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By Douglas Ketcham, Thomas Jetzer

While the neurological and vascular aspects of Hand-Arm Vibration Syndrome (HAVS) has been generally accepted as a medical condition, the medical criteria and the clinical findings used to establish the diagnosis has been more difficult to bring to consensus. The criteria was first quantified by the Taylor-Palmear scale.1 This criteria was subsequently modified in 1986 at the 1st Stockholm Workshop2,3 to included more acceptance for the neurological effects that characterized the predominate findings in some workers. The relationship between hand-arm vibration and Carpal Tunnel Syndrome was defined in NIOSH 97-1414. While the aforementioned documents have defined the clinical entities associated with hand-arm vibration exposure, agreement on the clinical findings and test to confirm the diagnosis has be been more difficult to bring to consensus. Clinicians assessing HAVS has relied on a number of varied neurological and vascular tests. The neurological testing has focused on assessing damage to the sensory capability of the fingers for the neurological component including tests to measuring ability to sense vibration, cold or other end point finger sensor functions. However, the vascular testing has been traditionally focused on the ability to either measure vascular function or to reproduce the vascular blanching that occurs in HAVS with cold water provocation. Recent assessment of this testing in the United Kingdom Coal Miner’s study has questioned the value of this testing especially in reviews by McGeoch.5 In an attempt to provide some type of definitive testing to substantiate vascular damage from hand-arm vibration exposure, angiography is an alternative or adjunct to cold water provocation testing. The standards that have been established to predict the level, type and incidence of HAVS have been based on clinical studies and reports that have essentially been all male populations. However, the recent entry of women into more vibration intensive jobs has brought about the exposure of some women to high levels of vibration previously only previously experienced by men. However, there have been only few studies that look at HAVS in women6. Although exposed the same vibration levels, it has not been clear that the latency and type of pathology of HAVS in women will be the same as for men. The purpose of this study is to look at recent case studies of men and women exposed to jobs with high levels of hand-arm vibration with extensive clinical testing for both the neurological and vascular components of HAVS as well as other associated upper extremity conditions such as Carpal Tunnel Syndrome.

Jan 6, 2006

By Richard Birk

Rf sputtered quartz has been successfully used in multilayer interconnects for MOS devices. The target potential was 2000 v peak to peak with a frequency of 13.56 Mc per sec. The sputtering rate was approximately 60A per min with an operating pressure of argon gas at 10 to 15 p. The dielectric strength is 8.0 x 10' v per cm and the pinhole density is less than 2 x 10-2 per sq mm. Infrared absorption peaks for the Si-O vibrational bands we at 9.4, 12.4, and at 22.5 p. The etch rate of the sputtered SiO2 is 1200A per min. MOS devices have been fabricated using multilayer interconnects with no degradation of electrical characteristics. MULTILAYER interconnects require an insdating film between the metal layers which can be deposited below any potential eutectic temperature. Sputtered Si4, which can be deposited with substrate temperatures below 200°C, satisfactorily meets the multilayer insulation requirements and has been used to prepare MOS circuits with multilayer interconnects. The physical and electrical properties of rf sput-

Jan 1, 1969

By R. D. Peterson

As underground mine operations expand, the ventilation systems supporting them become complex. Complexity increases with periodic ventilation changes. New diagonal connections require a rebalance of resistance to maintain airflow in affected splits in the system. Incidents of mine fires and explosions have occurred in U.S. coal mines when diagonal connections resulting from ventilation changes have resulted in changing airflow directions. MSHA regulations prohibit the reversal of airflow and poor ventilation practice in general, but regulations cannot stipulate or recommend proactive preventative measures because every situation is different. This paper discusses the phenomenon of diagonal branches and recommends practical precautionary measures that can be taken to prevent airflow reversal in planned ventilation changes.

Jan 1, 2012

By William Nicoll

Those who use electric detonators in firing blasts will be interested in a new electrical testing instrument known as the ‘Blasters’ Friend’, recently devised by the New York Blasting Supply Co. of New York. Owing to the necessarily delicate construction of the platinum wire bridge in the shell of a detonator, it frequently happens that it becomes broken or disconnected; thus destroying the circuit and rendering the detonator worthless. In many cases, misfires and premature explosions are caused by defective detonators. Heretofore, to detect the deficiencies of a detonator before using has been an impossibility, owing to the absence of a testing instrument adapted to the purpose.

Jan 1, 2010

By R. H. Marshall, J. Welchner, E. S. Rowland

THIS paper presents results on an exten¬sion into the realm of high-carbon steels of some work recently published' on the effects -of time at temperature, quenching temperature and prior structure on the hardenability of one 0.20 and four 0.40 per cent carbon alloy steels. It was shown at that time that unless the conditions of time, temperature and prior structure are substantially the same in performing the hardenability test as in conducting harden¬ing of parts in production, the correlation of hardenability information with the [ ] hardness and properties of production parts is often not of satisfactory accuracy. The general effects of these variables on the austenitic grain size, distribution of excess carbides and critical cooling rate have been known for many years and one or more have been investigated by Shepherd ,2 3 Davenport and Bain,4 Digges,5,6 Digges and Jordan,7 Post and associates' and Roberts and Mehl,9 to mention only a few. There has been no systematic investigation, however,' into the quantitative variations produced on the hardenability of commercial high¬carbon steels by changes in these factors of time, temperature and prior structure. PROCEDURE A plain carbon hypereutectoid steel, S.A.E. 52100 and Graph-Mo, a molyb¬denum-bearing high-carbon steel contain¬ing some graphite, were chosen for this investigation. The chemical analyses of these electric-furnace steels are given in Table I. [ ] The procedure used was exactly that reported previously,' hence the details will not be repeated here. Normalized (1650°F.) and spheroidized prior structures were utilized on all steels with hot-rolled and quenched (1600°F. oil) prior conditions added for the plain carbon steel. The end-quench test developed by Jominy10 was selected for use in this investigation and, with the noted exceptions, the American Society for Testing Materials standard. procedure was followed. The effect of time at temperature was examined at intervals of 0, 10 and 40 min. and 4 hr., and a few i6-hr. tests were run. Salt-bath heating of the specimens was employed to control and minimize the

Jan 1, 1944

By Billy J. Thorne

The damage model in PRONTO simulates the dynamic fracture behavior of brittle rock. It is based on work started by Kipp and Grady, [lg] continued by Taylor, Chcn and Kuszmaul [I91 [20] and recently.modified by B. J. Thorne (first documented here). The essential feature of this model is the treatment of the dynamic fracture process in rock as a continuous accrual of damage in tension, where the damage mechanism is attributed to microcracking in the rock medium. The fundamental assumption of the damage model is that the material is permeated by an array of randomly distributed microcracks which grow and interact with one another under tensile loading.

Jan 1, 1989

By Douglas Ketcham, Thomas Jetzer

While the neurological and vascular aspects of Hand-Arm Vibration Syndrome (HAVS) has been generally accepted as a medical condition, the medical criteria and the clinical findings used to establish the diagnosis has been more difficult to bring to consensus. The criteria was first quantified by the Taylor-Palmear scale.1 This criteria was subsequently modified in 1986 at the 1st Stockholm Workshop2,3 to included more acceptance for the neurological effects that characterized the predominate findings in some workers. The relationship between hand-arm vibration and Carpal Tunnel Syndrome was defined in NIOSH 97-1414. While the aforementioned documents have defined the clinical entities associated with hand-arm vibration exposure, agreement on the clinical findings and test to confirm the diagnosis has be been more difficult to bring to consensus. Clinicians assessing HAVS has relied on a number of varied neurological and vascular tests. The neurological testing has focused on assessing damage to the sensory capability of the fingers for the neurological component including tests to measuring ability to sense vibration, cold or other end point finger sensor functions. However, the vascular testing has been traditionally focused on the ability to either measure vascular function or to reproduce the vascular blanching that occurs in HAVS with cold water provocation. Recent assessment of this testing in the United Kingdom Coal Miner’s study has questioned the value of this testing especially in reviews by McGeoch.5 In an attempt to provide some type of definitive testing to substantiate vascular damage from hand-arm vibration exposure, angiography is an alternative or adjunct to cold water provocation testing. The standards that have been established to predict the level, type and incidence of HAVS have been based on clinical studies and reports that have essentially been all male populations. However, the recent entry of women into more vibration intensive jobs has brought about the exposure of some women to high levels of vibration previously only previously experienced by men. However, there have been only few studies that look at HAVS in women6. Although exposed the same vibration levels, it has not been clear that the latency and type of pathology of HAVS in women will be the same as for men. The purpose of this study is to look at recent case studies of men and women exposed to jobs with high levels of hand-arm vibration with extensive clinical testing for both the neurological and vascular components of HAVS as well as other associated upper extremity conditions such as Carpal Tunnel Syndrome.

Jan 6, 2006

By P Cameron

MetPlant conferences have focused on ensuring mining projects are well designed then optimised to operate safely and effectively at the top end of world’s best practice to ensure shareholders are not just happy but delighted. This assumes the MetPlant was built right the first time. However, reality is, too often Plant Metallurgists (PlantMets) find after commissioning they are faced with the expensive task of correcting errors or modifying shortcomings to achieve product quality at name-plate capacity, i.e. get it right the second time. Why do companies spend good money to engineer an excellent feasibility study then allow “wise men” remote from the project team to impose cuts in budget and schedule, often under the guise of value engineering? Since mining is full of uncertainties, such actions can increase the risks of failure with the result that some MetPlants do not work well. Can PlantMets influence the remote wise men who often are also imposing the rules for lending and the required returns to appreciate the uncertainties of mining and their associated risks then let the project team get it right the first time? PlantMets can negotiate with the wise men from the outset of the project and bring them into an outer layer of the team where they can understand the risks then share responsibility and accountability to achieve the common goal of building a MetPlant which works well the first time and deliver the forecast profits. Since shareholders are not in the business to make losses they appoint a Board of Directors to deliver the best outcomes for the shareholders. Thus the Board should seek effective advice on the risk reward implications from the PlantMet before making their decisions.CITATION:Cameron, P, 2015. Do all metplants work well? PlantMets can ensure they do, in Proceedings MetPlant 2015, pp 2–9 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Sep 7, 2015

By Baojun Zhao

Primary lead production using the lead blast furnace in conventional practice is carried out using sinter feed. At YMG, China, the sinter plant has been replaced with a lead ISASMELT furnace. The ISASMELT furnace produces lead bullion plus a high-lead slag, which is cast into lumps to provide a suitable feed for the blast furnace. In the present study the relative microstructures and reduction characteristics of industrial lead sinters and synthetic ISASMELT slag in CO/CO2 gas mixtures have been measured and compared. The microstructure and property changes, and the mechanisms of reduction in each case are examined and discussed. The results of the study are used to explain the successful implementation of cast slag feed in commercial ISASMELT- lead blast furnace practice. Key words: lead slag, lead sinter, lead blast furnace, reduction kinetics and mechanisms

Jan 1, 2008

By C. D. Harrison, J. W. Parkinson

This paper compares the ash slagging potential of Illinois No. 6 seam coal as raw coal, as commercially cleaned coal processed in a baum-jig plant, and as coal cleaned to a reduced ash specification at the Electric Power Research Institute's (EPRI) Coal Cleaning Test Facility. The comparison is based on ASTM ash fusibility data, a slagging index, gravity fractionation analyses of critical mineral matter compounds, and comparative pilot combustion tests. The first three grounds of comparison are laboratory data. The final comparison involves burning about 13.6 t (15 st) of each coal at Conoco's 4.40-kW/h (1.5 million-Btu per hr) test combustor. The evidence of these four comparisons indicates that lowering the ash specification of coal before combustion can significantly improve the ash slagging characteristics of Illinois No. 6 seam coal.

Jan 1, 1987

By J. C. Loretto

"OPENING REMARKS Yesterday and today we have heard some very interesting papers on operating matters and some of you are probably wondering what we are now doing talking about Communications in Plant Design. Let me tell you! Before the techniques we have heard being discussed can be used, there has to be a properly operating plant. It is certainly a fact that many mineral processing plants achieve only limited success and a number of them can even be said to be failures. Some of you sitting here are probably living with operating problems that are clue to errors in the design.If the histories of these problem plants are examined, it will be found that in many cases, the necessary skills were available during the period of the plant design. There was extensive operating know¬ledge together with a full range of project expertise. Why then the failures? In a substantial number of cases it can be traced to the old, old problem of communications. As plants get bigger, money costs more and smooth startups become more important, it becomes less and less economic to fix up any design errors during plant operations.During our careers in mineral processing, nearly all of us will be involved in at least one plant design and I feel that it is as well if we understand some of these communication difficulties that can lead to a problem plant. There is little point in us being experts in mineral processing if the knowledge we have acquired doesn't somehow get incorporated into the plant.I would, therefore, like to present this short paper that mentions a few of the significant communication problems that can occur during the design of mining and mineral processing plants, together with some thoughts on answers to these problems."

Jan 1, 1973

By Tan Zhenxiang

INTRODUCTION Koolyanobbing is an open cut iron ore mine, which is located in Yilgarn region of Western Australia. To prevent the operators from suffering silicosis diseases and protect the air from being polluted, a series of dust control measures have been taken. These measures include ventilation and dust control system for sample preparation shed, dust collecting system for drill rig, dust suppression system for ore processing plant, dust control for haul road. The details related to individual dust control measure are dealt as follows. SAMPLE PREPARATION SHED DUST CONTROL The sample preparation is one of the major dust sources at Koolyanobbing. The activity is being carried out at the sample preparation shed. It typically needs to go through the following stages, that is, crushing, splitting, drying and pulverising. The amount of dust generated from crushing and splitting is mainly determined by the moisture content contained in the pre- pared sample. A significant amount of dust is generated at the sample pulverising stage due to cleaning sample bowl with com- pressed air. To protect the sample preparing personnel's health and make the dust level in the air meet the requirement from the health and safety authority, a central ventilation and dust control system has been installed at the sample preparation shed. As shown in Fig. l, the system consists of suction heads, suction lines, dust collector and vacuum fan. The fan creates vacuum environment in the system, therefore the dust is drawn into the dust collector through the suction heads and suction lines. The dust collector is of fabric filter. When the dusty air comes to the filter, the dust in the air is collected and retained on the surface of the filter while the clean air passes through and enters the atmosphere. The retained dust is blowed out by the pressured air pulses and deposits into the dust bin underneath the filter. A time relay device is used to control the cleaning time and the cleaning interval. DRILL RIG DUST CONTROL A hydraulic percussion drill is used to drill blast holes. To carry out the drilling operation properly and efficiently, the cut- tings are being flushed out of the hole by the compressed air. In order to prevent from the fine particles in the cuttings escaping to the air, a dust collector is attached to the drill. The collector mainly consists of suction head, cyclone and bag filter. Refer to Fig. 2. The suction head is installed at the lower end of the feed beams and is movable. The moving range is up to 250 mm. It is not only used to restrict the cuttings, but also used to prevent water from entering the filters when drilling wet hole. A 406 mm diameter primary cyclone is used to separate the heaviest particles in the cuttings. It is also used as blast holes sampling equipment. One part of the dust particles are collected by a sample bag through a splitter attached to the end of the cy- clone. The rest of the particles fall down to the ground through the closing rubber. The bag filter is driven by a hydraulic motor (1). It is used to collect the lighter particles in the cuttings. The filtering area is 16 m2 and the dust separation efficiency is up to 99.9%. The working principle of the filter is demonstrated in Fig. 3. When the rock drill (9) flushing is turned on, the pressurised air from the compressor is directed to the rock drill and to the pres- sure switch (10). The pressured air will open the pressure switch to de-energise and close the solenoid valve (4) The pressure affecting the cut-off cylinder (5) keeps the exhaust port flap open. When the flushing valve (8) is closed, the pressure affecting the cut-off cylinder disappears and the internal intake opening flap is closed by a spring. The pressure also ceases to affect the pressure switch and the spring switches the contact to the point 2. The time relay (11) is now activated and gives a 0.5 second current impulse to the solenoid valve and keeps the current cut off for approx 8 seconds. When the solenoid valve is live, it opens and lets an impulse of pressured air to the filters (2). These impulses will clean the filters.

Jan 1, 1997

By J. M. Pachter

Property sales and acquisition are prominent features of today's coal industry. Before selling or buying a site, a company must know the property's economic net worth. Any evaluation of economic net worth would be inadequate if determinations of a property's environmental liabilities and costs were omitted. Short-and long-term costs can result from liabilities related to reclamation, water treatment, subsidence, and hazardous waste disposal. A structured, interdisciplinary approach can aid in the delineation, summation, and scheduling of these costs and liabilities.

Jan 1, 1987

By F. Block, K. Kohli

Outcrop barrier pillars serve to keep mine personnel and the public safe from sudden uncontrolled flows of water accumulated in active and abandoned underground mine workings. When an outcrop barrier fails, the result is an outbreak of water to the surface and is termed as blowout. Mine blowouts are associated with above-drainage mines and can occur through the coal outcrop and sealed portals. A blowout is often catastrophic, a threat to the people on the surface living or working in the path of a potentially large flood. In addition, blowouts can destroy homes, cause landslides and severe erosion and release pollution and acid mine drainage. This paper provides guidance on the planning, design, evaluation and inspection of barriers to address the problem of mine blowouts associated with above-drainage coal mines.

Jan 1, 2007

1. Domestic Production and Use: In 1984, 12 companies operated 27 primary aluminum reduction plants, with 3 firms accounting for 57% of production. Washington, Oregon, and Montana accounted for 35% of the production; Indiana, Kentucky, Missouri, and Tennessee 25%; Alabama, Arkansas, Texas, South Carolina, and North Carolina 20%; other States 20%. Based on published producer prices, output of primary metal in 1984 was valued at $7.2 billion. Aluminum consumption by 25,000 firms was centered in the east-central United States. Packaging accounted for an estimated 35% of domestic consumption in 1984, transportation, 20%; building, 18%; electrical, 9%; consumer durables, 8%; and other uses, 10%.

Jan 1, 1985

By Juan B. Yianatos

"After almost 100 years, since the first commercial application began in Australia, flotation has shown an extraordinary growth and nearly 2 billion tons of ore per year are presently treated by flotation processes. During this time flotation has promoted a wide scope of research activities ranging from fundamental chemistry and hydrodynamic studies to studies of industrial operations. In general, fundamental studies have been mainly related to ideal situations. In recent years, however, large efforts have been focusing on achieving a better insight into the actual sub-processes provided by the development of new and more sophisticated instrumentation. Since the massive incorporation of flotation columns, around 15 years ago, a renewed interest in flotation fundamental studies, process modelling and new cell designs have been observed worldwide. The key role of the froth has been recognized as an independent and sometimes rate limiting process step. Thus, separation of pulp and froth process stages seems the most appropriate in terms of process modelling, diagnostic, design and scale-up purposes.In relation to flotation equipment development, until the middle of the 1970?s, only the sub-aeration mechanical cells were dominant. Since the 1980?s, the use of pneumatic cells and forced air mechanical cells has emerged strongly. Also, in the last decade, flotation equipment has shown a dramatic increase in size, reaching values of 200m3 in unitary mechanical cells and more than 300m3 in columns. The general feeling, however, is that, despite the great advance observed in terms of process knowledge, the mechanisms and principles of industrial flotation cells design and scale-up are still not fully understood.Advances in process instrumentation and control now in use allow for more efficient operations, both in metallurgical performance and savings in operating costs.INTRODUCTIONFlotation is a widely used process within the minerals processing industry, as well as being used for water treatment and de-inking of recycled paper. Froth flotation started in Australia at the beginning of the 20th century and since then flotation technology has made significant advances. Flotation was firstly applied to sulfide ores. The largest tonnages treated by flotation are copper and copper/molybdenum ores, handling about 50% of the total ore processed. Also significant are phosphate, iron ore and coal treatments. At present, Chile is the foremost copper producer in the world with around 35% of the world?s production. Figure 1(a) shows the evolution of copper production in Chile over the last decade. The total amount of fine copper produced in year 2001 was 4.7 million tons, from which 3.2 million tons was processed by flotation while 1.5 million tons went through LIX-SX-EW processes, which also showed significant development during the same period (Anon, 2001). The total flotation treatment of copper ores in Chile is about 325 million tons per year (Anon, 2002), so the world treatment of copper ore by flotation can be estimated at about 1 billion tons per year. Consequently a total of nearly 2 billion tons of ore per year is presently processed worldwide by flotation (Fuerstenau, 2001). In order to handle the higher tonnage of low-grade ore, a worldwide trend towards the development and use of larger flotation machines began in the 1960?s. Figure 1(b) shows that the trend became extremely marked from the beginning of the 1990?s, which is consistent with the strong increase in copper production during the same period."

Jan 1, 2003

By M. Mahfoud

The effect of grain refinement on the tensile and fatigue crack propagation behavior of sand cast magnesium alloy AM60B has been investigated in the present study, C2Cl6 in the amount of 0,3% was used to grain refine the melt, The fracture toughness tests were conducted in laboratory air at room temperature (25°C) using a sine-wave cyclic frequency of 20Hz and a load ratio of R = 0,1, The response in the Paris's regime and the critical stress range were determined, Preliminary findings have shown that C2Cl6 has a significant effect on both the tensile properties and fatigue crack propagation of the alloy tested, Grain refinement increased both the yield and ultimate tensile strength by more than 46%, and decreased the crack growth rate from 2,7 to 1,4 MPa Vm , However, the grain size seems to have a smaller effect on threshold stress intensity factor range. The fracture surfaces of specimens were examined optically and under the scanning electron microscope (SEM) to determine the relationship between grain size and fatigue properties.

Jan 1, 2005

In a ætypicalÆ gold deposit each tonne of ore will contain tens of millions of very fine gold particles, whereas; at Bendigo the majority of gold in each tonne of ore is present in just five to 15 very coarse gold particles, a distribution more akin to diamond deposits. At Bendigo the minimum sample size required for good assay repeatability is estimated at 4.5 t for each assay. Drill core samples are several orders of magnitude too small to generate representative assays.The drilling data are characterised by a nugget effect approaching 90 per cent, a very skewed distribution and, on average, under-report in situ grade by 50 per cent to 75 per cent. Since 2002 Bendigo Mining NL has completed 47 000 m of diamond drilling, 1200 m of on reef development, collected and processed 100 bulk samples (150 t each), 800 mini bulk samples (50 kg each) and processed in excess of 25 000 t of ore through a pilot plant. The results of this work have provided the information required to develop and verify a robust grade estimation procedure. No standard geostatistical manipulation of the drilling assay data can generate an accurate grade estimate as the samples and associated assays are not representative of the ore being sampled. The recognition of this fact was critical as a radical transformation of the raw drill assay data was required to develop a workable methodology for grade estimation in such a high nugget environment. The aim of the transformation was to reduce the nugget effect and high variance and so approach a lognormal assay distribution. Ideally the average drill grade would approximate actual in situ grade and the assay distribution would reflect actual grade distribution within the reefs. Following the data transformation simple block modeling within the defined resources allows grade estimates to be made that can be used in the estimation of Indicated Resources and hence Probable Reserves. The grade estimates have been checked by extensive bulk sampling and processing of 25 000 t of ore (three per cent of total resource) through a pilot plant with planned full scale mining to provide the ultimate verification.

Jan 1, 2004

By A Esfahanipour, M Osanloo

Determination of cut-off grade?strategy is one of the most important stages of open pit mine planning and design. It is the parameter directly influencing the financial, technical, economic, legal, environmental, social and political issues in relation to mining operation. Choosing the optimum cut-off grade strategy that maximises the economic outcome has been a major topic of research workers for nearly one century. Many researchers have contributed in devising methods and algorithms, such as dynamic programming, linear programming, optimal control and so on for various aspects of its determination. In this paper, a non-linear mathematical programming for cut-off grade strategy optimisation is presented, considering the three main stages of mining operation introduced by K F Lane. In this model maximisation of net present value of mining operation, under the three constraints of mining stagesÆ capacities, considered as the optimisation criteria. Due to the discrete representation of the mining resource, the proposed non-linear formulation is approximated by a non-linear signomial geometric programming. According to non-convexity and the complexity of the proposed model, an augmented Lagrangian genetic algorithm was used to find the optimum cut-off grade strategy under varying and fixed price circumstances. To validate the proposed non-linear model efficiency, the results were compared with the results obtained by the K F Lane methodology. It was found that the proposed non-linear model works efficiently in the determination of cut-off grade strategy. According to the simplicity of the structure of non-linear programming modelling in comparison with dynamic programming it is hoped that, further development of this model would certainly provide the ability of considering managerial and technical flexibilities as well as incorporating more real mining conditions in the determination of cut-off grade strategy optimisation.

Sep 26, 2011

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