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By Dirk Verhulst, V. I. Lakshmanan

Why Chloride Hydrometallurgy?The most available, cheapest and best known reagent for treating ores and other raw materials for the metallurgical industry is sulfuric acid. Hydrochloric acid is second in line. What often happens is that a process is developed on the basis of sulfuric acid, and that at some point the question arises: wouldn't hydrochloric acid do this better?Considering hydrochloric acid immediately opens a very interesting field of research. To summarize a few comments from another paper presented at this symposium [1]: chlorides are far more soluble than sulfates (with a few interesting exceptions); the hydrogen ion activity is greater in chloride than in comparable sulfate solutions; higher oxidative conditions are possible; regeneration is more straightforward; more diversity is possible and better conditions for the separation of species can be found for solvent extraction and ion exchange; sulfur in the ore can be separated as elemental S; higher metal concentrations in solution and more flexibility in the chosen oxidation state means significantly lower energy costs.Also, the volatility of many chlorides at higher temperature allows further separation without the need to go to a different system. Chlorides also form molten salts with a low melting point, providing another means of separation and purification in the same chloride medium.

Jan 1, 2011

By Jordan Mayorga, Joseph Kopp, Robert Boehm, Daniel P. Cook

"Solar generated power has long been considered a useful energy source only for low-energy density and non-mission critical use, such as providing electricity for residential applications. The success of Concentrating Solar Power (CSP) facilities, such as the 64 MW Nevada Solar- 1 near Las Vegas, have demonstrated that solar does have application to high energy density industries such as materials and chemical production. This paper will discuss the current operating con_guration of the Solar-1 facility and show how proposed modi_cations, such as addition of thermal storage and use of liquid salts as the working uid, can further improve the e_ciency and energy production of the plant.IntroductionThe United States as a nation is the largest consumer of energy in the world at an estimated 29 trillion kWh per year[1], which is roughly 15% of total global energy consumption[2]. On a per capita basis, the United States also leads most of the world, using an average of 96,000 kWh per person[3]. Roughly 40% of the energy consumed in the United States was produced from petroleum, 23% from coal, 23% from natural gas, 9% from nuclear and the remaining 5% from renewable sources such as solar, geothermal, wind, and hydroelectric[1].Energy demands associated with the industrial-scale production of chemicals and materials is a signicant portion of the United States total energy consumption. Roughly 33% of the energy consumed in the United States is used by the industrial sector, with 22% of this amount used in chemical production, 16% used in petroleum rening, and 14% used in the smelting and rening of metals[1]. Energy costs are also a signicant, if not the most signicant, portion of the total production costs for many materials. For example, roughly 30% of the cost of producing aluminum is the electricity used in the Hall-Heroult process [4], while the cost of energy is roughly 15% of the total cost of producing steel products [5].The primary sources of power for the industrial sector have been coal, petroleum, hydro- electric and nuclear. The use of alternative energy sources, e.g. solar, wind, geothermal, for industrial materials production has been slow in coming because they are intermittent and low-energy density sources, i.e. no solar power at night, no wind power when the air is still, etc. The success of Concentrating Solar Power (CSP) facilities, such as the 64 MW Nevada Solar-1 (NS-1) near Las Vegas, have demonstrated that solar can have application to high energy density industries such as materials and chemical production.This paper will discuss the current conguration of the NS-1 facility, and potential modications to the facility that will increase both its power e_ciency and power density."

Jan 1, 2010

By Caisa Samuelsson, Fredrik Engström, Bo Björkman, Margareta Lidström Larsson

"Large amounts of by-products are generated by the Swedish steel industry each year. The EAF-process generates about 400 000 ton of slag, from which 80% is deposit. An alternative to deposit is to use slag as road construction material. However, metal content in the slag can be a problem, due to the leaching. The aim of this work was to investigate how stable these materials are when ageing and kept outside. Five different EAF-slags from domestic steel plants were used in this study. The materials were characterised after 0, 6, 12, 18 and 24 month to evaluate the ageing process. Scanning electron microscope (SEM), x-ray diffraction pattern (XRD) and a standard test for leaching were used. The changes in behaviour differ between the five materials. The total leachability decreases with time for all samples. CaCO3 is formed on slag surfaces as CaO reacts with moister and CO2 in the air. Introduction The slag generation in the Swedish steel industry is about 1.5 million tonnes annually, of which more than 500 000 ton is generated in EAF (Electric Arc Furnace), AOD- (Argon Oxygen Decarburization) converters and during the refining of steel in the ladle metallurgy. Some of the slags are used in different applications, but most of the steelmaking slags produced in Sweden are landfilled today. The chemistry, mineralogy and physical characteristics of slags make it a suitable material in construction, replacing for example, gravel and rock [1]. In some respects, in road construction, it may even be technically superior to virgin material. Slag from scrapbased steelmaking is used for road construction in Europe. The reason for the low utilization in Sweden is mainly due to potential leaching of harmful elements, legislations and competition with easily available natural raw materials. Except the potential leaching, the technical obstacles for not using some slags in construction include:"

Jan 1, 2008

By Clemens Schmetterer, Patrick J. Masset

"The surface tension represents an important property for the modelling of high temperature processes. In this study the surface tension of two Al2O3 – CaO – SiO2 model slags and the influence of the admixture of 5 up to 30 wt.% FeO were studied. The surface tension measurements were carried out using the sessile drop technique on BN substrates under Ar atmosphere (10-6 atm O2) up to 1500 °C.IntroductionThe aim of VIRTUHCON1 is the virtualization of high temperature conversion processes, a task that requires thorough understanding of these processes. In many of these conversion processes slag plays an important role to control the properties of the product, to protect the reactor lining or simply as waste. Slag surface tension is one of the materials properties that is needed for the description of such processes, since it influences the interactions between the components in the reactor, e.g. at the slag – Fe interface in the blast furnace.Surface and interfacial tensions have thus received considerable attention in research, but the number of investigations in this particular pseudo-quaternary system is surprisingly low. Furthermore, the literature data are subject to different measurement conditions and techniques which complicates the data analysis and comparison.The slag atlas [1] offers a compilation of the available literature until 1986 (shown in Table I), but literature search has not revealed more recent studies of this system until now. For example, Elliott and Mounier [2] determined the surface tension of ACSF slags using the double tube maximum bubble pressure technique at 1200 °C. They kept their slags in contact with Cu-S-F mattes, and the slag therefore contained a certain amount of sulphur which acts as a surfactant and lowers the surface tension. The compositions of their slags were scattered over a wide composition range and they did not use a common ACS base mixture for their tests, either. The surface tension values vary between 417 and 446 mN/m, but due to the reasons just mentioned no trend in the measurements can be observed and the influence of FeO admixture on the surface tension cannot be deduced. Further information including the temperature dependence is available from Pavlov et al. [3], Ishchanov and Shushkov [4] and Murav’eva and Kaplun [5]; the diagram on page 446 in Ref. [1] has been drawn from these sources. Both positive and negative temperature coefficients are reported in these works. SiO2 is the only pure constituent that has a positive temperature coefficient [6], but a correlation of the temperature coefficient with the SiO2 content was not found to be conclusive."

Jan 1, 2011

By Dong Liang, Honggang Zhong, Zhenxing Yin, Qijie Zhai

"2507 super duplex stainless steel (SDSS) has been widely applied in a marine environment, attributing to its excellent pitting corrosion resistance and mechanical properties which are particularly determined by the nitrogen precipitation behaviors and volume fraction of ferrite. In this paper, various cooling rates were obtained by applying four different moulds with the common gating system. By which the influence of cooling rates on nitrogen precipitation behaviors and the ferrite fraction in cast 2507 SDSS was comparatively investigated. The results showed that nitrogen porosity could easily precipitate in cast 2507 SDSS under standard atmospheric pressure. The number of nitrogen holes increased with decreasing the cooling rates, and the holes mainly distributed in three zones, i.e. the interface between the horizontal and vertical columnar grains, top vertical columnar grains and the final solidification region. Additionally, higher ferrite fraction was obtained with lower cooling rates.IntroductionDuplex stainless steels (DSS) have a dual-phase microstructure consisting of ferrite (d) and aus-tenite (?). Due to the combined advantageous properties of d and ? phase, their application rapid-ly increased in industry [1, 2]. Super duplex Stainless Steel (SDSS) is the third generation of du-plex stainless steels, of which the alloy elements Cr, Ni and N content are higher than the stand-ard 2205 DSS. Because it has high contents of alloy elements, the SDSS has better mechanical properties, and its pitting resistance equivalent number (PREN) reached a point 43. Hence SDSS has been used in petroleum chemical industry, the marine equipment and harsh corrosion environments [3]. SDSS contains ferrite stabilizing elements, such as Cr, Mo and Si, and austenite stabilizing elements like Ni, Mn and N [4]. Many researchers have studied the effects of these elements on the stabilization of d and ? phase and the ratio of the two phases. High nitrogen con-tent is another prominent feature of SDSS. Nitrogen addition to SDSS is very effective for improving its mechanical properties [5] and corrosion resistance [6], such as pitting resistance in NOx environment. To increase the nitrogen content in steels, a lot of work had been done. N. Nakamura and S. Takaki [7] examined the behavior of nitrogen absorption in Fe-23Cr alloy powder by sintering in nitrogen gas atmosphere, they found nitrogen content easily up to 1.0 wt. %. Using devised NH3 gas injection system, W. Park et al. [8] successfully produced austenitic Fe–23.5Cr alloys containing over 3 wt. % of nitrogen. Further-more, W.P. Tong et al. [9] stated that nitrogen percent was extraordinary high (about 10 wt. %) in pure iron plate. However, the above methods are difficult to be applied to large-scale industrial production."

Jan 1, 2012

By P. F. Kerr

This is not a conventional professional paper. It deals mostly with personal experiences. These concern a background in applied mineralogy. Your committee asked me to do this. I accepted with a California enthusiasm which has since diminished with the approach of a Chicago winter. Nevertheless, I wish to thank your committee and also to apologize in advance for omissions and inadequate statements, as such a paper must possess. My introduction to applied mineralogy took place in 1922 at Stanford University. Physicists had recently demonstrated that crystalline powders would reflect x-rays in a systematic manner. Professor A.F. Rogers sug¬gested that significant x-ray reflections might be obtained from powdered opaque minerals. With the aid of Professor D.L. Webster in the Physics Department, I constructed an x-ray diffraction outfit. It was a crude affair, but it worked. Starting with 1924, we secured recognizable patterns of a goodly number of ore minerals (1,2,3). Today x-ray diffraction outfits are common, and a card system of mineral identification is constantly used.

Jan 1, 1981

By Shinya Otsuka

Activity coefficient of oxygen in sulfide-rich and metal-rich melts in copper-sulfur binary were determined at 1423 and 1523 K by means of a modified coulometric titration technique using the following cell: 0 ( is Cu-S melts) I Zr02 (+Ca0) I air, Pt The activity coefficient values obtained in the present study increase rapidly with sulfur composition in the vicinity of xs = 0.3333. The data obtained for the matte saturated with the metal-rich melts are in good agreement with those obtained by Kuxmann and Benecke, Schmied 1, and Eguchi and Yazawa. Those obtained for the metal-rich melts are in good agreement with the results of Sano and Sakao.

Jan 1, 1983

By Richard S. Dennis

Acid recovery employs ion exchange (I-X) resin as separation media for inorganic acids from dissolved metallic salts by physical adsorption and without the use of chemicals. This technology has been used for years on spent etching and plating liquors to recover acid for reuse in the bath and to reduce waste acid neutralization costs. It is also used for electrolyte treatment to facilitate valuable metal recovery via acidity reduction. TETRA's ccrxr'" I-X contactor has been used successfully for acid separation from its metallic salt counterpart in a simple, continuous operating mode using strong base anion resins. Efficient separation is enhanced by acid reconcentration to nearly its original strength or as high as 14-20%. Continuous treatment also recovers heat to the tankhouse or bath and improves metal quality due to consistent acid quality. Conventional fixed bed ion exchange (I-X) systems are impractical for acid recovery because of complex control design and large resin inventories needed to process very low liquid-to-resin treatment ratios associated with strong acid concentrations.

Jan 1, 1996

By Muhlis Nezihi Saridede, Burak Birol

"Plastic wastes become a huge problem day after day due to the growth of plastic industry. Hence, plastic wastes are used as a raw material for other industries to eliminate this problem. Polyethylene Terephthalate (PET), which is a commonly used for plastic bottles, may be used as a reductant for iron production because of its C and H content. In this study, composite pellets containing iron ore concentrate, flux and reductant were prepared. Crystallized PET bottles and coke were used as reductant after ground. The prepared pellets were reduced at 1400°C for 30 min. and iron nuggets were produced successfully. Usage of waste PET purely as reductant in composite pellets gives a higher metallization degree and proper carbon content than coke or PET and coke mixture.IntroductionPlastics can be seen everywhere, especially at packaging industry in our common life. The increase of plastic usage ends up with an important problem, the increase of plastic wastes. Many studies have been carried out about usage of plastics as reductant in blast furnace such as Ogaki et al.[1], Heo and Baek [2], Saridede [3], Minoru et al.[4], etc. Besides, Kato et al. [5], Nomura and Kato [ 6] and Rongfang et al. [7] have pointed out the use of plastics in coke ovens regarding to its calorific content. In EAF steelmaking, a mixture of coal/coke and plastics can be used as an energy resource instead of only coal or coke. [8] Also, the usage of PET and PC in self-reducing composite pellets increased the reduction rate. [12]PET (Polyethylene terephthalate ), which is commonly used for soft drink plastic bottles, is an important municipal waste due to its C and H content. Its molecular formula is (C10H8O 4)n. Demir and Dincer showed that PET can be crystallized at 250°C to have the ability to be ground to a size of -100 µm. [11]"

Jan 1, 2011

By Robert E. Moore

Renewed interest in olivine refractories has led to efforts to characterize them employing modern techniques of experimentation and data analysis. Initial studies have focused on determination of physical and thermophysical properties. Special equipment for the determination of thermal shock resistance and creep behavior have been constructed. Optimal compositions for maximizing various properties are being identified using appropriate statistical techniques. The overall goal is to develop response surfaces for each of a selected group of engineering design and use properties. Development of ?olivine Refractories? in the United States The term "olivine refractories" is used here because it does appear that domestic deposits of this rock will be the focus of renewed interest and "olivinell is the preferred term in this country. There are extensive deposits of high quality olivines extending through parts of Georgia. North Carolina and in the state of Washington. The eastern olivines are much more localized and extensively altered compared to the western materials. The Washington olivines exist as massive rock deposits in the Twin Sisters mountain area northeast of Seattle and their inaccessi-bility has slowed efforts to develop them. The North Carolina olivines have been used in steel plant applications since the 1930's. Geologists use the term "olivine" to describe assemblages of ortho-silicates. 2RO.SiO2, wherein the RO may be MgO. FeO. MnO. etc. When the RO consists essentlally of MgO and FeO. the material is called dunite and. as such, is synonymous with "refractory olivine." Refractory olivines utilizing North Carolina materials were developed for brick products by Birch and Harvey in this country around the mid-1930's. (I) Their work was completely independent of that of V. M. Goldschmidt and co-workers who used massive dunites located in Denmark. (2) These deposits are currently being mined by A/S Olivine of Denmark for the manufacture of a rather complete line of brick shapes for use in steel-plant. glassplant. and cement kiln applications. Birch and Goldschmidt

Jan 1, 1982

By Takeshi Azakami

By combining the iron reduction process with the usual rotary kiln process, the direct production of metallic zinc from EAF dust is proposed. After thermodynamic estimation and desk-top experiments it is confirmed that the process is hopeful under suitable conditions. In order to get some practical test data the enlargement of the process scale was planned and the bench scale tests were carried on successfully. In these experiments a zinc ingot of PW grade was produced from EAF dust.

Jan 1, 2003

By Helena Byrdziak

Polish Copper Industry, located in the Lepica-Glogów region and operated since the 1970's, includes four mines and two smelters, "Legnica" and "Glogów", the latter consisting of "Glogów" I" and "Glogów II" both having different technologies. The "Legnica" and the "Glogów I" smelters using shaft furnaces, so sulfur elimination largely takes place during batchwise converting, resulting in fluctuation SO2-concentration between less than 1% up to 10% in the converter pas W the sulfuric acid plants. The ensuing difficulties of the past have now largely been overcome. Introduction of flash smelting at "Glogów II" with subsequent acid making by double SO2-conversion from the stable process gas, contributed significantly to further reduction Of SO2-emission. In 1994 a new double conversion sulfuric acid plant was installed at "Glogów l" as well as a "Solinox" desulfurisation plant at "Legnica", further reducing SO2 emission considerably, The next step towards this goal under consideration is a semi-dry desulfurization system for the "Glogów I" power station, SO2- abatement measures by KGHM and the results thereby achieved are presented.

Jan 1, 1996

By Grigore Matei

The thermodynamic properties of CU2S-FeS system are important not only in the case of copper smelting but also in the case of general pyro-mctallurgy, However there are not many reported activity data In this study, activities of FeS and CU2S in the CU2S-FeS system were calculated using the Darken's method from the activity data of the CU2S-FeS-Sb2SJ systems measured by the transportation method at 10S0°C. The activities of CU2S and FeS in the CU2S-FeS system showed negative deviation from the ideal behaviour and satisfied the relation of the Gibbs-Duhem equation,

Jan 1, 2003

By Fernando Castro

Electric furnace steelmaking dust is a polluting residue that needs to be treated in order to recover metals contained and to produce an environmentally acceptable residue. Some hydrometallurgical approaches for its treatment have been evaluated, namely: caustic soda leaching followed by electrolytic recovery of zinc, ammonia leaching followed by zinc compounds precipitation and acetic acid leaching followed by lead, zinc hydroxide and gypsum precipitation.

Jan 1, 1992

By Satian Niltawach

Iron sulphate jarosite through which iron in zinc sulphide concentrate feed is removed from the production circuit of conventional roast-leach-electrowin process, is chemically unstable and environmentally hazardous even if it is mixed with lime. If zinc silicate ore is used at similar chemical conditions in place of calcine in the jarosite precipitation, the resultant silico-jarosite residue having been mixed with lime is chemically stable and environmentally friendly. The recovery of zinc from silicate ore is also higher than that from calcine.

Jan 1, 1994

By N. B. Gray, I. F. Taylor

"Gas injection to promote chemical reactions or mixing is a feature of many metallurgical processes. Often the aim of gas injection is to bring about a chemical reaction between the gas and liquid but most of the past physical and mathematical modelling work has ignored the influence of such reactions. In the work reported here, cold model studies have been conducted in which gas reacts with the liquid into which it was injected. The rate of liquid mixing has been measured as an indication of the mechanical energy transfer. It has been found that gas generated chemically within the liquid is significantly less effective at promoting mixing than the equivalent volume of inert gas. The relative ineffectiveness of chemically produced gas is thought to be due to smaller bubble sizes in comparison to the inert gas case. Small bubbles characteristic of chemically generated gas move with low slip velocities relative to the liquid and lead to different turbulence generation mechanisms.IntroductionIn processes such as steelmaking, copper conversion, bath smelting and ladle steel finishing gas is injected into liquid metal where it reacts chemically or simply serves as a source of agitation. An understanding of fluid flow phenomena in such situations is an essential pre-requisite to the calculation of process intensity and the optimisation of vessel productivity. Traditional physical cold modelling approaches to prediction of liquid flow in such situations are now often augmented by the techniques of computational fluid dynamics. Even with the availability of numerical modelling techniques cold physical models continue to have an important role for validation because it is generally difficult to obtain quantitative data from high temperature processes.Almost all previous cold modelling work has been based on the injection of an inert gas into water or some other non-reactive liquid. Such models do not include the significant increase in gas volume inherent in some processes. For example the oxidation of carbon in steelmaking leads to a twofold increase in molar gas flux through the reaction:"

Jan 1, 1996

By Chao Li, Lim Hongxu, Yuyue Wang, Xie Yang

"A intergrated process of sulfuric acid leaching, sodium chloride leaching, lead chloride crystallization, lead hydroxide synthesis and roasting was carried out for the recovery of lead, cadmium, copper and zinc from lead smelting dust containing various metals. The results showed that the separation of cadmium, zinc and copper from dust could be obtained after sulfuric acid leaching and corresponding leaching rate were 92.12%, 90.25% and 88.26% respectively. The subsequent sodium chloride leaching carried out for lead with optimized parameters as: sodium chloride concentration 250g/L, leaching temperature 90°C, leaching time 2h, pulp density 33g/L, 0.12mol/L CaCh; The lead compounds crystallization rate reached 86.67%, and then transferred into mPbO·nH2O, the product of 98.66% ß-PbO could be obtained through roasting under 502°C. In the end, a feasible method of ß-PbO preparation from lead containing dust was put forward.IntroductionThe pyro-metallurgy flue dust from smelting lead activities are often stockpiled and pose potential environmental risks due to the heavy toxic elements, such as Pb, Cd, As, Cu, Cl, and Zn which are contained in the dust. With the rapid depletion of rich ore resources in recent years, it has become increasingly more financially attractive to recover valuable metals from previously stockpiled dust, while simultaneously reducing the potential of environmental pollution from toxic elements contained in the dust. Nowadays, pyro-metallurgical and hydrometallurgical routes or both combined methods can be developed to treat secondary materials such as lead ash, leach residues etc. By comparison the hydrometallurgical processes are often considered more eco-friendly.Some chloride leaching processes for recovering lead have been employed using either NaCl, or MgC2 and CaCl2, or FeCl3 [1] The effectiveness of the brine leaching method is based on the formation of complex metal chlorides in concentrated chloride solutions [2] Similarly, Other metals such as zinc, cadmium and copper contained in the flue dust are often treated with sulfuric acid, hydrochloric acid, ammonium solution and sodium hydroxide etc. as lixiviants [3] The metals from leach solutions thus has been obtained by precipitation, ion exchange, solvent extraction or replacement [4]"

Jan 1, 2014

By Florian Aurelian, Mihai Popescu

"It will be tested four types of “geochemical barriers”. All those mixtures were contacted with mine waters containing uranium, radium and heavy metals. The loading capacity was determined. The optimum mixture was determined and its efficiency was tested within an uranium areal, where the activity was stopped. It was determined the possibility to recover the radioactive elements and the heavy metals from the investigated barriers.IntroductionThe paper presents the results concerning the performances of some “geochemical barriers” used for the decontamination of mine waters from uranium mining sites, which were tested in lab and in situ.ExperimentalThe research activity was carried out in lab and on the site.In the lab a module was constructed in order to follow up the uptake capacity of the “permeable reactive geochemical barriers” used to remove the radiolelements from the contaminated waters originated from the uranium mining industry. The barriers, which were used, are made of cheap natural materials, which can be easily got (wood chips, peat coal, sawdust, iron span, steel and zeolitic tuff). The following types of barriers were tested:•, 1st barrier: peat coal, sawdust, zeolite on weight ratio of 1/1/1;•, 2nd barrier: bentonite, sand, wood chips, peat coal on weight ratio of 1/1/1/1;•, 3rd barrier: iron span, steel, sawdust, peat coal on weight ratio of 2/1/1;•, 4th barrier: iron span, steel, sand, firry wood chips on weight ratio of 1/1/1.Lab researches concerning the uranium uptake capacity of the above described “reactive barriers” pointed out that the 3rd mixture (iron span, steel, sawdust, peat coal on a ratio of 2/1/1) didn’t reach the maximum uranium uptake capacity not even after eleven contact stages (the uptake capacity being of 70.6 mg U/ kg of mixture) and the mixture of peat coal, sawdust and zeolite has an uranium uptake capacity of 26.6 mg U/kg of mixture and becomes saturated after four contact stages.Each one of the components involved in physical-chemical processes of sorption, reduction and precipitation, will determine the diminution of uranium and other metals contents upstream the permeable reactive barrier."

Jan 1, 2008

By Chetan P. Malhotra

This paper describes an online control system and simulation environment for reheating furnaces. The system can be configured for implementing manual control as well as automatic control using either look-up tables or online model predictions. The simulator is also used for offline generation of optimized normal operation and delay setpoints for look-up tables and generating ideal heating curves for model-based control. Finally, it is employed to compare the performance of the above control strategies over a typical period of operation of a pusher-type reheating furnace. Keywords: Reheating furnace, control strategy, model-based control

Jan 1, 2003

By Helfried Nafe

"For about a century thermodynamically absurd facts have been propagated in conjunction with the iron-carbon phase diagram. These facts concern fundamental relationships of chemical thermodynamics. Attention is turned here to the discussion of only one of the relevant aspects of the subject, i.e. the definition of the thermodynamic activity of the solute and its implications for the iron-carbon solution.IntroductionThe view on the iron-carbon solution is characterized by the assumption that the solute may appear in two different forms, i.e. graphite and cementite. Accordingly, two carbon solubilities are differentiated, on the one hand for graphite and, on the other hand, for cementite. As a consequence, two versions of the phase diagram exist simultaneously, the application of which depends on the prevailing conditions, (i) the so-called stable phase diagram with graphite as solute and (ii) the metastable one that is based on the cementite-in-iron solution. These diagrams are joined together in the double phase diagram that originates from Heyn [l ], with the first ideas mainly going back to Stansfield [2] and Charpy [3].Thermodynamically, the most inadequate implication of the Fe-C double phase diagram is that the carbon activity may take values larger than unity. With the standard state of the activity being that of the pure substance, i.e. the Raoultian one, such a value implies the nonsensical existence ofa state purer than pure. The explanation of this physical state, ifthere is any, vaguely refers to supersaturation and, in the wider sense, to the physico-chemical phenomenon of metastability. Other aspects of chemical thermodynamics are likewise involved. Therefore, the comprehensive investigation into the present subject requires more topics to be considered than only one separate issue. Not only should the criticism of the present view be in the focus but also the discussion of new ideas capable of reconciling the experimental facts, known about the F e-C system, with the fundaments of chemical thermodynamics. All this, however, cannot be provided here because of the limited space available. As a consequence, in what follows only a part of the whole problem is under scrutiny, i.e. the definition of the thermodynamic activity and its role for the interpretation ofrelevant experimental facts."

Jan 1, 2014