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By John Dorn

THE phenomenon of diffusion, according to the most prevalent conceptions at the present time, undoubtedly played an important part in the formation and distribution of metals and minerals in the earth's crust. Apparently there is good evidence that in the geological rate of cooling diffusion caused numerous materials to separate into individual masses or into duplex structures. As is well known, the early steels were made by cementation; that is, by heating wrought ferrous metal in contact with carburizing materials so as to produce a relatively high carbon content on the surface. If the process was continued long enough, the carbon diffused throughout the piece. A more homogeneous product depended upon further heating and forging, so that the carbon diffused to a fairly uniform concentration throughout the metal. In the modern metallurgical industry, diffusion is the basis for many operations; for example, the production of hard surfaces oil steels by carburizing, nitriding, cementing with chromium, silicon, boron and beryllium. Castings or ingots as they solidify do not have homogeneous structures, but these structures are made largely homogeneous by suitable process of heat-treating and the resulting diffusion. It is in modern physical metallurgy, however, that we become greatly concerned about the mechanism of the phenomenon of diffusion. The rates of diffusion, effect of temperature and time on diffusion, and the relation of diffusion to the many properties of the parent metal and the diffusing metal have become important; also, we are concerned with the diffusion of a single metal into a complex alloy. For example, what is the mechanism whereby carbon and nitrogen travel into steel? What is the effect of alloying elements in the ferrous material on the rates of diffu-sions? What is the effect of simultaneous diffusion of carbon and nitro-gen? How does chromium, beryllium, boron, or the like, diffuse into the steel, and what are the effects of alloying elements in the steel previous to the cementation process? These inquiries are by no means limited

Jan 1, 1937

By C. Caballero, M. Rosales, C. León, A. Valencia, R. Fuentes, A. Moyano

Slopping is the formation of waves in the converter due to the gas injection by tuyeres. Those waves produce a premature wearing of the refractory lining of the reactor due to its great amplitude. The affected zones are the tuyere line (outlet gas from tuyeres) and the front of this line. In the present work, a theoretical and experimental study is made to develop a theory that determines the variables involved in slopping, characterizing the more important parameters of operation in the phenomenon of slopping. In addition, this theory will allow for determination of new technological alternatives of the blast injection permitting to depress the slopping phenomenon.

Jan 1, 2007

By L. B. Lindemuth

To those who are in a position to carry the thought to a conclusion; I would like to present a theory for the cause of blisters in galvanized sheets. Blisters that are caused from piping and shrinkage cavities will not be considered because the reason for their formation is entirely obvious. Blisters that occur periodically with no apparent system of ocation, number, size or grouping, and then disappear with no. apparent change in manufacturing method, are the ones to which this theory would apply. Examination of blisters of the latter type has shown that they contain hydrogen gas at atmospheric pressure, and that occasionally traces of oxide or sulfide are found on the inner surface of the blisters. These two characteristics have led to the rather general idea that hydrogen gas generated in pickling, and that iron oxide supposed to be inherent in the ingot and causing weak spots were, in some manner, responsible for the development of blisters in galvanizing. The theory which I wish to advance is that these blisters are caused by moisture that has penetrated the steel after the annealing operation. This moisture comes from the atmosphere, or from pickling or washing and when it is suddenly expanded into superheated steam in galvanizing, the increase in volume is so great that it cannot escape with sufficient rapidity through the small opening where it entered as moisture.The pressure so generated forces the sheet apart along those lines of lamination ;hat may be found in practically all flat sections of steel rolled comparatively cold. The increase in volume. from moisture to steam at 800° F. is 2244 times the original volume of the moisture. The pressure generated by ;he moisture heated to 800° F. and entirely confined would be enough to expand or explode any container. This would explain the source of sufficient pressure to cause a sheet to blister.

Jan 3, 1927

By C. P. Crawford

Bureau of Mines Technical Paper 172, by S. H. Katz and H. C. Porter, entitled "Effects of Moisture on the Spontaneous Heating of Stored Coal", says at the outset, "Spontaneous fires in storage piles of bituminous coal' have been the source of trouble and loss since the industrial utilization of coal began. In Europe the idea arose that spontaneous combustion is more liable to happen during wet weather than during dry. Statements favoring or opposing this idea have crept into the literature. Conflicting conclusions, based on experiment as well as opinions based on observations of various degrees of reliability, are given in most of the recorded discussions of the subject. "Because of the uncertainty of the effect of moisture and its seeming importance among the conditions that affect spontaneous combustion in stored coal, the work described in this paper was undertaken by the Bureau of Mines. The experiments showed that a coal from Illinois oxidized faster when dry, whereas a sample of Pittsburgh coal oxidized faster when moist. These discordant results and similarly inconsistent results from the observations of different investigators may be coupled with the fact that under actual conditions of, storing, both coal and air always contain a considerable amount of moisture." The foregoing report of the investigations of the Bureau demonstrates that the mystery of spontaneous combustion has not yet been solved. This fact adds to the fascination of the subject. I became interested in the matter about ten years ago in observing what was probably one of the best exhibitions of this phenomenon. The old dump at Castle Gate No. 1 Mine contained boney coal and track cleanings generally. In winter when snow fell upon this old dump, the snow was soon melted by the heat of the dump which was comparatively warm at all times. Within 48 hours afterward little blue flames were in evidence on the surface of the pile. Few of the gas feeders were sufficiently constant to maintain a steady flame at any given point, but shifting emissions of gas were ignited one by another, resulting in a continuous popping and apparent running about of the flames. Another interesting exhibition of spontaneous heating was to be seen a few years ago in the storage coal piles of the local sugar factories. This coal was piled in concrete lined pits and the latter were filled with water. However, or this occasion the coal extended above the surface of the water. At every plant where this condition existed the coal was affected heating, and in each case the affected area was in a plane horizontal to and from 8 to 1.4 inches above the water level. The height of the hot area above the surface of the water appeared to be affected by the fineness of the coal. It is well known that oily rags have a tendency to heat when allowed to accumulate in some location protected from free air circulation. For some reason, as yet unknown, this does not apply to petroleum or its derivatives. Now, the most common explanation of spontaneous combustion is that the combustible material oxidizes by being brought into contact with air in the presence of moisture, the theory being that the moisture acts as a catalytic agent. My theory is that spontaneous combustion is due to oxidation of combustible matter by free oxygen carried in solution by a liquid, the oxidation taking place only as, when, and at the place where this oxygen is released from solution by the evaporation of the liquid. Also, this oxidation takes place to some degree regardless of the condition of the combustible-whether it be lump coal, coal dust, straw, wheat flour, coke, or any other combustible but, as the speed of oxidation is directly influenced by temperature, it follows that spontaneous combustion only becomes noticeable or serious in cases where the resulting heat' cannot escape as fast as it is generated.

Jan 1, 1925

By M. Aushouri, S. H. Mansouri, N. Aminizadeh

A thermo-chemical model of the Peirce-Smith copper converter has been developed to predict the molten temperature. The primary assumption of the model was that all matte, slag and gaseous phases in the converter were in thermal and chemical equilibrium. In this model, the matte components were considered only as copper, iron and sulfur elements. In the slag making stage, all the reacted iron was converted to fayalite. The reaction rate of iron and oxygen in this stage was considered to be constant. The converter temperature was calculated by heat balance over time. The model was validated by a detailed comparison with measured industrial data. A good agreement was obtained. The converter temperature depends on process parameters such as oxygen efficiency and molten emissivity.

Jan 1, 2007

By M. Aushouri, S. H. Mansouri, N. Aminizadeh

A thermo-chemical model of the Peirce-Smith copper converter in blowing the copper stage has been developed to predict the molten temperature. The key assumption of the model was that white metal and gas phases in the converter were in thermal and chemical equilibrium. In this model, the chemical reaction of white metal and oxygen was accomplished completely. So long as sulfur existed in the bath, the generation of Cu2O was frozen. The reaction rate was considered to be constant and controlled by the reacted sulfur. The converter temperature was calculated by heat balances over time. The model was validated by a detailed comparison with measured industrial data. A good agreement was obtained. The converter temperature depended on process parameters such as oxygen efficiency, molten emissivity and oxygen enrichment.

Jan 1, 2007

By M. Abdelkhalek, M. Hepworth, D. Tao, B. K. Parekh

Pre-combustion coal cleaning and post-combustion flue gas desulfurization (FGD) using lime or limestone are the primary methods employed to reduce sulfur dioxide (SO2) emission from coal combustion. These processes generate voluminous pyrite and gypsum solid wastes that are usually landfilled, occupying thousands of acres of land and creating serious land and water pollution problems due to the release of acids and toxic substances. An integrated process has been developed for the combined utilization of gypsum and pyrite wastes by converting them into useful products including lime, sulfur, and direct reduced iron (DRI). The process includes four major steps. The first step is to concentrate pyrite from coal preparation tailings using flotation or gravity separation. The second is the thermal decomposition of pyrite into pyrrhotite and sulfur. This is followed by the reduction of pyrrhotite with carbon in the presence of lime to produce iron and calcium sulfide. The fourth step involves the reaction of calcium sulfide with gypsum to produce lime. The chemical reactions involved in the process were studied using thermogravimetric analysis (TGA) and X-ray diffraction (XRD)techniques. Process variables studied included reaction temperature, time, reactant composition, and purity of reactants.

Jan 1, 2000

By J. Antrekowitsch

Keywords: residues, fluorides, chlorides, zinc, steel mill dust The recyclability of various nonferrous metal wastes often suffers from a relatively high fluorine and chlorine content. Both are inserted in most cases by the use of plastic contaminated scrap and a wide variety of different coatings. These halogens lead to poor product qualities and off gas contamination. Especially the history of zinc recovery from steel mill dusts shows, that the today common hydrometallurgical options are on their limit and therefore are not sufficient in most cases. This thermochemical study should give more information about different pyrometallurgical options, that offer both a chlorine and fluorine reduction and efficient zinc recovery, preferably in one process step. Selective evaporation in different atmospheres and conversion with the use of hydrogen are the main parts in this study. The results combined with the relatively small information available from literature should provide a basis for further investigations in this field.

Jan 1, 2005

By S. Gopalan, J. D. Milshtein, S. N. Basu

Production of syngas is proposed utilizing the W/W03 redox system and employing a solarpowered two-step thermochemical cycle. Three chemical reactions occur in two chambers. Assisted by a solar concentrator, a high temperature reaction reduces W03 powder to metallic tungsten in both chambers. Subsequently, the temperature in one of the chambers is lowered and H2(g) is produced via re-oxidation of the tungsten powder using steam. The temperature in the other chamber is simultaneously lowered to an intermediate temperature and CO(g) is produced via oxidation of the tungsten powder using C02(g)· The gas streams coming out of the two chambers result in the syngas production. A complete thermodynamic analysis of the system is described. The W/W03 redox cycle offers greater gravimetric fuel productivity compared to previously proposed systems, and the entire cycle can be operated below 1273K.

Jan 1, 2013

By B. McFadzean, K. Moller

"The mechanism whereby thiol collectors adsorb onto a mineral surface has been widely studied. Most of these studies examine the mineral surface at equilibrium state and, often, well above monolayer coverage. However, the formation of species at the mineral surface is a complex process that is both kinetically and thermodynamically controlled. In a typical industrial application, the dosage of collector will be around monolayer level. This study uses isothermal titration microcalorimetry to measure the heat evolved during the reaction of sodium ethyl xanthate (SEX) and sodium isobutyl dithiocarbamate (SIBDTC) and their mixtures with galena and chalcopyrite. The sensitivity of the instrument allows heats of reaction of sub-monolayer quantities of thiol collector to be measured.The study found that both the magnitude and kinetics of the reaction between a collector and a mineral surface was dependent on the type of mineral and the type of collector. Proposals are made for the reactions based on literature and the evidence from this investigation. It was found that when collectors were reacted with mixtures of galena and chalcopyrite, that the magnitude of the reaction was lower compared to that measured for the pure minerals alone. This may be due to galvanic interactions between the minerals, resulting in a passivating effect on one or both of the minerals."

Jan 1, 2014

By Chuang Y-Y

A summary is made on the thermodynamic analysis for two of the four ternary systems of the quaternary Cu-Fe-Ni-S. The analysis is being extended to ternary Cu-Fe-S and then to the quaternary. An analysis is already made for the metal ternary but is not reported here. Experiment is being carried out to measure the liquidus surface. of Fe-Ni-S equilbrium with the fcc solid solutions of (Fe, Ni). The presentation at the Symposium will include all the results obtained at the time of presentation.

Jan 1, 1983

By A. Nivala, S. Ulgiati, M. Canino

Mining and processing of bastnaesite ore, (Ln)CO3F, for lanthanides extraction is investigated in this paper. This series of elements proved to be applicable for a wide range of high-tech uses. In spite of the strategic importance of lanthanides, no LCA and energy analyses of their extraction have ever been published. We perform in this paper a Life Cycle Assessment of the Lanthanide production cycle, based on available database and literature data from Mountain Pass mine (USA) and other worldwide mining and processing sites, most of which in China. We investigated three main steps: mining, milling (including transport, grinding and drying), and flotation (for lanthanide chloride extraction). We do not investigate here the separation of pure oxides from lanthanide chloride, a compound which is also marketed as such. The conventional LCA was integrated by means of energy and emergy evaluations, aimed at investigating respectively the global energy cost and the environmental sustainability of the process. Indicators of material intensity, thermodynamic efficiency, and environmental impact (including LCA and ecological footprint impact categories) are calculated and discussed.

Jan 1, 2005

By Jillian Spindura

This work investigates the carbothermic reduction of the complex sulphide mineral, pentlandite, in the presence of lime. The effects of change in temperature and the use of different carbon sources are studied and the role of these variables on the reducibility of pentlandite mineral is discussed. The microstructures of the heat-treated pellets are examined using X-ray diffraction and scanning electron microscopic techniques. The latter analytical method also allows any variation in the morphology and composition of the metallic phases formed, with temperature, to be considered. The kinetics of the reduction process is studied and the magnitude of the overall activation energy is determined from the plots of percentage reduction versus time.

Jan 1, 1996

By A Kamaraj, M Mohanasundaram, R Kumar, P Tikare

This study presents a comprehensive thermodynamic optimisation and sustainability analysis of the secondary copper smelting process for Waste Printed Circuit Board (WPCB) recycling. The study investigates various scenarios with different proportions of WPCB in the input stream, ranging from 0 per cent to 100 per cent. Through thermodynamic modelling using FactSage™ version 8.1, the optimisation process is conducted in three stages. The results of the thermodynamic modelling indicate that the best-case scenario for WPCB recycling is achieved with a 40 per cent proportion of WPCB in the input stream. This case exhibits a maximum copper recovery of 99.93 per cent while minimising the formation of other waste. In addition to the thermodynamic analyses, environmental factors such as the carbon emission index and resource utilisation efficiency are studied. The 40 per cent WPCB recycling case exhibits a resource utilisation efficiency of 93.055 per cent and a carbon emission rate of 0.133. The present investigation highlights the significant benefits of a 40 per cent WPCB recycling scenario through a secondary copper smelting process in terms of base metal recovery and energy efficiency, thus emphasising its potential for sustainable PCB waste management and resource utilisation.

Aug 21, 2024

By S. Sridhar, R. E. Aune, M. Hayashi

Thermophysical properties of silicate melts are strongly structure dependent. It is well known that the viscosities of slags increase with increasing the degree of polymerization of silicate anions. Even the thermodynamic properties of slags are dependent on the types of species and the population of the same in the melt. Thus, a link between the thermophysical and thermochemical properties of silicate melts is logically expected. The present paper elucidates the salient features of Darken?s excess stability approach to the Gibbs energies of solutions as applied to the viscosities of silicate melts. It is demonstrated, that the second derivatives of the viscosities of binary silicate melts with respect to composition indicate a maxima corresponding to the existence of stable compounds in these systems. The concept was successfully applied to the following systems: Al2O3-SiO2, CaO-SiO2, FeO-SiO2, MgO-SiO2and MnO-SiO2. In all the cases, the second derivative plots of viscosities with respect to composition showed peaks corresponding to the metasilicates. The second derivatives of the activation energies of viscous flow with respect to temperature has earlier been shown to reflect the formation of associates/embryos in the homogeneous silicate melts, indicating the readiness of the melt to separate a solid phase. Thermodynamic coupling of thermal diffusivities in the case of the system CaO-Al2O3-SiO2from the laser-flash measurements of these slags as a function of temperature are examined as part of the present study. Densities are estimated from integral molar enthalpies in the case of silicate systems and the results are presented. Keywords: silicate melts, viscosity; activation energy, thermal diffusivity; density

Jan 1, 2004

By Pengfu Tan

A thermodynamic model has been developed to predict the distribution behaviors of Cu, Fe, S, O, Pb, Zn, As, and heat balance in a lead blast furnace. The modeling results have been validated by the plant data of a lead smelter in Asia. The model can be used to predict for any set of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxygen-enriched air. The effects of the blast air, industrial oxygen, and coke charge on the distributions of Cu, Fe, S, O, Pb, Zn, As, and heat balance, and on the lead loss in slag have been presented and discussed.

Jan 1, 2005

By Alhondra de los Santos, Jesús L. Valenzuela, Jose R. Parga

"The present study evaluated the feasibility of using iron species generated by electrocoagulation (EC) as an adsorbent for removal As(III/As(V) from aqueous media. The full potential of EC was evident in that more than 99 percent of arsenic was removed without addition of chemical reagents. The adsorbent iron-species generated by EC was characterized by Chemical Analyses, X-Ray Diffraction and Scanning Electron Microscopy. The experimental data were correlated by employing a Langmuir adsorption isotherm. Thermodynamic parameters such as ?H o , ?S o and ?Go were calculated. The adsorption process was found to be exothermic and spontaneous.1. IntroductionArsenic contamination in potable water supplies is a serious health problem in many countries around the world. Groundwater arsenic contamination in La Comarca Lagunera Mexico was first reported 30 years ago [1]. Arsenic concentration has been found in well water from several communities ranging from 0.25 to 1.0 ppm. The elevated concentration of arsenic in water, above that originating from natural sources, has been attributed to the use of organoarsenical pesticides in the cotton fields and also to the millions of tons of waste slag generated at a local lead smelter [1]. The main arsenic species present in natural waters are arsenate ions 3- 4 AsO (oxidation state V) and arsenic ions H3AsO3, - 2 3 H AsO and 2- 3 HAsO oxidation state III). However, As(V) ions are most prevalent in oxygenated water while As(III) is found for anaerobic conditions, such as in well water or in groundwater. Conventional methods of arsenic removal rely on chemical-based treatment with lime, alum coagulation, iron coagulation and chemical oxidation. Other processes used with varying degrees of success include adsorption onto activated carbon, reverse osmosis, nanofiltration, manganese dioxide, magnetite and ionexchange resins [1-3]. These conventional processes generate a considerable quantity of secondary hazardous waste such as solid sludge, which also pose serious environmental problems. These drawbacks have forced various industries to search for effective, alternative treatment technologies for arsenic with a preference for electrochemical methods."

Jan 1, 2008

By Jeffrey R. Taylor

The distribution of low concentrations of Cr, Mn, Rh, Co, Ni, Ag and Fe between copper matte and bullion phases has been measured at 1200oC. These results. together with values for nine other elements, have been used to develop a simple model to describe the distributions in terms of known thermodynamic properties?. The Temkin model for ionic melts was assumed to apply to the sulphide species in the Cu-S matte? phase and it is shown that the choice of sulphide species is particularly important for successful representation of the experimental .results?. In general, the lowest sulphlde (minimum sulphur :. metal ratio)? formed by the. metal is most suitable, although Ni, Co, Rh and Pd appear to associate with more sulphur in the melt than suggested by the? composition of their lowest sulphide. A correlation between the composition of the metal sulphide species formed in the ternary system and the? position of the minimum in the free energy of mixing curve in the metal-sulphur binary -system is? proposed.

Jan 1, 1983

By Yap Chu-Phay

ALTHOUGH chronologically, the Sb-Bi system was the first one studied by the writer, the theoretical basis of the equations used in this paper is fully discussed in the writer's paper on the iron-carbon system,1 because he believed that many would be more interested in the iron-carbon alloys. He suggests, therefore, that the reader consult that paper to familiarize himself with the theoretical aspect of the thermodynamic treatment outlined herein. This paper is divided into two parts: Part I deals with the Sb-Bi system and Part II deals with the lead-rich side of the Sb-Pb system. Although the former system has not much practical interest now, it has great theoretical interest in that it, is the one system that for a long time was thought to have (and under specific conditions still has) an anomalous solidus, which no amount of physical investigation could adequately account -for. The latter system of course, is particularly interesting in the lead-rich end. It will be shown that the thermodynamic method is capable of predicting reliably the equilibrium position of the solidus, and thus acts as a check on the experimentally derived solidus.

Jan 1, 1931

By Yap Chu-Phay

IN 1923, when the writer began his studies in metallurgy, he came upon an article by Professor Honda on the, Equilibrium Diagram of the Iron-carbon System, 1 which made a profound impression on him. What interested him most was this sentence: "In the recent diagram of the iron-carbon system, the solidus is usually shown as a curve bending considerably downward. But it can be shown by thermodynamics that if the liquidus is straight or slightly curved, the same must also be true for the solidus. Hence, in my constitutional diagram, the lower portion of the solidus is slightly bent upward." Ever since then the writer has been interested in thermodynamics, especially chemical thermodynamics. The applications of thermo-dynamics to the metallic systems have been, in the writer's opinion, sadly neglected, although we continually use the phase rule in our study of equilibria in the liquid and solid states of metallic alloys. Many investigators, among whom may be mentioned Heycock and Neville, and s Honda and his coworkers, have applied the simple Raoult-van't Hoff law of depression of freezing point, mainly to determine the heat of fusion, but no attempt has been made to investigate the applicability of the thermo-dynamic laws of solution (as opposed to the laws of solution derived from other sources) to metallic systems" showing either limited or complete solid solutions. Perhaps the reason for this neglect is that until recently there have been so few reliable data on the solidus, which is much more difficult to determine than the liquidus. The writer has under way at the present time an investigation of a number of systems, the solidi of which have been more or less reliably determined. Recently, the writer has not only shown the valid applicability of the thermodynamic laws of solution as applied to the system antimony-bismuth but has also suggested a method of attacking problems involving complete and incomplete equilibria.2 In the present paper, the same method of approach is employed. For convenience, we shall divide this paper into two parts:

Jan 1, 1931