Noncontact Measurements of Thermophysical Properties of Molybdenum at High Temperatures

Four thermophysical properties of both solid and liquid molybdenum, namely, the density, the thermal expansion coefficient, the constant-pressure heat capacity, and the hemispherical total emissivity, are reported. These thermophysical properties were measured over a wide temperature range, including the undercooled state, using an electrostatic levitation furnace developed by the National Space Development Agency of Japan. Over the 2500 to 3000 K temperature span, the density of the liquid can be expressed as _L(T)=9.10×10³–0.60(T–T _m) (kg·m^–3), with T _m=2896 K, yielding a volume expansion coefficient _L(T)=6.6×10^–5 (K^–1). Similarly, over the 2170 to 2890 K temperature range, the density of the solid can be expressed as _S(T)=9.49×10³–0.50(T–T _m), giving a volume expansion coefficient _S(T)=5.3×10^–5. The constant pressure heat capacity of the liquid phase could be estimated as C _PL(T)=34.2+1.13×10^–3(T–T _m) (J·mol^–1·K^–1) if the hemispherical total emissivity of the liquid phase remained constant at 0.21 over the temperature interval. Over the 2050 to 2890 K temperature span, the hemispherical total emissivity of the solid phase could be expressed as _TS(T)=0.29+9.86×10^–5(T–T _m). The latent heat of fusion has also been measured as 33.6 kJ·mol^–1.     

Non-contact measurements of thermophysical properties of niobium at high temperature

Four thermophysical properties of both solid and liquid niobium have been measured using the vacuum version of the electrostatic levitation furnace developed by the National Space Development Agency of Japan. These properties are the density, the thermal expansion coefficient, the constant pressure heat capacity, and the hemispherical total emissivity. For the first time, we report these thermophysical quantities of niobium in its solid as well as in liquid state over a wide temperature range, including the undercooled state. Over the 2340 K to 2900 K temperature span, the density of the liquid can be expressed as _L (T) = 7.95 × 10³ – 0.23 (T – T _m)(kg · m^–3) with T _m = 2742 K, yielding a volume expansion coefficient _L(T) = 2.89 × 10^–5 (K^–1). Similarly, over the 1500 K to 2740 K temperature range, the density of the solid can be expressed as _s(T) = 8.26 × 10³ – 0.14(T – T _m)(kg · m^–3), giving a volume expansion coefficient _s(T) = 1.69 × 10^–5 (K^–1). The constant pressure heat capacity of the liquid phase could be estimated as C _PL(T) = 40.6 + 1.45 × 10^–3 (T – T _m) (J · mol^–1 · K^–1) if the hemispherical total emissivity of the liquid phase remains constant at 0.25 over the temperature range. Over the 1500 K to 2740 K temperature span, the hemispherical total emissivity of the solid phase could be rendered as _TS(T) = 0.23 + 5.81 × 10^–5 (T – T _m). The enthalpy of fusion has also been calculated as 29.1 kJ · mol^–1.     

Thermal expansion of niobium in the range 1500–2700 K by a transient interferometric technique

The linear thermal expansion of niobium has been measured in the temperature range 1500–2700 K by means of a transient (subsecond) interferometric technique. The basic method involves rapidly heating the specimen from room temperature up to and through the temperature range of interest in less than 1 s by passing an electrical current pulse through it and simultaneously measuring the specimen temperature by means of a high-speed photoelectric pyrometer and the shift in the fringe pattern produced by a Michelson-type interferometer. The linear thermal expansion is determined from the cumulative shift corresponding to each measured temperature. The results for niobium may be expressed by the relation (l-l ₀)/l ₀=5.4424×10^–3–8.8553×10^–6 T+1.2993×10^–8 T ² –4.4002×10^–12 T ³+6.3476×10^–16T⁴ 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 2700 K.Paper presented at the Ninth International Thermal Expansion Symposium, December 8–10, 1986, Pittsburgh, Pennsylvania, U.S.A.     

Non-Contact Measurements of Surface Tension and Viscosity of Niobium, Zirconium, and Titanium Using an Electrostatic Levitation Furnace

The surface tension and viscosity of liquid niobium, zirconium, and titanium have been determined by the oscillation drop technique using a vacuum electrostatic levitation furnace. These properties are reported over wide temperature ranges, covering both superheated and undercooled liquid. For niobium, the surface tension can be expressed as (T)=1.937×10³–0.199(T–T _m) (mN·m^–1) with T _m=2742 K and the viscosity as (T)=4.50–5.62×10^–3(T–T _m) (mPa·s), over the 2320 to 2915 K temperature range. Similarly, over the 1800 to 2400 K temperature range, the surface tension of zirconium is represented as (T)=1.500×10³–0.111(T–T _m) (mN·m^–1) and the viscosity as (T)=4.74–4.97 ×10^–3(T–T _m) (mPa·s) where T _m=2128 K. For titanium (T _m=1943 K), these properties can be expressed, respectively, as (T)=1.557×10³–0.156(T–T _m) (mN·m^–1) and (T)=4.42–6.67×10^–3(T–T _m) (mPa·s) over the temperature range of 1750 to 2050 K.     

Measurement of the heat capacity of molybdenum (Standard Reference Material) in the range 1500–2800 K

Measurement of the heat capacity of molybdenum (Standard Reference Material 781 of the National Bureau of Standards) in the temperature range 1500–2800 K by a subsecond-duration, pulse-heating technique is described. The results of the measurements on three specimens are in agreement within 0.6%. The heat capacity of molybdenum in the temperature range 1500–2800 K based on the present results is expressed by the following function (standard deviation =0.5%): C _p =–3.0429+4.7215×10^–2 T–2.3139×10^–5 T ²+4.7090× 10^–9 T ³ where T is in K and C _p is in J · mol^–1 · K^–1. The inaccuracy of the reported results is estimated to be not more than 3%.     

Relaxation times of molecular ions OH− in glasses at very low temperature

This paper presents a detailed study of the temperature dependence of the longitudinal relaxation time T ₁ and of the coherence time T ₂ of a population of ionic molecular impurities in silica glass. Electric dipolar echoes taken in a temperature range 4–22 mK and a frequency of 370 MHz show that T ₁ is governed by a one-phonon process; consequently T ₁ varies like T ^–1; experimental data show that T ₂ also varies like T ^–1 and this in contradiction with predictions which lead to T ^–2. The relaxation of the spontaneous and stimulated echoes shows that there is a wide distribution of relaxation times (T ₁ and T ₂) ; from the amplitude of the signal it is also possible to extract both the longitudinal and the transverse electric moment; the coupling constant of the impurities with the strain is found to be as large as 3 eV.     

Containerless Property Measurements of Liquid Palladium

Some thermophysical properties of liquid and supercooled palladium were measured using containerless techniques. Over the 1640–1875 K temperature interval, the density could be expressed as (T)=10.66× 10³ –0.77(T–T_m)(kg·m^–3) and the ratio between the isobaric heat capacity and the hemispherical total emissivity could be rendered as (J·mol^–1·K^–1), where T_m=1828 K. The volume expansion coefficient was also determined as 7.2 × 10^–5 K^–1.     

Variable—Range hopping in Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-K<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript> glasses

The dc conductivity of the glasses in the Fe₂O₃-Bi₂O₃-K₂B₄O₇ system was studied at temperatures between 223 and 393 K. At temperatures from 300 to 223 K, T^–1/4 (T is temperature) dependence of the conductivity was found, however, both Mott variable-range hopping and Greaves intermediate range hopping models are found to be applicable. Mott and Greaves parameters analysis gave the density of states at Fermi level N (E_F) = 3.13 × 10²⁰–21.01 × 10²⁰ and 1.93 × 10²¹–16.39 × 10²¹ cm^–3eV^–1 at 240 K, respectively. The variable-range hopping conduction occurred in the temperature range T = 300–223 K, since W_D was found to be large (W_D = 0.08–0.14 eV for these glasses) and dominated the conduction at T < 300 K.     

Thermophysical Property Measurements of Liquid and Supercooled Iridium by Containerless Methods

Thermophysical properties of equilibrium and supercooled liquid iridium were measured using noncontact diagnostic techniques in an electrostatic levitator. Over the 2300–3000 K temperature range, the density can be expressed as ρ (T)=19.5×10³ − 0.85(T− T_m) (kg·m⁻³) with T_m=2719 K. The volume expansion coefficient is given by 4.4 × 10⁻⁵ K⁻¹. In addition, the surface tension can be expressed as γ (T)=2.23 × 10³ − 0.17(T−T_m)(10⁻³N·m⁻¹) over the 2373–2833 K span and the viscosity as η(T)=1.85 exp [3.0× 10⁴/(RT)](10⁻³Pa·s) over the same temperature range.     

The thermal conductivity of propane

This paper presents thermal conductivity measurements of propane over the temperature range of 192–320 K, at pressures to 70 MPa, and densities to 15 mol · L^–1, using a transient line-source instrument. The precision and reproducibility of the instrument are within ±0.5%. The measurements are estimated to be accurate to ±1.5%. A correlation of the present data, together with other available data in the range 110–580 K up to 70 MPa, including the anomalous critical region, is presented. This correlation of the over 800 data points is estimated to be accurate within ±7.5%.Nomenclature a _n, b_ij, b_n, c_n Parameters of regression model - C Euler's constant (=1.781) - P Pressure, MPa (kPa) - P _cr Critical pressure, MPa - Q ₁ Heat flux per unit length, W · m^–1 - t time, s - T Temperature, K - T _cr Critical temperature, K - T ₀ Equilibrium temperature, K - T _re Reference temperature, K - T _r Reduced temperature = T/T _cr - T _TP Triple-point temperature, K Greek symbols Thermal diffusivity, m² · s^–1 - T _i Temperature corrections, K - T Temperature difference, K - T _w Temperature rise of wire between time t ₁ and time t ₂, K - T ^* Reduced temperature difference (T–T _cr)/T_cr - _corr Thermal conductivity value from correlation, W · m^–1 · K^–1 - _cr Thermal conductivity anomaly, W · m^–1 · K^–1 - _e Excess thermal conductivity, W · m^–1 · K^–1 - ^* Reduced density difference - Thermal conductivity, W^–1 · m^–1 · K^–1, mW · m^–1 · K^–1 - _bg Background thermal conductivity, W · m^–1 · K^–1 - ₀ Zero-density thermal conductivity, W · m^–1 · K^–1 - Density, mol · L^–1 - _cr Critical density, mol · L^–1 - _re Reference density, mol · L^–1 - _r Reduced density Paper presented at the Tenth Symposium on Thermophysical Properties, June 20–23, 1988, Gaithersburg, Maryland, U.S.A.     

The effect of boron addition on brittle-to-ductile transition temperature and its strain rate sensitivity in gamma titanium aluminide

Temperature dependence of tensile properties ofTi–47Al–2Mn–2Nb–0.8TiB₂ alloy was investigated andbrittle-to-ductile transition temperature (T _BD) wasevaluated accordingly within the strain rate range from 10^–5 to10^–1 s^–1. T _BD and its strain rate sensitivity inTi-47Al-2Mn-2Nb-0.8TiB₂ alloy were compared withthose in Ti-47Al-2Mn-2Nb alloy. It is found that theminor addition of 1.0 at% boron reduces T _BD by more than100 K and that T _BD in both alloys shows a positivesensitivity to the strain rate. But the B-doped alloy has a lower BDTactivation energy (256 kJ/mol) than that of B-free alloy(324 kJ/mol). The effect of boron on T _BD and its strain ratesensitivity is attributed to the reduction in the grain size.     

The critical constants of long-chain normal paraffins

Because of the recent availability of the critical constants of normal alkanes up to octadecane, some modifications in the estimation procedures for the critical constants have become necessary. It has been shown that the equation of Ambrose for the critical temperature of normal alkanes leads to the result that as n , the limiting value for the critical temperature is equal to the limiting value for the normal boiling point and the limiting value for the critical pressure is 1 atm. Currently, the CH₂ increment for the critical volume is considered constant. The recent data of Teja have shown that the CH₂ increment increases indefinitely in a homologous series until the critical volume reaches its limiting value. This has made the current procedure for estimating the critical volume obsolete. Taking into account the new measurements of Teja, we have now developed new equations for estimating the critical constants. The limiting values for an infinitely long alkyl chain for T _b, T _c, P _c, and V _c have been found to be 1021 K, 1021 K, 1.01325 bar, and 18618 cm³ · mol^–1, respectively. These new concepts have been applied to the estimation of various properties other than the critical constants.Nomenclature M Molar mass, kg·mol ^–1 - V _c Critical volume, cm³·mol^–1 - V ₁ Saturated liquid volume, cm³·mol^–1 - P _c Critical Pressure, bar - T _c Critical temperature, K - T _b Normal boiling point, K - T _B Boyle temperature, K - T _A Temperature at which the third virial coefficient is zero, K - V _c Limiting value of critical volume = 18,618 cm³ · mol^–1 - P _c Limiting value of critical pressure=1.01325 bar - T _c Limiting value of critical temperature = 1021 K - T _b Limiting value of normal boiling point = 1021 K - P _b Pressure at the normal boiling point, 1 atm - Z _c Critical compressibility factor - Z _c Limiting value for the critical compressibility factor = 0.22222 - R Gas constant, 83.1448×10^–6m³ · bar · K^–1 · mol^–1 - Acentric factor - X (T _c–T _b)/T _c - X ₁ (T _c–T)/T _c - X ₂ 1–(T _B/T)^5/4 - X ₃ 1–(T _A/T)^5/2 - Y P _c/RT _c - Surface tension, mN · m^–1 - B Second virial coefficient, cm³ · mol^–1 - B Limiting value for the second virial coefficient = –30,463 cm³ · mol^–1 - C Third virial coefficient, cm⁶ · mol^–2 - C _b Third virial coefficient at the normal boiling point, cm⁶ · mol^–2 - C _c Third virial coefficient at the critical temperature, cm⁶ · mol^–2 - C _B Third virial coefficient at the Boyle temperature, cm⁶ · mol^–2 - H _vb Enthalpy of vaporization at the normal boiling point, kJ · mol^–1 - n Number of carbon atoms in a homologous series - p Platt number, number of C-C-C-C structural elements - a, b, c, d, e, etc Constants associated with the specific equation - T _c ^* , T _b ^* , P _c ^* , V _c ^* , etc. Dimensionless variables     

Thermophysical Properties of Molten Germanium Measured by a High-Temperature Electrostatic Levitator1

Thermophysical properties of molten germanium have been measured using the high-temperature electrostatic levitator at the Jet Propulsion Laboratory. Measured properties include the density, the thermal expansivity, the hemispherical total emissivity, the constant-pressure specific heat capacity, the surface tension, and the electrical resistivity. The measured density can be expressed by _liq=5.67×10³–0.542 (T–T _m ) kg·m^–3 from 1150 to 1400 K with T _m=1211.3 K, the volume expansion coefficient by =0.9656×10^–4 K^–1, and the hemispherical total emissivity at the melting temperature by _{T, liq}(T _m)=0.17. Assuming constant _{T, liq}(T)=0.17 in the liquid range that has been investigated, the constant-pressure specific heat was evaluated as a function of temperature. The surface tension over the same temperature range can be expressed by (T)=583–0.08(T–T _m) mN·m^–1 and the temperature dependence of the electrical resistivity, when r _liq(T _m)=60·cm is used as a reference point, can be expressed by r _{e, liq}(T)=60+1.18×10^–2(T–1211.3)·cm. The thermal conductivity, which was determined from the resistivity data using the Wiedemann–Franz–Lorenz law, is given by _liq(T )=49.43+2.90×10^–2(T–T _m) W·m^–1·K^–1.     

Non-Contact Measurements of the Thermophysical Properties of Hafnium-3 Mass% Zirconium at High Temperature

Several thermophysical properties of hafnium-3 mass % zirconium, namely the density, the thermal expansion coefficient, the constant pressure heat capacity, the hemispherical total emissivity, the surface tension and the viscosity are reported. These properties were measured over wide temperature ranges, including overheated and undercooled states, using an electrostatic levitation furnace developed by the National Space Development Agency of Japan. Over the 2220 to 2875 K temperature span, the density of the liquid can be expressed as _L (T)=1.20×10⁴–0.44(T–T _m ) (kgm^–3) with T _m =2504 K, yielding a volume expansion coefficient _L (T)=3.7×10^–5 (K^–1). Similarly, over the 1950 to 2500 K span, the density of the high temperature and undercooled solid -phase can be fitted as _S (T)=1.22×10⁴–0.41(T–T _m ), giving a volume expansion coefficient _S (T)=3.4×10^–5. The constant pressure heat capacity of the liquid phase can be estimated as C _PL (T)=33.47+7.92×10^–4(T–T _m ) (Jmol^–1K^–1) if the hemispherical total emissivity of the liquid phase remains constant at 0.25 over the 2250 K to 2650 K temperature interval. Over the 1850 to 2500 K temperature span, the hemispherical total emissivity of the solid -phase can be represented as _TS (T)=0.32+4.79×10^–5(T–T _m ). The latent heat of fusion has also been measured as 15.1 kJmol^–1. In addition, the surface tension can be expressed as (T)=1.614×10³–0.100(T–T _m ) (mNm^–1) and the viscosity as h(T)=0.495 exp [48.65×10³/(RT)] (mPas) over the 2220 to 2675 K temperature range.     

Theory of nuclear spin relaxation in a two-dimensional disordered HTcS in the normal state

The nuclear spin relaxation rateT ₁ ^–1 is calculated for a disordered two dimensional highcritical temperature superconductor taking into consideration the inelastic scattering of the electrons on the impurities. The deviation from the Korringa law of the formT ₁ ^–1 =AT+ B has been obtained if the quantum correction to the transport is dominated by the magnetic correlations.     

Aerobic composting of tobacco industry solid waste—simulation of the process

Solid waste accumulated during the processing of tobacco for cigarette manufacture mostly contains tobacco particles and flavoring agents. Its main characteristics are a high content of nicotine (2,000 mg per kg of total solids), which is a toxic compound, and high value of total organic carbon of the aqueous extract (12,620.0 mg l^–1). Because of this fact tobacco waste cannot be disposed of with urban waste.The aim of this work was to stabilize tobacco solid waste by aerobic composting. The experiments were carried out in closed thermally insulated column reactors (1.0 l and 25 l) under adiabatic conditions and at an airflow rate of 0.9 l min^–1 kg^–1 of volatile solids for 16 days. During the process, temperature changes in the reactor, CO₂ production and the numbers of mesophilic and thermophilic organisms in the mixed microbial culture were closely monitored. Nicotine concentration in the samples was analyzed at the start and at the end of process. It was estimated that at the end of composting the volume and mass of total solids in the tobacco waste were reduced by about 50% and those of nicotine by 80%. A simple empirical model was used to simulate the biodegradation rate of the organic fraction of the solid waste. It was found that the selected model describes aerobic composting fairly well, although only two kinetic parameters (k₀ and n) were estimated.List of symbols c_pS specific heat capacity of the substrate, kJ kg^–1 K^–1 - c_pz specific heat capacity of air, kJ kg^–1 K^–1 - F_Ku and F_Ki molar airflow at the reactor inlet and outlet, mol h^–1 - H_r reaction enthalpy, kJ kg^–1 of dry substrate - k specific rate, Eqs. (5) and (9), h^–1 - k_o constant in Eq. (9), day^–1 - m_o initial mass of the substrate, kg - m_S mass of dry substrate, kg - n order of the reaction in Eq. (5) - n_K molar amount of oxygen, mol - Q_v airflow volume, m³ h^–1 - r_K oxygen depletion rate, mol kg^–1 h^–1 - r_S degradation rate, kg kg^–1 h^–1 - _z air density, kg m^–3 - SD mean square deviation - t time, h - T temperature in reactor, °C - T_o temperature of substrate at the beginning of reaction, °C - T_K temperature of compost at the end of reaction, °C - T_u temperature of air at the reactor inlet - space time, day - w_S mass fraction of compost, m_sm_o^–1, kg kg^–1     

Thermophysical Property Measurements of Supercooled and Liquid Rhodium

The density, the isobaric heat capacity, the surface tension, and the viscosity of liquid rhodium were measured over wide temperature ranges, including the supercooled phase, using an electrostatic levitation furnace. Over the 1820 to 2250 K temperature span, the density can be expressed as (T)=10.82×10³–0.76(T–T _m ) (kgm^–3) with T _m =2236 K, yielding a volume expansion coefficient (T)=7.0×10^–5 (K^–1). The isobaric heat capacity can be estimated as C _P (T)=32.2+1.4×10^–3(T–T _m ) (Jmol^–1K^–1) if the hemispherical total emissivity of the liquid remains constant at 0.18 over the 1820 to 2250 K interval. The enthalpy and entropy of fusion have also been measured, respectively, as 23.0 kJmol^–1 and 10.3 Jmol^–1K^–1. In addition, the surface tension can be expressed as (T)=1.94×10³–0.30(T–T _m ) (mNm^–1) and the viscosity as (T)=0.09 exp[6.4×10⁴(RT)] (mPas) over the 1860 to 2380 K temperature range.     

Electrical transport in heavy rare-earth vanadates

This paper reports measurements of electrical conductivity () and Seebeck coefficient (S) between 300 and 1250 K and differential thermal analysis (DTA) and thermogravimetric analysis (TGA) between 300 and 1200 K, together with X-ray diffraction studies of heavy rare-earth vanadates (RVO₄ with R=Tb, Dy, Ho, Er and Yb). All these vanadates have been found to have a tetragonal unit cell. The DTA study shows a flat dip in the temperature interval 1075 to 1300 K, indicating a possible structural phase transition of these compounds. Practically no weight loss has been observed in TGA from 300 to 1200 K in any of the vanadates. All RVO₄ are semiconducting materials with the room-temperature value lying in the range 10^–12 to 10^{–3 –1} m^–1, becoming of the order of 10^{–2 –1} m^–1 around 1000 K. The electrical conductivity of all vanadates exhibits an exponential increase in the temperature intervals 420 K toT ₁ andT ₁ toT ₂, with different values of the activation energy. A log againstT ^–1 plot shows a peak aroundT ₃ and drops to a minimum value aroundT ₄, before increasing again with temperature.T ₄ >T ₃ >T ₂ >T ₁ are different for different vanadates and these are termed break temperatures.T ₄ lies well within the temperature range of the DTA peak and can be termed the phase transition temperature. In the lower temperature interval the electrical conduction is essentially extrinsic. The localized charge carriers on defect centres conduct by a hopping mechanism. The defect centres are V⁴⁺ ions in all vanadates with R⁴⁺ centres in some of them. It is concluded that in the temperature intervalT ₁ <T <T ₂ the conduction mechanism is of the intrinsic band type, with oxygen 2p and vanadium 3d as the valence and conduction bands, respectively. Related parameters like the energy band gap and the mobilities of the charge carriers have also been evaluated. The low values of mobility suggest that large polarons with intermediate coupling are the charge carriers rather than bare electrons in the intrinsic region. All these vanadates tend to become metallic, but before this is achieved the phase change makes the conductivity smaller.     

FTIR investigation of structural modifications during low-temperature ageing of polycarbonate

Conformational changes are sought during low-temperature ageing of solution-cast films of BPA-polycarbonate, by observing the conformationally sensitive IR aromatic breathing band at 1600 cm^–1. Preliminary results using the carbonyl band at 1775 cm^–1 had shown some indication of ageing-induced changes in the distribution of conformations. The present results obtained on the 1600 cm^–1 band show no indication whatever of conformational rearrangements. This result, at variance with observations of conformational rearrangements accompanying sub-T _g annealing, lends support to the concept that sub-T _g annealing and low temperature ageing are two distinct processes.     

Activated hopping of the hydroxide ion through electrodeposited thin films of electrochromic cobalt oxyhydroxide

Thin films of cobalt(II) oxyhydroxide on platinum have been prepared by electrodeposition. The chemical diffusion coefficient D of the hydroxide ion through the material has a marked temperature dependence, showing a simple activated behaviour in the range 273–292 K. The activation energy to ionic movement was rather large at 54.5 kJ mol^–1 which, it is proposed, is ascribable to ion hopping. When spins have changed alignment, at the Néel transition temperature T _Nr the activation energy more than doubled to 125 kJ mol^–1; and the diffusion coefficients obtained above this temperature also increased dramatically. It is proposed that structural changes occur in the electrodeposited oxide at about T _Nr hence the change in activation energy.