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By J. Dahner

Total milling cost is composed of energy, liner and grinding media costs. In primary high ball load milling, the grinding media play the biggest role in total milling cost. This cost can be drastically reduced by improving the impact condition inside the mill. The impact condition inside the mill is influenced by shell liner design (as well as feed end and discharge design) and the type of discharge. The improvement of the impact condition will result in a significant decrease in grinding media consumption. The softened impact condition allows for better alloy optimization, resulting in a further reduction in grinding media consumption. Optimized liner design can also improve energy consumption as less energy is wasted in the projection of the grinding media. Magotteaux utilizes tools to simulate and show the grinding media trajectories for shell and end liners. This paper will present some practical examples where the media and energy consumption can be or has been reduced by optimizing liner design. Keywords Comminution, grinding, liner design, grinding media wear.

Jan 1, 2011

By Jacek Paraszczak, Stefan Planeta

"RésuméDans la première partie de cet article on discute Ie contexte technico-économique de l'usage des foreuses à l'eau sur béquille dans des mines sud-africaines. Par la suite on présente les résultats d'une étude comparative du forage avec les foreuses à l'huile et à l'eau par rapport aux foreuses pneumatiques. La performance des foreuses est discutée sous les deux aspects: l'aspect technique concernant Ie taux de pénetration et la quantité d'eau rejetee dans les galeries et l'aspect de fa santé et sécurité au travail, et plus particuliérement, les niveaux de bruit et de vibrations ainsi que Ie brouillard de l'huile. On conclut par l'évaluation du potentiel de forage à I'aide des foreuses hydrauliques dans Ie contexte canadien.AbstractIn the first part of this paper the technical and economical aspects of water-powered drilling are discussed. This technology, originally employed in South Africa, received some interest from Canadian mine operators. In this context a comparative experimental study of pneumatic and hydraulic (oil- and water-powered) jackleg drills has been realized. The performance of the drills is compared and the results reviewed with regards to technical aspects (penetration rate, amount of water spilled) as well as health and safety considerations (noise and vibration level, presence of oil mist). The potential for application of hydraulic jackleg drill is discussed."

Jan 1, 1995

The metallurgical works of the Electrolytic Zinc Company is situated on the Derwent Estuary, approximately five miles north of the city of Hobart and near a relatively dense housing area. Zinc concentrates, consisting chiefly of zinc and sulphur, have been roasted at Risdon for 53 years;- recently at rates of 1, 100 tons per day. The zinc content of the ores is converted to zinc calcine (ZnO), which is a dusty material. The calcine is leached with acid to form zinc sulphate, which is then electrolysed to make zinc. The sulphur is oxidised during roasting to sulphur dioxide, part of which is converted to sulphuric acid and part is dissolved in estuarine water which is then discharged to the Derwent Estuary. Photographic slides were exhibited showing the unaffected green flora of the nearby hills, of clear exit stacks, of green lawns, and of a w ll lrcnt nines hnlP anlf nniir.qa within the Wnrka hnnnrla_rv_

Jan 1, 1971

Jan 1, 1879

By A. L. Engel

The Stayton Mining District in San Benito County, Calif., near Hollister, includes several square miles with many occurrences of antimony ore. The sample submitted for the test described in this paper came from a vein said to have been traced and sampled for 5,000 feet on the surface, 1,500 feet carrying 2-1/2 to 3 percent antimony and the remainder 1/2 to 2 percent. Thirty thousand tons 'With a content of 3 percent antimony are said to be blocked out. A drift of 200 feet on the vein has shown ore containing 4.2 percent antimony. The present sample assayed 3.8 percent. Previous flotation investigation of this are resulted in a recovery of only 71.6 percent in concentrates containing 56.8 percent Sb. It was desired to develop a method of treatment that would give better results. The antimony in the sample occurred as the mineral stibnite, Sb2S3, antimony sulfide.

Jan 1, 1949

By M. M. Rao, P. G. Winchell, R. J. Russell

A detailed analysis has been used to correlate the avalable thermodynami c da In on iron-ric11 Fe-Ni (41loys in the body-centered a, and the face-centered y phases. The inp ut injovrt~ation required by the a am lysis consists of tile heat of the a, to y transformation at 1123°K, the heat of mixing of y at 1123°K, tile specific heats of both a, and y (decomposed into Debye, electronic, and magnelic contributions), and the positional and magnetic entropies of both a, and y. PYLrrzary oirt.bul of the analysis is the free energy of each phase as a Junction of temperature and composition. FOr Fe-Ni alloys the adjustment of twenty-one parunletevs allows the accurate reproduction of enthalpy data for both phases, the heat of mixing- for y, the a/y equilibrinm compositions in the Fe-Ni phase diagram, and the usually accepted enthalpy and entropy of a and y iron. Also obtaitzed are fuirly accurate reproductions of electronic specific heat coefficients predicted from electron- to-atom ratio interpolations and To temperatuves eslimanted from transformation studies. Also considered in the calculation are the elastic constants, Curie temperatures, saturation magnlelizalion values, and indications of short- range order. The measnred activity coefficient of iron in anstetnite could not be accurately matched. The major source of uncertainty in the model is thought to be the magnetic contribution to the entropy of austenite. Calcrclations were extended to Fe-ni-C alloys using available carbon-acliuity data. The free energy of transformation from martensile to r at fixed composition was obtained as a function of nickel and carbon contetzt, and binary thetal-carbon phase diagrams Were estimaled as a function of nickel contenl. We needed thermodynamic information for Fe-Ni and Fe-Ni-C alloys at temperatures between 400" and 800°K in order to interpret the results of several phase-transformation studies. The most recent theoretical analysis of the thermodynamics of Fe-Nialloysl was based on a lumped-parameter, regular-solution model and used the Fe-Ni phase diagram available at that time.' Because significant difficulties were encountered in attempting to extend this analysis to Fe-Ni-C alloys, and because more experimental data has become available recently, we decided to attempt a new correlation. The analysis used here allows the extrapolation of measured and calculated thermodynamic values to lower temperatures and the extension of the thermodynamic analysis to Fe-Ni-C alloys. The structure of this correlation consists of expressions containing a total of twenty-one adjustable parameters. The forms of these expressions are discussed in the next section; however, a less formal summary is presented now to provide a physical overview of the model and to indicate its connections to prior work. Primary input information for this correlation is described below. The measured values of the specific heat of iron3 and its analysis475 and theoretical estimates of the specific heat of y* iron at low tempera- loys at 1123°K has been measured by solution calori-metry.7 The enthalpies of both a, and y have been measured most recently by Scheil and Saftig,B who used a dry-ice calorimeter. These data are used to formulate expressions for the heat of mixing of y and the heat of transformation of a, to y both at 1123°K. The a and y solubility limits in the Fe-Ni phase diagram have been redetermined recently9 by methods which assure a close approach to equilibrium. The a to y transformation can occur without change in nickel content or free energy at a temperature called TO; TO temperatures for various nickel contents have been estimated from transformation studies. The computed free-energy functions are adjusted by means of the parameters to fit both the phase diagram and the TO temperatures. Primary emphasis is placed on the phase diagram fit. Iron activities have been measured in Fe-Ni austenite10 between 973" and 1173°K. These activity data, which cannot be fitted accurately with our model, indicate that iron is substantially ideal in iron-rich austenite. Secondary, but helpful, information for the present correlation is provided by neutron diffraction and saturation magnetization measurements on both body-centered and face-centered Fe-Ni alloys."-'3 These results were interpreted11 in terms of composition-insensitive, localized magnetic moments on both iron

Jan 1, 1968

By S. M. Runke

An ever-increasing demand for beryllium and beryllium alloys has directed attention to the milling of low-grade domestic deposits as a possible means of supplying part of the Nation's ore requirements. The United States generally produces less than 10 percent of its annual supply. For example, new supply in 1953 was estimated at about 9,250 tons, of which the United States imported 8,500 tons. Domestic production was only 750 tons.2/ Since record high prices for beryl in 1952 and 1953 did not greatly increase domestic product ion, the United States must develop mechanical beneficiation processes to use low-grade deposits and reduce dependence on foreign sources

Jan 1, 1954

By Wei-ling Wang, Ryosuke O. Suzuki, Xiang-ning Meng, Miao-yong Zhu

"A finite-element thermal-stress model of continuous casting mold is conducted to predict deformation of copper plates and its change with different cooling structure. The results show that deformation behavior of copper plates is mainly governed by cooling structure and thermal- mechanical conditions, deformation amount is related to structure geometry, and a small deformation mutation occurs in cooper-nickel boundary due to different properties. The maximum deformation of hot surface centricities of wide face locate at 100 mm below meniscus and that of narrow face locate at meniscus and terminal of water slots and significant curvature fluctuations on both sides of copper-nickel boundary. The maximum deformation of centricities is increased up to 0.05 mm with thickness increment 5 mm of copper plates, and maximum deformations are only depressed 0.01 mm and 0.02 mm with increments of 1 mm nickel layer thickness and 2 mm water slot depth respectively.IntroductionIn conventional continuous casting of steel, a large amount of sensible and latent heat of molten steel dissipate in primary cooling zone and make continuous casting mold under enormous heating load giving rise to thermal stress, deformation, high-temperature fatigue and creep not only depress mold life-span, but reduce casting stability [1] Many studies focused more on heat transfer, solidification and shrinkage of solidifying shell to provide inverse proposals for optimizing cooling system and even designing new taper of mold [2,3], but it is generally useless to those of having been manufactured or being put into production. Therefore, mold-related forward problems show necessity to be discussed deeply, and stress and deformation distributions based on special thermal conditions in mold should be analyzed in order to explore suitable cooling structure of mold directly. Samarasekera et al. [4] examined heat flow and distortion of two-dimensional longitudinal sections and investigated effect of cooling water velocity, copper plates thickness and carbon content on formation of rhomboidity and longitudinal comer cracks. O'Connor et al. [5] developed a three-dimensional mathematical model to compute thermo-mechanical state in thin-slab mold and calculated temperature and deformation of mold wall to assess roles of various process parameters on impacting mold life. Thomas et al. [6] predicted temperature, distortion and residual stress in mold and indicated increased distortion requires increased remachining, which reduces mold life and increased residual stress increases the probability of a catastrophic crack failure. Park et al. [7l determined heat-flux profiles in funnel-shaped and parallel thin-slab molds based on an inverse heat conduction model and thermocouple temperature measured in-plant and put them into three- dimensional finite-element thermal-stress model to predict temperature, distortion and residual stress of mold wall. Korie et al. [SJ focused on prediction of temperature, distortion and residual stress in mold and in particular to clarify that mold life is significantly affected by temperature and its rigidity, but little effect by mechanical including clamping force, bolt prestress, friction and ferrostatic pressure. Meng et al. [9l predicted temperature and thermal stress in a slab mold and analyzed effect by cooling system geometry and casting speed quantitatively. In present study, a three-dimensional finite-element thermo-mechanical model with type-switched element is transformed from previous heat-transfer finite-element model [9l, and mold deformation is simulated in order to shed light on thermo-mechanical behavior with special thermal conditions and different mold geometry at high casting speed."

Jan 1, 2013

By D Clarke, I Minniakhmetov

This paper describes the application of the SBRE framework to model the Olympic Dam deposit, one of the largest copper and uranium deposits in the world. Geostatistical simulations are the best practice for quantifying uncertainty in the mineral value chain and estimating resources. However, these simulations are currently undertaken on an ad hoc basis in the mining industry due to the high requirements in computing resources and capabilities in advanced geostatistics. The SBRE project provides a standard framework to test, build, and run conditional simulation workflows, which has been applied to the Olympic Dam deposit. Conventional geostatistical methods face challenges when modelling the Olympic Dam deposit, such as non-stationarity, non-linear correlations, and a large number of grid blocks to simulate. To address these challenges, a combination of methods was used, including projection pursuit multivariate transform, trend-residual decorrelation, pluri-Gaussian simulations, and turning-bands simulations. Various tools and applications were used to build the model, including in-house developed applications, Autovariogram software (Varify), and the RMSP python library. All computations were accomplished on the AWS cloud using the EC2-Batch service. The final set of simulations was validated using various methods, such as grade-tonnage curves, histograms, swath plots, and variogram reproductions, as well as validation using historical samples back-testing. The study highlights the importance of an automated, modular, and scalable framework in the development of conditional simulation workflows and describes the learning gained from trials of different combinations of methods and software

May 24, 2023

By W. B. Mather

GEOLOGICAL studies have revealed the occurrence of hundreds of pegmatite dikes in north- east Brazil, Fig. 1, in the three states of Rio Grande do Norte, Paraiba, and Ceara. Heretofore data have not been available on the possible production of lithium minerals from these areas, and in March, April, and May 1953 the author undertook a reconnaissance survey covering a cross-section of the pegmatites. Sixty-one pegmatites were examined. The pegmatites of Rio Grande do Norte and Paraiba are located in an arid region (Seratao), and except in the most southerly portion there is a mini- mum of vegetation and overburden. The region is easily prospected and relatively accessible by jeep or truck. The pegmatites examined in Ceara are in an area of lush vegetation along the flanks of the Jaqueribe River valley. It is therefore more difficult to prospect, and the dirt roads, as a means of access, leave much to be desired. For all practical purposes rail transportation, except in Ceara, is not available. The rocks of the area1-4 are composed of Pre-Cambrian schist, gneiss, quartzite, and marbles. They have been intruded by granites, monzonites, and diorites and cut by quartz veins and pegmatites.

Jan 9, 1954

By James A. Bachmann, Christopher J. Gray

On December 26, 1994, at 1:00 am, Santa Fe Pacific Gold's Twin Creeks Mine experienced a major highwall failure involving over 2.5 million tons. The resulting effects of this slide were thousands of ounces of gold that were now deferred and an unstable wall above which made mining the slough material unsafe.

Jan 1, 1996

By Thompson D. R, Milton R, Perry K. M A

From the Department for Research in Industrial Medicine (Medical Research Council), The London Hospital; and the De Havilland Aircraft Company:M.R.C. INVESTIGATIONS IN 1936In 1936 the Industrial Pulmonary Disease Committee of the Medical Research Council investigated both clinically and radiologically a group of fifty workers who had been exposed for a number of years to the inhalation of alumina in the reduction factory of the British Aluminium Company. The results are shown in Table 1.They also considered the sickness records of all the workers (Hill, 1936), as compared with those in other parts of the factory (Table 2).

Jan 1, 1945

The rapid advance in the adaptation of scientific knowledge to the treatment of ores, resulting in improved chemical and metallurgical processes, has enormously increased the possibility of working lodes profitably, which a few years ago were passed over as unpayable. By the discovery of chlorination, and later of "Cyanidation," by the highly improved methods of concentration, and by the rapid advance in our knowledge of smelting (for which we are greatly indebted to Americanmetallurgists), and by the gradual replacement of scientifing principles and enlightened management, for rule-of-thumb methods formerly in vogue, many large low grade bodies have been opened, and are now paying dividends, which were,twenty years ago, looked upon as hopelessly unpayable. It has been more especially in these large low grade ore bodies, that modern methods have been benefical; for small lodes must be rich to pay at all, as they cannot be worked on the same gigantic scale, but even in these a percentage of metal is saved which formerly was absolutely lost.To make these large deposits remunerative it is, however necessary to try and find the point of greatest economic advantage, to handle the ore in vast quantities, to erect huge plats to treat it, to substitute automatic appliances for hand labour as far as possible, and to combine several processes supplementary to one another, so that ore which is not amenable to one process, shall be saved, by another; and by doing...

Jan 1, 1901

By Don Hickey

The MTA in conjunction with LIRR, are in the process of expanding one of the largest commuter railroads in the country, with over 260,000 passengers a day. The LIRR, which provides 700 passenger trains every 24 hours, can?t continue on the present growth course as a joint tenant in Penn Station with Amtrak and NJT. For this reason, in conjunction with the fact that over 53% of LIRR?s current riders into Penn Station are ultimately bound for the East Side of Manhattan opening, have created the need for the expansion of the LIRR. The complete expansion will cost approximately 6.3 billion dollars and all of the contracts are to be completed by 2013.

By M Eggers, H Baxter

This paper discusses the geotechnical condition of bedding shears and small- and large-scale faults and shears in Archean banded iron formation (BIF) bedrock, based on observations of core and televiewer images. Information that can be collected includes the orientation of defects, infill thickness, strength and material type, defect shape and surface roughness.The spacing and continuity of bedding shears may be critical to slope design where performance is structurally controlled with bedding dipping out of a wall. The intensity of development of the bedding shear is a useful indicator of the amount of shearing a bedding surface has been subjected to. This can allow for engineering judgement to be used in adopting peak or residual shear strengths along defect surfaces when developing the design.The spacing and continuity of bedding shears may also contribute to the blockiness and degradation of a rock mass where the structural orientation is otherwise favourable. Additionally the condition, thickness and strength of infill of major fault structures can affect slope design and performance, depending on orientation.Comparison of the condition of structures observed in core with the corresponding in situ televiewer image has been made to assess what characteristics are most accurately captured by each technique and whether the additional information gathered from using the televiewer technique is justified by the cost. The question of whether the data collected by a televiewer is sufficient to ultimately replace the need for core is considered.CITATION:Baxter, H and Eggers, M, 2013. Fault and shear characterisation in archean banded iron formation bedrock - a comparison between core and televiewer data collection techniques, in Proceedings Iron Ore 2013 , pp 47-56 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Aug 12, 2013

By Ken Dyck, Chuck Edwards

"Cameco's McArthur River is the world's largest high grade uranium mine. Production started in late 1999. Cameco carried out the engineering design and construction management for the McArthur River project, including all aspects of mining, ore handling and ore transportation. The ore composition was expected to vary dramatically (0 to 30% U3O8; 0 to 25% clay; etc). To cope with the composition swings, sizing screens were selected to provide classification in the grinding circuit. The grinding circuit started up close to the design to provide minus 500 micron slurry. The 50% solids (wt) ground ore slurry proved to be difficult to transport to and process at the Key Lake Mill. Slurry containing high concentrations of high density pitchblende (about spgr 8.0) and low concentration of stabilizing clays, would settle in containers. Ore transport efficiency to Key Lake was found to be unacceptable.A test classification cyclone was installed in the grinding circuit at McArthur River early in 2002. The cyclone operating parameters were not typical, but the cyclone was made to work very successfully. Transportation efficiency to Key Lake increased due to more stable slurry. Preferentially ground (fine) pitchblende particles were easier to leach at Key Lake. The radiation exposure for operators and maintenance personnel to handle the more stable slurry was also reduced.The classification sizing screens were removed from the McArthur River grinding circuit and replaced by permanent classification cyclones late in 2002.INTRODUCTIONThe McArthur River mine and Key Lake mill operations are located in northern Saskatchewan, approximately 650 and 720 kilometres from Saskatoon, respectively. Figure 1 is a location map. McArthur River is the world's largest, high-grade uranium mine, with a production capacity of 18.7 million pounds U3O8 annually. (Rosner and Edwards 1998, Dyck 2000, Jamrozek 2000, Rodgers 2001) Proven and probable reserves are more than 473 million pounds U3O8. McArthur River ore, grading on average 21% U3O8, is milled at Cameco's Key Lake operation, 80 kilometres southwest by road. McArthur River production began in December 1999."

Jan 1, 2004

By Shintaro Takamiya, Kazunari Yoshida

"Recently, small sized micro-needles for medical are required more frequently by patients. The biggest reason is that it presents great burden on the patients, due to the size of the needle injection. People need to use a very small needle to lower the pain, but the downfall is that it makes them more expensive due to their complicated manufacturing method. Therefore, we need to fabricate a needle by wire-drawing to decrease its price. Tube-drawing is beneficial for its production value; however, in conventional tube-drawing it is difficult of control the wall thickness of the tube and makes it 1mmor lower in diameter. That is why, we propose fluid-mandrel drawing for new tube drawing. This method allows fabrication of a fine tube by using the pressure of the fluid in the tube. In this research, the goal is the fabrication of a fine tube by fluid-mandrel drawing and its evaluation. Finally, the fabrication of a fine tube by fluid-mandrel drawing was conducted and in result a tube with a diameter of 0.2mm, high strength and thin wall and fine inner surface was drawn, which can be used as a lesser pain micro-needle.INTRODUCTIONThe main manufacturing method of the current medical needles is roll forming. With this method, it is difficult to make a tube with a diameter lower than 1mm. Deep drawing has been proposed and used as method to further reduce the diameter, but this method is costly and the injection needle obtained by this method is several times more expensive.Therefore, we need to obtain a fine medical needle by drawing process that can be mass-produced and inexpensively manufactured. However, with the conventional drawing process, it is not possible to obtain a syringe needle with a reduced diameter easily, that is why, a fluid-mandrel drawing has been proposed which can reduce the diameter without damaging the inner surface. The methodology of the method is, a fluid is filled in the sealed tube and the pressure inside the tube during drawing is responsible for the good inner surface and wall thickness. It is also expected that the fluid can be easily discarded and that the tube can be manufactured on a long scale."

Jan 1, 2017

By E. Ghali, A. D. Bas

"Treatment of oxide, e.g. roasted gold ores has received relatively less attention than sulphidic ones and recently, handling of oxide gold ores is becoming essential. In this study, the influence of roasted gold ore (RGO) slurry (at 35% solid ratio) on the electrochemical dissolution of gold has been examined using pure gold and iron oxide minerals (hematite, maghemite, and magnetite) as disc electrodes by zeroresistance ammeter mode either in one or two separate containers. The presence of slurry decreased galvanic currents, i.e. corrosion rates due to the release and increase in the amount of soluble and/or insoluble species that could retard further the anodic behaviour of gold. Higher galvanic currents were observed in two separate containers than that in one container indicating the primary importance of galvanic interactions. SEM-EDS results observed iron hydro/oxide coatings on gold surface in case of magnetite test. However, in case of RGO electrode it is not a perfect passivation, although somewhat decreasing trend was observed on gold dissolution. These findings have revealed that passivation is not only a laboratory phenomenon, but also it could be responsible for the slowdown of gold dissolution in industrial practice.INTRODUCTIONThe cyanidation of gold is an electrochemical corrosion process thus; the dissolution of gold can readily be studied by electrochemical techniques. The outcome/summary of previous electrochemical studies of gold leaching can partially be summarized as follows: Filmer (1982) and Lorenzen and van Deventer (1992) reported the negative effect of pyrite and pyrrhotite on gold leaching due to the galvanic interactions; Aghamirian and Yen (2005) studied gold galvanic corrosion in presence of sulphide mineral electrodes only in one cell using zero-resistance ammeter (ZRA) mode; Dai and Jeffrey (2006) discussed, individually, the anodic and cathodic behaviours between gold and sulphide minerals, and Azizi et al. (2010, 2011) used a bed reactor to examine the influence of sulphide minerals on gold dissolution in one and two separate cells. Accordingly, a slowdown in gold leaching has generally been attributed to the passivation phenomenon, although the indication of this phenomenon is still an undergoing debate. For instance, Mrkusic and Paynter (1970) identified the passivation as the film formation of dissolved species from calcine, Crundwell (2014) explained passivation, in the case of corrosion of metals, as the formation of a layer which is composed of a new chemical species on the mineral surface and this layer inhibits or blocks further reactions. He suggested that passivation is related to the oxidation of the metal, and the formation of a passive layer that retards the rate of dissolution by several orders of magnitude. Consequently, galvanic interactions, passivation phenomena, or combinations of them are considered significant electrochemical factors affecting gold dissolution (van Deventer, Reuter, Lorenzen, & Hoff, 1990; Azizi, Petre, & Larachi, 2012). It is important to note that generalizing the influence of a mineral/metal on gold dissolution may not be correct in all cases, since contrary behaviours/results (for pyrite) have been observed (Aghamirian & Yen, 2005). Therefore, electrochemical study of gold is still a subject of research and need to be examined further in detail."

Jan 1, 2016

By F. Karakas

Water based paint formulations consist of some industrial minerals with quantities varying from 20 to 50 %. Quality of paint is directly related to these minerals used as pigment or filler in the production. Titanium dioxide is the most important and expensive pigment in paint formulations. Other minerals such as calcite and calcined kaolin are used as filler and mainly as a substitute for TiO2. Consequently, particle-particle interactions including adsorption, coating and size distribution of pigment mixture directly affects the paint quality. In the present paper, a new type of pigment mixture for possible use in architectural water based paints was developed through grinding. The effect of different types of grinding methods on physical properties of TiO2 and calcite mixture and the quality of paint produced by these mixtures have been revealed. Three different types of mills; conventional ball mill, vibratory ball mill and high-speed attritor were used for grinding of TiO2 and calcite. Viscosity, zeta potential and particle size distributions were used to characterize the pigment mixtures obtained upon grinding. The quality of paint was evaluated by standards based on both wet and dry paints such as viscosity, density, opacity and gloss. The paint produced with the pigment mixtures prepared in vibratory ball mill and high speed attritor showed improvement in physical properties particularly in the distribution and dispersion of mineral particles. Keywords: grinding, pigment, paint, TiO2, calcite

Sep 1, 2012

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