tensile yield strength. The tensile yield strength of Prestrained (less than 10 pet) Zircaloy-4 sheet is found to be a linear function of the square root of the dislocation density, us predicted by work-hardening theories. ZIRCALOY is one of the most important structural alloys for nuclear reactor applications.''2 In order to understand the effects of the nuclear environment on Zircaloy structural members, the preirradiation microstructure must be characterized. This report will describe the substructure existing in cold-rolled Zircaloy-4 sheet as observed by electron microscopy and by X-ray diffractometry. I) EXPERIMENTAL PROCEDURE Commercial Zircaloy-4 strip was cold-rolled and annealed in argon at 760°C for 1 hr. The annealed sheet was again cold-rolled to a maximum of 50 pct reduction in thickness with segments of the strip being retained after 2.5, 5, 10, and 20 pct reductions. One-inch-square portions were chemically polished (50 parts HNO3, 50 parts H2O, 10 parts HF) and mounted onto lucite blocks using double-sided tape to prevent bending during handling. Thin foils suitable for transmission electron microscopy were prepared from each of the sheet samples. The sheets were mechanically polished through 600-grit paper to a 3 to 4 mil thickness and were chemically polished by immersion for 1 to 2 min in a solution containing: 50 parts HNO3, 50 parts H2O, and 10 parts HF, and rinsed in distilled water. The final metallographic procedure was to electropolish for less than 10 sec with an electrolyte of 10 parts perchloric acid and 90 parts glacial acetic acid, at 20 v, at room temperature using stainless-steel point cathodes and a vigorous stirring action. These foils were examined in a Philips EM 200 electron microscope using a 100-kv accelerating voltage.

Jan 1, 1968

By D. S. Tannhauser, I. Bransky

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

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