Diffusion and solubility of helium in lead fluoride single crystals in the superionic transition region

Temperature curves of the diffusion coefficients and solubilities of helium in pure and holmium-doped lead fluoride crystals are obtained in the superionic phase-transition range. Possible mechanisms of the interaction of helium with ions are discussed, along with mechanisms of the solubility and diffusion of helium in a crystal. Fiz. Tverd. Tela (St. Petersburg) 40, 759–760 (April 1998)     

The low-temperature solubility of helium in quartz

Technical Physics - The solubility of helium in α- and β-quartz single crystals, optical quartz crystals, and Pyrex glass has been studied by the method of thermal desorption of helium...     

Grain-boundary diffusion and solubility of helium in submicrocrystalline palladium

The diffusion and solubility of helium in palladium with a submicrocrystalline structure are investigated by thermal desorption of helium from He-saturated specimens at temperatures T = 293–508 K and saturation pressures P = 0.1–35 MPa. As the saturation pressure rises, the effective diffusion coefficient increases, exhibits a plateau, and then decreases to its initial value. Along with the four plateaus discovered earlier, the solubility versus saturation pressure dependence in the range 25.5–35.0 MPa demonstrates a fifth plateau, where the solubility is as high as (3.0 ± 0.4) × 10¹⁷ cm⁻³. It is shown that the helium diffuses along grain boundaries, at which clusters (traps) consisting of eight to ten vacancies are localized, and dissolves in these clusters. The high value of C _eff in the fifth plateau is explained by pairwise merging of adjacent vacancy clusters. From the D _eff(P) dependences, the vacancy clusters concentration is estimated as C* = 2.32 × 10¹⁶ cm⁻³. Within the experimental error, this value coincides with that obtained from the solubility data. Calculations of the energy of helium-defect interaction in submicrocrystalline Pd that are made using the molecular dynamics method support the experimental results.     

Mass spectrometric investigation of the low-temperature dimethyl ether oxidation in an atmospheric pressure laminar flow reactor

Low-temperature combustion is a major strategy today to reduce both soot and NO_x emission. Kinetic reaction models for low-temperature combustion which are validated against a wide range of experimental data are necessary e.g. for control purposes or as a basis for subsequent model reduction.In this study, the low-temperature oxidation of dimethyl ether in a highly diluted gas mixture was investigated experimentally in an atmospheric laminar flow reactor. The respective gas composition was analyzed by a time-of-flight mass spectrometer. This technique allows detection of all species simultaneously within the investigated temperature regime. Stoichiometries of ? = 0.8, 1.0, and 1.2 were studied with high temperature resolution in the range of 400–1200 K, and quantitative species mole fraction profiles have been determined.This wide temperature range comprises the different kinetic regimes occurring during the DME oxidation, which have been clearly resolved. The distinct negative temperature coefficient (NTC) region of the system was observed and extensive speciation is available. Special attention is given to species only occurring in the low-temperature region including formic acid and methyl formate.     

Mass-spectroscopic study of the diffusion and solubility of helium in submicrocrystalline palladium

By the method of helium thermal desorption from submicrocrystalline palladium presaturated in the gaseous phase, the diffusion coefficient D _eff and solubility coefficient C _eff of helium are measured in the range P=0–3 MPa and T=293–508 K. The pressure dependence of C _eff flattens at high pressures. At low saturation pressures, the temperature dependences of the diffusion and solubility coefficients may be divided into (1) high-temperature (400–508 K) and (2) low-temperature (293–400 K) ranges described by the exponentials D _{1, 2}=D ₀exp (−E _{1, 2} ^D /kT) and C _{1, 2}=C ₀exp (−E _{1, 2} ^S /kT). The energies of diffusion activation are E ₂ ^D =0.0036±0.0015 eV and E ₁ ^D =0.33±0.03 eV, and the solution energies are E ₂ ^S =−0.025±0.008 eV and E ₁ ^S =0.086±0.008 eV in the low-and high-temperature ranges, respectively. Mechanisms behind the diffusion and solution of helium are discussed.     

Mass spectrometric investigation of anions formed upon free electron attachment to nucleobase molecules and clusters embedded in superfluid helium droplets

Here we report the first mass spectrometric study of negative ions formed via free electron attachment (EA) to nucleobases (NBs) embedded in helium clusters. Pure and mixed clusters of adenine and thymine have been formed by pickup of isolated NB molecules by cold helium droplets. In contrast to EA of isolated molecules in the gas phase we observe a long-lived parent anion NB- and, in addition, parent cluster ions NB-n up to size n=6. Moreover, we show that a low energy electron penetrating into a doped helium droplet causes efficient damage of the embedded nucleobases via resonant, site selective, dissociative electron attachment.     

Mass-spectrometric analysis of diffusion and solubility of helium in cerium-gadolinium ceramics with a submicrocrystalline structure

Diffusion and solubility of helium in Ce_0.8Gd_0.2O_{1.9 − δ} ceramics (δ = 0, 0.015) with a submicrocrystal structure are studied by thermodesorption of helium from preliminarily saturated (in the gas phase) crystals at temperatures of 613 and 673 K in the saturated pressure range 0–21 MPa. It is shown that, in this ceramics (δ = 0), the defect-trap diffusion mechanism operates. The main positions for dissolution are neutral anion vacancies formed as a result of thermal dissociation of impurity-vacancy complexes and saturated up to ∼1 × 10¹⁹ cm⁻³ at P = 6 MPa and T = 673 K. The dissociation energy of the complex and the energy of helium dissolution in the neutral anion vacancy are estimated at ∼2 eV and below −0.3 eV, respectively.     

Ionic conductivity and anion diffusion in single crystals of lead chloride

The ionic conductivity and self-diffusion of chlorine ions in undoped single crystals of zone-refined lead chloride have been measured over the temperature range 625–370K. These measurements suggest that the conductivity and self-diffusion are due to simple vacancy migration as confirmed by the observed correlation factor. The activation energy of formation of vacancies is found to be 1.55 eV and that for migration of an anion is 0.38 eV. In the extrinsic region, the two measurements show marked discrepancies which are explained by assuming the presence of oxygen impurity ions in the lattice, and the mechanisms for their contribution to the observed excess conductivity are discussed.     

Electronic structure of lead (II) fluoride and lead (II) chloride crystals

The method of complete neglect of differential overlap was used to calculate the electronic structure of α PbF₂, β PbF₂, and PbCl₂ crystals which form the basic matrices for the synthesis of new superionic conductors. It was shown that the electronic subsystem is fairly stable on transition from the high-symmetry β PbF₂ crystal to the low-symmetry α PbF₂. The electronic structure of the cotunnite crystal PbCl₂ was calculated for the first time. Fiz. Tverd. Tela (St. Petersburg) 40, 235–236 (February 1998)     

The holographic investigation of diffusion of azo-dye in liquid crystals host

The diffusion of azo-dye (DR-1) in a planar liquid crystals host (5CB) at various temperatures has been investigated by laser-induced holographic grating relaxation technique. The decay of the diffraction intensity provides information about the diffusion of photoexcited azo-dye molecules. The relaxation time constants can be derived from the time dependence of the diffraction intensity fitted by a single exponential function. Thus, the diffusion coefficients parallel and perpendicular to the director of liquid crystals at various temperatures can be obtained from the plots of the reciprocal of the relaxation time versus the square of the grating vector. From the analysis of the holographic grating relaxation, the diffusion is faster along the molecular director than for the perpendicular case, and the diffusion increases with rising temperature either parallel or perpendicular to the nematic director of liquid crystals. PACS 42.40.Eq; 42.40.Lx     

氧原子在α钛晶体中扩散的第一性原理研究

在材料领域杂质原子的迁移是一个基础而永恒的主题.采用基于密度泛函理论的第一性原理方法,研究了氧原子在α钛(α-Ti)晶体中的间隙占位情况,并计算了氧原子稳定占位点间隙能、电子态密度、电荷差分密度及其邻近钛原子的位移情况.采用基于过渡态搜索理论的CI-NEB(climbing image nudged elastic band)方法预测了稳定态氧原子在α-Ti晶体中的扩散路径、扩散势垒及相应的跳转频率,并由此推算出氧原子在不同位点之间跳转的扩散系数.研究结果表明,间隙氧原子在六角密排钛晶体结构中共有七种占位,但仅存在三个可稳定占据的间隙位点:八面体中心位点、六面体中心位点及0.28 nm钛—钛键中心位点.各稳定间隙位点之间的扩散具有不对称性,因此可确定三种稳定间隙氧原子位点间存在七条独立扩散路径.获取计算不同路径扩散系数所需要的微观参数,包括扩散势垒、扩散长度、不同扩散路径上鞍点氧原子的跳转频率,最终预测了不同间隙位点之间氧原子的扩散系数值,其中八面体中心扩散到邻近键位的扩散系数与实验值相符合.通过对间隙氧原子扩散行为的深入了解,希望能对控制钛合金中氧的扩散、提高钛金属中氧的含量及相关研究提供基础理论支持.     

Nonclassical rotational inertia in helium crystals

It has been proposed that the observed nonclassical rotational inertia (NCRI) in solid helium results from the superflow of thin liquid films along interconnected grain boundaries within the sample. We have observed NCRI in large (4)He crystals grown at constant temperature and pressure, demonstrating that the superfluid grain boundary model cannot explain the phenomenon.     

Zeeman relaxation of CaF in low-temperature collisions with helium

The collision-induced Zeeman relaxation rate for collisions of CaF X2Sigma(v(')=0) with 3He is measured to be Gamma(Z)=(7.7+5.4/-2.5)x10(-15) cm(3)/s at 2 K. This rate is a direct measurement of the influence of spin-rotation coupling on Zeeman relaxation in the first rotational level of CaF. The relationship of this rate to known molecular constants is consistent with recent theory of cold molecular collisions and outlines the (2)Sigma molecules conducive to magnetic trapping.     

Atomistics of helium diffusion in copper and tungsten

Using previously determined interatomic potentials, the activation energy for migration of a single substitutional helium atom in copper and tungsten has been determined. The mechanism of migration involves the jump of the helium atom out of the vacancy concurrent with the jump of a host atom into that vacancy. The helium then occupies the vacant site created by the jumping host atom, resulting in a substitutional helium at a distance of √2 r ₀ (√3r ₀) from its original site in copper (tungsten). The rate-limiting step in the process is found to be the jump of the helium out of the vacancy, the activation energy for which is 2.15 eV in copper and 4.69 eV in tungsten.     

Equilibrium shape of rotating helium crystals

We have studied theoretically the effects of rotation on the equilibrium shape of the interface between superfluid and solid helium. Surface structures in the shape of hillocks and ridges appear in the presence of a vortex lattice in the superfluid. These structures are very sensitive to the orientation of the interface boundary with respect to the crystal planes when surface stiffness is very anisotropic, as occurs well below the roughening transition. We predict the appearance of ring shaped facets for fast rotation speeds. These effects should be observable by using optical techniques.     

Positronium diffusion in crystals

The temperature dependence of the diffusion coefficient is analyzed for the two cases of localized and delocalized positronium in a crystal. The diffusion coefficient for the localized positronium is calculated from the Kubo formula, while that for the free positronium is calculated in the relaxation-time approximation. The temperature dependence of the tunneling diffusion coefficient for positronium is specified by analogy with impuritons in a quantum crystal.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 25–28, July, 1981.     

Measurement of the electron-atom collision integral in low-temperature helium plasma

An expression is obtained for the electron-atom collision integral for axisymmetric low-temperature plasmas. The Legendre components of the collision integral are determined experimentally by the probe method. Comparison of the measured Legendre components with their theoretical values shows that, depending on the plasma conditions, the collisional regime or a regime of dominant collective interactions is established in the system. Zh. Tekh. Fiz. 67, 19–24 (April 1997)     

X-ray determination of thermal expansion of cadmium fluoride and lead fluoride

The lattice parameters of CdF₂ andβ-PbF₂ have been determined over the temperature range 300–670 K. The coefficient of expansion at room temperature is 21·3 × 10⁻⁶ K⁻¹ and 25·4 × 10⁻⁶ K⁻¹ for CdF₂ and PbF₂ respectively and it increases linearly with temperature over the range of temperature covered. The Grüneisen parameter decreases with temperature in both the crystals.