Showing papers on "Atmospheric temperature range published in 1998"

Semiconducting Ge clathrates: Promising candidates for thermoelectric applications

Abstract: Transport properties of polycrystalline Ge clathrates with general composition Sr8Ga16Ge30 are reported in the temperature range 5 K⩽T⩽300 K. These compounds exhibit N-type semiconducting behavior with relatively high Seebeck coefficients and electrical conductivity, and room temperature carrier concentrations in the range of 1017–1018 cm−3. The thermal conductivity is more than an order of magnitude smaller than that of crystalline germanium and has a glasslike temperature dependence. The resulting thermoelectric figure of merit, ZT, at room temperature for the present samples is 14 that of Bi2Te3 alloys currently used in devices for thermoelectric cooling. Extrapolating our measurements to above room temperature, we estimate that ZT>1 at T>700 K, thus exceeding that of most known materials.

“S-shaped” temperature-dependent emission shift and carrier dynamics in InGaN/GaN multiple quantum wells

Abstract: We report temperature-dependent time-integrated and time-resolved photoluminescence (PL) studies of InGaN/GaN multiple quantum wells (MQWs) grown by metalorganic chemical vapor deposition. We observed anomalous emission behavior, specifically an S-shaped (decrease–increase–decrease) temperature dependence of the peak energy (Ep) for InGaN-related PL with increasing temperature: Ep redshifts in the temperature range of 10–70 K, blueshifts for 70–150 K, and redshifts again for 150–300 K with increasing temperature. In addition, when Ep redshifts, the spectral width is observed to narrow, while when Ep blueshifts, it broadens. From a study of the integrated PL intensity as a function of temperature, it is found that thermionic emission of photocarriers out of local potential minima into higher energy states within the wells is the dominant mechanism leading to the thermal quenching of the InGaN-related PL. We demonstrate that the temperature-induced S-shaped PL shift is caused by a change in the carrier dyna...

Shape Transformation and Surface Melting of Cubic and Tetrahedral Platinum Nanocrystals

Abstract: We report transmission electron microscopic studies of in-situ temperature-induced shape transformation and melting behavior of polymer-capped cubic and tetrahedral nanocrystals. Our results indicate that the surface-capping polymer is removed by annealing the specimen at temperatures between 180 and 250 °C. The particle shapes show no change up to ∼350 °C. In the temperature range between 350 and 450 °C, a small truncation occurs in the particle shapes but no major shape transformation is observed. The particle shapes experience a dramatic transformation into spherical-like shapes when the temperature is raised above ∼500 °C, where surface diffusion or surface premelting (softening) takes place. Above 600 °C, surface melting becomes obvious leading to coalescence of the surfaces of neighboring nanocrystals and a decrease in the volume occupied by the assembled nanocrystals. The surface melting forms a liquid layer a few atomic layers deep around the still solid core of the nanocrystal. This temperature i...

Comparison of fluorescence-based temperature sensor schemes: Theoretical analysis and experimental validation

Abstract: The performance of the two most promising fluorescence-based temperature sensing techniques, namely the fluorescence intensity ratio (FIR) and fluorescence lifetime (FL) schemes, have been compared. Theoretical calibration graphs for the two methods illustrate the useful monotonic change of the response with temperature variation. Comparison of the responses and the sensitivities of the two schemes show that at very low temperatures the FIR method exhibits a significant variation with temperature, while the response of the FL method becomes constant with its sensitivity approaching zero. With increasing temperature, the FIR and the FL methods (with short relaxation times and shorter intrinsic lifetimes of the upper energy levels) share a similar sensitivity over a wide temperature range. The presence of a long relaxation time or a longer intrinsic lifetime of the upper level in the use of the FL method gives a less satisfactory response. Experimental data obtained for a range of dopant ions in various hos...

Intermediate Temperature Solid Oxide Fuel Cells Using a New LaGaO3 Based Oxide Ion Conductor I. Doped as a New Cathode Material

Abstract: ‐based perovskite oxides doped with Sr and Mg exhibit high ionic conductivity over a wide range of oxygen partial pressure. In this study, the stability of ‐based oxide was investigated. The ‐based oxide was found to be very stable in reducing, oxidizing, and atmospheres. Solid oxide fuel cells (SOFCs) using ‐based perovskite‐type oxide as the electrolyte were studied for use in intermediate‐temperature SOFCs. The power‐generation characteristics of cells were strongly affected by the electrodes. Both Ni and (Ln:rare earth) were suitable for use as anode and cathode, respectively. Rare‐earth cations in the Ln site of the Co‐based perovskite cathode also had a significant effect on the power‐generation characteristics. In particular, a high power density could be attained in the temperature range 973–1273 K by using a doped for the cathode. Among the examined alkaline earth cations, Sr‐doped exhibits the smallest cathodic overpotential resulting in the highest power density. The electrical conductivity of increased with increasing Sr doped into the Sm site and attained a maximum at . The cathodic overpotential and internal resistance of the cell exhibited almost the opposite dependence on the amount of doped Sr. Consequently, the power density of the cell was a maximum when was used as the cathode. For this cell, the maximum power density was as high as 0.58 W/cm2 at 1073 K, even though a 0.5 mm thick electrolyte was used. This study revealed that a ‐based oxide for electrolyte and a ‐based oxide for the cathode are promising components for SOFCs operating at intermediate temperature.

Temperature dependence of the absorption coefficient of cosmic analog grains in the wavelength range 20 microns to 2 millimeters

Abstract: We have measured the absorption coefficient per unit mass of cosmic dust analog grains, crystalline fayalite and forsterite, amorphous fayalite, and two kinds of disordered carbon grains, between 20 μm and 2 mm over the temperature range 295-24 K. The results provide evidence of a significant dependence on temperature. The opacity systematically decreases with decreasing temperature; at 1 mm, it varies by a factor of between 1.9 and 5.8, depending on the material, from room temperature to 24 K. The variations are more marked for the amorphous grains. The wavelength dependence of the absorption coefficient is well fitted by a power law with exponent β that varies with temperature. For the two amorphous carbons, β(24 K) ~1.2 with increases of 24% and 50% with respect to the room-temperature values. A 50% increase is found for amorphous fayalite, characterized by β(24 K) = 2. A less pronounced change of β with temperature, 14% and 10%, is observed for crystalline forsterite, β(24 K) = 2.2, and fayalite, β(24 K) = 2.3, respectively. For amorphous fayalite grains, the millimeter opacity at 24 K is larger by a factor of ~4 than that of the crystalline counterpart. In addition, a temperature dependence of the infrared bands present in the spectrum of the two crystalline silicates is found. The features become more intense, sharpen, and shift to slightly higher frequencies with decreasing temperature. The results are discussed in terms of intrinsic far-infrared-millimeter absorption mechanisms. The linear dependence of the millimeter absorption on temperature suggests that two-phonon difference processes play a dominant role. The absorption coefficients reported in this work can be useful in obtaining a more realistic simulation of a variety of astronomical data concerning dust at low temperatures and give hints to better identify its actual properties. In particular, they are used to discuss the origin of the diffuse far-infrared-millimeter interstellar dust emission spectrum. It is proposed that composite particles formed of silicate and amorphous carbon grains can reproduce the observations. The presence of these particles in the diffuse medium is consistent with the recent interstellar extinction model by Mathis.

Electrochemical‐Calorimetric Studies of Lithium‐Ion Cells

Abstract: An accelerated rate calorimeter in combination with a battery cycler and a precision multimeter was used to measure the heat dissipation from, and heat accumulated in, commercially available lithium-ion cells during cycling over a range of operating parameters within the limits recommended by the manufacturer. An integral energy balance was used to determine the total heat generated in the test cell during cycling. From the measurements during temperature transients the heat capacity of the test cell was found to be relatively independent of temperature, ranging from 0.82 to 1.07 J g -1 K -1 . This value agrees relatively well with separate measurements using an adiabatic calorimeter which yield slightly higher values. DC current interruption technique was used to determine the time-dependent area-specific impedance, , of the cell which was well correlated with steeply increased heat dissipation rate at the end of discharge. The reversible (entropic) heat effect derived from an energy balance was found to be exothermic during discharge and endothermic during charge. Using two different methods, values were obtained for the entropy of reaction (AS) during discharge of the cell. The resulting values obtained with method II, depending on the discharge rate, varied from -41.19 to -80.98 J K -1 per g mole of Li and showed a weak dependence on temperature, in the 35 to 55°C range. The rate dependence of the AS values needs further examination in a future study. By extrapolating to zero rate, the reversible entropy of the faradaic reaction for this cell was found to be -37 ± 3 J K -1 per g mole of Li within the temperature range. The entropic heat effect and the heat effect associated with nonfaradaic reactions are appreciable and should be included in thermal modeling.

Structural and Magnetic Properties of Fe2O3 Nanoparticles Dispersed over a Silica Matrix

Abstract: The structure and the magnetic properties of a series of Fe2O3−SiO2 nanocomposites (9−33 wt % Fe2O3), prepared by a sol−gel method and submitted to thermal treatments in the temperature range 300−900 °C, were investigated through XRD, TEM, EPR, and magnetic susceptibility measurements. Superparamagnetic iron(III) oxide nanoparticles with a narrow size distribution, dispersed over the amorphous silica matrix, are present in all the samples. They are mostly amorphous, antiferromagnetic in the samples treated at low temperatures. At T > 700 °C, a lot of γ-Fe2O3 crystalline ferrimagnetic nanoparticles (4−6 nm) are formed, while a further increase of the temperature results in the γ- to α-Fe2O3 transformation. The variation of iron oxide content affects the abundance of γ-Fe2O3 formation, which reaches the maximum percent values in the more dilute samples. In the more concentrated samples, while the amount of maghemite is still growing, antiferromagnetic α-Fe2O3 begins to form. As a consequence, the saturation...

Thermal Expansion of Nickel‐Zirconia Anodes in Solid Oxide Fuel Cells during Fabrication and Operation

Abstract: The thermal expansion of NiO-8 mol % Y{sub 2}O{sub 3}-stabilized ZrO{sub 2} (YSZ) composites and Ni-YSZ cermets in air and hydrogen have been investigated in the temperature range from 50 to 1,000 C. The average linear thermal expansion coefficient (TEC) of NiO-YSZ composites in air increased with NiO content over the entire composition range. While NiO in the composites was changed to Ni in the H{sub 2} stream, their expansions were governed by the reduction of NiO. For reduced, Ni-YSZ cermets, the TEC increases significantly with Ni content in the composition range > 60 vol% Ni. The TEC increased gradually during repeated thermal cycles between room temperature and 1,000 C. When cermets were measured in air, the Ni particles were fully oxidized to NiO above 900 C, and many cracks appeared in the samples.

Tunable magnetocaloric effect in ceramic perovskites

Abstract: A large entropy variation (magnetocaloric effect) has been discovered in ceramic perovskites with the formulas La0.65Ca0.35Ti1−xMnxO3−z and La0.5+x+yLi0.5−3yTi1−3xMn3xO3−z. Both Curie temperature and entropy change were studied from 4.2 to 400 K for different stoichiometric compositions and applied magnetic fields. Our conclusion is that these materials are excellent candidates for working materials in magnetic refrigeration and liquefaction devices in a wide temperature range.

Thermal quenching of F-center luminescence in Al2O3:C

Abstract: Using time-resolved photoluminescence spectroscopy we have measured the lifetime of the F-center luminescence from α-Al2O3:C. The measurements reveal a lifetime of 35–36 ms at room temperature, decreasing to <2 ms over the temperature range from 370 to 500 K. The decrease in the lifetime is shown to follow a classical Mott-Seitz dependence for thermal quenching of luminescence, with an activation energy W of ∼1.08±0.03 eV and a corresponding frequency factor ν of ∼1014 s−1. Similar values for the energy and frequency factor were also obtained from an analysis of thermoluminescence (TL) glow curves measured at different heating rates, when the TL is measured over a wavelength range corresponding to the F-center luminescence emission (centered at 420 nm). Furthermore, the parameters obtained were independent of the glow curve shape, the degree of trap filling, or the specific conditions under which the crystals were grown. This is interpreted as a demonstration that the well-known heating rate dependence of...

Temperature-dependent resistivity of single-wall carbon nanotubes

Abstract: Samples of single-wall carbon nanotubes containing tubes with an armchair wrapping have been produced and exhibit metallic behavior with an intrinsic resistivity which increases approximately linearly with temperature over a wide temperature range. Here we study the coupling of the conduction electrons to long-wavelength torsional shape fluctuations, or twistons. A one-dimensional theory of the scattering of electrons by twistons is presented which predicts an intrinsic resistivity proportional to the absolute temperature. Experimental measurements of the temperature dependence of the resistivity are reported and compared with the predictions of the twiston theory.

Amorphization of SiC under ion and neutron irradiation

Abstract: This paper presents results on the microstructure and physical properties of SiC amorphized by both ion and neutron irradiation. Specifically, 0.56 MeV Si ions have been implanted in single crystal 6H–SiC from ambient through >200°C and the critical threshold for amorphization was measured as a function of the irradiation temperature. From a high resolution transmission electron microscopy (HRTEM) study of the crystalline to amorphous transition region in these materials, elongated pockets of amorphous material oriented parallel to the free surface are observed. Single crystal 6H–SiC and hot pressed and sintered 6H and 3C SiC were neutron irradiated at approximately 70°C to a dose of ∼2.56 dpa causing complete amorphization. Property changes resulting from the crystal to amorphous transition in SiC include a density decrease of 10.8%, a hardness decrease from 38.7 to 21.0 GPa, and a decrease in elastic modulus from 528 to 292 GPa. Recrystallization of the amorphized, single crystal 6H–SiC appears to occur in two stages. In the temperature range of ∼800–1000°C, crystallites nucleate and slowly grow. In the temperature range of 1125–1150°C spontaneous nucleation and rapid growth of crystallites occur. It is further noted that amorphized 6H (alpha) SiC recrystallizes to highly faulted fcc (beta) SiC.

Structure and properties of ion-beam-modified (6H) silicon carbide

Abstract: The ion-beam-induced crystalline-to-amorphous phase transition in single crystal ( 6 H) α -SiC has been studied as a function of irradiation temperature. The evolution of the amorphous state has been followed in situ by transmission electron microscopy in specimens irradiated with 0.8 MeV Ne + , 1.0 MeV Ar + , and 1.5 MeV Xe + ions over the temperature range from 20 to 475 K. The threshold displacement dose for complete amorphization in α -SiC at 20 K is 0.30 dpa (damage energy=15 eV atom −1 ). The dose for complete amorphization increases with temperature due to simultaneous recovery processes that can be adequately modeled in terms of a single-activated process. The critical temperature, above which amorphization does not occur, increases with particle mass and saturates at about 500 K. Single crystals of α -SiC with [0001] orientation have also been irradiated at 300 K with 360 keV Ar 2+ ions at an incident angle of 25° over fluences ranging from 1 to 8 Ar 2+ ions nm −2 . The damage accumulation in these samples has been characterized ex situ by Rutherford backscattering spectrometry–channeling (RBS/C) along the [0001] direction, Raman spectroscopy, cross-sectional transmission electron microscopy (XTEM), and mechanical microprobe measurements.

Synthesis and properties of the negative thermal expansion material cubic ZrMo2O8

Abstract: A new phase, cubic ZrMo2O8, has been prepared by the low-temperature dehydration of ZrMo2O7(OH)2·2H2O. This material displays isotropic negative linear thermal expansion (α = −5.0 × 10-6 K-1) over a large temperature range. Unlike the previously reported cubic ZrW2O8, it does not undergo any phase transformations on heating at atmospheric pressure, and it does not display any pressure-induced phase transformations below 0.6 GPa at room temperature.

Structure and magnetic properties of SmCo7−xZrx alloys (x=0–0.8)

Abstract: The alloys with composition of SmCo7−xZrx(x=0–0.8) were synthesized and characterized in the temperature range of 10–1273 K and at fields up to 5 T. The experimental results show that a small amount of Zr substitution can contribute to a stabilization of the TbCu7 structure, and improve magneto-anisotropy Ha from 90 kOe for x=0–180 kOe for x=0.5 at room temperature, and from 140 kOe for x=0–300 kOe for x=0.5 at 10 K. It is probable that Zr may partly replace a dumbbell of Co atom pair in these alloys. The phase transition between CaCu5, TbCu7, Th2Zn17, and Ce2Ni7 at different heat treatment conditions was also discussed.

Temperature dependence of forward and reverse electron transfer from A1-, the reduced secondary electron acceptor in photosystem I.

Abstract: Electron-transfer reactions following the formation of P700(+)A1- have been studied in isolated Photosystem I complexes from Synechococcus elongatus between 300 and 5 K by flash absorption spectroscopy. (1) In the range from 300 to 200 K, A1- is reoxidized by electron transfer to the iron-sulfur cluster FX. The rate slows down with decreasing temperature, corresponding to an activation energy of 220 +/- 20 meV in this temperature range. Analyzing the temperature dependence of the rate in terms of nonadiabatic electron-transfer theory, one obtains a reorganization energy of about 1 eV and an edge-to-edge distance between A1 and FX of about 8 A assuming the same distance dependence of the electron-transfer rate as in purple bacterial reaction centers. (2) At temperatures below 150 K, different fractions of PS I complexes attributed to frozen conformational substates can be distinguished. A detailed analysis at 77 K gave the following results: (a) In about 45%, flash-induced electron transfer is limited to the formation and decay of the secondary pair P700(+)A1-. The charge recombination occurs with a t1/2 of about 170 micros. (b) In about 20%, the state P700(+)FX- is formed and recombines with complex kinetics (t1/2 = 5-100 ms). (c) In about 35%, irreversible formation of P700(+)FA- or P700(+)FB- is possible. (3) The transition from efficient forward electron transfer at higher temperatures to heterogeneous photochemistry at low temperatures has been investigated in different glass-forming solvents. The yield of forward electron transfer to the iron-sulfur clusters decreases in a narrow temperature interval. The temperature of the half-maximal effect varies between different solvents and appears to be correlated with their liquid to glass transition. It is proposed that reorganization processes in the surroundings of the reactants which are required for the stabilization of the charge-separated state become arrested near the glass transition. This freezing of protein motions and/or solvent reorganization may affect electron-transfer reactions through changes in the free-energy gap and the reorganization energy. (4) The rate of charge recombination between P700(+) and A1- increases slightly (about 1.5-fold) when the temperature is decreased from 300 to 5 K. This charge recombination characterized by a large driving force is much less influenced by the solvent properties than the forward electron-transfer steps from A1- to FX and FA/B.

Phase transitions in ferrimagnetic and ferroelectric ceramics by ac measurements

Abstract: Ac conductivity measurements were carried out on polycrystalline samples of a ferrimagnetic spinel (Zn0.44Mn0.56Fe2O4) and a ferroelectric perovskite (Sr0.25Bi4Ti3.25O12.75), in the temperature range 20–160 and 20–660 °C, respectively, and in the frequency range 5 Hz–13 MHz. The impedance response in both cases could be resolved into two contributions, associated with the bulk (grains) and the grain boundaries. An analysis by means of the ac conductivity power law showed evidence of a critical temperature of 132 and 536 °C, for the ferrimagnetic and the ferroelectric samples, respectively, which corresponds to the Curie temperature for each type of material. These results are interpreted in terms of the disorder increase approaching the phase transition.

Space-charge influenced-injection model for conduction in Pb(ZrxTi1−x)O3 thin films

Abstract: A comprehensive study of: leakage conduction in Pb(ZrxTi1-x)O-3 films with Pt electrodes is carried out. The conduction properties of films prepared in different ways (sol-gel coating, metalorganic chemical vapor deposition, sputtering) were studied by using different experimental techniques including variation of the applied voltage profile, photoassisted measurements, measurements at elevated temperatures, and variation of the prehistory of the samples. Based on the collective data, it is concluded that two different regimes of carrier injection (with the critical electric field of the crossover between these regimes being independent of the measuring technique) are responsible for true leakage conduction in Pt-Pb(ZrxTi1-x)O-3-Pt films. A space-charge influenced-injection model is proposed for the interpretation of the experimental results obtained. This model describes well the main features of the observed current-voltage characteristics and provides a reasonable fit for the current-voltage curves measured at elevated temperatures, the values of the fitting parameters being in good agreement with the results of other studies. The true leakage current in the Pt-Pb(ZrxTi1-x)O-3-Pt system is shown to be time dependent because of the influence of the injected charge entrapment during measurement. According to the present results, an activation energy of about 0.9 eV describes the temperature dependence of conduction in the range of 70-200 degrees C. It is shown that a possible origin of the crossover in the activation energy at the temperature range 120-140 degrees C widely reported in the Literature can be a consequence of the measuring procedure. (C) 1998 American Institute of Physics.

Free-volume distribution and positronium formation in amorphous polymers: Temperature and positron-irradiation-time dependence

Abstract: Positron annihilation lifetime spectroscopy was used to study the free-volume size distribution and the o-Ps (ortho-positronium) formation in two amorphous polymers. We performed positron lifetime measurements on poly(vinyl acetate) (PVAc) in the temperature range of 84–414 K and on poly(methyl methacrylate) (PMMA) in the temperature range of 84–454 K and as a function of time (<200 h) at four temperatures (T=84, 149, 224, and 249 K). The glass transition temperature Tg and secondary transition temperature were determined from the average o-Ps lifetime τ3 versus temperature. The width of the o-Ps lifetime distribution was evaluated using the maximum entropy method (MELT). Analysis by the MELT program on the spectra shows that (i) the standard deviation σ(τ3) of the o-Ps lifetime distribution in PVAc and PMMA increases slightly with temperature in the glassy state, and then increases significantly with temperature above the glass transition temperature Tg; (ii) the σ(τ3) in PMMA has no observable variation as a function of positron irradiation time, which suggests that the measured free-volume distribution is not influenced by the positron irradiation. The o-Ps formation probability shows large variations with temperature, thermal history, and measuring time. These effects are discussed in the framework of the spur model.

UV–VIS absorption cross-sections and atmospheric lifetimes of CH2Br2, CH2I2 and CH2BrI

Abstract: The UV–VIS absorption spectra of CH2Br2, CH2I2 and CH2BrI have been measured over the wavelength range 215–390 nm using a dual-beam diode array spectrometer. The spectra consist of broad continuous absorption bands. CH2Br2 exhibits its maximum cross-section of σ=2.71(±0.16)×10-18 cm2 molecule-1 at λ=219 nm. The magnitude of the peak cross-sections for the iodine-containing molecules above λ=210 nm are σ=1.62(±0.10)×10-18 cm2 molecule-1 at λ=248 nm and σ=3.78(±0.23)×10-18 cm2 molecule-1 at λ=288 nm for CH2I2, and σ=5.67(±0.34)×10-18 cm2 molecule-1 at λ=215 nm and σ=2.34(±0.14)×10-18 cm2 molecule-1 at λ=267 nm for CH2BrI. The temperature dependence of the absorption cross-sections was investigated over the temperature range 348–250 K. A decline in the cross-sections with decreasing temperature was observed in the tail of the spectra. At the peaks the opposite effect was observed. All three gases have been found in the atmosphere and the atmospheric photolysis rates of CH2Br2, CH2I2 and CH2BrI were calculated as a function of altitude and solar zenith angle using the measured cross-sections. Model calculations show that, during sunlit hours, CH2I2 and CH2BrI will be photolysed within minutes and hours, respectively. The photolysis of CH2Br2 is much slower and reaction with the OH radical is the dominant atmospheric loss process.