Pressure effect on the electromotive force of the type R thermocouple

ABSTRACT

The pressure effect on the electromotive force (EMF) of a Pt13Rh–Pt (type R) thermocouple was examined to determine the temperature measurement accuracy of solid pressure medium apparatuses in high-pressure experiments. Single-wire EMFs were measured up to pressure of 13?GPa and temperature of 1173?K with a Kawai-type multi-anvil apparatus for Pt13Rh and Pt based on the single-wire method. The pressure conditions along the wires were evaluated by in situ X-ray diffraction using synchrotron X-ray radiation. The pressure effect of the Seebeck coefficients of Pt13Rh and Pt were determined by the analysis of the single-wire EMFs and pressure–temperature profiles along the wires and was virtually consistent with those determined in previous studies at lower pressures and temperatures. For type R thermocouple, the difference between the nominal and real temperatures was determined to be as large as –75?K at 13?GPa and 873?K.     

TR-LII for sizing of carbon particles forming at room temperature

Time-resolved laser-induced incandescence (TR-LII) was applied for the determination of particle sizes during carbon-particle formation from supersaturated atomic carbon vapor that was generated by laser photolysis of carbon suboxide (C₃O₂) at room temperature. Thus, the solid carbon particles were formed under hydrogen-free conditions. The TR-LII technique was used for in situ size measurement of growing carbon particles and samples of final particles were analyzed by transmission electron microscopy (TEM). It was found that the particles grow to a final size of 4–12 nm within 0.02–1 ms. The properties of the obtained particles depend on the initial conditions in the reaction volume, i.e. concentration of carbon suboxide, pressure and type of gas diluter, photolysis wavelength, and laser pulse energy. The comparison of TR-LII and TEM particle sizing results yields information about the effective thermal energy accommodation coefficients for He, Ar, CO, and C₃O₂ molecules on carbon particles. PACS 61.46.Df; 07.60.-j; 78.70.-g     

Combined measurement of several kinetic coefficients of liquid semiconductors

An apparatus has been developed for combined measurement of several kinetic coefficients of solid and liquid semiconductors subjected to a high pressure of a neutral gas. The absolute thermal emf, the electrical conductivity, and the thermal conductivity of copper selenide (Cu₂Se) were measured over a wide temperature range including the transition to the liquid state. The results are interpreted on the basis of an effect of charged copper vacancies and a broadening of the allowed energy bands during melting.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii Fizika, No. 6, pp. 73–78, June, 1970.     

Experimental determination of interfacial energies for Ag2Al solid solution in the CuAl2--Ag2Al system

The equilibrated grain boundary groove shapes of solid solution Ag2Al in equilibrium with an Al-Cu-Ag liquid were observed from a quenched sample with a radial heat flow apparatus.The Gibbs-Thomson coefficient,solid-liquid interfacial energy and grain boundary energy of the solid solution Ag2Al have been determined from the observed grain boundary groove shapes.The thermal conductivity of the solid phase and the thermal conductivity ratio of the liquid phase to solid phase for Ag2Al-28.3 at the %CuAl2 alloy at the melting temperature have also been measured with a radial heat flow apparatus and Bridgman type growth apparatus,separately.     

Performance comparison of Pt/Au and Ni/Au Schottky contacts on AlxGa1-x N/GaN heterostructures at high temperatures

In contrast with Au/Ni/Al 0.25 Ga 0.75 N/GaN Schottky contacts,this paper systematically investigates the effect of thermal annealing of Au/Pt/Al 0.25 Ga 0.75 N/GaN structures on electrical properties of the two-dimensional electron gas in Al 0.25 Ga 0.75 N/GaN heterostructures by means of temperature-dependent Hall and temperature-dependent current-voltage measurements.The two-dimensional electron gas density of the samples with Pt cap layer increases after annealing in N 2 ambience at 600℃ while the annealing treatment has little effect on the two-dimensional electron gas mobility in comparison with the samples with Ni cap layer.The experimental results indicate that the Au/Pt/Al 0.25 Ga 0.75 N/GaN Schottky contacts reduce the reverse leakage current density at high annealing temperatures of 400-600℃.As a conclusion,the better thermal stability of the Au/Pt/Al 0.25 Ga 0.75 N/GaN Schottky contacts than the Au/Ni/Al 0.25 Ga 0.75 N/GaN Schottky contacts at high temperatures can be attributed to the inertness of the interface between Pt and AlxGa1-xN.     

Vibrational spectra of ammonia chemisorbed on platinum (111): I. Identification of chemisorbed states

Ammonia chemisorption on Pt(111) has been studied with high resolution electron energy loss spectroscopy (EELS), combined with thermal desorption spectroscopy (TDS). We detect two distinct molecular states of ammonia at different coverages. Near saturation monolayer coverage, ammonia is weakly chemisorbed (ΔH_ads ～ 9 kcal mol^?1) and coordinated to the metal surface via the nitrogen atom. The vibrational frequencies are shifted from the gas phase values, but not as strongly perturbed as in stable platinum-ammine complexes. Below 40% saturation coverage, a new molecular ammonia state is detected, which has a distinct vibrational and thermal desorption spectrum. This state has a considerably reduced ν(PtN) intensity, and the other frequencies are closer to those in solid ammonia, indicating a weaker interaction with the Pt surface. The thermal desorption spectrum of this lower coverage state is broad, from 160 to 450 K, and coverage dependent. Conversion between the two molecular states appears to be only a function of coverage. We propose that the two molecular states have different adsorption sites, and convert from one form to the other as the coverage is changed. No evidence is found for significant dissociation of ammonia on the Pt surface. At very low temperatures (100 K), solid ammonia multilayers may be grown.     

Hydrogen gas-sensing properties of Pt/WO<Subscript>3</Subscript> thin film in various measurement conditions

A well-known gasochromic material is Pt particle-dispersed tungsten trioxide (Pt/WO₃). Its optical properties could make it effective as a hydrogen gas sensor. In this study, Pt nanoparticle-dispersed WO₃ thin films were prepared using the sol–gel process, and their optical and electrical properties dependent on the working environment (i.e., temperature, hydrogen gas concentration, oxygen partial pressure, etc.) were investigated. The Pt/WO₃ thin films prepared at 400 °C showed the largest change in optical transmittance and electrical conductivity when exposed to hydrogen gas compared with the films prepared at other temperatures. The optical absorbance and electrical conductivity were found to be dependent on the hydrogen and oxygen gas concentration in the atmosphere because generation and disappearance of W⁵⁺ in the thin films depend on the equilibrium reaction between injection and rejection of H⁺ into and from the thin films. In addition, the equilibrium reaction depends on the hydrogen and oxygen gas concentrations.     

Heat transfer in the high-temperature phase of solid SF<Subscript>6</Subscript>

The temperature dependences of the thermal conductivity are calculated for solid SF₆ and Xe. The influence of thermal pressure in a crystal on the isochoric thermal conductivity is investigated. The contributions of the phonon-phonon and phonon-rotation interactions to the total thermal resistance of solid SF₆ are calculated using a modified method of reduced coordinates. The temperature dependence of the isochoric thermal conductivity of SF₆ is explained by a combined effect of thermal pressure and phonon-rotation interaction.     

Sensor based on a Pt/LaF3/SiO2/SiC structure for the detection of chlorofluorocarbons

A metal-insulator-semiconductor structure based on silicon carbide with a subgate layer of LaF₃ solid electrolyte is discussed as a gas sensor. The kinetics of the variation of the flat-band potential of a Pt/LaF₃/SiO₂/SiC structure in interaction with chlorofluorocarbons (Freons) is investigated in the temperature range from 300 to 530 °C. The activation energies of the gas sensitivity are estimated from the temperature dependences of the response rate of the sensor to various Freons. The possibility of detecting all the investigated chlorofluorocarbons at a concentration level of 10 ppm in air is demonstrated. Zh. Tekh. Fiz. 69, 80–85 (November 1999)     

Integration of individual TiO2 nanotube on the chip: Nanodevice for hydrogen sensing

Titania (TiO₂) exists in several phases possessing different physical properties. In view of this fact, we report on three types of hydrogen sensors based on individual TiO₂ nanotubes (NTs) with three different structures consisting of amorphous, anatase or anatase/rutile mixed phases. Different phases of the NTs were produced by controlling the temperature of post‐anodization thermal treatment. Integration of individual TiO₂ nanotubes on the chip was performed by employing metal deposition function in the focused ion beam (FIB/SEM) instrument. Gas response was studied for devices made from an as‐grown individual nanotube with an amorphous structure, as well as from thermally annealed individual nanotubes exhibiting anatase crystalline phase or anatase/rutile heterogeneous structure. Based on electrical measurements using two Pt complex contacts deposited on a single TiO₂ nanotube, we show that an individual NT with an anatase/rutile crystal structure annealed at 650 °C has a higher gas response to hydrogen at room temperature than samples annealed at 450 °C and as‐grown. The obtained results demonstrate that the structural properties of the TiO₂ NTs make them a viable new gas sensing nanomaterial at room temperature. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Thermal conductivity of high temperature gas mixture for lighting engineering

Paper presents experimental values of the coefficient of thermal conductivity of a ternary gaseous mixture (0·15 N₂-0·1 Ar-0·75 Kr) in the temperature range between approx. 1500 and 4000 K at about a mospheric pressure. The unsteady method based on the analysis of the heat flux from gas heated by the reflected shock wave to the end wall of a shock tube was used. Presented values agree well with rigorous kinetic theory calculations and with a combined Dulnev's model.Notation (in SI units) a thermal diffusivity - c _p isobaric heat capacity - E voltage - p pressure - T thermodynamic temperature - t time - x coordinate - temperature coefficient of resistance - mass density - coefficient of thermal conductivity Indexes 1 gas state before the experiment - 2 gas state behind the primary shock wave - 5 gas state behind the reflected shock wave - f relates to the solid wall - F relates to the solid wall on the solid-gas phase boundary - g relates to the test gas - G relates to the gas on the gas-solid phase boundary     

低温下粗糙表面接触间隙气体热导的研究

对低温非真空环境下粗糙接触界面间隙中介质气体的传热进行了理论分析．依据克努森数的大小,建立了不同传热区域的间隙气体热导理论模型．并对影响接触界面间隙热导的克努森数、普朗特数、热导率、适应系数、压力等参数进行了分析,为实际情况下接触界面的传热提供了理论基础．而且通过实验证明了在界面接触压力较小的情况下,即使对于硬度较小导热性能好的接触固体,间隙气体的导热量仍大于通过实际接触点的导热量．     

SrBi2Ta2O9 ferroelectric thin film capacitors: degradation in a hydrogen ambient

The effects of annealing in forming gas 5% hydrogen, 95% nitrogen; FGA) are studied on spin-coated SrBi₂Ta₂O₉ (SBT) thin films. SBT films on a platinum bottom electrode are characterized with and without a platinum top electrode. Films are characterized by residual stress measurements, scanning electron microscopy (SEM), Auger electron spectroscopy (AES), high-temperature X-ray diffraction (HT-XRD) and secondary ion mass spectrometry (SIMS). To determine the degree of strain, lattice constants of Pt are measured by X-ray diffraction (XRD). HT-XRD of blanket SBT/Pt/Ti films in forming gas revealed that the bismuth-layered perovskite structure of SBT is stable up to approximately 500 °C. After formation of an intermediate phase between 550 °C and 700 °C, SBT changes its structure to an amorphous phase. SIMS analysis of Pt/SBT/Pt samples annealed in deuterated forming gas (5% D₂, 95% N₂) showed that hydrogen accumulates in the SBT layer and at the platinum interfaces next to the SBT. After FGA of blanket SBT films, tall platinum–bismuth whiskers are seen on the SBT surface. It is confirmed that these whiskers originate from the platinum bottom electrode and grow through the SBT layer. FGA of the entire Pt/SBT/Pt/Ti stack shows two different results. For the samples with a high-temperature annealing (HTA) step in oxygen after top electrode patterning, peeling of the top electrode is observed after FGA. For the samples without a HTA step, no peeling is observed after FGA. The residual stress at room temperature is measured for blanket platinum wafers deposited at different temperatures. It is found that an increase in tensile stress caused by the HTA step in oxygen is followed by a decrease in stress caused by the hydrogen in the forming gas. Without HTA, however, an increase of stress is observed after FGA. PACS 77.84.-s; 81.40.-z; 77.55.+f     

Photophoresis—Light induced motion of particles suspended in gas

When irradiated sideways, by visible light, a particle can perform different kinds of motion, (e.g. in direction of irradiation, opposite to irradiation, vertical movement, helicoidally, etc.). This phenomenon is called photophoresis. Photophoresis is based on momentum transfer between the aerosol particle and surrounding gas molecules. Photophoresis strongly depends on the pressure of the surrounding gas. Particles mostly influenced by photophoresis are those of μm size. Two main types of forces describe photophoretic motion: ΔT force: The thermal accommodation coefficient α is constant over the particle surface. As a result of the thermal accommodation, gas molecules on the warm side of a particle leave the surface faster than gas molecules on the cold side. This leads to ΔT force on the particle towards the colder side. Typical motion of the particle will be either away from light irradiation (positive photophoresis), or in direction of light irradiation (negative photophoresis). In the case of negative photophoresis, the back side of the particle, due the nature of light absorption, will be heated more than front side of the particle. Δα force: If the particle is at a constant temperature, which is different from the temperature of the surrounding gas, and the thermal accommodation coefficient α varies over the particle surface, the net momentum between gas molecules and particle will be transferred. In this case, the result will be body fixed Δα force. Depending on the particle surface properties, Δα force can direct the particle in any possible photophoresis could also play important role in planet formation and astrophysics.     

Temperature and pressure dependences of the thermal conductivity of As2(Se1-xTex)3 solid solutions

The effect of temperature and pressure on the thermal conductivity of solid solutions based on the As₂(Se_{1 - x}Te_x)₃ system was investigated in glassy and polycrystalline samples at 273–450 K and hydrostatic pressures of up to 0.35 GPa. The compound As₂Se₃ was studied in a temperature range of 300–760 K. Analysis showed that the short-cange order structure in As₂Se₃ remains unchanged upon the glass—liquid transition right up to 760 K.     

Electrochemical characterisation of the Pt/YSZ interface exposed to a reactive gas phase

The Pt/yttria-stabilized cubic zirconia (YSZ) interface exposed to a reactive gas was characterised by solid electrolyte potentiometry and cyclic voltammetry. The catalytic reactions included total combustion of C₃H₈ and C₃H₆ to CO₂ and H₂O as well as NO reduction by C₃H₆ in the presence of O₂ under oxygen-rich and stoichiometric conditions. The solid electrolyte potentiometry as a function of the temperature in C₃H_x/O₂ (with x=6 or 8) reflected the catalytic properties of Pt for C₃H_x oxidation. In C₃H₆/NO/O₂, the reduction of NO was evidenced below 300 °C. The cyclic voltammetry evidenced the formation of an oxygen chemisorbed layer on the Pt surface under anodic potential. Propane had no effect on this chemisorbed layer, whereas propene weakened significantly the strength of this Pt–O bond. Addition of NO to C₃H₆/O₂ led to the disappearing of this chemisorbed layer. The use of solid electrolyte potentiometry in conjunction with cyclic voltammetry allowed us to determine the surface oxidation state of Pt during the catalytic reactions.     

Impedance study of BIMGVOX ceramics

The polycrystalline samples of Bi₂V_0.9Mg_0.1O_5.35 were synthesised. The conductivity of the samples with Pt electrodes was determined by non-linear least-squares analysis of the impedance spectra. The total conductivity of the samples exhibits Arrhenius-type dependence on temperature with two straight line sections. In the transition from one linear section to the other a time dependence of conductivity was observed. The conductivity decreases both on heating and cooling during several hours at constant temperature (between 665 and 680K and between 710 and 695K on heating and cooling respectively). During heating at temperatures between 685 and 790K the Arrhenius plot are not linear. It may be expected that a process of slow ordering/disordering of oxygen vacancies is responsible for this phenomenon. The values of conductivity at low temperatures were dependent upon the length of time the sample was allowed to reach equilibrium - the structure of the material seems to be frozen in a metastable state, probably β type. At high temperature region the conductivity do not depend on the thermal history of sample. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Schottky barrier height lowering induced by CoSi2 nanostructure

CoSi₂ nanostructures were formed through thermal agglomeration by annealing ultrathin Co film on Si substrate at high temperatures. The characteristics of the Schottky diodes with CoSi₂ nanostructures capped by a Pt layer were measured and fitted using thermionic emission theory. All the diodes have a ideality factor less than 1.1. The results show that the Schottky barrier height of these diodes significantly decreases as the annealing temperature for CoSi₂ agglomeration increases. The barrier height lowering is correlated with the agglomeration of CoSi₂ film and the formation of CoSi₂ nano-islands. The thermal field emission may be the major reason to cause barrier lowering. Although the Schottky contact interface consists of both CoSi₂ nano-islands and Pt film whose individual contact barrier height to Si is very different, the current-voltage-temperature measurements reveal that the interface homogeneity is not degraded as expected. The study demonstrates that the CoSi₂ nanostructures can both lower the Schottky barrier height and form an ideal Schottky contact with a Pt capping layer.     

Fundamental and practical aspects of CO2 sensors based of nasicon electrolytes

Potentiometric CO₂ sensors based on the Na⁺ conducting solid electrolyte Nasicon have been investigated. The sensor arrangement may be described as chemical sensor of type III, $$( - )Pt(or Au), Na_{0.9} CoO_2 |Nasicon|Na_2 CO_3 , Pt(or Au) ( + ),$$ , with Na_0.9CoO₂ as reference electrode and Na₂CO₃ as auxiliary or sensing electrode. It is shown that major problems are related to the magnitude of the voltage and long-term stability of this type of sensor. The measured EMFs are generally reduced compared to the values calculated from literature data of standard Gibbs energies of formation. This observation is ascribed to reactions at the interfaces and competing surface reactions. The interfacial processes may occur at both electrolyte / sensing and electrolyte / reference electrode, and represent charged capacitors. It has also been observed that the slope of the measured EMF as a function of the CO₂ partial pressure is reversed in some cases. This phenomenon may be related to the possible reduction of Na₂O which is dissolved in Nasicon during the formation of Na₂CO₃ upon an increase of the CO₂ partial pressure.