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By M Gerards, M Steinberg, T Graham

The quality and quantity of Australia’s secondary deposits, which include tailings streams and tailings dams, are higher than most countries’ primary deposits. In addition, these secondary deposits have already been mined and processed, meaning that the recovery of high-grade product requires low capital and operating costs.The most widely used process for the recovery of these valuable fine and ultra-fine hematite iron particles is the wet high-intensity magnetic separation technique, originally developed by Dr Jones over 55 years ago. Many of the original machines are still working today.The aim of this paper is to demonstrate the capabilities in terms of grade and yield of using sophisticated magnetic separation modules. All results and figures are obtained from test work and design and engineering work with material from the Pilbara. In addition, consideration is given to dewatering of iron ore product and tailings.Two types of tailings have been identified for processing. Firstly, tailings that have already been deposited in a tailings storage facility, and secondly, live tailings streams from an existing wet iron ore beneficiation plant. In both cases, the technical and practical results are shown along with relevant flow sheets and plant layouts. Finally, this paper highlights the total predicted power and water consumption, capital requirements and projected operating expenses.The results show that the operating costs are significantly lower than the mining and processing operations that are required for an equivalent amount of iron ore. The recovery of iron depends on various factors but is within the 30–50 per cent range at an equivalent grade to the mainstream product. Another significant benefit is that the magnetic separation process is water positive, meaning that water is released rather than added in the process.The processing of the Pilbara’s secondary deposits will therefore result in an overall reduction in operating costs, an increase in product yield from a plant, extend the life-of-mine and offer environmental benefits by reducing the tailings footprint and water usage.The quality and quantity of Australia’s secondary iron ore deposits and tailings are such that many other countries would judge these as equivalent to primary deposits. Furthermore, these tailings are already mined, available and liberated to such an extent that the recovery of a valuable product is highly economical in terms of capital expenses and operating expenses.CITATION:Steinberg, M, Graham, T and Gerards, M, 2015. Recovery of iron ore fines and ultrafines from tailings by using wet high-intensity magnetic separation – JONES WHIMS, in Proceedings Iron Ore 2015, pp 191–196 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Jul 13, 2015

By P A. Collier

The general view of the author is that all the good intentions of manufacturers can fail completely if the variations in circumstances in underground mining are not considered at all times. With a belief that it is the customer that has the experience and know ledge of problems which occur on long installations. Reilloc talk with customers in coal mines around the world, and have done so from their inception. With considerable experience in their home market, their technical approach was received with enthusiasm by coal companies in both Australia and South Africa, and whilst experience was obtained in other countries, it is the particularly close working relationship in these two areas that is covered in this paper. The refinement of manufacturing techniques and the fine tuning of the specification to which the chain is made was developed in conjunction with factual underground experience obtained by customers as they sought to improve their productivity and a reduction in working costs. With a reliable product the mines are able to concentrate on improved operational techniques to extend the useful working life and plan for multi-panel usage of the chain.

Jan 5, 1996

By J. Diao

In order to understand the flotation kinetic behavior of coal and associated mineral matter, a detailed investigation was conducted in a 2-liter Denver flotation cell using three high sulfur coals at three feed sizes, minus 28. 100 and 200 mesh. Subsequently. the flotation products were sieved into different size fractions and analyzed for their ash and pyritic sulfur content in order to delineate the effect of particle size on the rate at which each constituent floats. The results were tested with several different flotation kinetic models and the best model for coal was then chosen. The flotation rate constant and the ultimate recovery calculated from a kinetic model were used to delineate the effect of particle size, collector (dodecane) and frother (MIBC) dosages on the flotation kinetics of coal, ash and pyrite.

Jan 1, 1992

By Brent A. Slaker, Michael Murphy, John Ellenberger, Erik Westman

"Photogrammetry, as a tool for monitoring underground mine deformation, is an alternative to traditional point measurement devices, and may be capable of accurate measurements in situations where technologies such as laser scanning are unsuited, undesired or cost-prohibitive. An underground limestone mine in Ohio is used as a test case for monitoring of structurally unstable pillars. Seven pillars were photographed during four visits over a 63- day period. Using photogrammetry, point clouds of the mine geometry were obtained and triangulated surfaces were generated to determine volumes of change over time. Pillar spalling in the range of 0.29–4.03 m3 of rock on individual rib faces was detected. Isolated incidents of rock expansion prior to failure, and the isolated failure of a weak shale band, were also observed. Much of the pillars remained unchanged during the monitoring period, which is indicative of proper alignment in the triangulated surfaces. The photographs of some ribs were of either too poor quality or had insufficient overlap, and were not included. However, photogrammetry was successfully applied to multiple ribs in quantifying the pillar geometry change over time.IntroductionAdequately measuring underground rock mass movements is integral to understanding how rock masses behave and how to interact with them safely and efficiently. Many modern measurement techniques employed in underground mining environments rely on point measurements, such as through extensometers or borehole relief methods (Christiansson, 2006). These techniques, while commonplace, do not provide a comprehensive view of how the rock mass is behaving. The dynamic changes in stress states underground, coupled with the mechanical uncertainty of rock masses, near active excavations, creates a need for measurement systems which better capture the behavior of the rock mass. Photogrammetry is a technology capable of producing the wide-area displacement measurements required for a comprehensive understanding of rock mass movements.Digital photogrammetry is a means of obtaining threedimensional point clouds from digital photographs. By finding the same point across multiple images, all viewing an object from different angles, the location of that point in three-dimensional space can be inferred. Close range digital photogrammetry (CRDP) is photogrammetry applied to measuring objects or scenes less than 100 meters away (Atkinson, 1996), and is used for various functions in underground mining environments. These uses include, but are not limited to, mapping fracture networks (Kim, Kim, & Won, 2005)(Somervuori & Lamberg, 2010), characterizing fractures (Styles et al., 2010) and measuring volumes of blast rock (Heal, Hudyma, & Potvin, 2004)."

Jan 1, 2015

By J M. F Clout

Geological, textural and mineralogical classification of iron ores is routinely conducted by mine and exploration geologists on reverse circulation percussion, blasthole cone and bulk samples for grade control, defining ore and waste, determining lump:fines ratio and predicting downstream processing characteristics. Classification is based on physical hardness, colour, streak and other visual characteristics. However, logging is generally restricted to the five to 20 per cent of chips above about 2 mm. This means that most of the sample is too fine to be reliably logged for anything but colour or streak and the textural types must be inferred from other information. A recently developed software package called æRecognitionÆ allows automated identification and classification of iron ore textural types and gangue on a particle basis in polished section down to 0.01 mm using processed digital images. It is not designed to be used as a routine logging tool, but is applicable where higher definition is required at the resource evaluation stage on selected percussion, drill core or bulk samples. æRecognitionÆ processes data obtained after optical image analysis of fine iron ore samples. It contains several parts, like æRecognitionÆ, æCompositionÆ, æLiberation by Total IronÆ, æLiberation by PhasesÆ and æStatisticsÆ, which allow vast and diverse information to be obtained about the iron ore samples being studied. Identification and classification of the textural type of each particle is performed according to the CSIRO-Hamersley Iron Ore Group Classification Scheme. The recognition procedure encompasses a good knowledge of different ore types and a logical knowledge tree, managing fuzzy boundary problems and the potential for a few different ore types in the same particle to be considered. This new technology introduces strict criteria to make the process of identifying particles more objective. Automated recognition standardises the identification procedure and significantly saves time. It enables users without a strong background in mineralogy to perform accurate texture identification. The æRecognitionÆ package has a modern user-friendly interface and Word compatible output. The combination of all the features mentioned makes the package a convenient tool for detailed studies of fine iron ores.

Jan 1, 2005

By Edward Jacobsen

The Oak Creek Power Plant in Oak Creek, Wisconsin is currently undertaking an expansion project. In order to supply cooling water to this facility, a 27' (8.2m) diameter tunnel will be bored, in rock; to connect to 4 vertical Intake shafts located approximately 1.5 miles (2.4km) offshore in Lake Michigan. In 2004, Case Foundation Company was awarded a lump sum contract to Install these intake shafts. When complete, the plant is expected to circulate upward of 2 billion gallons per day (7.5 billion liters) through this system. Two shafts were drilled in a (shortened) construction season in 2005 and the remaining 2 shafts and 4 liner assemblies were completed in 2006. Future connection to the tunnel, in 2007, will be accomplished by mining upward to reach the lower portion of each liner and then removing its internal bulkheads to permit the flow of the lake water into the tunnel.

May 11, 2007

By Michael V. Wolski, Ryan O. McCarter, Kenneth A. Johnson

"The Central Subway is Phase 2 of the San Francisco Municipal Transportation Agency’s (SFMTA) Third Street Light Rail project and will extend the existing Phase 1 initial operating segment from its current connection to the Embarcadero line at Fourth and King streets along Fourth Street to Market Street, under the Bay Area Rapid Transit (BART) and Muni Metro tunnels and then north beneath Stockton Street to Chinatown (Fig. 1).Total new track to be constructed as part of the Phase 2 work consists of approximately 734 m (2,410 ft) of surface track and 2,636 m (8,650 ft) of tunnels. The tunnels were constructed as twin, singletrack bores by two tunnel boring machines (TBMs) (Johnson, 2014) moving north from the southern end of the launch box under the I 80 freeway between Bryant and Harrison streets. North of Chinatown Station the TBMs continued another approximately 683 m (2,240 ft) to a retrieval shaft near Columbus Ave. at Washington Square. The project also includes five cross passages to connect the two tunnels, and three underground stations (the Yerba Buena/ Moscone Station, Union Square/Market Street Station and Chinatown Station.)Excavation of the twin tunnels was performed with two TBMs, with both TBMs driving northward from the launch box. TBM excavation was performed such that the location of the machines was staggered to separate the active excavation faces by a minimum of 91 m (300 ft) between headings. This minimum separation was maintained until the first TBM arrived at the retrieval shaft plug, at which time the separation requirement was relaxed.Excavation began with the “southbound” (SB) tunnel which will ultimately accommodate the southbound TBM light rail trains followed by the second TBM in the “northbound” (NB) tunnel. With the completion of the drives in June 2014, cross passage excavation then began and was completed in April 2015. Overall, construction of the Central Subway tunnels was a success considering the nature and complexity of the project. Additional details of the completion of the Central Subway tunnels are presented in another paper from the RETC 2015 conference (Leong et al., 2015)."

Jan 1, 2015

By E. W. Williams

THE Ontario Research Foundation has developed a process for producing low-density steel shapes by direct reduction of iron oxide powders. The process is a combination of reduction, sintering (without compaction), and carburizing, and has been described by Cavanagh (1). Iron oxide powder, in the form of mill scale or highly concentrated iron ore, carefully sized, is poured into a porous mould. A reducing agent, generally coke breeze, is placed around this mould in a heat resistant sagger which is sealed off and heated to 2,000°F. for a number of hours. The coke/ ore ratio, the particle size distribution, the temperature and time of soaking, and the size and shape of the reduced product, determine the densities and carbon contents attained. The Defence Research Board sponsored a programme of research into some of the mechanical properties of the material (which was named Controlled Density Steel) and this paper is an account of various factors which govern the tensile strength of the steel. The ?practically attainable range of density is from 1.5 to 5.5 gm./ cc. but higher densities are obtained on hot working. This paper, however, is restricted to discussion of results for moulded products.

Jan 1, 1957

By J. Sepulveda

"Despite the recognized influence of product fineness on line capacity and downstream process performance, few mineral concentrators today use particle size measurement of the final product in automatic control applications for particle size. ‘Near-line’ particle size instrumentation has existed for decades and is utilized in modern concentrators, but low availability and measurement frequency, due to problems with slurry sampling and transport systems, make these technologies unreliable for use in automatic control. An innovative technology for real-time particle size measurement on individual hydrocyclones, named CYCLONEtrac™ PST (particle size tracking), has been developed by CiDRA Minerals Processing, and proven in commercial installations, demonstrating near 100% availability with minimal maintenance requirements, thus overcoming the limitations of previous technologies. Potential stakeholders require convincing, reliable information regarding the economic value delivered by automatic grind control projects. In this paper we present a methodology for estimating such value with the CYCLONEtrac™ PST technology, and demonstrate unique opportunities to improve process stability and performance. Based on actual plant data accumulated over time, the evaluation approach assesses and highlights the significant potential process improvement that can be expected with the particle size tracking technology. As an extension of previous work, in this paper we present the key operating criteria for optimizing the production of valuable metals and increase mill throughput by identifying the optimal grind size. As this requires operating closer to the process boundaries, accurate real-time particle size measurements, such as those provided by the CYCLONEtrac™ PST system, become essential for achieving the maximum potential value from every operation. For further illustration, data from three different copper plants is compared.Introduction Owners and operators of mineral concentrators constantly search for the most economically attractive way to increase the output of valuable metal. A logical approach is to identify a key parameter that has the greatest impact on the performance of multiple stages of the process and then use a holistic analysis methodology to determine how this key parameter can be controlled to optimize the final output.Particle size is widely recognized as such a key parameter; however, very few concentrators today use real-time particle size measurements for automatic control of the final product size due, to a large extent, to the inherent limitations of existing technologies. ‘Near-line’ particle size measurement instrumentation, which has been used for decades, typically suffers from low availability because the fundamental measurement technologies were developed for other, less demanding industries and then adapted to the harsh environment of the typical mineral concentration process. An outline of the key differences among the available technologies used for particle size measurement in comminution circuits has been completed in previous work, and plant data has proven the benefits of measurements on individual cyclones – something that, until now, has not been possible (Cirulis, 2017)."

Nov 1, 2018

By Xin Wang, Hongmin Zhu, Shuqiang Jiao

"The behavior of electrochemically depositing silicon in a molten high-melting-point fluoride electrolyte was studied at 1300 °C. The cathodic product was characterized by XRD, SEM and EDS. Though the analysis of structure and composition of deposition, it could certify that silicon deposited on the Mo rod and alloyed with molybdenum. A series of tests had been performed on the cathodic behavior of Si4+ ions in BaF 2-CaF 2-Na2S iF 6 molten salt. The influence of electrochemical parameters on the cathodic deposition of silicon was also investigated. The electrochemical behavior of Si4+ ions in applied fluoride melts was observed to proceed according to one-step reaction.IntroductionGreenhouse warming has been a serious global issue. lt is increasingly urgent for clean and renewable energy. Effective utilization of clean and inexhaustible solar energy has become very important. Solar cell (especially poly-Si solar cell) production has significantly increased this decade, as there is a growing demand for clean energy. Since the early 1980s, the annual growth of the photovoltaic (PY) solar cell industry is more than 30%. More than 90% of the annual solar cell production is based on crystalline silicon wafers. This rapid growth leads to a shortage of silicon of the adequate quality and price for the continued growth of this industry [I , 2J. The most conunonly used technology to produce silicon is the so-called Siemens process. This technology, involves the forming of gaseous Si compounds such as trichlorosilane (SiHCli) or silane (SiH4) with subsequent thermal decomposition of these back to Si. This technology is associated with transformations from solid to gas, and then back to solid phase, which lead to high irreversible thermodynamic losses and subsequent high energy consumption, the energy cost being around 200kWh/kg Si [3l_ The purity of the material from this process is very high (9 to 11 N). In general, what is needed for solar cell purposes are reported to require 4 to 6 N quality. To promote continued growth of the silicon-based PY industry, there is need for a low-energy silicon production process which can produce large amounts of silicon with an acceptable quality and a lower price particularly."

Jan 1, 2012

By Etienne Roy Grégoire

Since the early 1990s, the Canadian mining industry has been increasingly defined by the signing of Impact and Benefit Agreements (IBAs) between mining companies and Aboriginal peoples. While these agreements are intended to complement the legal system, they also serve to establish the legitimacy of mining projects and to encourage the harmonious integration of these projects into their social and environmental contexts. Beyond their practical implications, what are the effects of such agreements on the ability of Aboriginal communities to access the institutional space where the authorization of mining projects and the conditions of their implementation are decided? Can we view IBAs as a preliminary step towards the operationalization of the principle of Free, Prior and Informed Consent? This paper aims to explore the potential of IBAs as a sustainable solution to the legitimacy issues that result from the implementation of the formal regulatory framework governing mining activities in this jurisdiction. We highlight what constraints and opportunities the James Bay and Northern Quebec Agreement (JBNQA) engenders for local communities and draw attention to the ways in which the negotiation of the Raglan IBA and the environmental evaluation processes act upon each other. We find that certain structural problems - and problems of legitimacy ? related to mining in Northern Quebec cannot be solved by the sole signature of an IBA, which suggests the need for caution when considering such agreements as a panacea. The Raglan case demonstrates that IBAs, like other modes of regulation relying on the direct interface between companies and communities, would benefit from a stricter framework and more explicit ties with official regulation channels.

Aug 1, 2013

By P. Spolaore

In the frame of Bioshale FP6 project, the bioprocessing of a polymetallic and polymineral concentrate produced in an industrial operation in Lubin, Poland, was assessed. Following successful batch culture tests, processing in continuous conditions was tested to determine the main specifications for the application of the stirred-tank technology to this sulphide concentrate from black shale ores. The experimental work was carried out in a laboratory-scale unit consisting of 3 stirred tanks (50L or 20L) using an acidophilic and moderate thermophilic bacterial population. Different configurations of the unit and key operating parameters were tested (nutrient medium composition, solids concentration, rates of agitation and aeration). Scientific and technical approaches, such as bacterial community structure and mineralogical analysis were implemented in order to better understand the chemical and biochemical reactions occurring in the system. Using the data produced during the continuous operation, downstream processing assessment for both copper and silver recovery was also carried out. The best copper recovery obtained in the continuous operation was 92% and a hot brine leaching of the bioleach residue (PLINT process) allowed to recover 92% of the silver. A preliminary tech-no-economic evaluation of Lubin concentrate bioprocessing including bioleaching, copper and silver recoveries demonstrated the potential economic feasibility. Recovery of silver plays an important role in the economy of the process. This study presents promising values to further investigate this bioprocessing option.

Jan 1, 2014

By H. J. Handewith

"After having performed qualitative and quantitative tests on nearly 550 rock specimens from tunnel projects throughout the world and comparing the results with actual boring in eight distinctly different rock types which varied in compressive strength from 12,000 to over 34,000 psi, it has been concluded that any rock -andesite, granite and even taconite -can be machine-bored. The question is -can it be bored economically? The intent of this paper is to delineate the investigative needs to accurately and reliably answer this question. A piece of NX core in the hand represents less than 50 per cent of the worthwhile geologic information that could have been obtained from a given core hole. A thorough site investigation by competent personnel can gene-rally foretell to what extent, if any, varying geologic conditions will hinder machine progress.A laboratory testing technique has been developed that has been correlated well (80 to 120 per cent) with actual boring results. This technique will be discussed in detail. Rock cutter life is a function of the penetration rate and the forces required to sustain that rate. Cutters are now, and will be for .some time to come, the single, most expensive consumable item involved in continuous tunneling in hard rock. It is by strict attention to predicting these rates and forces that tunneling costs can be optimized."

Jan 1, 1970

By S. A. Allison

The Conference began with registration, followed by a well-attended cocktail party on the evening of Sunday 25th, where, in a convivial atmosphere, Dr Louw Alberts, President of Mintek, welcomed the delegates and wished them an enjoyable and informative week. The Conference was formally opened by the Minister Mineral and Energy Affairs, the Honourable Mr D. W. Steyn, at 9hOO on Monday. Sketching the history of Mintek and its predecessors, Minister Steyn described the objective and achievements of Mintek, as well as the background to mineral-processing research in South Africa and the policy of the South African government towards the development of the mineral industry.

Jan 1, 1984

By M Erskine, R Mills

This paper approaches tailings dam risk management from the perspective of how other high hazard industries approach the management of their catastrophic event risks, with the aim to provide recommendations from these learnings for the industry to adopt.

Jul 1, 2021

By Anjana C. P, K. Ranga Swamy

The hilly regions of Kerala are severely affected by excess rainfall, causing tremendous damage due to landslides and slope failures. It is necessary to strengthen the existing slope profiles to prevent such disasters and avoid their risk to human lives and civil infrastructures. This paper studies the effect of micro pile to reinforce the slopes in Idukki district of Kerala, where slope failures are frequent. Three-dimensional slope stability analysis is carried out on slopes from the Idukki to obtain safety factor values using the MIDAS GTS NX program. The slope is fully saturated herein by taking the model's piezometric surface at the ground level to simulate high rainfall intensity. The critical slopes are then modelled with micro piles to analyze their effectiveness in improving the stability under static conditions. Different micro pile arrangements are considered, and a series of slope stability analyses have been carried out to obtain the optimum configuration with the required safety factor. The FOS values increased by more than 50% with micro piles for all the slopes. The optimum micro pile arrangement obtained for each slope shows that micro pile distribution between the toe and middle of the slope is an effective location for reinforcing slopes.

Sep 1, 2022

By R. Q. Honaker

A significant problem in ultrafine particle classification is the significant amount of submicron particle by-pass to the coarse particle stream. In classifying cyclones, submicron particle by-pass to the underflow stream can be reduced by decreasing water recovery. Past studies have shown that a reduction can be realized when the feed solids concentration is increased or the apex diameter is reduced. However, both adjustments tend to increase the particle size cut point and negatively affect classification efficiency due to the impact on slurry rheology. The addition of a viscosity modifier to the feed stream of a classifying cyclone improved the classification performance and decreased the particle size cut point over a range of feed solids concentrations. The detailed test program investigated the use of the modifier in conjunction with varying apex diameters to identify conditions that minimize ultrafine by-pass. With small apex sizes, roping conditions were readily eliminated by the addition of viscosity modifiers. The addition of the modifier had no deleterious effect on froth flotation performance, which commonly serves as a downstream separation process. The fundamental and practical benefits of viscosity modifiers in classification processes are discussed in this publication.

Jan 1, 2006

By Andrew Middleton, Mick Stadter, Chris Crowe, David Chong

"The Level Crossing Removal Project – Package 1 is part of the Victorian Governments commitment to remove 50 of the most dangerous and congested level crossings across Melbourne. This involved removing three crossings on the Frankston Line in the south east suburbs of Melbourne. The works involved replacing approximately 2.5km of at grade track with three rail cuttings up to 8 m deep at each of the bridges that replace the level crossings. The cuttings are retained by piled retaining walls and during the main construction occupation approximately 250,000 cubic metres of soil was removed. The project has presented significant geotechnical challenges due to the location in residential suburbs and tight rail corridor and rail occupation timeframe. These challenges included temporary and permanent wall stability, foundations, earthworks and dewatering. As a result, careful design and innovative construction techniques have been necessary to limit impacts on the community and meet the project timeline.INTRODUCTIONThe Level Crossing Removal Project – Package 1 is part of the Victorian Governments commitment to remove 50 of the most dangerous and congested level crossings across Melbourne. This involved removing three crossings on the Frankston Line where it crosses North Road in Ormond, McKinnon Road in McKinnon and Centre Road in Bentleigh.The project involved replacing approximately 2.5km of at grade track with three rail cuttings up to 8 m deep at each of the bridges that replace the level crossings. The cuttings will accommodate three lines of rail tracks with the cuttings up to 25 m wide. The cuttings are retained by piled retaining walls and during the main construction occupation approximately 250,000 cubic metres of soil has been removed.The project presented significant challenges due to the location in residential suburbs and tight rail corridor and rail occupation timeframe. As a result, careful design and innovative construction techniques have been necessary to limit impacts on the community. The geotechnical challenges generally fell into one of three areas, earthworks, structures and groundwater. The primary earthworks challenge for the project was moving the 250,000 cubic metres of soil in a 10 day window, however, from a geotechnical viewpoint, obtaining a stable subgrade on which to operate the necessary construction plant in a short time frame with constrained site access and time to import materials was the key. Whilst closely watching the performance of the dewatering system, a range of contingency plans were developed to cope with any difficulties."

Jan 1, 1900

By L. Frost

The establishment of a retreat system of longwall mining in this submarine coal field has been under study for many years and, although in special cases there have been limited local applications of this method of mining, there has been no attempt until quite recently to establish a uniform system of longwall retreating' in this area (see Figure 1) Where retreat walls were established, it was strictly as a result of physical, rather than economic conditions. In some of the operations- of the Corporation, where the coal was liable to spontaneous combustion- or the area subject to bumps as in No. 2 Mine of the Cumberland Railway and Coal Company in Springhills the recovery of the coal on a retreat system was more or less a necessity.

Jan 1, 1964

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