Chlorination Kinetics of Titanium Nitride for Production of Titanium Tetrachloride from Nitrided Ilmenite

The kinetics of chlorination of titanium nitride (TiN) was investigated in the temperature range of 523 K to 673 K (250 °C to 400 °C). The results showed that the extent of chlorination slightly increased with increasing temperature and decreasing particle size of titanium nitride at constant flow rate of N₂-Cl₂ gas mixture. At 523 K (250 °C), the extent of chlorination was 85.6 pct in 60 minutes whereas at 673 K (400 °C), it was 97.7 pct investigated by weight loss measurement and confirmed by ICP analyses. The experimental results indicated that a shrinking unreacted core model with mixed-control mechanism governed the chlorination rate. It was observed that the surface chemical reaction of chlorine gas on the surface of TiN particles was rate controlling in the initial stage and, during later stage, internal (pore) diffusion through the intermediate product layer was rate controlling step. Overall the process follows the mixed-control model incorporating both chemical reaction and internal diffusion control. The activation energy for the chlorination of TiN was found to be about 10.97 kJ mol^?1. In processing TiCl₄ from TiN and TiO_0.02C_0.13N_0.85, the solids involved in the chlorination process were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM) and Energy-dispersive X-ray spectrometer (EDX). The SEM/EDX results demonstrated the consumption of TiN particles with extent of chlorination that showed shrinking core behavior.     

Intrinsic Kinetics of Chlorination of WO<Subscript>3</Subscript> Particles With Cl<Subscript>2</Subscript> Gas Between 973 K and 1223 K (700 °C and 950 °C)

Chlorination is one of the methods applied in extractive metallurgy for the treatment of minerals to obtain valuable metals, such as titanium and zirconium. The possibility of applying chlorination metallurgy to other metals such as tungsten was the major aim of this study. The kinetics of the chlorination of tungsten oxide (WO₃) particles has been investigated by thermogravimetry between 973 K and 1223 K (700 °C and 950 °C) and for partial pressures of chlorine ranging from 15 to 70 kPa. The starting temperature for the reaction of WO₃ with chlorine is determined to be about 920 K (647 °C). The influence of chlorine diffusion through the bulk gas phase and through the particle interstices in the overall rate was analyzed. In the absence of these two mass-transfer steps, a reaction order of 0.5 with respect to chlorine partial pressure, and an activation energy of 183 kJ/mol were determined. For tungsten oxide particles of less than 50-μm size, a complete rate expression has been obtained.     

Stability of Ni3(Al,Ti) Gamma Prime Precipitates in a Nickel-Based Superalloy Inconel X-750 Under Heavy Ion Irradiation

Phase stability of Ni₃(Al, Ti) precipitates in Inconel X-750 under cascade damage was studied using heavy ion irradiation with transmission electron microscope (TEM) in situ observations. From 333 K to 673 K (60 °C to 400 °C), ordered Ni₃(Al, Ti) precipitates became completely disordered at low irradiation dose of 0.06 displacement per atom (dpa). At higher dose, a trend of precipitate dissolution occurring under disordered state was observed, which is due to the ballistic mixing effect by irradiation. However, at temperatures greater than 773 K (500 °C), the precipitates stayed ordered up to 5.4 dpa, supporting the view that irradiation-induced disordering/dissolution and thermal recovery reach a balance between 673 K and 773 K (400 °C and 500 °C). Effects of Ti/Al ratio and irradiation dose rate are also discussed.     

Chlorination of hafnium dioxide by gaseous chlorine in the presence of carbon

The thermodynamic simulation of chlorination of hafnium oxide by gaseous chlorine in the presence of carbon at T = 450–1000°C is performed. It is shown that the main reaction products are gaseous hafnium tetrachloride, carbon monoxide, and carbon dioxide; as the temperature increases, the partial pressure of CO increases, while that of CO₂ decreases. In the mentioned temperature range, the variations in the enthalpy, entropy, and the Gibbs energy of chlorination reactions are calculated and the composition of the gas phase under the conditions of thermodynamic equilibrium is determined. In the course of studying the kinetics of chlorination of HfO₂ in the presence of carbon in the range T = 600–950°C, it is established that its limiting stage depends on the process temperature. Below 700°C, its rate is limited by the chemical reaction on the surface of nonporous solid spherical particles of the body with the formation of the volatile product; above 700°C, it is limited by the mass transfer of gaseous substances.     

High-Temperature Mechanical Behavior of Extruded Mg-Y-Zn Alloy Containing LPSO Phases

The high-temperature mechanical behavior of extruded Mg_97?3x Y_2x Zn _x (at. pct) alloys is evaluated from 473 K to 673 K (200 °C to 400 °C). The microstructure of the extruded alloys is characterized by Long Period Stacking Ordered structure (LPSO) elongated particles within the magnesium matrix. At low temperature and high strain rates, their creep behavior shows a high stress exponent (n = 11) and high activation energy. Alloys behave as a metal matrix composite where the magnesium matrix transfers part of its load to the LPSO phase. At high-temperature and/or low stresses, creep is controlled by nonbasal dislocation slip. At intermediate and high strain rates at 673 K (400 °C) and at intermediate strain rates between 623 K and 673 K (350 °C and 400 °C), the extruded alloys show superplastic deformation with elongations to failure higher than 200 pct. Cracking of coarse LPSO second-phase particles and their subsequent distribution in the magnesium matrix take place during superplastic deformation, preventing magnesium grain growth.     

Chlorination kinetics of ZnO with Ar-Cl2-O2 gas and the effect of oxychloride formation

The chlorination rate of ZnO with Ar-Cl₂-O₂ gas was measured from 1023 K to 1273 K and the effects of temperature and partial pressures of chlorine and oxygen were investigated. The rate-determining step of chlorination was considered to be the dissociation of intermediate between ZnO and Cl₂ from linear relationship between reciprocal values of reaction rate and partial pressure of chlorine. The activation energy of chlorination was 58.2±2.5 kJ/mol. This comparatively low activation energy as a chemically controlled reaction was consistent with estimated rate-determining step of the dissociation of unstable compound. Increasing the partial pressure of oxygen slightly increased the chlorination rate, and this effect is considered to be caused by the increase in the formation rate of zinc oxychloride. To clarify the formation of zinc oxychloride, the equilibrium between Ar-Cl₂-O₂ gas and ZnO was investigated by the transpiration method at 1073 K. Calculated partial pressures of ZnOCl from experimental results were in the same order with or one order of magnitude larger than those estimated from reported Gibbs energy of formation of ZnOCl. Zinc oxychloride formation in ZnO chlorination must be taken into consideration as well as ZnCl₂ and Zn₂Cl₄ formation.     

Effective Dissolution of Platinum by Using Chloride Salts in Recovery Process

Platinum (Pt) is typically recovered by employing dissolution processes in aqueous solutions; however, these processes require a long processing time and considerable quantities of acids with strong oxidants owing to the high chemical stability of Pt. In order to develop an efficient dissolution process, we studied chlorination treatments for Pt prior to dissolution. Chlorination was carried out at 673?K to 873?K (400?°C to 600?°C) using copper(II) chloride (CuCl₂) as a chlorine source. While pure Pt was insoluble in hydrochloric acid (HCl(aq)), the entire Pt component of the treated sample dissolved in HCl(aq) under certain conditions. Therefore, the proposed method can be used as a new, environmental friendly Pt recovery process.     

Carbochlorination kinetics of titanium dioxide with carbon and carbon monoxide as reductant

Kinetic study of the chlorination of titanium dioxide (rutile and anatase) was carried out in a fixedbed reactor at temperature ranging from 800 °C to 1000 °C and normal pressure. In our experiment, titanium dioxide powder and gaseous chlorine with carbon or carbon monoxide as reductant were used. The products of the reaction are all in gaseous phase under the temperatures and pressure studied. With CO as reductant, reaction is of noncatalytic gas-solid nature and experimental data fit the shrinking core model. When using C as reductant, solid-solid reaction is involved. Reactivity is highly enhanced by solid carbon and it is concluded that an activated C-TiO₂-Cl complex contributes to the enhanced reactivity. A reaction model based on phase boundary control applies to the experimental data. Thermodynamic analysis supports the experimental observation.     

Volatility Diagrams for the Cr-O and Cr-Cl Systems: Application to Removal of Cr2O3-Rich Passive Films on Stainless Steel

Effective diffusional surface treatments of stainless steels require that the naturally forming Cr₂O₃-rich passive layer be removed to ??activate?? or depassivate the surface. Volatility diagrams can be used to understand the possible etching reactions in the Cr-O and Cr-Cl systems and reveal five effective methods for removal of Cr₂O₃-based passivating films: (1) exposure to acetylene (C₂H₂) at 673?K (400?°C) and higher temperatures (providing sooting is avoided); (2) exposure to atomic hydrogen at 10 to 0.001?kPa (0.1 to 0.0001 bar) at 373?K to 673?K (100?°C to 400?°C); (3) exposure to wet oxygen above 573?K (300?°C), forming the volatile species CrO₂(OH)₂; (4) exposure to gaseous HCl at 100?kPa (1 bar) above 473?K (200?°C); and (5) oxidation of Cr₂O₃ to CrO₃ using ozone or atomic oxygen, followed by exposure of CrO₃ to gaseous H₂ or HCl. The last process takes advantage of the fact that CrO₃ is removed more effectively using gaseous H₂ and HCl than is Cr₂O₃.     

Negative Strain-Rate Sensitivity of Mg Alloys Containing 18R and 14H Long-Period Stacking-Ordered Phases at Intermediate Temperatures

The strain-rate sensitivity of a Mg-10Dy-1Zn (wt pct) alloy containing different long-period stacking-ordered (LPSO) phases has been investigated in the strain rate range of 10^?3 to 1 s^?1 from room temperature to 673 K (400 °C). Both alloys containing 18R-LPSO and 14H-LPSO phases show negative strain-rate sensitivity (–0.02  to –0.01) at intermediate temperatures [423 K to 523 K (150 °C to 250 °C)]. The serration behavior of the Mg-10Dy-1Zn alloy containing 18R-LPSO phase is related to dynamic strain aging. However, the appearance of serrated flow in the Mg-10Dy-1Zn alloy containing 14H-LPSO phase is mostly rooted in the formation of microcracks in \( \left\{ {10\overline{1} 2} \right\} \) planes.     

Reverse Shape Memory Effect Related to α → γ Transformation in a Fe-Mn-Al-Ni Shape Memory Alloy

In this study, we investigated the shape memory behavior and phase transformations of solution-treated Fe_43.61Mn_34.74Al_13.38Ni_8.27 alloy between room temperature and 1173 K (900 °C). This alloy exhibits the reverse shape memory effect resulting from the phase transformation of α (bcc) → γ (fcc) between 673 K and 1073 K (400 °C and 800 °C) in addition to the shape memory effect resulting from the martensitic reverse transformation of γ′ (fcc) → α (bcc) below 673 K (400 °C). There is a high density of hairpin-shaped dislocations in the α phase undergoing the martensitic reverse transformation of γ′ → α. The lath γ phase, which preferentially nucleates and grows in the reversed α phase, has the same crystal orientation with the reverse-transformed γ′ martensite. However, the vermiculate γ phase, which is precipitated in the α phase between lath γ phase, has different crystal orientations. The lath γ phase is beneficial to attaining better reverse shape memory effect than the vermiculate γ phase.     

Microstructure and Mechanical Behavior of Powder Metallurgy Mg98.5Gd1Zn0.5 Alloy

The Mg_98.5Gd₁Zn_0.5 alloy produced by a powder metallurgy route was studied and compared with the same alloy produced by extrusion of ingots. Atomized powders were cold compacted and extruded at 623 K and 673 K (350 °C and 400 °C). The microstructure of extruded materials was characterized by α-Mg grains, and Mg₃Gd and 14H-LPSO particles located at grain boundaries. Grain size decreased from 6.8 μm in the extruded ingot, down to 1.6 μm for powders extruded at 623 K (350 °C). Grain refinement resulted in an increase in mechanical properties at room and high temperatures. Moreover, at high temperatures the PM alloy showed superplasticity at high strain rates, with elongations to failure up to 700 pct.     

Microstructural Changes by Annealing in Ultrafine-Grained Electrodeposited Pure Iron

In situ neutron diffraction during annealing was performed for ultrafine-grained as-deposited and cold-rolled pure iron. Changes in the integrated intensity and full-width at half-maximum in the diffraction profiles during annealing were measured. EBSD measurements were performed before and after annealing to obtain microstructural change. Abnormal grain growth was clearly found at 673 K (400 °C) upon annealing; this observation corresponds to the hydrogen desorption behavior of the as-deposited specimen. The texture changes from {111}〈hkl〉 to {211}〈hkl〉 between 673 K and 873 K (400 °C and 600 °C) upon continuous heating. Such a texture change is postulated to decrease the Lankford value from 7.6 to 2.2. The 40 pct cold-rolled specimen exhibited a complicated textural evolution upon annealing, which was caused by the intrusion of recrystallization at deformation bands.     

Effect of Annealing Temperature on the Thermoelectric Properties of the Bi0.5Sb1.5Te3 Thin Films Prepared by Radio-Frequency Sputtering

The effect of annealing temperature on the crystallinity, thermoelectric properties, and surface morphology of the Bi_0.5Sb_1.5Te₃ thin films prepared on SiO₂/Si substrate by radio-frequency (RF) magnetron sputtering was investigated using X-ray diffraction (XRD), the four-point probe method, and scanning electron microscopy (SEM). XRD results show that the crystallite structure of the Bi _x Sb_2–x Te₃ thin films belong to Bi_0.5Sb_1.5Te₃. When the Bi _x Sb_2–x Te₃ thin films were annealed between 423 K and 523 K (150 °C and 250 °C) for 10  minutes, the crystallinity of the thin films continuously increases with the temperature increase. In addition, the (015) reflection plane as the preferred orientation and the oxidation compound of Bi_3.73Sb_1.5O₃ first appeared when the Bi_0.5Sb_1.5Te₃ thin films were annealed at 523 K (250 °C) for 10 minutes. An activation energy of 51.66 kJ/mol for crystallite growth of Bi_0.5Sb_1.5Te₃ thin films annealed between 423 K and 523 K (150 °C and 250 °C) for 10 minutes was obtained. The resistivity was 2.69 × 10² and 5.93 × 10  μΩ·m, respectively, for the as-deposited Bi_0.5Sb_1.5Te₃ thin films and annealed at 523 K (250 °C) for 10 minutes. The maximum values of the Seebeck coefficient and power factor were 256.5 μV/K and 1.12 × 10³ μW/m·K², respectively, for the Bi_0.5Sb_1.5Te₃ thin films annealing treatment at 523 K (250 °C) for 10 minutes.     

Kinetics of chlorination of tantalum pentoxide in mixture with sucrose carbon by chlorine gas

The mechanism and kinetics of β-Ta₂O₅ chlorination, mixed with sucrose carbon, have been studied by a thermogravimetric technique. The investigated temperature range was 500 °C to 850 °C. The reactants and reaction residues were analyzed by scanning electronic microscopy (SEM), X-ray diffraction (XRD), and Brunauer-Emmett-Teller method for surface area (BET). The effect of various experimental parameters was studied, such as carbon percentage, temperature, chlorine partial pressure, and flow, use of the multiple sample method, and carbon previous oxidation. The carbon percentage and previous treatment have an effect on the system reactivity. The temperature has a marked effect on the reaction rate. In the 500 °C to 600 °C temperature interval, the apparent activation energy is 144 kJ/mol of oxide, while at higher temperatures, the activation energy decreases. With high chorine partial pressures, the order of reaction is near zero. The kinetic contractile plate model, X=kt, considering carbon oxidation as the controlling stage, is the one with the best fit to the experimental data. A probable mechanism for the carbochlorination of β-Ta₂O₅ is proposed: (1) activation of chlorine on the carbon surface, (2) chlorination of Ta₂O₅, (3) oxidation of carbon, and (4) recrystallization of β-Ta₂O₅.     

High temperature chlorination kinetics of a niobium pyrochlore

The chlorination kinetics of a niobium (Cb) pyrochlore has been studied between 1873 and 2223 K, the chlorine concentration in helium varying between 0 and 20 pct. The pyrochlore was subjected to a preliminary thermal treatment at 1473 K in order to remove fluorine which escaped under the form of niobium oxyfluorides. This left NaNbO₃, CaNb₂O₆ and residual refractory oxides. The large chlorination reaction rate difference between NaNbO₃ and CaNb₂O₆ made possible the definition of distinct chlorination reaction rates for these constituents. It was found that the decomposition of CaNb₂O₆ is the controlling step in the chlorination of this constituent, while Nb₂O₅ (NbO₂ + NbO₂ at the prevailing temperatures) chlorination is very fast. The reaction is second order with respect to CaNb₂O₆ concentration and first order with respect to chlorine partial pressure between 1873 and 2023 K, a distinct reaction rate equation being obtained at 2223 K. Reaction rate constants have been calculated and vary between 3 and 10 moleJ.kg ·min for the temperature range considered. The NaNbO₃ reaction rate is first order with respect to total Nb₂O₅ concentration and 2.5 order with respect to chlorine partial pressure for the temperature range covered (1973 to 2223 K). Reaction rate constants are much higher than in the former case, being respectively 148 (1873 K), 214 (2023 K) and 518 (2223 K) mole/kg-min. Reaction orders may be affected by an error varying between 16 and 40 pct. The reaction rate constants are found accurate within 40 pct for CaNb₂O₆ and 25 pct for NaNbO₃.     

Mechanical Performance of Ferritic Martensitic Steels for High Dose Applications in Advanced Nuclear Reactors

Ferritic/martensitic (F/M) steels are considered for core applications and pressure vessels in Generation IV reactors as well as first walls and blankets for fusion reactors. There are significant scientific data on testing and industrial experience in making this class of alloys worldwide. This experience makes F/M steels an attractive candidate. In this article, tensile behavior, fracture toughness and impact property, and creep behavior of the F/M steels under neutron irradiations to high doses with a focus on high Cr content (8 to 12) are reviewed. Tensile properties are very sensitive to irradiation temperature. Increase in yield and tensile strength (hardening) is accompanied with a loss of ductility and starts at very low doses under irradiation. The degradation of mechanical properties is most pronounced at <0.3T _M (T _M is melting temperature) and up to 10 dpa (displacement per atom). Ferritic/martensitic steels exhibit a high fracture toughness after irradiation at all temperatures even below 673 K (400 °C), except when tested at room temperature after irradiations below 673 K (400 °C), which shows a significant reduction in fracture toughness. Creep studies showed that for the range of expected stresses in a reactor environment, the stress exponent is expected to be approximately one and the steady state creep rate in the absence of swelling is usually better than austenitic stainless steels both in terms of the creep rate and the temperature sensitivity of creep. In short, F/M steels show excellent promise for high dose applications in nuclear reactors.     

Acceleration or Suppression of α-Phase Precipitation Using Isothermal ω Phase in Ti-20 at.pct Nb Alloy

Homogeneous precipitation of a fine α phase in the β matrix of Ti alloys is a promising method for obtaining a highly strengthened Ti-based alloy. Isothermal ω particles are known to be the nucleation sites for fine α-phase precipitation, but an understanding of the kinetics of α-phase formation on isothermal ω particles is still lacking. This study aimed to reveal the effect of isothermal ω particles on α-phase precipitation onset time. Two-step isothermal aging of a Ti-20 at.pct Nb alloy after solid solution treatment at 1273 K (1000 °C) was carried out. The first step of the aging at 633 K (360 °C) involved the formation of isothermal ω particles in the β matrix. This was followed by a second aging step at 673 K, 723 K, and 773 K (400 °C, 450 °C, and 500 °C) for α-phase precipitation. Suppression of α-phase nucleation on the isothermal ω particles occurred at 673 K (400 °C), whereas acceleration of α-phase nucleation on the isothermal ω particles was observed at 723 K and 773 K (450 °C and 500 °C). Thermodynamic stability of the isothermal ω particles and solute partitioning were controlling factors for the α-phase precipitation kinetics.