High-Temperature Corrosion Behavior of Superalloys in Molten Salts – A Review

The use of molten salts based on fluorides/chlorides/nitrates/sulfates or carbonates is now an accepted practice in energy conversion technologies and many other industrial processes. However, compatibility of molten salts with the structural alloys and materials corrosion has been of real concern at such temperatures (600–900°C). Hence, the material development and corrosion studies turn out to be an essential part of research. The results of recent studies are reviewed to understand the developments that have occurred in the latter part of the last decade. The corrosion kinetics of modern materials in variety of molten salts with focus on reaction mechanisms and corrosion products is investigated by scientists around the globe. Emphasis has also been given on the composition of the oxide films/corrosion products on alloys of interest in wide a range of melts. By and large, molten salt corrosion has been predominantly studied by gravimetric, electrochemical techniques and, morphology and chemical analysis of corrosion products by means of XRD, SEM/EDX, ICP/AAS, etc. This article gives in-depth insight into the composition of materials, the molten salt mixtures, and various aggressive environments mainly high temperatures and long exposures.     

Free energy and electrical resistivity of molten alloys

The free energies of mixing for molten indium-antimony, cadmium-antimony, indium-bismuth, lead-bismuth and tin-bismuth were calculated from the variation of electrical resistivity with composition employing the model of Takeuchi and Endo. Resistivities measured in this laboratory with an electrodeless technique for In-Sb alloys, together with published values for Cd-Sb, In-Bi, Pb-Bi and Sn-Bi alloys were used in the calculations.

Evaluation of the resistivity data gave the composition dependence of the derivatives of the chemical potentials of the constituents and the integral molar free energies of mixing. No assumptions regarding ideal entropy were made to obtain these free energy values although a statistically random mixture of ions is presumed in the scattering model.

Conclusions drawn from a comparison between the calculated free energy values and published thermodynamic data for these systems are discussed in terms of departures from regularity and the variations in the effective free electron concentration.     

Electrical conductivity of molten mixtures of potassium and sodium fluorides with calcium fluoride

The electrical conductivity of molten mixtures of calcium fluoride with sodium and potassium fluorides was investigated by impedance spectroscopy. The calcium fluoride additions to alkali metal fluoride melts decrease their electrical conductivity. Small additions of potassium and sodium fluorides to CaF₂ do not change its conductivity essentially.     

Thermodynamic analysis of the interaction of partially hydrophobic cationic polyelectrolytes with sodium halide salts in water

Isothermal titration calorimetry was used to determine the temperature and concentration dependence of the enthalpy of mixing of 3,3- and 6,6-ionene fluorides, bromides, and iodides with low molecular weight salts (NaF, NaCl, NaBr, and NaI) in water. The magnitudes of the enthalpies, measured in the temperature range from 273 to 318 K, depended on the number of methylene groups on the ionene polyion (hydrophobicity), and on the anion of the added salt (ion-specificity). All enthalpies of mixing of 3,3- and 6,6-ionene fluorides with low molecular weight salts (NaCl, NaBr, and NaI) were negative, which is in contrast to the predictions of standard theories of polyelectrolyte solutions. This fact was interpreted in the light of the ion–water short-range interactions that are not accounted for in those theories. In contrast, the enthalpies of mixing of 3,3- and 6,6-ionene bromides and iodides with NaF were positive, being in accord with theory. Using the calorimetric data, we performed a model thermodynamic analysis of the polyelectrolyte–salt mixing process to obtain changes in the apparent standard Gibbs free energy, enthalpy, entropy, and heat capacity relative to the pure ionene fluorides in water. The results prove that halide ions replace fluoride counterions with a strength increasing in the order chloride < bromide < iodide. The process is enthalpy governed, accompanied by a positive change in the heat capacity.     

Polarization effects in ionic solids and melts

Ionic solids and melts are compounds in which the interactions are dominated by electrostatic effects. However, the polarization of the ions also plays an important role in many respects as has been clarified in recent years thanks to the development of realistic polarizable interaction potentials. After detailing these models, we illustrate the importance of polarization effects on a series of examples concerning the structural properties, such as the stabilization of particular crystal structures or the formation of highly-coordinated multivalent ions in the melts, as well as the dynamic properties such as the diffusion of ionic species. The effects on the structure of molten salt interfaces (with vacuum and electrified metal) is also described. Although most of the results described here concern inorganic compounds (molten fluorides and chlorides, ionic oxides...), the particular case of the room-temperature ionic liquids, a special class of molten salts in which at least one species is organic, will also be briefly discussed to indicate how the ideas gained from the study of ‘simple’ molten salts are being transferred to these more complex systems.     

The influence of pressure on the electrical conductivity of molten zinc chloride and its Mixtures with potassium chloride

Abstract

The electrical conductivities of molten ZnCl₂ and its mixtures with KCl were measured as functions of pressure, temperature, and composition. The measuremkents were performed in an internally heated pressure vessel in which the melts were contained in open quartz glass cells. The addition of KCl to molten ZnCl₂ causes a large increase of the conductivity at all pressures and temperatures. With increasing pressure the conductivity increases in pure molten ZnCl₂ and in mixtures rich in ZnCl₂ and decreases in mixtures with more than 30 mol% of KCl.     

Connecting electronic entropy to empirically accessible electronic properties in high temperature systems

A quantitative theoretical model connecting the thermopower and electronic entropy of molten systems is proposed, the validity of which is tested for semiconductors and metallic materials. The model accurately provides the entropy of mixing for molten semiconductors, as shown for the representative system Te–Tl. Predictions of the electronic entropy of fusion for compounds are in agreement with available data and offer a novel means to identify the correct electrical conductivity model when Hall measurements are not available. Electronic entropy for molten semiconductor and metallic systems is shown to reflect order in the molten and solid state. The model proves accurate at predicting the electronic state entropy contribution to the electronic entropy of mixing.     

Hopping and tunneling transport over a wide temperature range in chemically synthesized doped and undoped polypyrrole

Polypyrrole was synthesized by the chemical oxidation method in the presence of phosphoric acid by varying oxidant to monomer molar ratio for the optimization of electrical conductivity. The conductivity in doped polypyrrole reached up to a maximum value of 9.18 S/cm. Granular morphology was observed in chemically synthesized polypyrrole. Neutralization of doped polypyrrole was done with aqueous ammonium hydroxide and three orders of reduced conductivity were obtained in neutral polypyrrole. Doped and undoped samples of polypyrrole were then electrically characterized over a wide temperature range of 10–300 K. The measured electrical conductivity rises with the increase in temperature and shows the semiconducting nature of the material. Strong and weak temperature dependence of conductivity was revealed by undoped and doped polypyrrole samples respectively. An effort has been made to explore the electrical transport in doped and undoped polypyrrole by charge transport models. The experimental data obeys Kivelson’s hopping model in temperature range of 60–300 K and fluctuation assisted tunneling was the dominant conduction mechanism below 60 K.     

Volumetric and transport properties of <Emphasis Type="Italic">N</Emphasis>-Butyl-<Emphasis Type="Italic">N</Emphasis>-methylpyrrolidinium bis(Trifluoromethanesulfonyl)imide–methanol binary mixtures

Densities, viscosities, and ionic conductivities were measured for the binary mixtures containing the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide and methanol over the entire range of compositions at the temperature varying from 253.15 to 318.15 K. The densities and viscosities decrease monotonously with temperature and the content of ionic liquids (ILs). Furthermore, excess isobaric expansion coefficient has been calculated from the experimental densities. The dependence of temperature on the viscosity has been fitted to the Arrhenius law with high precision. The dependence of temperature on the ionic conductivity has also been gauged by both of the Arrhenius and Vogel–Tamman–Fulcher (VTF) equations. In fact, the shape of the curves shows that the temperature dependence of the conductivity does not follow a simple Arrhenius law, but a better fitting of experimental results is achieved using the VTF model. Additionally, the effects of ILs concentration on the viscosity and the conductivity have been examined using the Walden rule, which shows that the variation of conductivity is inversely proportional to viscosity. Excess molar volumes and viscosity deviations for all mixtures are evaluated and well fitted to the Redlich–Kister polynomial expansions. Physicochemical properties show two clearly distinguished behaviors corresponding to ILs-rich and methanol-rich regions, with distinct transport and volumetric properties. The obtained results are discussed in terms of dipolar interactions and hydrogen bonding establishment between ions of ILs and the methanol molecules.     

Fast ionic transport in Ag<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>TiS<Subscript>2</Subscript>

The enthalpy of the subsystem of silver ions in the intercalation compounds Ag _x TiS₂ has been calculated from the electrochemically measured thermodynamic functions of the silver subsystem. The ionic conductivity and the coupled chemical diffusion coefficients for silver in the intercalation compound have been measured. The activation energy for diffusion of silver ions is determined and the obtained value is interpreted from analyzing the concentration dependence of the enthalpy of the ionic subsystem. The conclusion has been drawn that the high diffusion mobility is associated with the competition between the covalent and elastic interactions, which decreases the activation energy for diffusion of ions.     

Lux-Flood basicity of binary silicate melts

Application of the hybrid polymeric model to depict silicate melt energetics allows to distinguish chemical interaction terms from strain energy contributions. It is thus shown that Lux-Flood basic oxides when admixed with silica in various proportions along simple binaries give rise to purely endothermic effects, while acidic Lux-Flood oxides give rise to athermal mixtures and amphoteric oxides promote both enthalpic and entropic (non-configurational) chemical interactions. The Lux-Flood acid–base character of the various oxides is shown then to be consistent with experimental determinations of nephelauxetic properties of the limiting oxide components in the mean donor ligand field approximation (optical basicity of Duffy and coworkers). The linear proportionality observed between endothermic heat of mixing and optical basicity difference allows to predict the polymerization extent in simple MO–SiO₂ molten systems in a wide T range with reasonable precision.     

Exploratory Studies of Some Molten Potassium Salts by Potassium-39 NMR

Potassium-39 NMR study of K⁺ ion in molten KSCN and some molten salt mixtures show that the resonance frequency is highly dependent on the nature of the counterion and the technique can be used for studying small changes in the environment of the potassium ion in liquid salts and salt mixtures.     

Preparation and characterization of magnetic nanoparticles with controlled magnetization

The effect of molar ratio of two hydrated iron salts used as precursors into a (co)precipitation-based synthesis method, on the composition, size and specific saturation magnetization of mixed iron oxides and oxyhydroxides magnetic nanoparticles as reaction products, was studied. The preparation procedure is based on a salt-assisted solid-state chemical reaction. The obtained products are magnetic multiphase components with the mean size ranging from 3 to 10 nm and specific saturation magnetization between 25 and 95.5 emu/g. The specific saturation magnetization modifies in a non-linear manner as the molar ratio of the iron salts varies. Excepting one sample, for which Fe²⁺/Fe³⁺ molar ratio was zero, all magnetic nanoparticles show a ferrofluid-like behaviour in the colloidal form. The small size, ferrofluid-like behaviour, and controlled specific saturation magnetization allow the use of new synthesized nanoparticles in specific biomedical or industrial applications.     

Prediction of gas tungsten arc welding properties in mixtures ofargon and hydrogen

A theory of gas tungsten arc welding (GTAW) arcs that treats the tungsten electrode, the arc, and the workpiece as a unified system has been applied to make predictions in two dimensions of the temperature distributions in the arc, the tungsten cathode, and the workpiece, for any given arc current and gas mixture. Predictions of arc temperatures, radii, and voltages are compared for argon and mixtures of argon and hydrogen. It is found that arcs in gas mixtures containing hydrogen are more constricted and have a higher maximum temperature and arc voltage than arcs in pure argon. The addition of hydrogen also significantly increases the volume of molten material in the weld pool due to the higher thermal conductivity of argon-hydrogen mixtures at temperatures at which molecules of hydrogen dissociate. Predictions are also compared for workpieces of steel and aluminum. The volume of molten material is very much less for aluminum, despite its lower melting point, because of the higher thermal conductivity of aluminum. Predicted arc voltages as a function of current for a mixture of 10% hydrogen in argon are in good agreement with experimental results     

Electrical conductivity of MgCO3 at high pressures and high temperatures

The electrical conductivity of polycrystalline magnesite (MgCO₃) was measured at 3-6 GPa at high temperatures using complex impedance spectroscopy in a multi-anvil high-pressure apparatus. The electrical conductivity increased with increasing pressure. The activation enthalpy calculated in the temperature range 650-1000 K also increased with increasing pressure. The effect of pressure was interpreted as being the activation volume in the Arrhenius equation, and the fitted data gave an activation energy and volume of 1.76±0.03 eV and −3.95±0.78 cm³/mole, respectively. The negative activation volume and relatively large activation energy observed in this study suggests that the hopping of large polarons is the dominant mechanism for the electrical conductivity over the pressure and temperature range investigated.     

In-situ control of different oxygen fugacity experimental study on the electrical conductivity of lherzolite at high temperature and high pressure

At pressure 1.0-4.0 GPa and temperature 1073-1423 K and under the control of oxygen fugacity (Mo+MoO₂, Fe+FeO and Ni+NiO), a YJ-3000t multi-anvil solid high-temperature and high-pressure apparatus and Solartron-1260 impedance/Gain-Phase analyzer were employed to analyze the electrical conductivity of lherzolite. The experimental results showed that: (1) within the range of the selected frequencies (10³-10⁶ Hz), either as viewed from the relationship between the real or imaginary part of complex impedance and the frequency, or from the relationship between modulus, phase angle and frequency, it can be seen clearly that the complex impedance has a strong dependence on frequency; (2) with the rise of temperature (T), the electrical conductivity (σ) increased, and Lg σ and 1/T follows the Arrhenius relationship; (3) with the rise of pressure, the electrical conductivity decreased, and activation enthalpy and temperature-independent pre-exponential factor decreased as well. And the activation energy and activation bulk volume of the main charge carrier in the lherzolite have been obtained for the first time, which are 1.68±0.02 eV and 0.04±0.01 cm³/mol, respectively; (4) under the given pressure and temperature, the electrical conductivity tends to increase with increasing oxygen fugacity, and under the given pressure, the activation enthalpy and pre-exponential factor tend to decrease with the rise of oxygen fugacity; (5) at 2.0 GPa and the control of the three solid buffers, Mo+MoO₂, Fe+FeO and Ni+NiO, the exponential factors of electrical conductivity variation range with oxygen fugacity are , and the theoretical model for the relationship between the electrical conductivity of lherzolite and the oxygen fugacity under high pressure has been established for the first time; (6) the electrical conduction mechanism of small polarons provides a reasonable explanation to the variation of conductivity of lherzolite with oxygen fugacity.     

Excess molar volumes and isentropic compressibilities of binary liquid mixtures containing n-alkanes at 298.15 K

Excess molar volumes (V ^E) and deviation in isentropic compressibilities (Δβ _s) have been investigated from the density ρ and speed of sound u measurements of six binary liquid mixtures containing n-alkanes over the entire range of composition at 298.15 K. Excess molar volume exhibits inversion in sign in one binary mixture, i.e., n-heptane + n-hexane. Remaining five binary mixtures, n-heptane + toluene, cyclohexane + n-heptane, cyclohexane + n-hexane, toluene + n-hexane and n-decane + n-hexane show negative excess molar volumes over the whole composition range. However, the large negative values of excess molar volume becomes domainant in toluene + n-hexane mixture. Deviation in isentropic compressibility is negative over the whole range of composition in the case of all the six binary mixtures. Existence of specific intermolecular interactions in the mixtures has been analyzed in terms of excess molar volume and deviation in isentropic compressibility.     

Electrical conductivity of the molten EuBr2–MBr binary mixtures (M = Li, Na, K, Rb, or Cs)

The electrical conductivity of all EuBr₂–alkali metal bromide liquid mixtures was measured as function of temperature over the whole composition range. The activation energy, E_A, was evaluated for all liquid mixtures. It was revealed that the classical Arrhenius dependence did not stand for any individual mixture. The obtained results were discussed in terms of complex formation in the melts.     

基于热膨胀性质的ZrO2 固体电解质性能与相关系模型

ZrO₂固体电解质室温下各相的相对含量、高温可相变量是决定材料抗热震性和导电性能的关键因素.固体电解质抗热震性与导电性能的匹配,对低氧含量下的钢水定氧起着重要作用.以此为前提,建立了电解质材料体系的抗热震性与室温相比例之间的线性模型,提出了其高温电导率与相变之间的演化模型.为制备用于测低氧活度的高精度冶金氧传感器提供参考依据.     

Electrical properties of unusual ionic melts

The paper reviews the advances that have been made in recent years in the understanding of electrical transport in fully ionized molten salts, partly dissociated molecular liquids and liquid ionic stoichiometric alloys like CsAu. Special emphasis is placed on the recently observed temperature and pressure induced gradual transition between the limiting cases of molecular insulators and ionic melts. At supercritical temperatures salts undergo a continuous transition from an insulating vapour to a highly conducting ionic fluid if the density is increased sufficiently. This transition is due to a shift of the ionization equilibrium between molecules and ions, in favour of the ions, with increasing density. Poorly conducting molten salts and polar substances like water and ammonia also become more ionic, and consequently better conductors, at very high pressures.

Recent thermodynamic, magnetic and electrical measurements on liquid alloys which are composed of two metallic elements and which are non-metallic at definite stoichiometric compositions are discussed. Special emphasis is placed on the liquid Cs-Au system which resembles in many respects the molten alkalimetal halides.