Correlation Between Viscosity and Electrical Conductivity of Aluminosilicate Melts

The linear relations between logarithm of viscosity and logarithm of electrical conductivity deduced in our previous paper for MO-SiO₂ (M = Mg, Ca, Sr, Ba) and M₂O-SiO₂ (Li, Na, K) melts are extended in this study. It is found that the linear law for MO-SiO₂ system is also followed for the melts of FeO-SiO₂ and MnO-SiO₂ (when electronic conduct can be neglected relative to ionic conduct). The relation between viscosity and electrical conductivity is mainly dependent on the valences of cations of basic oxides. For the $ \sum {{\text{M}}_{x} {\text{O-SiO}}_{2} } $ melt containing several basic oxides, there are two situations: In the case where all cations are divalent (or univalent), the relation is the same as that of MO-SiO₂ melt (or M₂O-SiO₂ melt); in the case of existing both divalent and univalent cations, the coefficients for the linear relation can be calculated based on the coefficients of MO-SiO₂ and M₂O-SiO₂ melts, with the weight factors from the renormalized mole fractions of $ \sum {\text{MO}} $ and $ \sum {{\text{M}}_{ 2} {\text{O}}} $ . It is also found that Al₂O₃ has little effect on the relation, and the law for $ \sum {{\text{M}}_{\text{x}} {\text{O-SiO}}_{ 2} } $ melt can be approximately applied to $ \sum {{\text{M}}_{\text{x}} {\text{O-Al}}_{ 2} {\text{O}}_{ 3} {\text{-SiO}}_{ 2} } $ melt.     

Fabrication and Characterization of Naturally Selected Epitaxial Fe-{111} Y2Ti2O7 Mesoscopic Interfaces: Some Potential Implications to Nano-Oxide Dispersion-Strengthened Steels

The smallest features of ≈2 to 3 nm in nanostructured ferritic alloys (NFA), a variant of oxide dispersion-strengthened steels, include the Y₂Ti₂O₇ complex oxide cubic pyrochlore phase. The interface between the bcc Fe-Cr ferrite matrix and the fcc nanometer-scale Y₂Ti₂O₇ plays a critical role in the stability, strength, and damage tolerance of NFA. To complement other characterization studies of the actual nanofeatures (NF) themselves, mesoscopic interfaces were created by electron beam deposition of a thin Fe layer on a 5 deg miscut {111} Y₂Ti₂O₇ bulk single crystal surface. While the mesoscopic interfaces may differ from those of the embedded NF, the former facilitate characterization of controlled interfaces, such as interactions with point defects and helium. The Fe-Y₂Ti₂O₇ interfaces were studied using scanning electron microscopy, including electron backscatter diffraction, atomic force microscopy, X-ray diffraction, and transmission electron microscopy (TEM). The polycrystalline Fe layer has two general orientation relationships (OR) that are close to (a) the Nishiyama–Wasserman (NW) OR $ \left\{ {110} \right\}_{\text{Fe}} ||\left\{ {111} \right\}_{{{\text{Y}}_{2} {\text{Ti}}_{2} {\text{O}}_{7} }} $ 110 Fe | | 111 Y 2 Ti 2 O 7 and $ \left\langle {100} \right\rangle_{\text{Fe}} ||\left\langle {110} \right\rangle_{{{\text{Y}}_{2} {\text{Ti}}_{2} {\text{O}}_{7} }} $ 100 Fe | | 110 Y 2 Ti 2 O 7 and (b) $ \left\{ {100} \right\}_{\text{Fe}} ||\left\{ {111} \right\}_{{{\text{Y}}_{2} {\text{Ti}}_{2} {\text{O}}_{7} }} $ 100 Fe | | 111 Y 2 Ti 2 O 7 and $ \left\langle {100} \right\rangle_{\text{Fe}} ||\left\langle {110} \right\rangle_{{{\text{Y}}_{2} {\text{Ti}}_{2} {\text{O}}_{7} }} $ 100 Fe | | 110 Y 2 Ti 2 O 7 . High-resolution TEM shows that the NW interface is near-atomically flat, while the {100}_Fe grains are an artifact associated with a thin oxide layer. However, the fact that there is still a Fe-Y₂Ti₂O₇ OR is significant. No OR is observed in the presence of a thicker oxide layer.     

Reaction Mechanism and Kinetics of Enargite Oxidation at Roasting Temperatures

Roasting of enargite (Cu₃AsS₄) in the temperature range of 648?K to 898?K (375?°C to 625?°C) in atmospheres containing variable amounts of oxygen has been studied by thermogravimetric methods. From the experimental results of weight loss/gain data and X-ray diffraction (XRD) analysis of partially reacted samples, the reaction mechanism of the enargite oxidation was determined, which occurred in three sequential stages:

1. $4{\text{Cu}}_{ 3} {\text{AsS}}_{ 4} \left( {\text{s}} \right){\text{ + 13O}}_{ 2} \left( {\text{g}} \right){\text{ = As}}_{ 4} {\text{O}}_{ 6} \left( {\text{g}} \right){\text{ + 6Cu}}_{ 2} {\text{S}}\left( {\text{s}} \right){\text{ + 10SO}}_{ 2} \left( {\text{g}} \right) $
2. $ 6{\text{Cu}}_{ 2} {\text{S}}\left( {\text{s}} \right){\text{ + 9O}}_{ 2} \left( {\text{g}} \right){\text{ = 6Cu}}_{ 2} {\text{O}}\left( {\text{s}} \right){\text{ + 6SO}}_{ 2} \left( {\text{g}} \right) $
3. $ 6{\text{Cu}}_{ 2} {\text{O}}\left( {\text{s}} \right){\text{ + 3O}}_{ 2} \left( {\text{g}} \right){\text{ = 12CuO}}\left( {\text{s}} \right) $

The three reactions occurred sequentially, each with constant rate, and they were affected significantly by temperature and partial pressure of oxygen. The kinetics of the first stage were analyzed by using the model X?=?k ₁ t. The first stage reaction was on the order of 0.9 with respect to oxygen partial pressure and the activation energy was 44?kJ/mol for the temperature range of 648?K to 898?K (375?°C to 625?°C).     

Effect of Slag Composition on the Concentration of Al2O3 in the Inclusions in Si-Mn-killed Steel

The thermodynamic equilibria between CaO-Al₂O₃-SiO₂-CaF₂-MgO(-MnO) slag and Fe-1.5 mass pct Mn-0.5 mass pct Si-0.5 mass pct Cr melt was investigated at 1873 K (1600 °C) in order to understand the effect of slag composition on the concentration of Al₂O₃ in the inclusions in Si-Mn-killed steels. The composition of the inclusions were mainly equal to (mol pct MnO)/(mol pct SiO₂) = 0.8(±0.06) with Al₂O₃ content that was increased from about 10 to 40 mol pct by increasing the basicity of slag (CaO/SiO₂ ratio) from about 0.7 to 2.1. The concentration ratio of the inclusion components, \( {{X_{{{\text{Al}}_{2} {\text{O}}_{3} }} \cdot X_{\text{MnO}} } \mathord{\left/ {\vphantom {{X_{{{\text{Al}}_{2} {\text{O}}_{3} }} \cdot X_{\text{MnO}} } {X_{{{\text{SiO}}_{2} }} }}} \right. \kern-0pt} {X_{{{\text{SiO}}_{2} }} }} \) , and the activity ratio of the steel components, \( {{a_{\text{Al}}^{2} \cdot a_{\text{Mn}} \cdot a_{\text{O}}^{2} } \mathord{\left/ {\vphantom {{a_{\text{Al}}^{2} \cdot a_{\text{Mn}} \cdot a_{\text{O}}^{2} } {a_{\text{Si}} }}} \right. \kern-0pt} {a_{\text{Si}} }} \) , showed a good linear relationship on a logarithmic scale, indicating that the activity coefficient ratio of the inclusion components, \( {{\gamma_{{{\text{SiO}}_{2} }}^{i} } \mathord{\left/ {\vphantom {{\gamma_{{{\text{SiO}}_{2} }}^{i} } {\left( {\gamma_{{{\text{Al}}_{2} {\text{O}}_{3} }}^{i} \cdot \gamma_{\text{MnO}}^{i} } \right)}}} \right. \kern-0pt} {\left( {\gamma_{{{\text{Al}}_{2} {\text{O}}_{3} }}^{i} \cdot \gamma_{\text{MnO}}^{i} } \right)}} \) , was not significantly changed. From the slag-steel-inclusion multiphase equilibria, the concentration of Al₂O₃ in the inclusions was expressed as a linear function of the activity ratio of the slag components, \( {{a_{{{\text{Al}}_{2} {\text{O}}_{3} }}^{s} \cdot a_{\text{MnO}}^{s} } \mathord{\left/ {\vphantom {{a_{{{\text{Al}}_{2} {\text{O}}_{3} }}^{s} \cdot a_{\text{MnO}}^{s} } {a_{{{\text{SiO}}_{2} }}^{s} }}} \right. \kern-0pt} {a_{{{\text{SiO}}_{2} }}^{s} }} \) on a logarithmic scale. Consequently, a compositional window of the slag for obtaining inclusions with a low liquidus temperature in the Si-Mn-killed steel treated in an alumina ladle is recommended.     

Effect of Tungsten on Primary Creep Deformation and Minimum Creep Rate of Reduced Activation Ferritic-Martensitic Steel

Effect of tungsten on transient creep deformation and minimum creep rate of reduced activation ferritic-martensitic (RAFM) steel has been assessed. Tungsten content in the 9Cr-RAFM steel has been varied between 1 and 2 wt pct, and creep tests were carried out over the stress range of 180 and 260 MPa at 823 K (550 °C). The tempered martensitic steel exhibited primary creep followed by tertiary stage of creep deformation with a minimum in creep deformation rate. The primary creep behavior has been assessed based on the Garofalo relationship, \( \varepsilon = \varepsilon_{\text{o}} + \varepsilon_{\text{T}} [1-\exp (-r^{\prime} \cdot t)] + \dot{\varepsilon }_{\text{m}} \cdot t \) , considering minimum creep rate \( \dot{\varepsilon }_{\text{m}} \) instead of steady-state creep rate \( \dot{\varepsilon }_{\text{s}} \) . The relationships between (i) rate of exhaustion of transient creep r′ with minimum creep rate, (ii) rate of exhaustion of transient creep r′ with time to reach minimum creep rate, and (iii) initial creep rate \( \dot{\varepsilon }_{\text{i}} \) with minimum creep rate revealed that the first-order reaction-rate theory has prevailed throughout the transient region of the RAFM steel having different tungsten contents. The rate of exhaustion of transient creep r′ and minimum creep rate \( \dot{\varepsilon }_{\text{m}} \) decreased, whereas the transient strain ? _T increased with increase in tungsten content. A master transient creep curve of the steels has been developed considering the variation of \( \frac{{\left( {\varepsilon - \varepsilon_{\text{o}} } \right)}}{{\varepsilon_{\text{T}} }} \) with \( \frac{{\dot{\varepsilon }_{\text{m}} \cdot t}}{{\varepsilon_{\text{T}} }} \) . The effect of tungsten on the variation of minimum creep rate with applied stress has been rationalized by invoking the back-stress concept.     

Mass spectrometric determination of activities for alloys with complex vapor species: Bi-Pb and Bi-Tl

For solutions from which complex species vaporize (Bi₂, Si₂, Al₂O, Sb₄, and so forth) new methods of determining the thermodynamic properties from mass spectrometric data are demonstrated. In order to test the feasibility of these new techniques, experiments have been carried out on the liquid Bi-Pb and Bi-Tl systems for which adequate thermodynamic data are available. In evaluating the thermodynamic properties, the ion current ratiosI _Pb ⁺/IBi₂/+ andI _Tl ⁺/IBi₂/+ were employed,e.g. $$\log {\text{ }}\gamma _{{\text{Bi}}} {\text{ = - }}\mathop {\int {\frac{{N_{Pb} }}{{1{\text{ + }}N_{Pb} }}d} }\limits_{N_{Bi} = 1}^{N_{{\text{Bi}}} = N_{Bi} } {\text{ }}\left\{ {{\text{log}}\frac{{{\text{1}}_{{\text{Pb}}}^{\text{ + }} {\text{ }}N_{Bi}^2 }}{{I_{Bi2}^ + {\text{ }}N_{Pb} }}} \right\}$$ Measuring these particular ion current ratios eliminates errors resulting from the fragmentation of the complex vapor species in evaluating the thermodynamic properties. A dimer-monomer technique, which corrects for fragmentation, was also demonstrated. The results using these two independent approaches are in good agreement with each other as well as with previous investigations. The activity coefficients in both systems adhere to the quadratic formalism over large composition ranges,e.g. $$\begin{gathered} \log {\text{ }}\gamma _{{\text{Pb}}} {\text{ = - 0}}{\text{.255 }}N_{Bi}^2 {\text{ }}N_{{\text{Bi}}} {\text{< 0}}{\text{.8}} \hfill \\ \log {\text{ }}\gamma _{{\text{Tl}}} {\text{ = - 0}}{\text{.805 }}N_{Bi}^2 {\text{ }}N_{{\text{Bi}}} {\text{< 0}}{\text{.7}} \hfill \\ \end{gathered} $$      

Kinetics of the Oxidation of Bismuthinite in Oxygen�CNitrogen Atmospheres

Bismuth is present in copper concentrates mainly as the mineral bismuthinite (Bi₂S₃). In some cases of smelting of concentrates, a substantial amount of bismuth can lead to contaminated copper cathodes. Thus, understanding the behavior of Bi₂S₃ at high temperatures is crucial to assessing the potential of bismuth removal in the pyrometallurgical process. Therefore, the oxidation of bismuthinite in mixtures of oxygen?Cnitrogen atmospheres was investigated using a thermogravimetric analysis technique. The results indicate that the oxidation process occurs through the following consecutive reactions: $$ \begin{gathered} {\text{First stage: }}{\text{Bi}}_{ 2} {\text{S}}_{ 3} \left( {\text{s,l}} \right) + 3{\text{O}}_{2} \left( {\text{g}} \right) = 2{\text{Bi}}\left( {\text{l}} \right) + 3{\text{SO}}_{ 2} \left( {\text{g}} \right) \hfill \\ {\text{Second stage: }}2{\text{Bi}}\left( {\text{l}} \right) + 3/2{\text{O}}_{2} \left( {\text{g}} \right) = {\text{Bi}}_{2} {\text{O}}_{3} \left( {\text{s,l}} \right) \hfill \\ \end{gathered} $$ The kinetics of the oxidation of bismuthinite (first stage) was studied, and the model ln(1 ?C X) = ?Ck_app t describes the kinetics of this reaction well. The bismuthinite oxidation dependence on oxygen partial pressure was of 0.9 order, and the intrinsic kinetic constants were obtained in the temperature range of 873 K to 1273 K (600 °C to 1000 °C), which were used to determine the activation energy of 91 kJ/mol. The results indicate that the oxidation of bismuthinite is a process controlled by chemical reactions. From this study, it can be concluded that the removal of bismuth from the Bi₂S₃-containing concentrates through a mechanism involving gaseous bismuth compounds is not feasible during an oxidizing roasting and/or smelting of concentrates containing Bi₂S₃.     

Enrichment Mechanism of Phosphate in CaO-SiO2-FeO-Fe2O3-P2O5 Steelmaking Slags

The phosphate-enrichment behavior has experimentally been investigated in CaO-SiO₂-FeO-Fe₂O₃-P₂O₅ steelmaking slags. The reaction ability of structural units in the slags has been represented the mass action concentration \( N_{i} \) from the developed ion and molecule coexistence theory (IMCT)- \( N_{i} \) model based on the IMCT. The defined enrichment possibility \( N_{{{\text{c}}i{\text{ {-}c}}j}} \) and enrichment degree \( R_{{{\text{c}}i{\text{{-}c}}j}} \) of solid solutions containing P₂O₅ from the developed IMCT- \( N_{i} \) model have been verified from the experimental results. The effects of binary basicity, the mass percentage ratio \( {{ ( {\text{pct Fe}}_{t} {\text{O)}}} \mathord{\left/ {\vphantom {{ ( {\text{pct Fe}}_{t} {\text{O)}}} { ( {\text{pct CaO)}}}}} \right. \kern-0pt} { ( {\text{pct CaO)}}}} \) , and mass percentage of P₂O₅ in the initial slags on phosphate-enrichment behavior in the slags has also been discussed. The results show that the P₂O₅ component can easily be bonded by CaO to form tricalcium phosphate 3 CaO·P₂O₅, and the formed 3CaO·P₂O₅ can react with the produced dicalcium silicate 2CaO·SiO₂ to generate solid-solution 2CaO·SiO₂-3CaO·P₂O₅ under fixed cooling conditions. The maximum value of the defined enrichment degree \( R_{{{\text{C}}_{ 2} {\text{S{-}}} {\text{C}}_{ 3} {\text{P}}}} \) of solid-solution 2CaO·SiO₂-3CaO·P₂O₅ is obtained as 0.844 under conditions of binary basicity as 2.5 and the mass percentage ratio \( {{ ( {\text{pct Fe}}_{t} {\text{O)}}} \mathord{\left/ {\vphantom {{ ( {\text{pct Fe}}_{t} {\text{O)}}} { ( {\text{pct CaO)}}}}} \right. \kern-0pt} { ( {\text{pct CaO)}}}} \) as 0.955 at fixed cooling conditions.     

Effects of Interfacial Lattice Mismatching on Wetting of Ni-Plated Steel by Magnesium

In this study, wetting has been characterized by measuring the contact angles of AZ92 Mg alloy on Ni-electroplated steel as a function of temperature. Reactions between molten Mg and Ni led to a contact angle of about 86 deg in the temperature range of 891 K to 1023 K (618 °C to 750 °C) (denoted as Mode I) and a dramatic decrease to about 46 deg in the temperature range of 1097 K to 1293 K (824 °C to 1020 °C) (denoted as Mode II). Scanning and transmission electron microscopy (SEM and TEM) indicated that AlNi + Mg₂Ni reaction products were produced between Mg and steel (Mg-AlNi-Mg₂Ni-Ni-Fe) in Mode I, and just AlNi between Mg and steel (Mg-AlNi-Fe) in Mode II. From high resolution TEM analysis, the measured interplanar mismatches for different formed interfaces in Modes I and II were \( 17{\kern 1pt} \;{\text{pct}}_{{\{ 10\overline 11\}_{\text{Mg}} //\{ 110\}_{\text{AlNi}} }} \)-\( 104.3\;{\text{pct}}_{{\{ 110\}_{\text{AlNi}} //\left\{ {10\overline{1}0} \right\}_{{{\text{Mg}}_{ 2} {\text{Ni}}}} }} \)-\( 114\,{\text{pct}}_{{\left\{ {0003} \right\}_{{{\text{Mg}}_{ 2} {\text{Ni}}}} //\{ 111\}_{\text{Ni}} }} \) and \( 18\,{\text{pct}}_{{\{ 10\overline 11\}_{\text{Mg}} //\{ 110\}_{\text{AlNi}} }} \)-\( 5\,{\text{pct}}_{{\left\{ {110} \right\}_{\text{AlNi}} //\{ 110\}_{\text{Fe}} }} \), respectively. An edge-to-edge crystallographic model analysis confirmed that Mg₂Ni produced larger lattice mismatching between interfaces with calculated minimum interplanar mismatches of \( 16.4\,{\text{pct}}_{{{\text{\{ 10}}\overline 1 1 {\text{\} }}_{\text{Mg}} / / {\text{\{ 110\} }}_{\text{AlNi}} }} \)-\( 108.3\,{\text{pct}}_{{{\text{\{ 110\} }}_{\text{AlNi}} / / {\text{\{ 10}}\overline 1 1 {\text{\} }}_{{{\text{Mg}}_{ 2} {\text{Ni}}}} }} \)-\( 17.2\,{\text{pct}}_{{{\text{\{ 10}}\overline 1 1 {\text{\} }}_{{{\text{Mg}}_{ 2} {\text{Ni}}}} / / {\text{\{ 100\} }}_{\text{Ni}} }} \) for Mode I and \( 16.4\,{\text{pct}}_{{{\text{\{ 10}}\overline1 1 {\text{\} }}_{\text{Mg}} / / {\text{\{ 110\} }}_{\text{AlNi}} }} \)-\( 0.6\,{\text{pct}}_{{{\text{\{ 111\} }}_{\text{AlNi}} / / {\text{\{ 111\} }}_{\text{Fe}} }} \) for Mode II. Therefore, it is suggested that the poor wettability in Mode I was caused by the existence of Mg₂Ni since AlNi was the immediate layer contacting molten Mg in both Modes I and II, and the presence of Mg₂Ni increases the interfacial strain energy of the system. This study has clearly demonstrated that the lattice mismatching at the interfaces between reaction product(s) and substrate, which are not in direct contact with the liquid, can greatly influence the wetting of the liquid.     

Thermochemical decomposition of hydrogen sulfide with nickel sulfide

In this research, the two-step thermochemical cycle shown below is proposed and experimental studies were made on the cycle. $$\frac{\begin{gathered} {\text{Ni}}_{\text{3}} {\text{S}}_{\text{2}} + {\text{H}}_{\text{2}} {\text{S}} = {\text{3NiS + H}}_{\text{2}} \hfill \\ {\text{3NiS = Ni}}_{\text{3}} {\text{S}}_{\text{2}} {\text{ + 0}}{\text{.5S}}_{\text{2}} {\text{(g)}} \hfill \\ \end{gathered} }{{{\text{H}}_{\text{2}} {\text{S = H}}_{\text{2}} {\text{ + 0}}{\text{.5S}}_{\text{2}} {\text{(g)}}}}$$ In the case where Ni₃S₂ alone was used without inert additions, nickel sulfide sintered or partly fused due to the melting point depression resulting from the thermal decomposition of formed NiS. Such sintering could be prevented by mixing the nickel sulfide powders with Al₂O₃ or MoS₂. The cyclic reactions were thereby shown to provide a stationary high decomposition rate of H₂S. Polysulfides, such as MS₂, have previously been employed in this kind of cycle. This research showed that the use of lower sulfides such as Ni₃S₂ may be regarded as rather promising based on the thermodynamic investigation of the respective reactions composing the cycle. The comparison between the sulfurization reactions of NiS to NiS₂ and of Ni₃S₂ to NiS further showed that the latter was superior to the former with respect to the kinetics and thermodynamical properties of the reaction.     

Sulfate Formation and Decomposition of Nickel Concentrates

Nickel sulfide concentrates from two Canadian nickel concentrators were investigated to improve the understanding of SO₂ formation and release during processing. The concentrates were heated in gases of various oxygen concentrations up to 1573 K (1300 °C) in a thermal gravimetric analysis unit to simulate what may take place during calcine collection and processing. The resulting SO₂ gases were also measured. It was determined that during oxidation, there are competing reactions, such as \( 3{\text{FeS}} + 5{\text{O}}_{2} = {\text{Fe}}_{3} {\text{O}}_{4} + 3{\text{SO}}_{2} \) leading to mass loss, or \( 2{\text{FeS}} + 5{\text{O}}_{2} + {\text{SO}}_{2} = {\text{Fe}}_{2} \left( {{\text{SO}}_{4} } \right)_{3} \) causing mass gain. At temperatures up to approximately 973 K (700 °C), sulfates were formed readily, whereas at higher temperatures, they would decompose, evolving SO₂. By lowering the oxygen content in the surrounding gas, the sulfates decomposed more readily. In an argon or hydrogen atmosphere or in vacuum, it is possible to enhance the sulfate decomposition greatly, possibly allowing for reduced SO₂ emissions from the electric furnaces.     

Determination of Gibbs Energy of Formation of Molybdenum-Boron Binary System by Electromotive Force Measurement Using Solid Electrolyte

The standard Gibbs energies of formation of Mo₂B, ??MoB, Mo₂B₅, and MoB₄ in the molybdenum-boron binary system were determined by measuring electromotive forces of galvanic cells using an Y₂O₃-stabilized ZrO₂ solid oxide electrolyte. The results are as follows: $$ \begin{aligned} \Updelta_{\text{f}} {\text{G}}^\circ \left( {{\text{Mo}}_{2} {\text{B}}} \right)/{\text{J}}\,{\text{mol}}^{ - 1} & = - 193100 + 44.10T \pm 700\left( {1198{\text{ K to }}1323{\text{ K}}\left( {925^\circ {\text{C to }}1050^\circ {\text{C}}} \right)} \right) \\ \Updelta_{\text{f}} {\text{G}}^\circ (\alpha {\text{MoB}})/{\text{J}}\,{\text{mol}}^{ - 1} & = - 164000 + 26.45T \pm 700\left( {1213{\text{ K to }}1328{\text{ K}}\left( {940^\circ {\text{C to }}1055^\circ {\text{C}}} \right)} \right) \\ \Updelta_{\text{f}} {\text{G}}^\circ \left( {{\text{Mo}}_{2} {\text{B}}_{5} } \right)/{\text{J}}\,{\text{mol}}^{ - 1} & = - 622500 + 117.0T \pm 3000\left( {1205{\text{ K to }}1294{\text{ K}}\left( {932^\circ {\text{C to }}1021^\circ {\text{C}}} \right)} \right) \\ \Updelta_{\text{f}} {\text{G}}^\circ \left( {{\text{MoB}}_{4} } \right)/{\text{J}}\,{\text{mol}}^{ - 1} & = - 387300 + 93.53T \pm 3000\left( {959{\text{ K to }}1153{\text{ K}}\left( {686^\circ {\text{C to }}880^\circ {\text{C}}} \right)} \right) \\ \end{aligned} $$ where the standard pressure is 1 bar (100 kPa).     

A Thermodynamic Model for Representation Reaction Abilities of Structural Units in Fe-S Binary Melts Based on the Atom-Molecule Coexistence Theory

A thermodynamic model for calculating the mass action concentrations of structural units in Fe-S binary melts based on the atom-molecule coexistence theory, i.e., AMCT-N _i model, has been developed and verified through a comparison with the reported activities of both S and Fe in Fe-S binary melts with changing mole fraction $ x_{\text{S}} $ of S from 0.0?to 0.095?at temperatures of 1773?K, 1823?K, and 1873?K (1500 °C, 1550 °C, and 1600 °C) from the literature. The calculated mass action concentration $ N_{\text{S}} $ of S is much smaller than the reported activity $ a_{\text{R, S}} $ of S in Fe-S binary melts with changing mole fraction $ x_{\text{S}} $ of S from 0.0?to 0.095. The calculated mass action concentration $ N_{\text{S}} $ of S can correlate the reliable 1:1?corresponding relationship with the reported activity $ a_{\text{R, S}} $ or $ a_{\%,\text {S}} $ of S through the introduced transformation coefficients with absolutely mathematical meaning or through the defined comprehensive mass action concentration of total S with explicitly physicochemical meaning. The calculated mass action concentrations $ N_{i} $ of structural units from the developed AMCT-N _i thermodynamic model can be applied to describe or predict the reaction abilities of structural units in Fe-S binary melts. The reaction abilities of Fe and S show a competitive relationship each other in Fe-S binary melts in a temperature range from 1773?K to 1873?K (1500 °C to 1600 °C). The calculated mass action concentration $ N_{{{\text{FeS}}_{ 2} }} $ of FeS_2?is very small and can be ignored because FeS_2?can be incongruently decomposed above 1016?K (743 °C). The very small values for the calculated mass action concentrations $ N_{{{\text{FeS}}_{ 2} }} $ of FeS_2?in a range of mole fraction $ x_{\text{S}} $ of S from 0.0?to 1.0?as well as a maximum value for the calculated mass action concentration $ N_{\text{FeS}} $ of FeS with mole fraction $ x_{\text{S}} $ of S as 0.5?are coincident with diagram phase of Fe-S binary melts. A spindle-type relationship between the calculated mass action concentration $ N_{i} $ and the calculated equilibrium mole number $ n_{i} $ can be found for FeS and FeS_2?in Fe-S binary melts. The Raoultian activity coefficient $ \gamma_{S}^{0} $ of S relative to pure liquid S(l) as standard state and the infinitely dilute solution as reference state in Fe-S binary melts can be determined as 1.0045?in a temperature range from 1773?K to 1873?K (1500 °C to 1600 °C). The standard molar Gibbs free energy change $ \Updelta_{\text{sol}} G_{{{\text{m, S }}({\text{l}}) \to [{\text{S}}]_{{ \, [{\text{pct \, S}}] = 1.0}} }}^{{\Uptheta,\%}} $ of dissolving liquid S for forming [pct S] as 1.0?in Fe-S binary melts relative to 1?mass percentage of S as standard state can be formulated as $ \Updelta_{\text{sol}} G_{{{\text{m, S }}({\text{l}}) \to [{\text{S}}]_{{ \, [{\text{pct \, S] }} = \, 1.0}} }}^{{\Uptheta,\, \%}} \,\, = -0.219\,-\,33.70T\,\,\left( {\text{J/mol}} \right).$      

Oxidation and Condensation of Zinc Fume From Zn-CO<Subscript>2</Subscript>-CO-H<Subscript>2</Subscript>O Streams Relevant to Steelmaking Off-Gas Systems

The objective of this research was to study the condensation of zinc vapor to metallic zinc and zinc oxide solid under varying environments to investigate the feasibility of in-process separation of zinc from steelmaking off-gas dusts. Water vapor content, temperature, degree of cooling, gas composition, and initial zinc partial pressure were varied to simulate the possible conditions that can occur within steelmaking off-gas systems, limited to Zn-CO₂-CO-H₂O gas compositions. The temperature of deposition and the effect of rapidly quenching the gas were specifically studied. A homogeneous nucleation model for applicable experiments was applied to the analysis of the experimental data. It was determined that under the experimental conditions, oxidation of zinc vapor by H₂O or CO₂ does not occur above 1108 K (835 °C) even for highly oxidizing streams (CO₂/CO = 40/7). Rate expressions that correlate CO₂ and H₂O oxidation rates to gas composition, partial pressure of water vapor, temperature, and zinc partial pressure were determined to be as follows:

$$ {\text{Rate}}\left( {\frac{\text{mol}}{{{\text{m}}^{2} {\text{s}}}}} \right) = 406 \exp \left( {\frac{{ - 50.2 \,{\text{kJ}}/{\text{mol}}}}{RT}} \right)\left( {p_{\text{Zn}} p_{{{\text{CO}}_{2} }} - p_{\text{CO}} /K_{{{\text{eq}},{\text{CO}}_{2} }} } \right)\,\frac{\text{mol}}{{{\text{m}}^{2} \times {\text{s}}}} $$

$$ {\text{Rate}}\left( {\frac{\text{mol}}{{{\text{m}}^{2} {\text{s}}}}} \right) = 32.9 \exp \left( {\frac{{ - 13.7\, {\text{kJ}}/{\text{mol}}}}{RT}} \right)\left( {p_{\text{Zn}} p_{{{\text{H}}_{2} {\text{O}}}} - p_{{{\text{H}}_{2} }} /K_{{{\text{eq}},{\text{H}}_{2} {\text{O}}}} } \right)\,\frac{\text{mol}}{{{\text{m}}^{2} \times {\text{s}}}} $$

It was proven that a rapid cooling rate (500 K/s) significantly increases the ratio of metallic zinc to zinc oxide as opposed to a slow cooling rate (250 K/s). SEM analysis found evidence of heterogeneous growth of ZnO as well as of homogeneous formation of metallic zinc. The homogeneous nucleation model fit well with experiments where only metallic zinc deposited. An expanded model with rates of oxidation by CO₂ and H₂O as shown was combined with the homogenous nucleation model and then compared with experimental data. The calculated results based on the model gave a reasonable fit to the measured data. For the conditions used in this study, the rate equations for the oxidation of zinc by carbon dioxide and water vapor as well as the homogeneous nucleation model of metallic zinc were applicable for various temperatures, zinc partial pressures, CO₂:CO ratios, and H₂O partial pressures.

     

Distribution Ratios of Phosphorus Between CaO-FeO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Na<Subscript>2</Subscript>O/TiO<Subscript>2</Subscript> Slags and Carbon-Saturated Iron

In order to effectively enhance the efficiency of dephosphorization, the distribution ratios of phosphorus between CaO-FeO-SiO₂-Al₂O₃/Na₂O/TiO₂ slags and carbon-saturated iron (\( L_{\text{P}}^{\text{Fe-C}} \)) were examined through laboratory experiments in this study, along with the effects of different influencing factors such as the temperature and concentrations of the various slag components. Thermodynamic simulations showed that, with the addition of Na₂O and Al₂O₃, the liquid areas of the CaO-FeO-SiO₂ slag are enlarged significantly, with Al₂O₃ and Na₂O acting as fluxes when added to the slag in the appropriate concentrations. The experimental data suggested that \( L_{\text{P}}^{\text{Fe-C}} \) increases with an increase in the binary basicity of the slag, with the basicity having a greater effect than the temperature and FeO content; \( L_{\text{P}}^{\text{Fe-C}} \) increases with an increase in the Na₂O content and decrease in the Al₂O₃ content. In contrast to the case for the dephosphorization of molten steel, for the hot-metal dephosphorization process investigated in this study, the FeO content of the slag had a smaller effect on \( L_{\text{P}}^{\text{Fe-C}} \) than did the other factors such as the temperature and slag basicity. Based on the experimental data, by using regression analysis, \( \log L_{\text{P}}^{\text{Fe-C}} \) could be expressed as a function of the temperature and the slag component concentrations as follows:

$$ \begin{aligned} \log L_{\text{P}}^{\text{Fe-C}} & = 0.059({\text{pct}}\;{\text{CaO}}) + 1.583\log ({\text{TFe}}) - 0.052\left( {{\text{pct}}\;{\text{SiO}}_{2} } \right) - 0.014\left( {{\text{pct}}\;{\text{Al}}_{2} {\text{O}}_{3} } \right) \\ \, & \quad + 0.142\left( {{\text{pct}}\;{\text{Na}}_{2} {\text{O}}} \right) - 0.003\left( {{\text{pct}}\;{\text{TiO}}_{2} } \right) + 0.049\left( {{\text{pct}}\;{\text{P}}_{2} {\text{O}}_{5} } \right) + \frac{13{,}527}{T} - 9.87. \\ \end{aligned} $$

     

Quasi-Chemical Viscosity Model for Fully Liquid Slag in the Al2O3-CaO-MgO-SiO2 System—Part I: Revision of the Model

A model has been developed that enables the viscosities of the fully liquid slag in the multi-component Al₂O₃-CaO-FeO-Fe₂O₃-MgO-Na₂O-SiO₂ system to be predicted within experimental uncertainties over a wide range of compositions and temperatures. The Eyring equation is used to express viscosity as a function of temperature and composition. The model links the activation and pre-exponential energy terms in the viscosity expression to the slag internal structure through the concentrations of various Si_0.5O, $ {\text{Me}}^{n + }_{2/n} {\text{O}} $ , and $ {\text{Me}}^{n + }_{ 1/n} {\text{Si}}_{0. 2 5} {\text{O}} $ viscous flow structural units (SUs). The concentrations of these SUs are derived from a quasi-chemical thermodynamic model of the liquid slag using the thermodynamic computer package FactSage. The model describes a number of slag viscosity features including the charge compensation effect specific for the Al₂O₃-containing systems. The predictive capability of the model is enhanced by the physical aspects of the model parameters—the correlation with other physicochemical properties as well as experimental viscosity data is used to determine model parameters. The present series of two papers outlines (a) recent significant improvements introduced into the model formalism and (b) application of the model to the Al₂O₃-CaO-MgO-SiO₂ system, review of experimental viscosity data, and optimization of the corresponding model parameters for this system.     

Isothermal Reaction of NiO Powder with Undiluted CH<Subscript>4</Subscript> at 1000 K to 1300 K (727 °C to 1027 °C)

In this study, isothermal reaction behavior of loose NiO powder in a flowing undiluted CH₄ atmosphere at the temperature range 1000 K to 1300 K (727 °C to 1027 °C) is investigated. Thermodynamic analyses at this temperature range revealed that single phase Ni forms at the input \( {{n_{{{\text{CH}}_{ 4} }}^{\text{o}} } \mathord{\left/ {\vphantom {{n_{{{\text{CH}}_{ 4} }}^{\text{o}} } {\left( {n_{{{\text{CH}}_{ 4} }}^{\text{o}} + n_{\text{NiO}}^{\text{o}} } \right)}}} \right. \kern-0pt} {\left( {n_{{{\text{CH}}_{ 4} }}^{\text{o}} + n_{\text{NiO}}^{\text{o}} } \right)}} \) mole fractions (\( X_{{{\text{CH}}_{ 4} }} \)) between ~0.2 and 0.5. It was also predicted that free C co-exists with Ni at \( X_{{{\text{CH}}_{ 4} }} \) values higher than ~0.5. The experiments were carried out as a function of temperature, time, and CH₄ flow rate. Mass measurement, XRD and SEM-EDX were used to characterize the products at various stages of the reaction. At 1200 K and 1300 K (927 °C and 1027 °C), the reaction of NiO with undiluted CH₄ essentially consisted of two successive distinct stages: NiO reduction and pyrolytic C deposition on pre-reduced Ni particles. At 1200 K (927 °C), 1100 K (827 °C), and 1000 K (727 °C), complete oxide reduction was observed within ~7.5, ~17.5, and ~45 minutes, respectively. It was suggested that NiO was essentially reduced to Ni by a CH₄ decomposition product, H₂. Possible reactions leading to NiO reduction were suggested. An attempt was made to describe the NiO reduction kinetics using nucleation-growth and geometrical contraction models. It was observed that the extent of NiO reduction and free C deposition increased with the square root of CH₄ flow rate as predicted by a mass transport theory. A mixed controlling mechanism, partly chemical kinetics and partly external gaseous mass transfer, was responsible for the overall reaction rate. The present study demonstrated that the extent of the reduction can be determined quantitatively using the XRD patterns and also using a formula theoretically derived from the basic XRD data.     

Multicomponent Interstitial Diffusion in and Thermodynamic Characteristics of the Interstitial Solid Solution ε-Fe3(N,C)1+x : Nitriding and Nitrocarburizing of Pure α-Iron

A series of gas nitriding and gas nitrocarburizing experiments was performed at 823 K (550 °C) to investigate the growth kinetics of ε-Fe₃(N,C)_1+x /γ′-Fe₄N_1-z -double layers on pure α-iron substrates. The growth rate and composition of the (sub)layers were determined by (sub)layer-thickness measurements using light optical microscopy and electron-probe microanalyses (EPMA), respectively. Models for the growth of bilayers into a substrate, controlled by the interstitial diffusion of two elements (N and C), were applied to the experimental data to determine the intrinsic diffusion coefficients of N and C in ε-Fe₃(N,C)_1+x as well as the self-diffusion coefficient of N in γ′-Fe₄N_1?z . For ε-Fe₃(N,C)_1+x , it was found that the four components of the diffusion matrix, $ D_{\text{NN}}^{\varepsilon } ,\,D_{\text{CC}}^{\varepsilon } ,\,D_{\text{NC}}^{\varepsilon } $ and $ D_{\text{CN}}^{\varepsilon } $ , are all positive. The significant values of the off-diagonal diffusivities $ D_{\text{NC}}^{\varepsilon } $ and $ D_{\text{CN}}^{\varepsilon } $ indicate profound interaction of both interstitial species. Thereby, additional information is obtained about the thermodynamic properties of the ε phase in the ternary Fe-N-C system.     

The kinetics of formation of h2o and co2 during iron oxide reduction

The kinetics of the chemical reaction-controlled reduction of iron oxides by H₂/H₂O and CO/CO₂ gas mixtures are discussed. From an analysis of the systems it is concluded that the decomposition of the oxides takes place by the two dimensional nucleation and lateral growth of oxygen vacancy clusters at the gas/oxide interface. The rates of decomposition of the oxides under conditions of chemical reaction control are dependent not only on the partial pressures of the reacting gases at the reaction temperature but also on the oxygen activity of the prevailing atmosphere. Application of this model to the kinetic data leads to the determination of the maximum chemical reaction rate constants for the decomposition of the iron oxide surfaces. Assuming the reactions H₂ (g) + O(ads) → H₂O(g) andCO(g) + O(ads) → CO₂ (g) to be rate controlling the maximum chemical reaction rate constants for the reduction of iron oxides are given by $$\Phi _{{\text{H}}_{\text{2}} } = 10^{.00} exp \left( {\frac{{ - 69,300}}{{RT}}} \right)mol m^{ - 2} s^{ - 1} atm^{ - 1} $$ and $$\Phi _{CO} = 10^{4.40} \exp \left( {\frac{{103,900}}{{RT}}} \right)mol m^{ - 2} s^{ - 1} atm^{ - 1} $$ The maximum chemical reaction rate constants do not necessarily indicate the maximum rates which can be achieved in practice since these will depend on the limitations imposed by mass transport in the systems. The rate constants are important however since they indicate for the first time the upper limit of any reduction rate in these systems. The fractions of reaction sites which appear to be active on wüstite surfaces in equilibrium with iron are calculated. A direct relationship between chemical reaction rates on liquid iron surfaces and rates on atomically rough iron oxide surfaces is postulated.