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Reaction rate constants of ion-molecule interchange reaction as function of temperature, flow velocity, activation energy and constant part of steric factor P
The ultraviolet absorption spectrum of carbonyl sulfide is investigated in order to assess the importance of the photolytic sink for OCS in the troposphere. Absorption cross sections were measured at wavelengths between 185 and 300 nm in a double-beam spectrometer at temperatures of 295 and 225 K. The results are found to be in good agreement with previous reports in the short wavelength region, but significantly lower than the value of 2 x 10 to the 22nd sq cm/molecule proposed by Rudolf and Inn (1981) between 280 and 300 nm, which may be attributed to trace contaminants or dimerization. A marked temperature effect is noted at wavelengths greater than 240 nm and below 190 nm. As no evidence of absorption at wavelengths greater than 270 nm was found, estimates of the solar photodissociation rate of tropospheric OCS based on the present cross sections yield a value of about 2 x 10 to the -9th/sec, corresponding to a tropospheric lifetime of about 20 years. It is therefore concluded that solar photolysis represents a negligible sink for OCS.
It is well known that convection is a dominant mass transport mechanism when materials are solidified on Earth's surface. This convection is caused by gradients in density (and therefore gravitational force) that are brought about by gradients in temperature, composition or both. Diffusion of solute is therefore dwarfed by convection and the study of fundamental parameters, such as dendrite tip shape and growth velocity in the absence of convection is nearly impossible. Significant experimental work has therefore been carried out in orbiting laboratories with the intent of minimizing convection by minimizing gravity. One of the best known experiments of this kind is the Isothermal Dendritic Growth Experiment (IDGE), supported by NASA. Naturally such experiments are costly and one objective of the present investigation is to develop an experimental method whereby convection can be halted, in solidification and other experiments, on the Earth's surface. A second objective is to use the method to minimize convection resulting from the residual accelerations suffered by experiments in microgravity.
Coefficients for oxygen absorption in the infrared induced by collisions with O2 and N2 are reported over the range 1400-1800/cm and 225-356 K. These coefficients are used to calculate the absorption for O2 in air as a function of temperature and wavenumber, and comparisons are made with previous determinations. In addition, structured absorption features superimposed on the broad collision-induced absorption band, which were observed at all temperatures studied, are interpreted in terms of the presence of (O2)2 and O2-N2 van der Waals molecules.
The mechanical behavior of dendritic web Si ribbons close the melting point was studied experimentally. The goal of the study was to generate data for modeling the generation of stresses and dislocation structures during growth of dendritic web Si ribbons, thereby permitting modifications to the production process, i.e., the temperature profile, to lower production costs for the photovoltaic ribbons. A laser was used to cut specimens in the direction of growth of sample ribbons, which were then subjected to tensile tests at temperatures up to 1300 C in an Ar atmosphere. The tensile strengths of the samples increased when the temperature rose above 1200 C, a phenomena which was attributed to the diffusion of oxygen atoms to the quasi-dislocation sites. The migration to the potential dislocations sites effectively locked the dislocations.
Fe-Cr ferritic-martensitic (FM) steels are promising structural material candidates for fusion and advanced fission reactors due to their attractive mechanical properties and volumetric swelling resistance. However, significant discrepancies exist regarding the effect of solutes and irradiation temperature on cavity swelling under ion versus neutron irradiation conditions. In this study, simultaneous dual ion irradiations (8 MeV Ni 3+ ions and energy-degraded 3.5 MeV He 2+ ions) were used to quantify the cavity swelling behavior in ultra-high purity Fe and Fe-Cr alloys (3-14 wt.% Cr), Fe-10 wt.% Cr-780 wt.ppm C, and Eurofer97 FM steel. The irradiations were conducted over a wide temperature range (400-550°C) with a mid-range dose of ~30 displacements per atom (dpa) and 0.1 appm/dpa He implantation rate. Here, using state-of-the-art transmission electron microscopy (TEM), we reveal that pure Fe has a ~50°C lower peak swelling temperature difference than Fe-Cr alloys, which is attributed to higher vacancy mobility in pure Fe. Chromium solute appears to strongly suppress cavity swelling in Fe-Cr alloys for temperatures below ~470°C, but seems to have little effect or slightly enhances swelling above ~470°C. Cavities were observed in all the irradiated samples between 400-550°C. This indicates that the narrow temperature range of observable cavities reported in prior ion irradiated Fe-Cr ferritic alloy studies is likely an artifact associated with the use of low ion energies (<5 MeV), which leads to pronounced near-surface and implanted ion effects that suppress cavity swelling even at midrange depths (particularly at high temperatures).
Absorption cross-sections for HNO3 and N2O5 have been measured in the wavelength region 220-450 nm, using a dual beam diode array spectrometer with a spectral resolution of 0.3 nm. The results for both compounds are in good agreement with recommended values at room temperature. However, the cross-sections of both HNO3 and N2O5 show a marked reduction with decreasing temperature in the range 295-233 K. The calculated photolysis rate of HNO3 at the low temperatures and high solar zenith angles characteristic of the polar winter and spring is significantly lower than previously estimated.
The absolute rate constant for the reaction O((3)P) + HOBr has been measured between T = 233K and 423K using the discharge-flow kinetic technique coupled to mass spectrometric detection. The value of the rate coefficient at room temperature is (2.5 +/- 0.6) x 10(exp -11)cu cm/molecule/s and the derived Arrhenius expression is (1.4 +/- 0.5) x 10(exp -10) exp((-430 +/- 260)/T)cu cm/molecule/s. From these rate data the atmospheric lifetime of HOBr with respect to reaction with O((3)P) is about 0.6h at z = 25 km which is comparable to the photolysis lifetime based on recent measurements of the UV cross section for HOBr. Implications for HOBr loss in the stratosphere have been tested using a 1D photochemical box model. With the inclusion of the rate parameters and products for the O + HOBr reaction, calculated concentration profiles of BrO increase by up to 33% around z = 35 km. This result indicates that the inclusion of the O + HOBr reaction in global atmospheric chemistry models may have an impact on bromine partitioning in the middle atmosphere.
Excellent structural stability, high operating voltage, and high capacity have made Na 3 V 2 (PO 4 ) 2 F 3 a promising cathode material for sodium-ion batteries. However, high-temperature battery performances and heat generation measurements have not been systematically reported yet. Carbon-coated Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT (multi-walled carbon nanotube) samples are fabricated by a hydrothermal-assisted sol-gel method and the electrochemical performances are evaluated at three different temperatures (25, 45, and 55 °C). Furthermore, the well-crystallized Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT samples exhibit good cycling stability at both low and high temperatures; they deliver an initial discharge capacity of 120–125 mAhg -1 at a 1 C rate with a retention of 53 % capacity after 1,400 cycles with 99 % columbic efficiency. The half-cell delivers a capacity of 100 mAhg -1 even at a high rate of 10 C at room temperature. Furthermore, the Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT samples show good long-term durability; the capacity loss is an average of 0.05 % per cycle at a 1 C rate at 55 °C. Additionally, ionic diffusivity and charge transfer resistance are evaluated as functions of state of charge, and they explain the high electrochemical performance of the Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT samples. In-situ heat generation measurements reveal reversible results upon cycling owing to the high structural stability of the material. Excellent electrochemical performances are also demonstrated in the full-cell configuration with hard carbon as well as antimony Sb/C anodes.
The compound GdRh 2 Si 2 crystallizes in the body-centered tetragonal ThCr 2 Si 2 structure and exhibits A-type antiferromagnetic order below its Néel temperature T N = 107 K where the Gd moments are ferromagnetically aligned in the ab-plane with the moments in adjacent planes aligned antiferromagnetically. Previously, the nonlinear low-field magnetization versus field M ab ( H ∥ [1, 0, 0]) measurements on single crystals were interpreted in terms of a mean-field model. Here, in this work, we reinterpret this nonlinearity more simply in terms of the response of the ordered moments in four noninteracting tetragonal domains to the applied field and find good agreement with our theory.
Negative ion photoelectron spectroscopy (NIPES) coupled with electrospray ionization (ESI) has been proved to be a powerful gas-phase spectroscopic tool for characterizing electronic structures and chemical bonding of a variety of cluster anions and corresponding neutral radicals involved in the condensed phase reactions and transformations. Since the acquisition of cryogenic and temperature-controlling capabilities, broader range of research scope has been covered. This review summarizes our recent investigations on metal complexes employing cryogenic ESI-NIPES that provide us essential information towards understanding complicated condensed phase reactions including hydrocarbon activations and electron transfer reactions, and afford us spectroscopic probe of highly reactive transient species and intimate redox pairs. Special attention has been drawn to connect gas phase photodetachment processes with solution phase redox reactions. Photodetachment of transition metal-EDTA complexes has been systematically investigated to model the sequential oxidation reactions of these species in solutions. The obtained gas phase electron affinity (EA) is compared with the solution redox potential (E1/2) and the metal ionization potential (IP) for several series of homologous metal complexes to emphasize their intrinsic correlations with deviations being largely modulated by different degrees of ligand participations.
Continuum-scale models that can reliably predict the behavior of helium in tungsten are of interest to the fusion community due to the projected impact of these materials on fusion reactor operation. In this work, we perform molecular dynamics simulations of spherical helium bubbles of various sizes in tungsten at different temperatures and depths with the goal of determining a mathematical model of the pressure and density at which the bubbles initially expand or burst as a function of depth, size, temperature, and surface orientation. The bubbles are small enough that their loop-punching pressures cannot be accurately predicted with continuum mechanics, and their expansion behavior is important, as it appears to cause many of the features observed on helium-irradiated tungsten surfaces. We vary the temperature, bubble size, bubble depth, and surface orientation in each case, recording the bubble pressure and density that result in bubble expansion. An exponential function with three adjustable parameters is found to fit the results well; the parameters that best fit our results are provided.
We have studied the fundamental rotational relaxation and excitation collision of OH – J = 0 ↔ 1 with helium at different collision energies. Using state-selected photodetachment in a cryogenic ion trap, the collisional excitation of the first excited rotational state of OH – has been investigated and absolute inelastic collision rate coefficients have been extracted for collision temperatures between 20 and 35 K. Furthermore, the rates are compared with accurate quantum scattering calculations for three different potential-energy surfaces. Good agreement is found within the experimental accuracy, but the experimental trend of increasing collision rates with temperature is only in part reflected in the calculations.
Solid-state ionic conductors that exhibit pure ionic transport of hydride anions are rare. Here, we investigate two alkaline earth metal hydrides, barium hydride and calcium hydride, using neutron scattering techniques to understand how the local atomic environment plays a role in the diffusion of hydride ions. At high temperatures, barium hydride exhibits exceptional transport properties with ionic conductivities that are higher than those of many of the typical proton and oxide ion conductors in use today. Total neutron scattering and pair distribution function analysis reveal how a structural phase transition converts barium hydride from a modest ionic conductor into a fast ionic conductor through the introduction of disorder, deuterium site splitting, and dynamic structural fluctuations. Furthermore, neutron vibrational spectroscopy is employed to probe changes in the temperature evolution of the lattice dynamics and local energy landscape. These results improve our fundamental knowledge of the interplay between structure and dynamics governing a rare conduction process of hydride ions in solid-state materials.
Silicon oxynitride films were deposited by plasma-enhanced chemical-vapor deposition. The elemental composition was varied between silicon nitride and silicon dioxide: SiO(0.3)N(1.0), SiO(0.7)N(1.6), SiO(0.7)N(1.1), and SiO(1.7)N(0.%). These films were annealed in air, at temperatures of 40-240 C above the deposition temperature (260 C), to determine the stability and behavior or each composition. the biaxial modulus, biaxial intrinsic stress, and elemental composition were measured at discrete intervals within the annealing cycle. Films deposited from primarily ammonia possessed considerable hydrogen (up to 38 at.%) and lost nitrogen and hydrogen at anneal temperatures (260-300 C) only marginally higher than the deposition temperature. As the initial oxygen content increased a different mechanism controlled the behavior or the film: The temperature threshold for change rose to approximately equal to 350 C and the loss of nitrogen was compensated by an equivalent rise in the oxygen content. The transformation from silicon oxynitride to silica was completed after 50 h at 400 C. The initial biaxial modulus of all compositions was 21-3- GPa and the intrinsic stress was -30 to 85 MPa. Increasing the oxygen content raised the temperature threshold where cracking first occurred; the two film compositions with the highest initial oxygen content did not crack, even at the highest temperature (450 C) investigated. At 450 C the biaxial modulus increased to approximately equal to 100 GPa and the intrinsic stress was approximately equal to 200 MPa. These increases could be correlated with the observed change in the film's composition. When nitrogen was replaced by oxygen, the induced stress remained lower than the biaxial strength of the material, but, when nitrogen and hydrogen were lost, stress-relieving microcracking occurred.
The cluster expansion formalism for alloys is used to construct surrogate models for three refractory high-entropy alloys (NbTiVZr, HfNbTaTiZr, and AlHfNbTaTiZr). These cluster expansion models are then used along with Monte Carlo methods and thermodynamic integration to calculate the configurational entropy of these refractory high-entropy alloys as a function of temperature. Many solid solution alloy design guidelines are based on the ideal entropy of mixing, which increases monotonically with N , the number of elements in the alloy. However, our results show that at low temperatures, the configurational entropy of these materials is largely independent of N , and the assumption described above only holds in the high-temperature limit. This suggests that alloy design guidelines based on the ideal entropy of mixing require further examination.
The phase offset of quantum oscillations is commonly used to experimentally diagnose topologically nontrivial Fermi surfaces. This methodology, however, is inconclusive for spin-orbit-coupled metals where π -phase-shifts can also arise from non-topological origins. Here, we show that the linear dispersion in topological metals leads to a T 2 -temperature correction to the oscillation frequency that is absent for parabolic dispersions. We confirm this effect experimentally in the Dirac semi-metal Cd 3 As 2 and the multiband Dirac metal LaRhIn 5 . Both materials match a tuning-parameter-free theoretical prediction, emphasizing their unified origin. For topologically trivial Bi 2 O 2 Se, no frequency shift associated to linear bands is observed as expected. However, the π -phase shift in Bi 2 O 2 Se would lead to a false positive in a Landau-fan plot analysis. Our frequency-focused methodology does not require any input from ab-initio calculations, and hence is promising for identifying correlated topological materials.
Measurements of sputtering yields and composition profiles have been carried out using backscattering spectrometry for samples of CrSi2 on Si irradiated wth 200-keV Xe ions. When the CrSi2 layer is thinner than the ion range, the sputtering yield ratio of Si to Cr increases from 3.5 for room-temperature irradiation to 65 at 290 C. For a thick sample, the corresponding increase is from 2.4 to 4.0 only. These changes are explained in terms of a rise in the Si surface concentration ot 290 C. The driving force for this process seems to be the establishment of stoichiometric CrSi2 compound. Transport of Si to the surface is by ion mixing in the thin sample and thermal diffusion through the thick layer.