PVT measurements of water-ammonia refrigerant mixture in the critical and supercritical regions

The PVTx properties of H₂O + NH₃ mixture (0.2607 mole fraction of ammonia) have been measured in the near- and supercritical regions. Measurements were made along 40 liquid and vapor isochores in the range from 120.03 to 727.75 kg m⁻³ and at temperatures from 301 to 634 K and at pressures up to 28 MPa. Temperatures and densities at the liquid–gas phase transition curve, dew- and bubble-pressure points, and the critical parameters for the 0.7393 H₂O + 0.2607 NH₃ mixture were obtained using the quasi-static thermograms and isochoric (P–T) break-point techniques. The expanded uncertainty of the density, pressure, temperature measurements at the 95% confidence level with a coverage factor of k = 2 is estimated to be 0.06%, 0.02–0.09%, and 15 mK, respectively.     

Isochoric Heat Capacity Measurements for 0.5 H2O+0.5 D2O Mixture in the Critical Region

The isochoric heat capacity C _V of an equimolar H₂O+D₂O mixture was measured in the temperature range from 391 to 655 K, at near-critical liquid and vapor densities between 274.05 and 385.36 kgm^–3. A high-temperature, high-pressure, nearly constant-volume adiabatic calorimeter was used. The measurements were performed in the one- and two-phase regions including the coexistence curve. The uncertainty of the heat-capacity measurement is estimated to be ±2%. The liquid and vapor one- and two-phase isochoric heat capacities, temperatures, and densities at saturation were extracted from the experimental data for each measured isochore. The critical temperature and the critical density for the equimolar H₂O+D₂O mixture were obtained from isochoric heat capacity measurements using the method of quasi-static thermograms. The measurements were compared with a crossover equation of state for H₂O+D₂O mixtures. The near-critical isochoric heat capacity behavior for the 0.5 H₂O+0.5 D₂O mixture was studied using the principle of isomorphism of critical phenomena. The experimental isochoric heat capacity data for the 0.5 H₂O+0.5 D₂O mixture exhibit a weak singularity, like that of both pure components. The reliability of the experimental method was confirmed with measurements on pure light water, for which the isochoric heat capacity was measured on the critical isochore (321.96 kgm^–3) in both the one- and two-phase regions. The result for the phase-transition temperature (the critical temperature, T _{C, this work}=647.104±0.003 K) agreed, within experimental uncertainty, with the critical temperature (T _{C, IAPWS}=647.096 K) adopted by IAPWS.     

Experimental Study of the Isochoric Heat Capacity of Diethyl Ether (DEE) in the Critical and Supercritical Regions

Two- and one-phase liquid and vapor isochoric heat capacities (C _{V ρ} T relationship) of diethyl ether (DEE) in the critical and supercritical regions have been measured with a high-temperature and high-pressure nearly constant-volume adiabatic calorimeter. The measurements were carried out in the temperature range from 347 K to 575 K for 12 liquid and 5 vapor densities from 212.6 kg·m⁻³ to 534.6 kg·m⁻³. The expanded uncertainties (coverage factor k =  2, two-standard deviation estimate) for values of the heat capacity were 2% to 3% in the near-critical region, 1.0% to 1.5% for the liquid isochores, and 3% to 4% for the vapor isochores. The uncertainties of density (ρ) and temperature (T) measurements were 0.02% and 15 mK, respectively. The values of the internal energy, U(T, V), and second temperature derivative of pressure, (∂² P/∂T ²) _ρ , were derived using the measured C _V data near the critical point. The critical anomaly of the measured C _V and derived values of U(T, V) and (∂² P/∂T ²) _ρ in the critical and supercritical regions were interpreted in terms of the scaling theory of critical phenomena. The asymptotic critical amplitudes (A₀⁺ and A₀^- ){({A_0^+} {\rm and} {A_0^- )}} of the scaling power laws along the critical isochore for one- and two-phase C _V were calculated from the measured values of C _V . Experimentally derived values of the critical amplitude ratio for C_V (A₀⁺ /A₀^- = 0.521){C_{V} \left({A_0^+ /A_0^- = 0.521}\right)} are in good agreement with the values predicted by scaling theory. The measured C _V data for DEE were analyzed to study the behavior of loci of isothermal and isochoric C _V maxima and minima in the critical and supercritical regions.     

Thermodynamic Properties of Methanol in the Critical and Supercritical Regions

The isochoric heat capacity of pure methanol in the temperature range from 482 to 533 K, at near-critical densities between 274.87 and 331.59 kg· m⁻³, has been measured by using a high-temperature and high-pressure nearly constant volume adiabatic calorimeter. The measurements were performed in the single- and two-phase regions including along the coexistence curve. Uncertainties of the isochoric heat capacity measurements are estimated to be within 2%. The single- and two-phase isochoric heat capacities, temperatures, and densities at saturation were extracted from experimental data for each measured isochore. The critical temperature (T_c = 512.78±0.02K) and the critical density (ρ_c = 277.49±2 kg · m⁻³) for pure methanol were derived from the isochoric heat-capacity measurements by using the well-established method of quasi-static thermograms. The results of the C_VVT measurements together with recent new experimental PVT data for pure methanol were used to develop a thermodynamically self-consistent Helmholtz free-energy parametric crossover model, CREOS97-04. The accuracy of the crossover model was confirmed by a comprehensive comparison with available experimental data for pure methanol and values calculated with various multiparameter equations of state and correlations. In the critical and supercritical regions at 0.98T_c≤ T ≤ 1.5T_c and in the density range 0.35ρ_c ≤ ρ leq 1.65 ρ_c, CREOS97-04 represents all available experimental thermodynamic data for pure methanol to within their experimental uncertainties.     

Isochoric Heat Capacity of CO2 + n-Decane Mixtures in the Critical Region

The isochoric heat capacity of two binary (CO₂+n-decane) mixtures (0.095 and 0.178 mole fraction of n-decane) have been measured with a high- temperature, high-pressure, nearly constant volume adiabatic calorimeter. Measurements were made at nineteen near-critical liquid and vapor densities between 87 and 658 kg·m⁻³ for the composition of 0.095 mole fraction n-decane and at nine densities between 83 and 458 kg·m⁻³ for the composition of 0.178 mole fraction n-decane. The range of temperatures was 295 to 568 K. These temperature and density ranges include near- and supercritical regions. The measurements were performed in both one- and two-phase regions including the vapor + liquid coexistence curve. The uncertainty of the heat- capacity measurements is estimated to be 2% (coverage factor k=2). The uncertainty in temperature is 15 mK, and that for density measurements is 0.06%. The liquid and vapor one- and two-phase isochoric heat capacities, temperatures (T _S), and densities (ρ_S) at saturation were measured by using the well-established method of quasi-static thermograms for each filling density. The critical temperatures (T _C), the critical densities (ρ_C), and the critical pressure (P _C) for the CO₂+n-decane mixtures were extracted from the isochoric heat-capacity measurements on the coexistence curve. The observed isochoric heat capacity along the critical isochore of the CO₂+n-decane mixture exhibits a renormalization of the critical behavior of C _{V X} typical for mixtures. The values of the characteristic parameters (K ₁, K ₂), temperatures (τ₁ ,τ₂), and the characteristic density differences were estimated for the CO₂+n-decane mixture by using the critical-curve data and the theory of critical phenomena in binary mixtures. The ranges of conditions were defined on the T-x plane for the critical isochore and the ρ-x plane for the critical isotherm, for which we observed renormalization of the critical behavior for the isochoric heat capacity.     

Isochoric Specific Heat Capacity of Difluoromethane (R32) and a Mixture of 51.11 mass% Difluoromethane (R32) + 48.89 mass% Pentafluoroethane (R125)

The isochoric heat capacity (c _v ) of difluoromethane (R32) and a mixture of 51.11 mass% R32 + 48.89 mass% pentafluoroethane (R125) was measured at temperatures from 268 K to 328 K and at pressures up to 30 MPa. The reported density measurements are in the single-phase region and cover a range of ρ > 800 kg · m⁻³. The measured data are compared with results measured by other researchers. Also, the measured data are examined with available equations of state. As a result, it is found that the measured c _v ’s agree well with those of other researchers in the measurement range of the present study.     

Selective growth of well-aligned carbon nanotubes by APCVD

Well-aligned good-quality carbon nanotube (CNT) array was grown on silicon substrate by atmospheric pressure chemical vapor deposition (APCVD) through SiO₂ masking. First, the patterned substrate was pretreated with NH₃ and then CNTs were synthesized at 800 °C using Ni as the catalyst, acetylene (C₂H₂) as the carbon source material and N₂ as the carrier gas. Effects of the NH₃-pretreatment time, the flow ratio of [C₂H₂]/[NH₃] and the CNT growth time on the qualities of CNT array were analyzed in detail. It was found that good-quality CNTs with an average length of around 15 μm could be grown by pretreating the Si substrate with NH₃ for 10 min and then conducting the CNT growth with a flow ratio of [C₂H₂]/[NH₃] = 30/100. Furthermore, the field emission property of CNT array was investigated using a diode structure. It was found that the turn-on electric field decreased with increasing CNT length. The turn-on electric field as low as about 2 V/μm with an emission current density of 10 μA/cm² was achieved for a CNT-array diode with the tube length near 18 μm. For the same device, the emission current density could be elevated to 10 mA/cm² with the applied voltage of 3.26 V/μm.     

Effect of the self-organized cluster structure in LaSrMnO films on the slope of the temperature dependence of resistivity

We have studied the effect of atomic ordering in a nanodimensional clustered structure of amorphous LaSrMnO films on the slope of the temperature dependence of resistivity ρ(T) in the regions where dρ/dT > 0. It is established that a high concentration of clusters of a “metallic” phase (C _met = 9%) capable of fertromagnetic ordering leads to a giant temperature coefficient of resistivity (TCR), with its value (normalized slope) reaching (dρ/dT)/ρ = 1.6 × 10⁴% K⁻¹. Samples with a small concentration of such clusters (C _met = 0.1%) possess paramagnetic properties and their normalized TCR decreases by three orders of magnitude to (dρ/dT)/ρ = 1.7 × 10¹% K⁻¹. This behavior is explained by self-consistent changes in the atomic, magnetic, and electron subsystems.     

Low-temperature magnetoresistance of biaxially strained 24-nm-thick La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> films

The lateral unit cell parameter in nanodimensional La_0.67Ca_0.33MnO₃ (LCMO) films grown on (001)-oriented LaAlO₃ substrates is significantly (approximately 4%) smaller than the value measured along the normal to the substrate plane. At T < 140 K, the temperature dependence of the resistivity ρ of LCMO films follows the relation ρ − ρ (T = 4.2 K) ≈ρ₂(H)T ^4.5, where ρ₂ is independent of the temperature but decreases with increasing magnetic field H. It is shown that this decrease is related both to a decay of the spin waves in ferromagnetic domains and to the transformation of antiferromagnetic phase inclusions into ferromagnetic ones.     

PVTx Measurements for a H2O + Methanol Mixture in the Subcritical and Supercritical Regions

PVTx relationships for a H₂O + CH₃OH mixture (0.36 mole fraction of methanol) were measured in a range of temperatures from 373 to 673 K and pressures between 0.042 and 90.9 MPa. The density ranged from 37.76 to 559.03 kg · m^–3. Measurements were made with a constant-volume piezometer surrounded by a precision thermostat. The temperature inside the thermostat was maintained uniform within 5 mK. The volume of the piezometer (32.68 ± 0.01 cm³) was previously calibrated from well-established PVT values of pure water (IAPWS), and was corrected for both temperature and pressure expansions. Uncertainties of the density, temperature, and pressure measurements are estimated to be 0.16%, 30 mK, and 0.05%, respectively. The uncertainty in composition is 0.001 mole fraction. The method of isochoric and isothermal break points was used to extract the phase transition temperatures, pressures, and densities for each measured isochore and isotherm. The values of the critical temperature, pressure, and density of the mixture were also determined from PVTx measurements in the critical region.     

Crystal Structure of Double Co(NH3)6 3 + Np(V) Malonates Co(NH3)6(NpO2C3H2O4)2A·H2O (A = OH and NO3)

X-ray diffraction analysis of Co(NH₃)₆(NpO₂C₃H₂O₄)₂NO₃·H₂O (I) and Co(NH₃)₆(NpO₂· C₃H₂O₄)₂OH·H₂O (II) showed that they consist of [NpO₂C₃H₂O₄] _n ^{n -} infinite anionic chains, [Co(NH₃)₆]^{3 +} cations, NO₃ ^- (I) and OH^- (II) anions, and molecules of crystallization water. The anionic chain structure is similar to that in the known compound Co(NH₃)₆(NpO₂C₃H₂O₄)₂C₃H₃O₄. Neptunium(V) atoms occur in hexagonal-bipyramidal environment. The coordination capacity of malonate anions is 6, and they simultaneously coordinate three neptunyl(V) cations NpO₂ ⁺ in the chain.     

Phase conversions in calcium manganites with changing Ca/Mn ratios and their influence on the electrical transport properties

The phase-interconversions between the spinel-, brownmillerite-, defect rocksalt and perovskite-type structures have been investigated by way of (i) introducing deficiency in A-sites in Ca_xMn_2−xO₃ (0.05 ≤ × ≤ 1) i.e., by varying Ca/Mn ratio from 0.025 to 1 and (ii) nonstoichiometric CaMnO_3−δ (CMO) with 0.02 ≤ δ ≤ 1. The temperature dependence of resistivity (ρ–T) have been investigated on nonstoichiometric CaMnO_3−δ (undoped) as well as the CMO substituted with donor impurities such as La³⁺, Y³⁺, Bi³⁺ or acceptor such as Na¹⁺ ion at the Ca-site. The ρ–T characteristics of nonstoichiometric CaMnO_3−δ is strongly influenced by oxygen deficiency, which controls the concentration of Mn³⁺ ions and, in turn, affects the resistivity, ρ. The results indicated that the substitution of aliovalent impurities at Ca-site in CaMnO₃ has similar effects as of CaMnO_3−δ (undoped) annealed in atmospheres of varying partial pressures whereby electron or hole concentration can be altered, yet the doped samples can be processed in air or atmospheres of higher . The charge transport mechanisms of nonstoichiometric CaMnO_3−δ as against the donor or acceptor doped CaMnO₃ (sintered in air,  ~ 0.2 atm) have been predicted. The ρ (T) curves of both donor doped CaMnO₃ as well as non-stoichiometric CaMnO_3−δ, is predictable by the small polaron hopping (SPH) model, which changes to the variable range hopping (VRH) at low temperatures whereas the acceptor doped CaMnO₃ exhibited an activated semiconducting hopping (ASH) throughout the measured range of temperature (10–500 K).     

Isochoric Heat Capacity Measurements for Heavy Water Near the Critical Point

Isochoric heat capacity measurements of D₂O are presented as a function of temperature at fixed densities of 319.60, 398.90, 431.09, and 506.95 kg·m^–3. The measurements cover a range of temperatures from 551 to 671 K and pressures up to 32 MPa. The coverage includes one- and two-phase states and the coexistence curve near the critical point of D₂O. A high-temperature, high-pressure, adiabatic, and nearly constant-volume calorimeter was used for the measurements. Uncertainties of the heat capacity measurements are estimated to be 2 to 3%. Temperatures at saturation T _S () were measured isochorically using a quasi-static thermogram method. The uncertainty of the phase transition temperature measurements is about ±0.02 K. The measured C _V data for D₂O were compared with values predicted from a parametric crossover equation of state and six-term Landau expansion crossover model. The critical behavior of second temperature derivatives of the vapor pressure and chemical potential were studied using measured two-phase isochoric heat capacities. From measured isochoric heat capacities and saturated densities for heavy water, the values of asymptotic critical amplitudes were estimated. It is shown that the critical parameters (critical temperature and critical density) adopted by IAPWS are consistent with the T _S – _S measurements for D₂O near the critical point.     

Synthesis and characterization of high surface area molybdenum nitride

The synthesis of high surface area γ-Mo₂N materials using the nitridation of oxide precursors MoO₃, H₂MoO₅, and H₂MoO₅·H₂O with ammonia at 650°C is described. H₂MoO₅ and its hydrated form were obtained from the reaction of MoO₃ and diluted H₂O₂. The materials were characterized by means of X-ray powder diffraction, thermal analysis and nitrogen physisorption. Directly after the preparation, the nitride materials were subjected to different processing conditions: (1) contact to air, (2) inert gas or (3) treated with 1% O₂(g)/N₂(g) gas mixture (Passivation). The synthesis and passivation conditions critically affect the specific surface area of the final product. By means of XRD a minor quantity of MoO₂ was detected in most of the products. The highest specific surface area of the nitrides was 158.4 m²/g for γ-Mo₂N materials using H₂MoO₅·H₂O as the precursor. The high specific surface area corresponds to an average particle diameter of 4 nm, assuming a cubic morphology of the nanocrystals (d_p = 6/ρS_BET, ρ = 9.5 g/cc). The nitrogen physisorption isotherms of γ-Mo₂N are of type IV, but pore sizes and diameters differ significantly depending on the synthesis conditions due to different defect structures of the intermediates generated in the course of the topotactic transformation of the oxides to nitrides.     

Comparisons of Transparency AZO Films Using Sol-Gel and RF Sputtering Methods

In this research, we report the result of two different methods of making AZO films. In the first method, the AZO film was deposited on silicon wafer and glass substrate using a magnetic controlled RF sputtering system, with rf power (150 W) at two working pressures, 5 mtorr, and 10 mtorr, respectively. The deposition temperatures were 25, 100, 150, 200, and 300 °C, respectively. In the second method, the AZO film was made by sol-gel coating using (CH₃COO)₂ Zn⋅2H₂O mixed with AlCl₃⋅6H₂O and melting in HOC₂H₄NH₂ and CH₃OC₂H₅OH solvent and annealing at N₂ and/or 6% H₂/Ar for one hour. The transparencies of the films are all larger than 80%, and the resistivities may reach 10⁻³ Ω cm.     

Second-Order Derivatives of the Gibbs Energy for Liquid Mixtures of Alcohol + Heptane at Pressures up to 100 MPa

Second-order thermodynamic derivative properties, such as isobaric thermal molar expansions, isothermal and adiabatic molar compressibilities, and isochoric molar heat capacities of (ethanol, decan-1-ol, 2-methyl-2-butanol) +  heptane mixtures at pressures up to 100 MPa and in the temperature range from 293.15 K to 318.15 K were derived from experimental speed-of-sound u(T, p), density ρ(T, p = 0.1 MPa), and isobaric heat-capacity C _p (T, p = 0.1 MPa) data using appropriate thermodynamic relations. Excess values for the given properties were calculated according to the criterion of thermodynamic ideality of a mixture (Douhéret et al., Chem. Phys. Chem. 2, 148 (2001)), i.e., assuming that the chemical potential of component i in the ideal liquid mixture is equal to the chemical potential of component i in the mixture of perfect gases. The deviations from ideality for the mixtures under test have been explained in terms of the self-association of alcohols in solution which produces a strong departure from random mixing, the change in the non-specific interactions during mixing, and the packing effects.     

Isochoric Heat Capacity Measurements for Light and Heavy Water Near the Critical Point

The isochoric heat capacity was measured for D₂O at a fixed density of 356.075 kg·m^–3 and for H₂O at 309.905 kg·m^–3. The measurements cover the range of temperatures from 623 to 661 K. The measurements were made with a high-temperature, high-pressure, adiabatic calorimeter with a nearly constant inner volume. The uncertainty of the temperature is 10 mK, while the uncertainty of the heat capacity is estimated to be 2 to 3%. Measurements were made in both the two-phase and the one-phase regions. The calorimeter instrumentation also enables measurements of PVT and the temperature derivative (P/T)_V along each measured isochore. A detailed discussion is presented on the experimental temperature behavior of C_V in the one- and two-phase regions, including the coexistence curve near the critical point. A quasi-static thermogram method was applied to determine values of temperature at saturation T_S() on measured isochores. The uncertainty of the phase-transition temperature measurements is about ±0.02 K. The measured C_V data for D₂O and H₂O are compared with values predicted from a recent developed parametric crossover equation of state and IAPWS-95 formulation.     

Experimental researches on characteristics of vapor–liquid equilibrium of NH3–H2O–LiBr system

An improved system of NH₃–H₂O–LiBr was proposed for overcoming the drawback of NH₃–H₂O absorption refrigeration system. The LiBr was added to NH₃–H₂O system anticipating a decrease in the content of water in the NH₃–H₂O–LiBr system. An equilibrium cell was used to measure thermal property of the ternary NH₃–H₂O–LiBr mixtures. The pressure–temperature data for their vapor–liquid equilibrium (VLE) data were measured at ten temperature points between 15–85 °C, and pressures up to 2 MPa. The LiBr concentration of the solution was chosen in the range of 5–60% of mass ratio of LiBr in pure water. The VLE for the NH₃–H₂O–LiBr ternary solution was measured statically. The experimental results show that the equilibrium pressures reduced by 30–50%, and the amount of component of water in the gas phase reduced greatly to 2.5% at T=70 °C. The experimental results predicted much better characteristics of the new ternary system than the NH₃–H₂O system for the applications.     

Vortex State Microwave Resistivity in Tl-2212 Thin Films

We present measurements of the field induced changes in the 47 GHz complex resistivity, Δρ~(H, T), in Tl₂Ba₂CaCu₂O_8+x (TBCCO) thin films with T _c ≃ 105 K, prepared on CeO₂ buffered sapphire substrates. At low fields (μ₀ H < 10 mT) a very small irreversible feature is present, suggesting a little role of intergranular phenomena. Above that level Δρ~(H, T exhibits a superlinear dependence with the field, as opposed to the expected (at high frequencies) quasilinear behaviour. We observe a crossover between predominantly imaginary to predominantly real (dissipative) response with increasing temperature and/or field. In addition, we find the clear scaling property Δρ~(H, T = Δρ~[H/H ^* (T)], where the scaling field H ^∗ (T) maps closely the melting field measured in single crystals. We discuss our microwave results in terms of loss of flux lines rigidity.