Quantum effect induced reverse kinetic molecular sieving in microporous materials

We report kinetic molecular sieving of hydrogen and deuterium in zeolite rho at low temperatures, using atomistic molecular dynamics simulations incorporating quantum effects via the Feynman-Hibbs approach. We find that diffusivities of confined molecules decrease when quantum effects are considered, in contrast with bulk fluids which show an increase. Indeed, at low temperatures, a reverse kinetic sieving effect is demonstrated in which the heavier isotope, deuterium, diffuses faster than hydrogen. At 65 K, the flux selectivity is as high as 46, indicating a good potential for isotope separation.     

Method for measuring chemical diffusion coefficients in solids

Experiments were performed with temperature programmed desorption of hydrogen and deuterium adsorbates on small platinum spheres. Beyond the expected desorption peak of these adsorbates at around 300 K sample temperature an additional desorption peak at higher temperatures was observed. This additional peak is explained by the diffusion of hydrogen or deuterium atoms from the inside of the spheres to their surfaces with final desorption from these surfaces. The visibility of this second high temperature desorption peak is supported by a small diameter of the platinum spheres. Platinum spheres with diameters around 64 μm were used. The sample temperature at which the second peak was observed depends on the parameters: diameter of the platinum spheres, heating rate of the sample and chemical diffusion coefficient of hydrogen or deuterium in platinum. A theory, which assumes that the chemical diffusion coefficient can be described with an Arrhenius ansatz, was developed to simulate the occurrence of the second peak. The combination of these kinds of experiments with the theory gives a method to measure chemical diffusion coefficients. This method can be called temperature programmed diffusion. At 510 K sample temperature the diffusion coefficient 1.61×10⁻¹² m²/s of hydrogen in platinum and the diffusion coefficient 1.40×10⁻¹² m²/s of deuterium in platinum was measured.     

Hydrogen isotope exchange in a coverage obtained on Ir(111) by ethylene adsorption

HREELS and SIMS studies of hydrogen isotopc exchange in a coverage obtained on Ir(111) by ethylene adsorption are carried out at 180–450 K and at a hydrogen (deuterium) pressure up to 8×10⁶ Pa. The ethylidyne species have shown a high stability towards hydration and structural changes upon hydrogen (deuterium) exposures. Under these conditions hydrogen exchange in the methyl groups is a slow process. With increasing temperature the hydrogen exchange in the decomposition products of ethylidyne (C₂H species) is quick and depends on the exchanged amount of atomically adsorbed hydrogen.     

Parity nonconservation in hydrogen

We discuss the prospects for parity violation experiments in atomic hydrogen and deuterium to contribute to testing the Standard Model (SM). We find that, if parity experiments in hydrogen can be done, they remain highly desirable because there is negligible atomic-physics uncertainty and low energy tests of weak neutral current interactions are needed to probe for new physics beyond the SM. Analysis of a generic APV experiment in deuterium indicates that a 0.3% measurement of C _1D requires development of a slow (77K) metastable beam of ???5×10¹⁴D(2S)s ^???1 per hyperfine component. The advent of UV radiation from free electron laser (FEL) technology could allow production of such a beam.     

Adsorption and two-body recombination of atomic hydrogen on 3He-4He mixture films

We present the first systematic measurement of the binding energy E(a) of hydrogen atoms to the surface of saturated 3He- 4He mixture films at temperatures 70-400 mK. E(a) is found to decrease almost linearly from 1.14(1) K down to 0.39(1) K, when the population of the ground surface state of 3He grows from zero to 6x10(14) cm(-2), yielding the value 1.2(1)x10(-15) K cm(2) for the mean-field parameter of H- 3He interaction in 2D. Measuring by ESR the rate constants K(aa) and K(ab) for second-order recombination of hydrogen atoms in hyperfine states a and b, we find the ratio K(ab)/K(aa) to be independent of the 3He content and to grow with temperature.     

Temperature programmed desorption investigations of hydrogen and ammonia reactions on GaN

We report data for chemisorption and reaction of deuterium and isotopically labeled ammonia on single-crystalline GaN films grown on sapphire substrates. Temperature programmed desorption (TPD) and Auger electron spectroscopy (AES) studies, following exposure of the clean GaN film at room temperature to the probe reactant species, were conducted under UHV conditions. Deuterium desorption took place over a wide temperature range, 525–;800 K, with molecular deuterium as the only product. At low exposures, two distinct deuterium desorption peaks at ∼ 660 and 770 K were observed. The deuterium desorption peak at 660 K shifted to lower temperatures with increasing D adatom coverages. TPD experiments after ammonia adsorption on GaN revealed small amounts of hydrogen desorbed at ∼ 600 K and over a range 660–;770 K, suggesting partial decomposition of ammonia. Molecular ammonia desorption was observed at ∼ 560 and 600 K, with the low temperature desorption state growing with increasing ammonia exposures. Further studies on deuterium-precovered GaN films indicated that ammonia production resulted from recombination of NH_x species and hydrogen adatoms on the surface.     

Exotic behavior of hydrogen atoms in solid H2 at temperatures below 1 K

We present the first magnetic resonance study of atomic hydrogen embedded in solid H2 films for temperatures 150-900 mK. We found that at T approximately 150 mK average concentrations of H atoms of order 10(18 cm(-3) are very stable against recombination during two weeks of observations. The distribution of the population of the two lowest hyperfine states is found to be non-Boltzmann, with a very large occupation of the ground state. We consider the possibility of formation in solid H2 of regions with high local concentrations of H atoms, where collective quantum phenomena might occur.     

Heat transfer in solid HD at low temperatures

The lattice thermal conductivity of solid HD has been calculated in the temperature range 0.2–4°K. The important scatterers of phonons are found to be boundary walls of the crystal, isotopic impurities, phonons and molecules of ortho hydrogen and para deuterium. The presence of molecules of ortho hydrogen and para deuterium in solid HD which act as rotational impurities, are responsible for one and two phonon scattering processes in the system. The entire study is based on the Callaway model of the lattice thermal conductivity of an insulator. Excellent agreement is found between calculated and experimental values of phonon conductivity. The extra lattice thermal resistivity due to the presence of the ortho hydrogen and para deuterium is also calculated.     

Diffusion coefficients of hydrogen and deuterium in highly concentrated palladium hydride and deuteride phases

Fick's diffusion coefficients for hydrogen and deuterium were determined in palladium hydride and deuteride in the pressure range of gaseous hydrogen and deuterium from 10¹–10⁴ bar and the temperature range from 208 to 338K. This corresponds to the concentration range H, D/Pd from about 0.8 to near stochiometry. An electrical resistance relaxation method was used experimentally. Einstein's diffusion coefficients were calculated and the activation volumes and energies were evaluated. An attempt is made to interpret the anomalous behaviour of the diffusion coefficient in the low temperature range. The results are presented in terms of a compact formula.     

Electronic modifications and surface reactivity of an ion bombarded graphite surface

The first steps of structural and electronic modifications of a graphite surface bombarded with argon, hydrogen and deuterium ions were investigated using high resolution electron energy loss spectroscopy (HREELS). The energy and the damping of the low energy plasmon mode of graphite (E//C mode) were studied with respect to the bombardment settings. We show that argon bombardment affects the energy of the plasmon mode, while no similar change is observed after hydrogen (deuterium) bombardments. This can be related to the variation of inter-planar distance between two graphene layers. Moreover, the damping of the plasmon mode can be correlated with the interstitial defect concentration. Concerning the reactivity of the bombarded surfaces, we demonstrate that deuterium bombardment produce a non-deuterated surface. This last is very reactive to a further atomic deuterium exposure, as it is shown by the formation of C-D bondings. The deuterated sites can be removed after thermal annealings between 473 and 783 K. The occurrence of a chemical erosion mechanism accompanying this deuteration is discussed.     

Temperature dependence of impurity resistivity due to hydrogen in metals

Using a self-consistent calculation, we show that the impurity resistivity of metals containing hydrogen or deuterium decreases as temperature increases. We also predict a significant isotope effect that is largest at O K and vanishes at high temperatures. These effects should be common to all metal-hydrogen systems and could be detected by precision experiments.     

甲烷团簇与氘团簇的团簇源特性比较

利用瑞利散射法测量了特定喷嘴产生的甲烷团簇及氘团簇的大小随背压的变化曲线。将团簇大小的实验值与Hagena理论进行了比较,当背压超过3MPa时,两种团簇的实验值都明显高于理论值。实验发现,特定喷嘴在相同的背压下,常温(298K)甲烷团簇尺寸小于低温(80K)氘团簇尺寸,而甲烷团簇中氢原子数至少是氘团簇中氘原子数的1.98倍。     

Thermal Conductivity of poly-p-phenylene-2,6-benzobisoxazole Film along the In-Plane Axis in the 10–300 K Temperature Range

The thermal conductivities of compression molded thin films of poly-p-phenylene-2,6-benzobisoxazole (PBO) were measured in directions along an in-plane axis in the 10–300?K temperature range by a steady-state heat flow method, with interest in the use of the material for superconductivity applications. The thermal conductivities of the PBO films increased from 0.3?W/mK to 9.0?W/mK with increasing temperature from 10?K to 300?K and these were much higher than those of polyimide films, epoxy resin and glass fiber reinforced plastics at all temperatures. The 9.0?W/mK at 300?K was 60% of that of stainless steel (SUS304). It was 6?W/mK at 150?K, which was half that of SUS304 and was 3.3?W/mK at 77?K, which was 33% of that of SUS304. The thermal conductivities of the PBO films were lower than those of a cloth of high strength ultrahigh molecular weight polyethylene fiber reinforced plastics in the 30?K–180?K temperature range and were almost equivalent to its values in the 180?K–300?K temperature range. The main contribution to the thermal conduction in the PBO films was from thermal phonon conduction along the molecular chains. Although many kinds of high thermal conductivity polymeric materials have been prepared by a uni-directional drawing process or by adding high thermal conductive additives, the PBO film showed high thermal conductivity without a uni-directional drawing process or high thermal conductive additive.     

Measurement of the temperature dependence of the ddμ molecule formation rate in dense deuterium at temperatures of 85–790 K

Muon catalyzed fusion (MCF) in deuterium was studied by the MCF collaboration on the Joint Institute for Nuclear Research Phasotron. The measurements were carried out with a high-pressure deuterium target in the temperature range 85–790 K at densities of about 0.5 and 0.8 of the liquid hydrogen density. The first experimental results for the ddμ molecule formation rate λ _ddμ in the temperature range 400–790 K with a deuterium density of about 0.5 of the liquid hydrogen density are presented.     

Palladium-iron: A giant-moment magnetic thermometer for the millikelvin temperature range

We have calibrated the temperature dependence of the susceptibility ofbar|Pb+2.2 at. ppm Fe and ofbar|Pd+11 at. ppm Fe with an NBS superconducting fixed point device and with a Pt NMR thermometer in the temperature range 4.5 mK to 208 mK. In this temperature range, the data follow a Curie law with deviations of less than 1%. Its properties seem to makebar|Pd–Fe the most attractive thermometric substance for the temperature range 0.3 mK to 500 mK. For example, ourbar|Pd–Fe thermometer has a time constant of 1 s at 10 mK and of 0.1 s atT>30 mK.Dedicated to K. Dransfeld on the occasion of his 60th birthday     

高温高密度氢(氘)的物态方程——离解效应研究

 高温高压下流体氢将发生离解化学反应,形成具有相互作用的氢分子和氢原子混合体系,此时粒子间的相互作用复杂。利用单组分流体近似的范德瓦尔斯混合模型,将混合物粒子间的相互作用等效为单组分粒子间相互作用,从而简化了对体系的统计热力学处理;并由自由能函数极小化确定化学平衡时各组分含量、体系的内能、压强。研究了温度在10 000 K以下、密度在0.6 g/cm³以下（相应摩尔体积大于3.3 cm³/mol）区间的热致离解和压致离解现象对流体氢（氘）状态方程的影响。所得结果与双组分流体变分理论计算以及第一原理的分子动力学模拟、蒙特卡罗模拟结果以及二级轻气炮实验数据进行了比较,它们之间的一致性表明：用单组分流体近似的范德瓦尔斯混合模型处理氢（氘）分子的离解区域的物态方程是成功的。     

Interaction of hydrogen and deuterium with intrinsic atomic defects in high-purity electron-irradiated nickel

Abstract

High-purity nickel was irradiated with 2 MeV electrons at temperatures below 80 K to a dose of 1 × 10²³ e^?/m² in the as-prepared state and after charging with H or D. By means of magnetic after-effect measurements relaxations of anisotropic radiation-induced defects and of defect-hydrogen complexes were investigated in the temperature range between 4.2 and 500 K. The isochronal annealing behaviour of these relaxations and the isochronal recovery of the residual resistivity was measured simultaneously on the same specimens. At temperatures below the hydrogen mobility (< 160 K) in charged irradiated specimens relaxation maxima are observed at 45, 100, 115 and 140 K which show no isotope shift for H and D charging. The maxima below 160 K are explained by defect-hydrogen complexes, where radiation-induced defects reorient around immobile hydrogen atoms. Above 160 K, where hydrogen atoms get mobile, in charged irradiated specimens a broad relaxation maximum appears at 170 K which shows an inverse isotope shift for H and D charging. This 170 K maximum anneals in Stage III. A hydrogen diffusion maximum observed in charged specimens at 215 K prior to irradiation is missing after electron irradiation. The 170 K relaxation is explained by defect-hydrogen complexes, where hydrogen atoms reorient around immobile radiation-induced defects while the long-range hydrogen diffusion is suppressed by these defects. In such relaxation measurements hydrogen and deuterium atoms are used as a “probe” to investigate radiation-induced defects.     

钨中氢同位素热脱附实验的速率理论模拟研究

本文采用基于速率理论的模拟方法研究钨材料中氢同位素氘的热脱附谱. 热脱附数据来源于520 K下受等离子体辐照的多晶钨, 入射离子能量为40 eV, 剂量为1× 10²⁶ D/m². 通过调节速率理论中的俘获能、俘获率等参数, 最终获得与实验相符合的热脱附拟合谱. 拟合结果表明, 钨中俘获的氘存在于三种俘获态, 俘获能分别为1.14 eV, 1.40 eV和1.70 eV, 相应脱附温度峰值为500 K, 600 K和730 K. 这三个俘获能分别应对应于第一原理计算得到的空位俘获第3–5个氢原子的俘获能(含零点振动能修正)、空位俘获第1–2个氢原子的俘获能, 空位团簇对氢原子的俘获能. 模拟结果表明, 在本辐照实验条件下, 钨中空位及空位团簇是氘在钨中的主要俘获态.     

Structural transitions in hydrogen and deuterium at ultrahigh pressures

Abstract

Raman measurements indicate that normal hydrogen and deuterium compressed in a diamond-anvil cell at 77 K undergo phase transformations at 145 (±l5) GPa and 190 (±l20) GPa, respectively. The new observations reported for deuterium indicate that the transition in both isotopes is a structural change not associated with a simple rotational ordering mechanism. The possibility of a structural transition driven by band-gap closure is discussed.     

Deuterium transport and isotope effects in type 316L stainless steel at high temperatures for nuclear fusion and nuclear hydrogen technology applications

We present the first complete data set for the permeability, diffusivity, and solubility of both deuterium and hydrogen in 316L stainless steel (316L SS) obtained over a wide temperature range of 350–850 °C that accommodates both nuclear fusion and nuclear hydrogen technology applications. The deuterium results were also compared with the hydrogen results to estimate the isotope effect. The isotope effect ratio for diffusivity was different from the classical prediction. Furthermore, some of our results were compared with the results previously reported for 316 SS. Results and discussion are presented with an emphasis on the deuterium permeation and isotope effects.