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1.
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. $$\begin{gathered} \log {\text{ }}\gamma _{{\text{Pb}}} {\text{ = - 0}}{\text{.255 }}N_{Bi}^2 {\text{ }}N_{{\text{Bi}}} {\text{< 0}}{\text{.8}} \hfill \\ \log {\text{ }}\gamma _{{\text{Tl}}} {\text{ = - 0}}{\text{.805 }}N_{Bi}^2 {\text{ }}N_{{\text{Bi}}} {\text{< 0}}{\text{.7}} \hfill \\ \end{gathered} $$   相似文献   

2.
The phase transition and influence of the applied stress on the texture evolution in the as-cast Ni-Mn-Ga ferromagnetic shape-memory alloys were studied by the time-of-flight (TOF) neutron diffraction technique. The neutron diffraction experiments were performed on the General Purpose Powder Diffractometer (Argonne National Laboratory). Inverse pole figures were determined from the neutron data for characterizing the orientation distributions and variant selections of polycrystalline Ni-Mn-Ga alloys subjected to different uniaxial compression deformations. Texture analyses reveal that the initial texture for the parent phase in the as-cast specimen was composed of , , , and , which was weakened after the compression deformation. Moreover, a strong preferred selection of martensitic-twin variants (and ) was observed in the transformed martensite after a compression stress applied on the parent phase along the cyclindrical axis of the specimens. The preferred selection of variants can be well explained by considering the grain/variant-orientation-dependent Bain-distortion energy. This article is based on a presentation given in the symposium entitled “Neutron and X-Ray Studies for Probing Materials Behavior,” which occurred during the TMS Spring Meeting in New Orleans, LA, March 9–13, 2008, under the auspices of the National Science Foundation, TMS, the TMS Structural Materials Division, and the TMS Advanced Characterization, Testing, and Simulation Committee.  相似文献   

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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).  相似文献   

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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.  相似文献   

7.
The influence of solution-treatment temperature on the martensitic phase transformations observed in IMI 550 (Ti−4Al−4Mo−2Sn−0.5Si) has been investigated. When solution treatment is conducted at temperatures above 1233 K, a hexagonal martensite α′ is formed on rapid cooling. However solution treatment at temperatures between 1233 and 1123 K results in the formation of an orthorhombic martensite (α″) on rapid cooling. Finally, below 1123 K, the β phase is stable—no martensitic transformation occurs on rapid cooling. this transition from with decreasing solution-treatment temperature, is shown to be a result of alloy partitioning during solution treatment. Crystallographic analysis indicates that the transition in the martensite crystal structure with decreasing solution-treatment temperature is related to chemical short-range ordering (CSRO) in the high-temperature β phase.  相似文献   

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The dynamics of dislocations in both steady state and transient creep in alpha iron of about 99.5 pct purity was investigated in the temperature interval 773 to 923 K, and the applied stress range 24.5 to 220.5 MN m−2. The applied stress sensitivity parameter of the steady state creep rate m∲ = (∂ In ε/∂ In σ) T increased linearly with increasing applied stress σ from about 5 at σ = 24.5 MN m−2 to about 12 at σ = 196 MN m−2. The apparent activation energy of steady state creep rate was found to decrease linearly with stress from 89 K cal mol−1 at σ = 98 MN m−2 to 81 K cal mol−1 at a = 147 MN m−2. Measurements of the mean effective stress σ* by the strain transient dip test technique led to a nonlinear relation between σ* and σ, indicating a dependence of the ratio σ*/σ on the applied stress. The effective stress sensitivity parameter was lower than m′.However, the apparent activation energy was equal toQ. Using the stress sensitivity technique, the relation between transient creep rate and effective stress at various constant internal stresses and temperatures was obtained. The effective stress sensitivity of transient creep rate was found to be lessthan that of steady creep rate.  相似文献   

10.
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).  相似文献   

11.
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.  相似文献   

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

14.
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.  相似文献   

15.
Zinc-10 and 20 wt pct Pb alloys have been rapidly solidified by melt spinning to obtain a very fine scale dispersion of nanometer-sized Pb particles embedded in Zn matrix. The microstructure and crystallography of the Pb particles have been studied using transmission electron microscopy (TEM). Each embedded Pb particle is a single crystal, with a truncated hexagonal biprism shape with the 6/mmm Zn matrix point group symmetry surrounded by {0001},\(\left\{ {10\bar 10} \right\}\) and\(\left\{ {10\bar 11} \right\}\) facets. The Pb particles solidify with a well-defined orientation relationship with the Zn matrix of (0001)zn‖(111)pb and\([11\bar 20]_{Zn} ||[1\bar 10]_{Pb} \). The melting and solidification behavior of the Pb par- ticle have been studied using differential scanning calorimetry (DSC). The Pb particles solidify with an undercooling of approximately 30 K, by heterogeneous nucleation on the {0001} facets of the surrounding Zn matrix, with an apparent contact angle of 23 deg.  相似文献   

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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.  相似文献   

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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.  相似文献   

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