Thermophysical measurements on tungsten-3 (wt %) rhenium alloy in the range 1500–3600 K by a pulse heating technique

Simultaneous measurements of the specific heat capacity, c _p, electrical resistivity, ρ, and hemispherical total emittance, ε, of tungsten-3 (wt%) rhenium alloy in the temperature range 1500–3600 K by a subsecond-duration pulse heating technique are described. The results are expressed by the relations $$\begin{gathered} c_{\text{P}} = 0.30332 - 2.8727 \times 10^{ - 4} {\text{ }}T + 1.9783 \times 10^{ - 7} {\text{ }}T^2 \hfill \\ {\text{ }} - 5.6672 \times 10^{ - 11} {\text{ }}T^3 + 6.5628 \times 10^{ - 15} {\text{ }}T^4 , \hfill \\ \rho = - 24.261 + 8.1924 \times 10^{ - 2} {\text{ }}T - 3.7656 \times 10^{ - 5} {\text{ }}T^2 \hfill \\ {\text{ + 1}}{\text{.1850}} \times {\text{10}}^{ - 8} {\text{ }}T^3 - 1.3229 \times 10^{ - 12} {\text{ }}T^4 , \hfill \\ \varepsilon = 0.1945 + 5.881 \times 10^{ - 5} {\text{ }}T, \hfill \\ \end{gathered} $$ where T is in K, c_p is in J·g^?1·K^?1, and ρ is in μΩ·cm. The melting temperature (solidus temperature) was also measured and was determined to be 3645 K. Uncertainties of the measured properties are estimated to be not more than ±3 % for specific heat capacity, ±1 % for electrical resistivity, ± 5 % for hemispherical total emittance, and ±20 K for the melting temperature.     

Determination of standard Gibbs energies of formation of ternary oxides in the system Co-Sb-O by solid electrolyte emf method

An isothermal section of the phase diagram of the system Co-Sb-O at 873 K was established by isothermal equilibration and XRD analyses of quenched samples. The following galvanic cells were designed to measure the Gibbs energies of formation of the three ternary oxides namely CoSb₂O₄, Co₇Sb₂O₁₂ and CoSb₂O₆ present in the system.

Mechanism of the reduction of carbon/alumina powder mixture in a flowing nitrogen stream

The mechanism of the reduction of carbon/alumina powder mixture in a flowing nitrogen stream was studied. Five steps were found to be involved in the overall reaction. $$\begin{gathered} Al_2 O_{3f} (s) + 2C_f (s)\mathop \to \limits^{k_1 } Al_2 O(g) + 2CO(g) \hfill \\ Al_2 O(g) + solid surface\mathop \rightleftharpoons \limits_{k_2^\prime }^{k_2 } [Al_2 O]_s \hfill \\ [Al_2 O]_s + CO(g) + N_2 (g)\mathop \to \limits^{k_3 } 2AlN(s) + CO_2 (g) \hfill \\ CO_2 (g) + C_f (s)\mathop \rightleftharpoons \limits_{k_4^\prime }^{k_4 } CO(g) + [O]_c \hfill \\ [O]_c \mathop \to \limits^{k_5 } CO(g) \hfill \\ \end{gathered}$$ The consumption rates of Al₂O₃ and carbon, and the production rate of AIN, were determined to be $$\begin{gathered} \frac{{d[Al_2 O_3 ]}}{{dt}} = - 143.88(1 + m)exp( - 290 580/RT) [Al_2 O_3 ][C]^2 / \hfill \\ \left\{ {1 + 5.83 x 10^{14} exp( - 427 497/RT)\frac{{[CO_2 ]}}{{[CO]}}} \right\}^2 kg mol s^{ - 1} m^{ - 3} \hfill \\ \frac{{d[C]}}{{dt}} = - 409.504 exp ( - 254 500/RT) [Al_2 O_3 ][C]^2 / \hfill \\ \left\{ {1 + 5.83 x 10^{14} \exp ( - 427 497/RT)\frac{{[CO_2 ]}}{{[CO]}}} \right\}^2 kg mol s^{ - 1} m^{ - 3} \hfill \\ \frac{{d[AlN]}}{{dt}} = 53.24(1 + m) exp( - 290 580/RT) [Al_2 O_3 ][C]^2 / \hfill \\ \left\{ {1 + 5.83 x 10^{14} exp( - 427 497/RT)\frac{{[CO_2 ]}}{{[CO]}}} \right\}^2 kg mol s^{ - 1} m^{ - 3} \hfill \\ \end{gathered}$$ in the temperature range 1648–1825 K.     

Thermal expansion of molybdenum in the range 1500–2800 K by a transient interferometric technique

The linear thermal expansion of molybdenum has been measured in the temperature range 1500–2800 K by means of a transient (subsecond) interferometric technique. The molybdenum selected for these measurements was the Standard Reference Material SRM 781 (a high-temperature enthalpy and heat capacity standard). The results are expressed by the relation where T is in K and l ₀ is the specimen length at 20°C. The maximum error in the reported values of thermal expansion is estimated to be about 1% at 2000 K and not more than 2% at 2800 K.Paper presented at the Ninth Symposium on Thermophysical Properties, June 24–27, 1985, Boulder, Colorado, U.S.A.     

Phase relations in the system Cu-La-O and thermodynamic properties of CuLaO2 and CuLa2O4

Phase relations in the system Cu-La-O at 1200 K have been determined by equilibrating samples of different average composition at 1200 K, and phase analysis of quenched samples using optical microscopy, XRD, SEM and EDX. The equilibration experiments were conducted in evacuated ampoules, and under flowing inert gas and pure oxygen. There is only one stable binary oxide La₂O₃ along the binary La-O, and two oxides Cu₂O and CuO along the binary Cu-O. The Cu-La alloys were found to be in equilibrium with La₂O₃. Two ternary oxides CuLaO₂ and CuLa₂O₄₊ were found to be stable. The value of varies from close to zero at the dissociation partial pressure of oxygen to 0.12 at 0.1 MPa. The ternary oxide CuLaO₂, with copper in monovalent state, coexisted with Cu, Cu₂O, La₂O₃, and/or CuLa₂O₄₊ in different phase fields. The compound CuLa₂O₄₊, with copper in divalent state, equilibrated with Cu₂O, CuO, CuLaO₂, La₂O₃, and/or O₂ gas under different conditions at 1200 K. Thermodynamic properties of the ternary oxides were determined using three solid-state cells based on yttria-stabilized zirconia as the electrolyte in the temperature range from 875 K to 1250 K. The cells essentially measure the oxygen chemical potential in the three-phase fields, Cu + La₂O₃ + CuLaO₂, Cu₂O + CuLaO₂ + CuLa₂O₄ and La₂O₃ + CuLaO₂ + CuLa₂O₄. Although measurements on two cells were sufficient for deriving thermodynamic properties of the two ternary oxides, the third cell was used for independent verification of the derived data. The Gibbs energy of formation of the ternary oxides from their component binary oxides can be represented as a function of temperature by the equations:

Phase relationships in the system Cr-W-O and thermodynamic properties of CrWO4 and Cr2WO6

The phase diagram of the Cr-W-O system at 1000° C was established by metallographic and X-ray identification of the phases present after equilibration in evacuated silica capsules. Two ternary oxide phases, CrWO₄ and Cr₂WO₆ were detected. The oxygen potential over the three-phase mixtures, W+Cr₂O₃ s+CrWO₄, WO_2.90+CrWO₄+Cr₂WO₆ and Cr₂O₃+CrWO₄+Cr₂WO₆, were measured by solid state cells incorporating Y₂O₃ stabilized ZrO₂ electrolyte and Ni+NiO reference electrode. The Gibbs' energies of formation of the two ternary phases can be represented by the following equations $$\begin{gathered} W(s) + \tfrac{1}{2} Cr_2 O_3 (s) + \tfrac{5}{4} O_2 (g) \to CrWO_4 (s) \hfill \\ \Delta G^0 = - 172 047 + 48.725T ( \pm 230) cal mol^{ - 1} \hfill \\ Cr_2 O_3 (s) + WO_3 (s) \to Cr_2 WO_6 (s) \hfill \\ \Delta G^0 = - 3 835 + 0.235{\rm T} ( \pm 500) cal mol^{ - 1} \hfill \\ \end{gathered}$$      

Thermal expansion of manganese carbonate

Precision lattice parameters of manganese carbonate have been determined at different temperatures by the X-ray powder method in the temperature range 28 to 265° C. The data has been used to evaluate, by a graphical method, the two coefficients of thermal expansion,α _∥ along thec-axis andα _⊥ at right-angles to thec-axis. The temperature-dependence of the coefficients is represented by the following equations: 1 $$\begin{gathered} \alpha _\parallel = 22.942 \times 10^{ - 6} - 5.555 \times 10^{ - 8} T + 3.361 \times 10^{ - 10} T^2 ,{\text{ }}(1) \hfill \\ \alpha _ \bot = 0.740 \times 10^{ - 6} + 2.812 \times 10^{ - 8} T - 6.722 \times 10^{ - 12} T^2 ,{\text{ (2)}} \hfill \\ \end{gathered} $$ whereT is the temperature in ° C.     

Thermodynamic properties of Pt5La,Pt5Ce,Pt5Pr,Pt5Tb and Pt5 Tm intermetallics

The Gibbs’ energies of formation of Pt₅La, Pt₅Ce, Pt₅Pr, Pt₅Tb and Pt₅ Tm intermetallic compounds have been determined in the temperature range 870–1100 K using the solid state cell: $$Ta,M + MF_3 /CaF_2 /Pt_5 M + Pt + MF_3 ,Ta$$ . The reversible emf of the cell is directly related to the Gibbs’ energy of formation of the Pt₅M compound. The results can be summarized by the equations: $$\begin{gathered} \Delta G_f^ \circ \left\langle {Pt_5 La} \right\rangle = - 373,150 + 6 \cdot 60 T\left( { \pm 300} \right)J mol^{ - 1} \hfill \\ \Delta G_f^ \circ \left\langle {Pt_5 Ce} \right\rangle = - 367,070 + 5 \cdot 79 T\left( { \pm 300} \right)J mol^{ - 1} \hfill \\ \Delta G_f^ \circ \left\langle {Pt_5 Pr} \right\rangle = - 370,540 + 4 \cdot 69 T\left( { \pm 300} \right)J mol^{ - 1} \hfill \\ \Delta G_f^ \circ \left\langle {Pt_5 Tb} \right\rangle = - 372,280 + 4 \cdot 11 T\left( { \pm 300} \right)J mol^{ - 1} \hfill \\ \Delta G_f^ \circ \left\langle {Pt_5 Tm} \right\rangle = - 368,230 + 4 \cdot 89 T\left( { \pm 300} \right)J mol^{ - 1} \hfill \\ \end{gathered} $$ relative to the low temperature allotropic form of the lanthanide element and solid platinum as standard states The enthalpies of formation of all the Pt₅M intermetallic compounds obtained in this study are in good agreement with Miedema’s model. The experimental values are more negative than those calculated using the model. The variation of the thermodynamic properties of Pt₅M compounds with atomic number of the lanthanide element is discussed in relation to valence state and molar volume.     

Transient interferometric technique for measuring thermal expansion at high temperatures: Thermal expansion of tantalum in the range 1500–3200 K

The design and operational characteristics of an interferometric technique for measuring thermal expansion of metals between room temperature and temperatures in the range 1500 K to their melting points are described. The basic method involves rapidly heating the specimen from room temperature to temperatures above 1500 K in less than 1 s by the passage of an electrical current pulse through it, and simultaneously measuring the specimen expansion by the shift in the fringe pattern produced by a Michelson-type polarized beam interferometer and the specimen temperature by means of a high-speed photoelectric pyrometer. Measurements of linear thermal expansion of tantalum in the temperature range 1500–3200 K are also described. The results are expressed by the relation: $$\begin{gathered} (l - l_0 )/l_0 = 5.141{\text{ x 10}}^{ - {\text{4}}} + 1.445{\text{ x 10}}^{ - {\text{6}}} T + 4.160{\text{ x 10}}^{ - {\text{9}}} T^2 \hfill \\ {\text{ }} - 1.309{\text{ x 10}}^{ - {\text{12}}} T^3 + 1.901{\text{ x 10}}^{ - {\text{16}}} T^4 \hfill \\ \end{gathered}$$ where T is in K and l₀ is the specimen length at 20°C. The maximum error in the reported values of thermal expansion is estimated to be about 1% at 2000 K and not more than 2% at 3000 K.     

Solidification and interfacial structure of in situ Al-4.5Cu/TiB2 composite

In situ particle reinforced Al-4.5Cu/TiB₂ composite was fabricated with TiO₂, H₃BO₃, Na₃AlF₆ powders and Al-4.5Cu alloy by reaction in melt. The composite can be directly casted into moulds to make composite parts. TiB₂ particles distribute uniformly in the matrix. The average size of TiB₂ particles is 0.93 m. At the atomic scale, TiB₂ is hexagonal, and exhibits hexagon or quadrilateral shape. The orientation relationships exist in the interfaces between TiB₂ particle and -Al, and between the reinforced small Al₂Cu phase and -Al in the composite. They are . TiB₂ particle is nucleation site for -Al matrix growth in the composite. The interface between TiB₂ particles and the matrix is clean and well bonded. No reaction product has been found through HREM observation. This is beneficial to the strength of the composite. The as-cast Al-4.5Cu/TiB₂ composite exhibits mechanical excellent properties: the tensile strength is 416.7 MPa, the yield strength is 316.9 MPa, and the elongation is 3.3 pct.     

Parametric Design of Fusion Diagrams and Solubility of Phases

Relationships between the fusion diagrams and the thermodynamic characteristics of the phases involved are analyzed using a relatively simple, thermodynamically substantiated equation of salt crystallization isotherms. The dimensionless parameters \(\begin{gathered} {\text{RMn}}_{\text{2}} {\text{O}}_{\text{5}} {\text{ = RMnO}}_{\text{3}} + \frac{1}{3}{\text{RMn}}_{\text{3}} {\text{O}}_{\text{4}} + \frac{1}{3}{\text{O}}_{\text{2}} \hfill \\ \frac{{\Delta G}}{{RT}} \hfill \\ \end{gathered} \) and \(\frac{{\Delta Z_{{\text{AX}}} }}{{RT}}\) are shown to be basic to the thermodynamics of liquid–solid and liquid–liquid phase equilibria. A number of techniques for evaluating thermodynamic constants from fusion diagrams and calculating elements of fusion diagrams from thermodynamic data are described and exemplified by particular systems. The effects of the basic parameters on the solubility of phases and phase equilibria are examined, and critical values of these parameters are determined for the first time. Parametric criteria for liquid immiscibility in salt systems are established.     

High-temperature stabilities of YCuO2, BaCu2O2 and Ba2CuO3 from oxide electrolyte e.m.f. measurements

The oxygen potentials in the system YCuO₂/Y₂O₃/Cu and Y₂O₃/YCuO₂/CuO were measured over the ranges 1113–1255 K and 782–1122 K by employing oxide electrolyte galvanic cells with air/platinum as the reference electrode, and the expression $$\Delta G_{f, ox}^o (YCuO_2 )( \pm 0.19)(kJ mol^{ - 1} ) = - 5.346 + 0.00384{\text{ }}T (K)$$ was determined. Similar e.m.f. measurements were carried out on the electrodes BaCuO₂/BaCu₂O₂/Cu₂O and Ba₂CuO₃/BaCuO₂/BaCu₂O₂ were measured over the ranges 1003–1132 K and 1175–1235 K and from the results, the ΔG _f,ox ^o of BaCu₂O₂ and Ba₂CuO₃ were determined to be $$\begin{gathered} \Delta G_{f, ox}^o (BaCu_2 O_2 )(kJ mol^{ - 1} ) = - 25.09 + 0.01548{\text{ }}T (K) \hfill \\ \Delta G_{f, ox}^o (BaCu_2 O_3 )(kJ mol^{ - 1} ) = - 5.79 - 0.07492{\text{ }}T (K) \hfill \\ \end{gathered} $$      

The thermodynamic parameters of monomer and dimer molecules of cerium and praseodymium tribromides

The method of high-temperature mass spectrometry is used for studying the composition of saturated vapor over cerium and praseodymium tribromides. Monomer and dimer molecules are found in the temperature ranges of 789–994 K and 804–957 K for cerium and praseodymium, respectively. The partial pressures of vapor components are determined, p(Pa), the temperature dependences of which are approximated by the equations

$\begin{gathered} \log p(CeBr_3 ) = ( - 14.63 \pm 0.08) \times 10^3 /T + (14.54 \pm 0.09), T = 789 - 994 K; \hfill \\ \log p(Ce_2 Br_6 ) = ( - 19.72 \pm 0.61) \times 10^3 /T + (17.60 \pm 0.64), T = 918 - 980 K; \hfill \\ \log p(PrBr_3 ) = ( - 14.13 \pm 0.12) \times 10^3 /T + (14.09 \pm 0.14), T = 804 - 957 K; \hfill \\ \log p(Pr_2 Br_6 ) = ( - 18.90 \pm 0.50) \times 10^3 /T + (17.15 \pm 0.53), T = 903 - 955 K. \hfill \\ \end{gathered} $

The values of pressure of vapor components are used along with literature data for the calculation of enthalpies of sublimation in the form of monomer and dimer molecules by the procedures of the second and third laws of thermodynamics. Based on analysis of the results, thermodynamic parameters of monomer and dimer molecules (in kJ mol^?1) are recommended,

$\begin{gathered} \,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\Delta _s H^0 (CeBr_3 , 298.15) = 305 \pm 5, \Delta _s H^0 (PrBr_3 , 298.15) = 293 \pm 5, \hfill \\ \,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\Delta _s H^0 (Ce_2 Br_6 , 298.15) = 410 \pm 28, \Delta _s H^0 (Pr_2 Br_6 , 298.15) = 403 \pm 28, \hfill \\ \,\,\,\,\,\,\,\Delta _f H^0 (CeBr_3 , gas, 298.15) = - 587 \pm 6, \Delta _f H^0 (PrBr_3 , gas, 298.15) = - 597 \pm 7, \hfill \\ \Delta _f H^0 (Ce_2 Br_6 , gas, 298.15) = - 1372 \pm 28, \Delta _f H^0 (Pr_2 Br_6 , gas, 298.15) = - 1378 \pm 28. \hfill \\ \end{gathered} $

     

Thermodynamic properties of (TeO2)0.95 ? n ? z(ZnO)z(Na2O)n(Bi2O3)0.05 glasses

The heat capacity (C _p ⁰) of the tellurite glasses

Isothermal transformation and decomposition ofβ 1 phase in a CuZnAl alloy

In the present paper, the crystallography of isothermal transformation and decomposition ofβ, phase have been studied by means of transmission electron microscopy and diffraction in the CuZnAl shape memory alloy. It has been proved that the bainite formed inβ ₁, matrix when the samples were transformed isothermally at moderate temperature. The crystallography of the isothermal bainitic transformation is identical to that of martensite in the same system. When the specimens were aged at moderate temperatures for longer time, the bainite and matrix decomposed to equilibrium phases. The decomposition process can be summarized as follows: $$\begin{gathered} bainite (9R) \to 9R + \alpha \left( {fcc} \right) \to \alpha + \beta \left( {bcc} \right) \hfill \\ matrix (B2) \to 2H + B2 \to \beta \left( {bcc} \right) \hfill \\ \end{gathered} $$ There are definite orientation relationships among these phases during the decomposition process and they are shown below: $$\begin{gathered} \left( {111} \right)_\alpha \parallel \left( {001} \right)_B ,\left[ {0\bar 11} \right]_\alpha \parallel \left[ {\bar 110} \right]_B \hfill \\ \left( {111} \right)_\alpha 5^ \circ away from \left( {110} \right)_\beta ,\left[ {0\bar 11} \right]_\alpha \parallel \left[ {1\bar 1\bar 1} \right]_\beta \hfill \\ \left( {110} \right)_M \parallel \left( {001} \right)_{2H} ,\left[ {001} \right]_M \parallel \left[ {010} \right]_{2H} \hfill \\ \end{gathered} $$ Thus, the crystallography of isothermal transformation and decomposition ofβ ₁ phase and the sequence of transitions have been revealed.     

Study on the behavior of elastic-plastic fracture under mixed I+II mode loading in aluminum alloy Ly12-J-integral analysis

The elastic-plastic fracture behavior of aluminum alloy Ly12 under mixed I+II mode loading was studied by finite element method and fracture test. A mixed mode elastic-plastic fracture criterion of J-integral was proposed by using the J-resistance curve, and the maximum fracture effective plastic strain _p max of different mixed ratios at crack tip were also calculated. The results show that(1) the initiation J-integral values of different mixed ratios have the equation

Surface-diffusion studies on UO2 and MgO

An optical interferometric technique has been used to study the growth of grain boundary grooves and the decay of surface scratches on UO₂ and MgO at temperatures in the range 1100 to 1700° C. The results were interpreted using equations derived by W. W. Mullins and it was found that surface-diffusion was the predominant material transport process for both oxides under the experimental conditions used. Surface-diffusion coefficients and activation energies were calculated, and gave the following equations for the variation of the mass transfer surface-diffusion coefficientD _s with temperature. $$\begin{gathered} UO_{2.005, } {\text{ }}D_s = 1.3 x 10^8 exp^{ - 11000 \pm 15000} /RT[1200{\text{ to }}1{\text{400}}^\circ {\text{ C]}} \hfill \\ MgO, D_s = 8 x 10^4 exp^{ - 88500 \pm 15000} /RT[1200{\text{ to }}15{\text{00}}^\circ {\text{ C]}} \hfill \\ \end{gathered}$$ It was found that for UO₂ the rate of grooving increased markedly as the oxygen content of the oxide increased.     

Heat capacity of liquid benzene and hexafluorobenzene at atmospheric pressure

Heat capacity, Cp, of benzene and hexafluorbenzene was measured in the liquid phase at atmospheric pressure in the temperature range from 280 K to the boiling point. The results are expressed by the following equations: for C₆H₆, for C₆F₆, $$\begin{gathered} C_p = 1.5194 - 1.299x10^{ - 3} T + 6.927 \times 10^{ - 6} T^2 \hfill \\ for C_6 F_6 \hfill \\ C_p = 1.1913 - 1.072x10^{ - 3} T + 3.589 \times 10^{ - 6} T^2 \hfill \\ \end{gathered} $$ where C _p is in kJ · kg^?1 · K^?1 and T is in K. The limiting error of heat capacity calculated from these equations is 0.23% for benzene and 0.18% for hexafluorobenzene. From the data, equations for specific volume, thermal expansion coefficient, and the quantity (δT/δp)_s were obtained for benzene and hexafluorobenzene.     

Heat capacity and electrical resistivity of nickel in the range 1300–1700 K measured with a pulse heating technique

Measurements of the heat capacity and electrical resistivity of nickel in the temperature range 1300–1700 K by a subsecond duration pulse heating technique are described. The results are expressed by the relations: $$\begin{gathered} C_p = 21.735 + 9.8200 \times 10^{ - 3} T \hfill \\ \rho = 18.908 + 2.3947 \times 10^{ - 2} T \hfill \\ \end{gathered} $$ whereC _p is in J · mol^?1·K^?1,ρ is inμΩ·cm, andT is in K. Estimated maximum uncertainties in the measured properties are 3% for heat capacity and 1% for electrical resistivity.     

A Study of Structure, Electric and Magnetic Properties of the New Layered Cobalt Oxides Sr2Y1-x Ca x Co2O7-z

The crystal structure of Sr ₂ Y _0.8 Ca _0.2 Co ₂ O ₆ is orthorhombic below 270 K (Immm, a = 3.84029(7) Å, b = 3.80691(6) Å and c = 19.4980(3) Å at 20 K), transformed from tetragonal (I4/mmm, a = 3.82765(6) Å and c = 19.5795(3) Å) at 295 K. The crystal structure distortion is accompanied by an anomalous temperature dependence of the degree of buckling of the CoO ₂ plane and is correlated with the development of anisotropic antiferromagnetic ordering of magnetic moments (2.93(2) _B per Co at 20 K). A magnetically glassy state below about 35 K and variable range hopping conduction below about 64 K for were found by magnetic susceptibility and electrical resistivity measurements.