


Nº 6 (2024)
Articles
Corrosion of EP-823 STEEL (16Kh12MVSFBR) under conditions of high-temperature processing of spent nuclear fuel
Resumo
The corrosion behavior of EP-823 steel was studied during high-temperature treatment (HTT) with nitrogen. It was found that in nitrogen at temperatures of 650–800°C, the steel is subject to only slight surface corrosion. It is shown that there is a slight change in the surface composition and structure of steel, which does not have a significant effect on the reprocessing of model SNF. It is shown that on the surface of the material, processes of interaction of some electronegative components of ferritic-martensitic steel with components of the gas phase – nitrogen and impurity oxygen – occur with the formation of inclusions of nitride and oxide compounds of chromium and manganese of different stoichiometric compositions. The process is limited by the diffusion of these components from the volume of the alloy to the surface. The corrosion rates of EP-823 steel at temperatures of 650 and 800 ° C were 0.104 and 0.241 mm / year for 12 hours of exposure, and 0.013 and 0.02 mm/year for 84 hours of exposure, respectively. The nature of the destruction of the surface of the samples is continuous and uneven, localization of corrosion at the boundaries of steel grains is clearly observed, which is associated with the formation of secondary phases along the grain boundaries. At the temperature of the treatment, significant sensitization of steel occurs, chain-like precipitation of secondary phases is observed along the grain boundaries, which leads to the development of intercrystalline corrosion. Conclusions are made about the change in the structure of the material during high-temperature exposure and the nature of the corrosion damage of the material is determined; based on the results of X-ray fluorescence analysis, conclusions are made about the composition of the corrosion products of EP-823 steel.



Thermal stability and electrophysical properties of oxide tungsten bronzes produced by electrolysis of melts
Resumo
Oxide tungsten bronzes (OTB) of cubic, tetragonal and hexagonal structure were electrodeposited under galvanostatic conditions. Electrolysis of polytungstate melts 0.8Na2WO4–0.2WO3, 0.25Na2WO4–0.25K2WO4–0.5WO3 and 0.1K2WO4–0.55Li2WO4–0.35WO3 was performed at a temperature of 973 K and a cathode current density of 25 mA cm–2 for 20 min. The synthesized OTB powders were studied by X-ray diffraction analysis, laser diffraction, and scanning electron microscopy coupled with energy dispersive spectroscopy. To determine the upper limit of the thermal stability range, the phase composition of OTB powders with an average particle size of 40–50 μm was studied after isothermal annealing at 373–1173 K for 2 h in an air or argon atmosphere. OTB powders with a tetragonal structure were additionally studied by synchronous thermal analysis. The electrical resistance of the samples sintered at 473 K was measured in air using direct and alternating current. It has been established that the most stable are the hexagonal OTBs isostructural to K0.3WO3, since their phase composition does not change up to 773 K during heat treatment in air and remains constant over the entire studied temperature range in an inert atmosphere. Tetragonal OTB powders isostructural to K0.475WO3 and Na0.28WO3 are stable up to 1073 K in argon and partially oxidize in air above 673 K to form OTBs with lower alkali metal content, WO3 and Na2W2O7. The phase composition of cubic OTB isostructural to Na0.74WO3, is stable up to 673 K in air and up to 873 K in argon. Conductivity studies of all samples indicate mixed ion-electron conductivity with a predominance of the electronic component. Аt 298–573 K, the specific electrical conductivity values vary within the range of 0.035–0.051, 0.012–0.030 and 0.005–0.019 (Ohm⋅cm)–1 for the OTB samples of tetragonal, cubic and hexagonal structures, respectively.



Chlorinated graphite as positive electrode for aluminium-ion batteries with 1-ethyl-3-methylimidazolium chloride/aluminium chloride electrolyte
Resumo
The article defines the dependence type of the cathode polarization of an aluminum-ion battery based on chlorinated graphite of the initial EC-02 type in a low-temperature melt of aluminum chloride with 1-ethyl-3-methylimidazole chloride on the geometric characteristics of the electrode and the current density. It is determined that for the chlorinated graphite material the polarization values are slightly reduced compared to the initial non-chlorinated graphite of the same brand in a similar melt and are 25–50 mV at 1 mA/cm2. The dependence of polarization on the current density does not have a break between the values of 1 and 1.2 mA/cm2, observed for initial graphite, which characterizes the maximum rate of the current-generating reaction, which means an increase in the rate of the main process on the chlorinated graphite. Using a reference experiment on a glassy carbon electrode, the surficial density of chloroaluminate complexes intercalation sites was estimated as about 15%. Accordingly, the maximum degree of intercalation for such materials is 6. Since graphite chlorination does not lead to distortions geometric parameters of its interlayer gaps, the sorption density of chloroaluminate ions is found to increase after chlorination; in the case of non-chlorinated graphite, the degree of intercalation varies with current density from 9 to 18.



Cluster structure of nickel and its alloys with chromium in the liquid state
Resumo
Modern ideas about the structure of liquid metals and alloys are considered. The main emphasis is placed on the cluster model and its structural parameters. The effect of chromium concentration in nickel-chromium melts on the change in the parameters of the cluster structure is shown. The calculation results are compared with the previously obtained experimental X-ray diffraction data and the results of studying the temperature dependences of the physical properties of nickel and its alloys with chromium in the liquid state. Attention is drawn to the fact that at a temperature close to 1900ºС the cluster radius becomes less than 10 Ǻ and these are the critical temperatures characteristic of binary and multicomponent nickel melts, upon reaching which structural changes occur in the melts and the metallic liquid becomes more equilibrium. and microhomogeneous.



Study of kinematic viscosity and specific electrical resistance of wear-resistant cast irons IChKh28N2 and ICh300Kh25F4 in liquid state
Resumo
The results of an experimental study of the temperature dependences of the kinematic viscosity and specific electrical resistance of wear-resistant cast irons ИЧХ28Н2 and ICh300Kh25F4 in the liquid state are presented. The kinematic viscosity was determined by the method of damped torsional oscillations of a crucible with a melt. Specific electrical resistance was measured by the rotating magnetic field method. The measurements were carried out in the mode of two successive heatings of the samples from 1300 to 1650°C. After the first measurement, the sample was crystallized and cooled to a temperature of 25 °C at a rate of 1 °C/s. The second measurement was carried out without removing the sample from the laboratory setup and changing the atmosphere. The results of measuring the temperature dependences of kinematic viscosity and specific electrical resistance are discussed in the context of the concept of the microheterogeneous structure of liquid cast irons. Hysteresis of the temperature dependences of viscosity and electrical resistance obtained during the first heating of the samples to 1550°С was detected, which serves as indirect evidence of the destruction of microheterogeneities. The absence of hysteresis during the second heating of the sample after crystallization confirms the irreversible nature of the destruction of microheterogeneities. A conclusion is made on the recommended mode of high-temperature melt treatment (HTMT) of wear-resistant cast irons, which involves heating the melt to 1550°С. Heating of liquid wear-resistant cast irons IChKh28N2 and ICh300Kh25F4 to 1550°С leads to the destruction of micro-inhomogeneities, as a result of which, upon subsequent cooling and crystallization, an improved microstructure of the ingot is formed.



Kinetics of electroreduction of fluorozirconates in fluoride melts
Resumo
At present, the demand for aluminum alloys, including those with zirconium additives, is growing significantly. One of the methods for producing such alloys is the reduction of alkali and alkaline earth metal fluorozirconates in molten salts; this method is characterized by a high degree of extraction and process intensity. According to scientific and technical literature, the use of electrolysis can contribute to increasing the efficiency of such processes, in connection with which, it is relevant to study the electrochemical behavior of fluorozirconates in molten media. Using the cyclic chronovoltammetry method, some patterns of electroreduction of zirconium and aluminum from a low-melting melt of KF–AlF3–Al2O3–ZrO2 at a temperature of 750°C were studied, depending on the composition of the additive and the substrate material. A series of polarization curves were obtained, both in a pure melt and with additives of potassium fluorozirconate, at potential sweep rates from 0.01 to 2 V. It was shown that cathode currents of aluminum electrolysis appear at potentials of –1.6…–1.7 V, relative to the potential of the CO/CO2 electrode, and a further shift of the potential to the cathode region leads to the joint release of aluminum and potassium. When K2ZrF6 is introduced into the KF-AlF3-Al2O3 melt, a discharge area of zirconium ions appears on the cathode branch of the voltammograms at potentials of –1.4 and –1.6 V. When comparing the voltammograms obtained with the addition of zirconium oxide and potassium fluorozirconate under otherwise equal conditions, it was found that when the oxide is added, two inflections are observed on the cathode branch of the voltammograms at potentials of –1.4 and –1.7 V, while only one inflection is observed at a potential of –1.3 V upon reduction of fluorozirconate. The presence of two responses when introducing the oxide can be caused by both the electrolysis of elemental zirconium in two electrochemical stages and the discharge of zirconium-containing ions of different composition. Analysis of the diffraction patterns of the melts shows that, regardless of the composition of the additive, both potassium fluorozirconate and zirconium oxide can be present in the melt. Based on the data obtained, it can be concluded that zirconium can either discharge in several stages or form a number of intermediate compounds when interacting with the components of the melt.



Kinetics of electroreduction of zirconates on tungsten in fluoride melts
Resumo
Aluminum alloys with zirconium additives are increasingly used in the aerospace industry, instrument making and power engineering, due to the combination of increased corrosion and thermal resistance without compromising density and electrical conductivity. A promising method for producing such alloys is synthesis in molten fluorides of alkali and alkaline earth metals, using oxides as a consumable metal-containing component. According to existing scientific and technical data, the use of electrolysis can contribute to an increase in the efficiency of reducing zirconium oxide to metallic oxide, in connection with which, the study of the electrochemical behavior of zirconium ions in fluoride melts is relevant. The method of cyclic chronovoltammetry was used to study the main regularities of cathodic electroreduction of zirconium and aluminum ions from melts based on KF–AlF3 with additives of zirconium and aluminum oxides at a temperature of 750°C on a tungsten cathode. A series of polarization curves were obtained both in a pure melt and with additives of zirconium and aluminum oxides at potential scan rates from 0.1 to 2 V. It was shown that the discharge of aluminum ions is observed more negative than the potential of –1.6 V, and at a potential of –1.8 to –1.9 V, the Al peak corresponding to the reduction of aluminum ions is formed. In the region of potentials more positive than –1.6 V, the cathodic process AlxWy is also observed, presumably associated with the reduction of aluminum ions and the formation of its intermetallic compounds with tungsten. When ZrO2 is added to the melt under study, the voltammograms additionally show a Zr platform and an Al+Zr peak at potentials of –1.3 and –1.6 V, associated with the discharge of zirconium ions and the combined discharge of zirconium and aluminum ions, respectively. When scanning the potential to the anodic region, the Al’ peak is observed at a potential of about –1.6 V and the Al’ and Zr’ waves, associated with the oxidation of metallic aluminum and aluminum with zirconium from the intermetallic compound, respectively. For the tungsten electrode, an increase in the current densities of the Al+Zr peak and a potential shift with an increase in the potential scanning rate are expectedly observed, which indicates the electrochemical irreversibility of the process under study.



Preparation of dilute solutions of rare earth metal trichlorides by chlorination of their oxides in a molten NaCl-KCl equimolar mixture
Resumo
The article is devoted to the study and thermodynamic justification of the method for obtaining dilute solutions of rare earth metal trichlorides by chlorination of their oxides in a molten equimolar mixture of NaCl – KCl. And the effectiveness of this method is demonstrated by the example of lanthanum (III) and neodymium (III) oxides. Gibbs free energy of the reactions of La2O3 and Nd2O3 chlorination by different chlorinating agents has been calculated. The interaction of lanthanum (III) and neodymium (III) oxides in the molten equimolar mixture NaCl – KCl depending on the chlorination time and the material of reaction vessel (beryllium oxide and glass-carbon) has been studied experimentally. The results of thermodynamic modelling of the chlorination reactions of La2O3 and Nd2O3 by gaseous chlorine in this salt melt are presented. In the case of using a molten equimolar mixture of NaCl – KCl, a significant shift of the Gibbs energy to the negative region is observed compared with chlorination without the use of a salt medium. The effectiveness of chlorine as a chlorinating agent in the melt is based on the fact that in liquid NaCl-KCl Ln3+ ions form complexes with very small activity coefficient. The removal of synthesized lanthanum trichloride from the chlorination reaction zone due to its solubility in a low-viscosity NaCl-KCl melt has a beneficial effect on the rate of its flow. It has been shown that the formation of rare earth metal trichlorides occurs through the formation of LaOCl and NdOCl oxychlorides. The advantages of the proposed method of chlorination of rare earth metal oxides (REM) in the synthesis of solutions of their trichlorides in molten salts are shown.



Solubility of rare earth oxides in chloride, chloride-fluoride and fluoride melts of alkali and alkaline earth metals
Resumo
This paper presents a review of data on the solubility of rare earth oxides in halide melts of alkali and alkaline earth metals. The highest solubility of rare earth oxides is observed in fluoride melts, the lowest – in chloride melts. There are very few works devoted to the study of the solubility of rare earth oxides in mixed chloride-fluoride melts. The solubility of rare earth oxides decreases in the series La-Ce-Pr-Nd-Gd. The greatest number of works are devoted to the study of the solubility of neodymium, lanthanum and cerium oxides. There are practically no data on the solubility of “heavy” rare earth oxides (from Tb to Lu) in halide melts.



On the anniversary of Zakiryanova I.D.



In memory of Krasikov S.A.


