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By H. J. Roorda

With an increasing need to obtain metals by processing complex fine intergrown ores, the use of electron-optical techniques will become more important as a tool for mineralogical studies. Electron images enable a higher spacial resolution than can be obtained by optical microscopy and thus provide a powerful and necessary aid for the examination of small grains and finely locked particles. In this paper the mineralogy of Meggen ore was investigated. Both light-optical and electron-optical techniques were used to evaluate the mill feed and products of the concentrator. Detailed examination by reflected-light microscopy to assess the comportment of galena in the complex pyritic ore was inconclusive in establishing the cause for low lead recovery of only forty percent of the ore's lead content. Electron microprobe analyses indicated that the majority of the lead lost to the tailings was accounted for by extreme fine (often smaller than one micron) and complex intergrowths of galena in pyrite. The remainder was lost as fine free galena grains.

Jan 1, 1987

By Mark Jolly

"Instead of using the traditional batch casting process, the CRIMSON [1] (Constrained Rapid Induction Melting Single Shot Up-Casting) method employs a high-powered furnace to melt just enough metal to fill a single mould in a closed crucible. The crucible is transferred to a station for computer-controlled counter gravity filling of the mould for optimum filling and solidification. The CRIMSON method therefore holds the liquid aluminium for a minimum of time drastically reducing the energy losses attributed to holding the metal at temperature. With the rapid melting times achieved, of the order of minutes, there isn’t a long time at temperature for hydrogen to be absorbed or for thick layers of oxide to form. The metal is never allowed to fall under gravity and therefore any oxide formed is not entrained within the liquid. Thus higher quality castings are produced leading to a reduction in scrap rate and reduced overall energy losses.IntroductionEngineers at the University of Birmingham, England, with local company, NTec, have invented a new casting process that will reduce the energy costs of light-metal foundries. The technology, entitled CRIMSON, means that foundries need only heat the quantity of metal required to fill a single mould rather than large batches that use unnecessary energy and create waste. The complete concept of CRIMSON requires a change of philosophy in the approach to casting and requires the user to think holistically in order to reap the full benefits from the process. This paper will discuss the various aspects of energy wastage within the foundry sector and discusses the processes whereby the energy can be reduced. Primarily the author focuses on the aluminium sector but CRIMSON can be applied to many of the non-ferrous “light” alloys. Ferrous materials and non-ferrous “heavy” alloys can also benefit from some of the ideas but not necessarily directly from the application of CRIMSON."

Jan 1, 2010

By Grant E. Casley

Since 1970 Mount Isa fines Limited has made a significant increase in blister copper production from approximately 100,000 to 155,000 mt per annum and in fact 161,040 mt were produced in the calendar year 1974. Flowsheet developments including fluidised bed roasting and converter slag flotation are discussed, particularly their contributions to minimising major equipment changes in smelting and converting. The use of model- ling and simulation techniques for such an exercise is mentioned. The paper reports the alterations made to both equipment and operating techniques in the reverberatory furnace and converter sections to achieve the regular production of 250 mt of blister per converter day from a 41% Cu matte grade. The effects of flux composition on converting performance are highlighted. The air quality control programme is discussed in relation to its restriction of blister copper production.

Jan 1, 1976

By Onuralp Yücel, Mehmet Bugdayc, Murat Alkan

"In this study, iron based alloys (Fe-Mo, Fe-Cr-Ni, etc.) were produced by using aluminothermic methods starting from Mill Scales obtained continuous casting processes. Mill scales are an oxidised layer of steel alloys containing iron oxide, which includes + 2, + 3 values, on the surface of slabs and billets occurring during annealing in heating furnace at integrated iron and steel milling plant, and continuous casting unit. In the metallothermic experiments, different ratios of starting mixtures and addition of the oxide powders (Alz03, Si02, CaO, MgO) were examined, and their effects on the metal recovery and alloy compositions were carried out. The samples were characterized by using chemical analysis (AAS), XRD, XRF and SEM/EDS techniques.IntroductionSelf Propagating High Temperature Synthesis process (SHS) has many favour compared to the furnace applications, such as low energy requirement, low cost, very short processing time and simple operation, [l, 2]. In a SHS process, the ignition starts the combustion and propagates throughout the reactant mixture yielding the desired product. However, the disadvantages of the process such as inhomogeneous or unreacted products due to undesirable reaction rates needs to be overcome by changing some parameters such as ignition temperature, particle size, additive, atmosphere etc. [3, 4]. Mill scale is a layer of iron oxide which forms on ferrous materials cooling after being processed in hot rolling or continuous casting plants. Mill scale contains iron (II) and iron (III) oxides, which result in a 70% total iron content in oxide form. Not being able to reuse this material will prevent the raw material entering the production plant from being fully utilized [5]. This study aimed to produce Fe-based alloys via SHS (Self Propagating High Temperature Synthesis) metallurgy which is attractive process technique regarding fast and low-cost production ability of cast alloys by using high metallic iron content by reducing continuous casting mill scale."

Jan 1, 2013

By S. N. Monteiro, C. M. F. Vieira, A. P. N. M. de Sa, J. P. D. Vitorino

"This work has as its objective to characterize an ash waste and to evaluate its incorporation into a clay to produce bricks and roofing tiles. The waste is a type of fly-ash resulting from the incineration of a selected part of urban garbage, which is basically constituted of organic matter and plastics. The waste was submitted to mineralogical and chemical characterization. Compositions were prepared with incorporation of the waste in amounts of up to 20wt.% into athe clay. Rectangular specimens were prepared by extrusion and fired in a laboratory furnace at 900°C. The physical and mechanical properties evaluated were: linear shrinkage, water absorption and flexural rupture strength. The results showed that the waste is predominantly composed of quartz and calcium compounds. The incorporation of the ash was deleterious to the evaluated properties of the clay. It is suggested that the incorporation should be made in amounts below 5wt. % to avoid deleterious effect in the mechanical strength and water absorption of the clayey ceramic.IntroductionThe world attention has turned to a subject of great concern today, the production and disposal of large amounts of industrial wastes as well as wastes of various sources. When deposed in an unsuitable place, these wastes can cause considerable harm to human health and to the environment. Our planet suffers with air pollution, groundwater and soil contamination as well as silting of rivers and lakes with the growing amounts of our society wastes.The recycling of waste materials is of great interest to the industries, mainly due to the environmental agencies legislation. One of the practices for correct disposal of these wastes being investigated is to incorporate into red ceramics, such as bricks and roofing tiles. The natural variability of the characteristics of the clays associated with the relatively simple processing techniques and also the low performance required for the products allow the presence of relatively high levels of impurities in clayey ceramics."

Jan 1, 2011

By M. B. Mesina

Mechanical separation systems are widely used nowadays for scrap metal processing, but they have natural limitations in product quality. The quality of the final product is considerably improved when sensors are used in the separation process. This paper describes new methods using sensors for scrap metal sorting and quality control. An example is the electromagnetic sensor, which uses the electrical and magnetic properties of materials to distinguish between different non-ferrous metals. The measurement results of two prototypes are reported. The benefits and the possibility to integrate such systems into practical applications regarding the processing of secondary raw materials are also described.

Jan 1, 2003

By Lin Li, Xiang Li, Yifang Zheng, Jilai Xue, Jun Zhu

"Al drops and gas bubbles in the anode-cathode space of aluminum electrolysis cell are of great importance for cell operation improvement in metal loss, current efficiency and energy consumption. A direct observation on the Al drop, gas bubble and ultrasound was carried out through a see-through cell. The Al drop immersed into the cryolitic melt was found moving up and down irregularly in the anode-cathode space without electrolysis, which was then completely dissolved into the melt. During electrolysis, the Al drop came to the anode area and reacted with the gas bubbles generated on the anode. Under ultrasound, the gas bubbles were removed from the anode surface while the Al drop was kept on the side of anode. The observed phenomena were useful for technology improvement in reducing the anode-cathode distance or lowering the energy consumption in aluminum electrolysis.IntroductionDuring aluminum electrolysis, aluminum metal drop and anodic gas bubble are in close contact each other within the anode-cathode space, and the interaction between them can produce significant impact on metal loss, current efficiency and energy consumption. The motions of the Al drop and the gas bubble are also related to the dissolution of aluminum metal into cryolitic melt and the cell voltage drop due to the bubble layer covering the anode surface.A number of studies have been carried out using different types of see-through cells, where the dissolving process of metal Al into cryolitic melts (metal fog) in the anode-cathode space was directly observed and photographed [1, 2]. With the similar method, some direct observations on the anodic bubble behaviors with and without ultrasound were performed during aluminum electrolysis [3-6]. However, to our best knowledge, there is no published work on direct observation on the behavior of Al drops and anodic gas bubbles staying together within the same anode-cathode space, as well as the motion and interaction of them in cryolite-alumina melts."

Jan 1, 2011

By P. E. Nolan

The disproportionation of carbon monoxide is an important aspect of reduction processes, in the production of carbon filaments for composites, and in the removal of CO from CO,. It can also be a hindrance, causing carbon fouling of equipment and metal dusting. The reaction is thermodynamically favored at lower temperatures, but it occurs slowly. Catalysis of the reaction by transition metals has been examined. A materials science approach to the selection of a catalyst material and of optimum operating conditions is being taken in the present work. Of particular interest is characterization of a catalyst that can be repeatedly regenerated to prevent deactivation in long term use. Experimental data on a less studied catalyst, ruthenium, are reported.

Jan 1, 1992

By Samantha Moodley, Rauf Hurman Eric, Cevat Kucukkaragoz, Aditya Kale

"Two titania slags, rutile and synthetic rutile were chlorinated with petroleum coke and CO in a small bubbling fluidized bed reactor. The study aims to identify differences in chlorination mechanism, compare conversion rates, blowover and the chlorination of impurities for the various titania feedstocks at different temperatures.Chlorination rates were highest at 1000ºC; rutile chlorination significantly increases as temperature increases from 800ºC to 1000ºC. At 1000ºC, synthetic rutile had the highest chlorination conversion rate; this was followed by Slag B which in turn was more reactive than Slag A and rutile. The mechanism for slag, synthetic rutile (SR) and rutile chlorination differs. Synthetic rutile feed is porous, providing a larger surface area for the chlorination reaction, hence the highest conversion rates was attained. Titania slag becomes porous with the initial chlorination of FeO and MnO whilst rutile remains solid. As the porosity of slag particles increases so does its tendency to be elutriated. Ti2O3 is oxidized within the early stages of chlorination during the chlorination of FeO and MnO. Ti2O3 not oxidized is then rapidly chlorinated.IntroductionTitanium dioxide (TiO2) is the most common compound of titanium, about 95 - 98% of extracted titanium minerals is processed into TiO2 white pigment [1]. Two processing routes exist for the production of TiO2 pigments, i.e., sulphate and chloride based processes. In the chloride process, titania feedstock is fed to a fluidized bed reactor together with reductant and chlorine gas. A temperature of 1000 - 1300ºC is maintained in the reaction zone and apart from silica, zirconia, uranium and thorium, virtually all the metal oxides in the feed are converted to their respective chlorides [2]. Chlorine is recovered and recycled back to the reactor."

Jan 1, 2012

By J. P. Bellot

During the non-ferrous metal processing, the melting step under vacuum or under rarefied gas leads to volatile metal losses. It is the case of the metallurgical processing of the nickel-based, titanium-based or zirconium-based alloys where the evaporation losses don't allow a sufficient control of the alloy chemical composition. A theoretical approach has been carried out involving both a continuum description in the liquid phase and a molecular approach in the rarefied gas phase. The finite volume method is used in order to solve the coupled transport equationsin the liquid, whereas the Boltzmann equation is modelled by using a Monte Carlo method. At the liquid metal and metallic vapor interface, the volatilization and recondensation fluxes link up the two calculations. Simulation results are given for the melting and refining of reactive metals such as titanium alloys where the control of the chemical composition remains a major difficulty. The validity of the kinetic Langmuir's law is discussed for different operating conditions.

Jan 1, 1996

By Florian Kongoli

The behavior of cobalt as a by-product in the NilCu smelting and converting processes effects directly the quality of the final products as well as the revenues gained from the overall process. An effective way to evaluate and predict this important behavior is thermodynamic modeling which reduces the time and the cost of experimental investigation. In this work a thermodynamic model of cobalt-containing matte phase in NilCu smelting and converting processes is presented. The model predicts a priori the thermodynamic properties and phase relations of the ternary and multicomponent matte based solely upon the optimized parameters of the binary systems. This model can be used with other models such as those of slag, metal, gas etc. to predict various aspects of cobalt behavior such as matte- slag, metal-slag distribution, etc.

Jan 1, 1999

By Yuzura Sato

Viscosity has been measured for various molten binary alloys of nickel with iron, cobalt and chromium in order to clarify the behavior of viscous flow of molten nickel alloys. The entire concentration range for iron and cobalt and 0-67at% of chromium content were studied. The measurement method was an oscillating cup viscometry using an alumina crucible that was precisely machined. The temperature was up to about I 880K for all the measurements. The results represented good Arrhenian relationship although some measurements included overcooled temperatures. The isothermal viscosities increased monotonously with an addition of iron and chromium into nickel. The addition of cobalt increased after stationariness. The isothermal viscosities showed concave curves. Activation energies increased monotonously by adding all the elements into nickel. These phenomena were considered to be related to the thermodynamic properties 'such as the heat of mixing and the structures of mixture melts.

Jan 1, 2003

By Shengfan Zhou, XUEWEN WANG, Changjun Jiang, Mingyu Wang

In the process of extracting vanadium from stone coal by sulfuric acid leaching - P204 solvent extraction, Fe(III) can accumulate in the organic phase which reduces the extraction of vanadium. In order to eliminate the effects of the accumulation of iron, oxalic acid was used as the stripping agent to strip the Fe(III). The effects of oxalic acid concentration, phase ratio O/A, stripping time and shake velocity on the stripping of Fe(III) were studied. The results showed that the Fe(III) stripping rate can reach beyond 96% at the room temperature with 70g/L oxalic acid using an O/A of 2 at 160 rpm shake velocity for 20min. After 2-stage stripping, the concentration of Fe(III) in organic phase was 0.008g/L.

Jan 1, 2016

By A. J. Williams, T. N. Croft, M. Cross

"The computational modelling of extrusion and forging processes is now well established. In this work a novel approach is described which utilises finite volume methods on unstructured meshes. This technique can be used to solve simultaneously for fluid flow, heat transfer and non-linear solid mechanics and their interactions. The approach involves the solution of free surface non-Newtonian fluid flow equations in an Eulerian context to track the behaviour of the workpiece and its extrusion/forging, and the solution of the solid mechanics equations in the Lagrangian context to predict the deformation/stress behaviour of the die. Some preliminary examples of this approach will be discussed.IntroductionThe computational modelling of extrusion and forging processes is now well established. Within the last 20 years the finite element method has become the most commonly used technique to simulate metal forming processes [1]-[4]. The Lagrangian and Eulerian type of formulation have been the two major approaches to this problem.Lagrangian methods are efficient and suitable for handling non-linear problems in which small strains prevail, boundary conditions do not change with the course of deformation, and where mesh distortion is not a critical factor in the analysis. Unfortunately, the above points are essential to any accurate metal forming analysis. The problems of mesh distortion and element entanglement pose a serious drawback on the use of such methods. Some automatic remeshing techniques have been developed for Lagrangian finite element analyses of metal forming problems [5]-[7]. However, these methods are not robust and efficient enough to remedy the mesh distortion problems in general. An alternative is to update the mesh manually but this is not always possible, and even when it is feasible it involves major interaction by the user. In addition, remeshing is usually applied to the whole domain which is not necessary and increases CPU time. The complexities associated with remeshing also affect the ability to parallelise the code."

Jan 1, 2001

By John A. Herbst

Plantwide control of mineral processing operations has long been sought for its potential benefits. These benefits include minute-to-minute optimization, reacting to disturbances in ore characteristics and equipment status as they happen and the coordination of all unit operations in pursuit of the highest performance level. However several difficult challenges have kept us from fully realizing those benefits. One of these challenges has been to provide fairly complete quantitative descriptions of Unit operations to account for critical interactions within and 'between unit operations. In some cases we understand the physics and chemistry very well and can incorporate that 'knowledge into phenomenological models. In other cases our knowledge is incomplete, so we must rely on other forms of knowledge such as fuzzy logic or neural nets. Another challenge to be met has been to simultaneously compute a large number of manipulated variables. In the past this challenge was met by optimizing only unit-by-unit, rather than on a global basis to significantly reduce the number of variables. In this paper, a procedure that globally optimizes one or two important variables is outlined. This procedure comes much closer to true plantwide optimizing control while remaining computationally feasible. Finally, another major challenge is to choose a meaningful global objective that can be calculated With the models and can be effectively optimized. Financial goals seems to be the objectives of choice. This paper discusses recent progress In overcoming the challenges and illustrates a promising approach which is being pursued at :Mexicana de Cobre's 'La Caridad copper ore concentrator. At M de C, advanced ,control strategies have been 'installed one at a time in the crushing, grinding and flotation sections. During this period, the throughput of La Caridad, Mexico's largest copper concentrator, 'increased from 76;000 tpd to 90,000 tpd. Plantwide integration is expected' to gain an additional 3% improvement in profitability.

Jan 1, 1996

By Ilija Ilic

Recovery of tin from tinplate and production of good-quality detinned-plate for further processing in ironworks has been the subject of interest for many years. Tinplates are mostly used for production of tin containers for food industry and consumer goods. The research carried out so far included determination of the parameters of dissolution of tin from tinplates by alkaline solution of NaOH and electrochemical recovery of tin from the alkaline solutions. During leaching, NaNO3 and methanitrobenzoic acid (MNBA) as oxidants were studied. By leaching the waste tinplate which contains 0.31 % of tin with a solution of 1.12 mol/dm3 NaOH, 0.26 mol/dm3 Na2CO3 and 0.09 mol/dm3 MNBA at temperature of 70°C for 60 mm, a degree of tin leaching of 97 % was attained. MNBA facilitates oxidation of Sn2+ into Sn4+ suitable for obtaining compact, and not spongy, Sn cathode deposit, as it was the ease earlier. Recovery of tin by electrolysis from solutions obtained by leaching was studied to determine the effect of electrolyte composition on the quality of cathode deposit and the degree of electric current efficiency. Experimental results obtained at a laboratory level were checked on an enlarged laboratory set up where continuos leaching of tin from waste tinplate and its electrolytic recovery from the solution obtained were carried out. The experimental set-up -operated under semi-industrial conditions, and about 500 kg of waste tinplate was processed yielding about 1.160 kg of tin (99 % Sn).

Jan 1, 2000

By Marco Zurco, Claudia M. Mendez, Alicia E. Ares, Carlos E. Schvezov, Carlos M. Rodriguez

"Zinc-Tin alloys were solidified in horizontal form and the obtained results were analyzed. During solidification the distribution of temperatures were measured by using thermocouples located strategically along the length of the samples. From the measured temperatures the following parameters were derived; the local temperature gradient, the cooling rate and the velocities of the liquid and solids fronts. Comparing the structure of the samples and the values of these parameters it was found that the temperature gradient reaches minimum values of as low as - 0.6 °C/cm, and velocities of the fronts of around 0.1 cm/s. In addition, the grain size was measured along the samples. The results are presented and discussed in the frame of the results previously obtained for other alloys.IntroductionGenerally solidification leads to two types of grain morphologies: columnar and equiaxed. The origin of each one has been the subject of numerous theoretical and experimental researches in the field of metallurgy for many years [1-7]. The columnar-to-equiaxed transition, CET, is considered as an object of high technological relevance with respect to the directional solidification of metallic alloys. This structure transition may be sharp or gradual and it has been reported to be dependent on thermal conditions associated with the casting process, including melt convection, heat transfer coefficients at the metal-mold interface, growth rates, thermal gradients, cooling rates, transport of solute, alloy composition, melt superheat, mold temperature, mold design, casting size, casting geometry, and the concentration of nucleating particles. As a consequence, it is critical for industrial applications to understand the physical mechanisms which control this transition during solidification. Many studies highlight the importance of the relative growth of the equiaxed and columnar grains and develop expressions or numerical procedures to describe a criterion for the CET. A number of experimental investigations reported in the literature suggest that the CET occurs when GL in the melt reaches a minimum critical value [5-7]."

Jan 1, 2012

By John A. Herbst, William T. Pate

"Plantwide control of mineral processing operations has long been sought for its potential benefits. These benefits include minute-to-minute optimization, reacting to disturbances in ore characteristics and equipment status as they happen, and the coordination of all unit operations in pursuit of the highest performance level. However, several difficult challenges have kept us from fully realizing those benefits. One of these challenges has been to provide fairly complete quantitative descriptions of unit operations to account for critical interactions within and between unit operations. In some cases we understand the physics and chemistry very well and can incorporate that knowledge into phenomenological models. In other cases our knowledge is incomplete, so we must rely on other forms of knowledge such as fuzzy logic or neural nets. Another challenge to be met has been to simultaneously compute a large number of manipulated variables. In the past this challenge was met by optimizing only unit-by-unit, rather than on a global basis to significaritly reduce the number of variables. In this paper, a procedure that globally optimizes one or two important variables is outlined. This procedure comes much closer to true plantwide optimizing control while remaining computationally feasible. Finally, another major challenge is to choose a meaningful global objective that can be calculated with the models and can be effectively optimized. Financial goals seems to be the objectives of choice.This paper discusses recent progress in overcoming the challenges and illustrates a promising approach which is being pursued at Mexicana de Cobre's La Caridad copper ore concentrator. At M de C, advanced control strategies have been installed one at a time in the crushing, grinding and flotation sections. During this period, the throughput of La Caridad, Mexico's largest copper concentrator, increased from 76,000 tpd to 90,000 tpd. Plantwide integration is expected to gain an additional 3% improvement in profitability."

Jan 1, 1996

By M. Omneya El-Hussaini, M. Galal Abdel Wahab, A. Mohamed Mahdy, M. Fathi El Shahat

"Um-Gheig Pb-Zn representative sample was collected from the main adite of Um-Gheig mine along Red Sea coast in Egypt. Its chemical analysis shows that, it contains 16% Zn, 2.3% Pb, 0.1% Cd and 0.1% B as elements of interest. After H2SO4 agitation leaching, the chemical composition of Um- Gheig Pb-Zn deposit ore residue assayed 2.26% Pb, 1.5% Zn, 0.085 % B and 0.01% Cd. This residue was leached with 20% HCl at S/L ratio 1/3 for 2 hours at 80o C. The chloride leach liquor was found to contain 18 g/l Pb, 13 g/l Zn, 0.1 g/l Cd and 0.75 g/l B with the corresponding leaching efficiencies 79%, 86%, 100% and 88% respectively. Lead was precipitated from the chloride leach liquor using concentrated H2SO4 to obtain PbSO4 with precipitation efficiency 96%. While boron was extracted by the selective resin Amberlite IRA743 with loading efficiency of 80%. On the other hand, Zn and Cd were precipitated using Na2S solution with 86.7% and 100% recovery efficiencies respectively.IntroductionLead-zinc ores occur in Egypt in a few localities distributed along the Red Sea coast between El Qusier and Ras Banas.. The reserve of the ore deposits has been estimated by Soviet and German Experts to be about 900,000 Ton, [1]. Onal et al., [2] recovered Pb from Pb–Zn sample containing 10.17 % Pb and 10.98 % Zn from Aladag in Turkey. El-Sherif, [3] used concentrated HCl to leach lead-zinc ore sample of Um-Sammuki area in Egypt. As had been published by Marchioretto et al. [4], the precipitation of heavy metals with lime, sulfide and caustic soda are the most commonly used economical methods for metal removal. Lead was completely removed from the anaerobically digested sludge by precipitation with NaOH and Na2S at waste water treatment plants. Mahdy et al., [5] had successfully extracted boron from the bittern solution of Qaron Lake by ion exchange resin (Amberlite IRA 743). The extraction of boron was mainly depending upon the pH value. They extracted 80% of boron at pH 5.5, while at pH 3.9 about 74% boron was extracted. Kabay et al. [6] used the column-mode to remove 1g/l of boron from geothermal waste water of the Kizildere-Geothermal Power Station by using Diaion CRB 02 Nglucamine- type chelating resins. In this regard, the removal of lead, cadmium and boron allow the residue to be reclassified as non hazardous material."

Jan 1, 2008

By R. L. Nyirenda

An investigation of the reducibility of a cassiterite concentrate with charcoal was made in the temperature range of 1123-1373 K. The course of the reaction was monitored by a combination of sample weight loss measurements, product gas analysis, and chemical analysis of the reaction product. It was found that the cassiterite could be best reduced by a combination? of high temperature, reasonably high charcoal proportions, high charge poroslty, and the addition of a small percentage of lime. Analysis of kinetic data obtained from isothermal experiments using theory from the oxidation of carbon by carbon dioxide gave an activation energy value of 255 lci/mole for the consumption of carbon by reaction with cassiterite.

Jan 1, 1990