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.     

The diffusion and solubility of oxygen in solid nickel

Solid-state electrochemical measurements using various experimental procedures were made with the double cell: $$ Ni + NiO|ZrO_2 + Y_2 O_3 |Ni + \underline O |ZrO_2 + Y_2 O_3 |Ni + NiO $$ to determine the diffusivity and thermodynamic functions of oxygen dissolved in solid nickel. Non-steady state diffusion of oxygen in the specimen was caused by applying a preselected potential between the reference and specimen electrodes and was monitored by measuring time-dependent potentials and/or currents. The following results were obtained for the diffusivity of oxygen and the solubility of oxygen in nickel in equilibrium with NiO: $$D{\text{ = 4}}{\text{.9 }} \times {\text{ 10}}^{{\text{ - 2}}} {\text{ exp}}\left( {{\text{ - }}\frac{{{\text{164 kJ/mole}}}}{{{\text{R}}T}}} \right){\text{cm}}^{\text{2}} /{\text{sec (850 to 1400 }}{}^{\text{o}}{\text{C)}}$$ $$C_{\text{O}}^s {\text{ = 8}}{\text{.3 exp}}\left( { - \frac{{55{\text{kJ/mole}}}}{{{\text{R}}T}}} \right){\text{at}}{\text{. pct (800 to 1000 }}{}^{\text{o}}{\text{C)}}$$ The thermodynamic and transport behaviors of oxygen in solid nickel were fairly well described by a simple quasi-regular model and an interstitial diffusion model, respectively.     

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. $$\begin{gathered} \log {\text{ }}\gamma _{{\text{Pb}}} {\text{ = - 0}}{\text{.255 }}N_{Bi}^2 {\text{ }}N_{{\text{Bi}}} {\text{< 0}}{\text{.8}} \hfill \\ \log {\text{ }}\gamma _{{\text{Tl}}} {\text{ = - 0}}{\text{.805 }}N_{Bi}^2 {\text{ }}N_{{\text{Bi}}} {\text{< 0}}{\text{.7}} \hfill \\ \end{gathered} $$      

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.     

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.     

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).     

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.     

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.     

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.     

Iron redox equilibria in CaO-Al2O3-SiO2 and MgO-CaO-Al2O3-SiO2 slags

Measurements have been made of the ratio of ferric to ferrous iron in CaO-Al₂O₃-SiO₂ and MgO-CaO-Al₂O₃-SiO₂ slags at oxygen activities ranging from equilibrium with pCO₂/pCO≈0.01 to as high as air at temperatures of 1573 to 1773 K. At 1773 K, values are given by $\begin{gathered} \log {\text{ }}\left( {\frac{{Fe^{3 + } }}{{Fe^{2 + } }}} \right) = 0.3( \pm {\text{ }}0.02){\text{ }}Y + {\text{ }}0.45( \pm {\text{ }}0.01){\text{ }}\log \hfill \\ \left( {\frac{{pCO_2 }}{{pCO}}} \right) - 1.24( \pm {\text{ }}0.01) \hfill \\ \end{gathered} $ where Y=(CaO+MgO)/SiO₂, for melts with the molar ratio of CaO/SiO₂=0.45 to 1.52, 10 to 15 mol pct Al₂O₃, up to 12 mol pct MgO (at CaO/SiO₂≈1.5), and with 3 to 10 wt pct total Fe. Available evidence suggests that, to a good approximation, these redox equilibria are independent of temperature when expressed with respect to pCO₂/pCO, probably from about 1573 to 1873 K. Limited studies have also been carried out on melts containing about 40 mol pct Al₂O₃, up to 12 mol pct MgO (at CaO/SiO₂≈1.5), and 3.6 to 4.7 wt pct Fe. These show a strongly nonideal behavior for the iron redox equilibrium, with $\frac{{Fe^{3 + } }}{{Fe^{2 + } }} \propto \left( {\frac{{pCO_2 }}{{pCO}}} \right)^{0.37} $ The nonideal behavior and the effects of basicity and Al₂O₃ concentration on the redox equilibria are discussed in terms of the charge balance model of alumino-silicates and the published structural information from Mössbauer and NMR (Nuclear Magnetic Resonance) spectroscopy of quenched melts.     

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:

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

     

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).$      

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.     

Surface Tension of Liquid Fe-O Alloys: Revisiting Belton’s Two-Step Adsorption Model

The effect of oxygen adsorption on the surface tension of liquid iron was investigated using the constrained drop method. Experiments were carried out at 1823 K and 1873 K (1550 °C and 1600 °C) under a CO₂-H₂ gas mixture. The experimental results were interpreted using the Langmuir ideal adsorption model and Belton’s two-step adsorption model; the latter model showed better agreement with the experimental results. According to the two-step model, the surface tension of liquid Fe-O alloys at 1823 K and 1873 K (1550 °C and 1600 °C) can be respectively expressed as follows: $$ \sigma = 1882 - 260[0.25\ln (1 + 2407a_{\text{O}} ) + 0.75\ln (1 + 72a_{\text{O}} )]\quad \left[ {T = 1823\,{\text{K}}\left( {1550\,^\circ {\text{C}}} \right)} \right], $$ $$ \sigma = 1834 - 267[0.25\ln (1 + 1445a_{\text{O}} ) + 0.75\ln (1 + 46a_{\text{O}} )]\quad \left[ {T = 1873\,{\text{K}}\left( {1600\,^\circ {\text{C}}} \right)} \right]. $$      

An Insight into Slag Structure from Sulphide Capacities

The molar sulphide capacities $ C_{\text{S}}^{'} $ ?=?(mol?pct?S) ( $ P_{{{\text{O}}_{2} }} /P_{{{\text{S}}_{2} }} $ )^1/2 on four binary systems, MgO-SiO₂, CaO-SiO₂, MnO-SiO₂ and FeO-SiO₂ are elucidated so as to compare the magnitudes of the basicities of four metallic oxides and to estimate the temperature dependencies of the basicities of metallic oxides. The enthalpy changes of the reaction?2O^??=?O?+?O^2?, viz. the silicate polymerization reaction (denoted as $ \Updelta H_{(8)}^{^\circ } $ ) have been calculated from the slopes of the log $ C_{\text{S}}^{'} $ vs 1/T curves for four binary silicates. The $ \Updelta H_{(8)}^{^\circ } $ value is considered in the present work to be an index of the basicity of silicate melts. The basicities obtained on the basis of the $ \Updelta H_{(8)}^{^\circ } $ values are in the order MgO?<?CaO?<?MnO?<?FeO, which are determined by two effects; (i) ionicity of chemical bonds between metallic and oxygen ions and (ii) clustering of metallic oxides in silicates. It is also found that the basicity of the FeO-SiO₂ system is larger at higher temperatures.     

The Diffusion Coefficient of Scandium in Dilute Aluminum-Scandium Alloys

The diffusion coefficient of Sc in dilute Al-Sc alloys has been determined at 748 K, 823 K, and 898 K (475 °C, 550 °C, and 625 °C, respectively) using semi-infinite diffusion couples. Good agreement was found between the results of the present study and both the higher temperature, direct measurements and lower temperature, indirect measurements of these coefficients reported previously in the literature. The temperature-dependent diffusion coefficient equation derived from the data obtained in the present investigation was found to be \( D \left( {{\text{m}}^{2} /{\text{s}}} \right) = \left( {2.34 \pm 2.16} \right) \times 10^{ - 4} \left( {{\text{m}}^{2} /{\text{s}}} \right) { \exp }\left( {\frac{{ - \left( {167 \pm 6} \right) \left( {{\text{kJ}}/{\text{mol}}} \right)}}{RT}} \right). \) Combining these results with data from the literature and fitting all data simultaneously to an Arrhenius relationship yielded the expression \( D \left( {{\text{m}}^{2} /{\text{s}}} \right) = \left( {2.65 \pm 0.84} \right) \times 10^{ - 4} \left( {{\text{m}}^{2} /{\text{s}}} \right) { \exp }\left( {\frac{{ - \left( {168 \pm 2} \right) \left( {{\text{kJ}}/{\text{mol}}} \right)}}{RT}} \right). \) In each equation given above, R is 0.0083144 kJ/mol K, T is in Kelvin, and the uncertainties are ±1 standard error.     

Thermodynamics of dilute bcc Fe-Si alloys

The thermodynamic properties of silicon in the α-phase of the Fe-Si system in the region 0.028 <x _Si < 0.084 and 1100 < °C < 1370 has beem measured by the emf cell Mo, Si(s) | SiO₂-Li₂O | (Si-Fe)(s), Mo. The results are expressed in the form $$\log {\text{ }}\gamma _{Si}^\alpha {\text{ = 1}}{\text{.19 }} - {\text{7070/}}T + [ - 6.30 + 18,300/T]x_{Si} $$      

The Solubility and Diffusivity of Fluorine in Solid Copper from Electrochemical Measurements

The solubility and diffusivity of fluorine in solid copper were determined electrochemically using the double solid-state cell $$Ni + NiF_2 \left| {CaF_2 } \right|Cu\left| {CaF_2 } \right|Ni + NiF_2 .$$ In the temperature range 757 to 920°C, the diffusivity of fluorine in solid copper was found to be $$D_F \left( {{{cm^2 } \mathord{\left/ {\vphantom {{cm^2 } s}} \right. \kern-\nulldelimiterspace} s}} \right) = 9.32 \times 10^{ - 2} \exp \left( {\frac{{ - 98,910 {J \mathord{\left/ {\vphantom {J {mole}}} \right. \kern-\nulldelimiterspace} {mole}}}} {{RT}}} \right).$$ . The results obtained for the dissolution of fluorine as atoms in solid copper showed large scatter. However, the equilibrium dissolution of fluorine follows Sieverts’ law. Above the melting point (770°C) of CuF₂, the mean solubility of fluorine in solid copper, for the equilibrium Cu(s)+ CuF ₂(l), follows the relationship $$N_F^s (atom fraction) = 0.98 \exp \left( {\frac{{ - 79,500 {J \mathord{\left/ {\vphantom {J {mole}}} \right. \kern-\nulldelimiterspace} {mole}}}} {{RT}}} \right).$$      

The precipitation of epsilon-carbide in twinned martensite

Tempering of martensite has been investigated by means of thin foil electron microscopy in a high carbon steel, a high nickel steel, and a silicon steel. ε carbide has been unambiguously identified in each steel. It was found that the carbide was precipitated with the Jack orientation relationship: $$\begin{gathered} \left( {0001} \right)_\varepsilon \parallel \left( {011} \right)_{\alpha '} \hfill \\ \left( {10\bar 10} \right)_\varepsilon \parallel \left( {2\bar 11} \right)_{\alpha '} \hfill \\ \end{gathered} $$ In the silicon steel the ε carbide precipitated in the form of needles which grew with a \(\left[ {01\bar 10} \right]_\varepsilon \) close to \(\left[ {21\bar 1} \right]_{\alpha '} \) . This growth direction minimizes the surface energy of the needles, yet allows growth in a direction of low mismatch.