Hydrogen isotope exchange in proton-conducting oxides during proton and deuteron irradiation

It has been found that during accelerator beam deuteron irradiation of a proton-conducting oxide containing protium H/D isotope exchange between beam ions and dissolved ions takes place. This isotope exchange was also observed during high-energy proton irradiation of the oxide containing dissolved deuterium atoms. These results provide evidence to a new type of hydrogen isotope exchange. Any appreciable effects of conjugate diffusion of hydrogen and oxygen ions and of the interface processes on the isotope exchange rate were eliminated. In this type of exchange the rate of replacement of H⁺ by D⁺ and of D⁺ by H⁺ was determined only by the properties of the crystal. The discovered effect was used in our study to obtain experimental data characterizing the dynamic and equilibrium behavior of hydrogen isotopes in the oxide BaZr_0.9Y_0.1O_{3 ? δ}.     

Magnetic dipole fields at interstitial sites in disordered binary alloys of ferromagnetic crystals

The dipole fields at interstitial sites occupied by positive particles (μ ⁺,p) in f.c.c. and b.c.c. diluted binary alloys of ferromagnetic metals are investigated. The characteristic shapes of the distribution functions of the dipole fields is shown to depend on the interstitial site occupied by the positive particle, and they may give information on the formation of diatomic complexes of the light interstitials with substitutional impurity atoms as well as on the degree of short-range order of the alloy.     

Muonium quantum diffusion and localization in cryocrystals

We review our recent study of atomic muonium ( ⁺e^– or Mu, a light isotope of the hydrogen atom) diffusion in the simplest solids-van der Waals cryocrystals. We give experimental evidence of the quantum-mechanical nature of the Mu diffusion in these solids. The results are compared with the current theories of quantum diffusion in insulators. In solid nitrogen bothT ⁷ andT ^–7 temperature dependences of the Mu hop rate are observed directly for the first time, which is taken as a confirmation of a two-phonon scattering mechanism. In solid xenon and krypton, by contrast, the one-phonon interaction is dominant in the whole temperature range under investigation due to extremely low values of the Debye temperatures. Particular attention is dedicated to processes of inhomogeneous quantum diffusion and Mu localization. It is shown that at low temperatures static crystal disorder results in an inhomogeneity of the Mu quantum diffusion which turns out to be inconsistent with diffusion models using a single correlation time _c . Conventional trapping mechanisms are shown to be ineffective at low temperatures in insulators. The localization effects in Mu quantum diffusion are studied in detail in solid Kr. In all the cryocrystals studied muonium atom turns out to be localized at low temperatures.     

Experimental Results on Muon Catalyzed dt Fusion in H/D/T Mixture

Experimental study on muon catalyzed dt fusion in a triple mixture of hydrogen isotopes (H/D/T) was carried out at the JINR phasotron. The measurements have been performed at various temperatures and densities with liquid and gaseous H/D/T mixtures. Results are presented for the main characteristics of the dtμ cycle. A reduction of the number of dt fusions is observed when hydrogen is added to the D/T mixture, This is mainly due to muon loss to the pt and pd cycles, which have a high sticking probability. We also observe an increase of the cycle rate when the temperature of the H/D/T mixture rises. This confirms the theoretical prediction. This revised version was published online in August 2006 with corrections to the Cover Date.     

Exchange of injected hydrogen isotopes between diffusing and trapped states in Al

Abstract

Exchange of hydrogen isotopes between diffusing and trapped populations was found with successive injections of 25 keV D₂ ⁺ and 100 or 140 keV H₂ ⁺ into Al surface by simultaneously detecting elastically recoilled hydrogen and deuterium using 2 MeV He⁺.

When backward diffusion of injected hydrogen toward surface was supposed to be impeded or by-passed by structural changes in the subsurface layer due to ion bombardment, effective replacement cross-section of about 1.4 × 10^?18 cm² was observed. Otherwise, namely when the hydrogen backward diffusion is supposed to be rather free, the effective cross section of about 7.8 × 10^?18 was observed.

Due to the difference in energy of the first and second injections, this phenomenon is different from that so called “isotopic exchange”, which occurs through collisional process.     

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.     

D2O‐catalyzed proton transfer selectivity of 4 different NH protons in the same molecule

When N‐benzyl‐N′‐methylacetamidinium hydrochloride (pKa=11.8) is dissolved in D₂O/DCl(1 M), an equilibrium of 2 54:46 stereoisomers in an ~2:1 =(R)N^δ+H(D) D/H ratio is formed. Therefore, 2 R =N‐benzyl (E and Z) and 2 R =N‐methyl (E and Z) groups attached to the corresponding H(D) (Z and E) for a total of 8 ¹H‐NMR signals are observed. Consequently, their rates of H and D transfer to D₂O can be measured by means of the ¹H‐NMR broadness (line shape) of the =(R )N^δ+H doublets and =(R )N^δ+D broad singlets. Acidity selectivity is observed for both processes. In fact, the relative proton and deuterium transfer rates follow the acidity order: =(PhCH₂)N^δ+‐H(E) > =(PhCH₂)N^δ+‐H(Z) > =(Me)N^δ+‐H(E) > =(Me)N^δ+‐H(Z). Proton transfer rates are in the range of 8 to 0.5 s^‐1 with α = .92. This tendency is independently supported by the observed experimental chemical shift deuterium isotopic perturbation. The rate‐limiting step for proton exchange is the breaking of the hydrogen bond due to the fast amidine reprotonation (~10¹¹ s). =(R)N^δ+D/=(R)N^δ+H equilibration is reached at ~80 s, and it can be measured by the relative =(R) N^δ+H versus =(R) N^δ+D signal integrations. The equilibrium of the 4 =(R)N^δ+H(D) centers is shifted toward deuterium, but they are further shifted in the more basic centers. Equilibrium is completely shifted toward D in the 4 centers when OD^? contributes with the exchange process at pD > 3.     

Quantum diffusion of light interstitials in metals

A quantum theory of diffusion of self-trapped light interstitials in metals is presented. The theory encompasses both coherent and incoherent tunneling, but the approximation used neglects the dependence of the interstitial transfer matrix element on the vibrational state of the crystal. The coherent tunneling contribution is estimated by fitting the incoherent diffusion rate to experimental data for hydrogen and muon diffusion. It is predicted that coherent diffusion should be dominant below ～ 80 K for H in Nb and below ～ 190 K for μ⁺ in Cu. Experimental verifications of these predictions would require high purity strain free samples and low concentrations of the diffusing species.     

Mössbauer sum rules for use with synchrotron sources

The concentration dependence study of the formation rate of the muon molecules dtμ in equilibrium double D/T and triple H/D/T liquid mixtures of hydrogen isotopes requires an installation consisting of a target of volume 30 cm³ with helium cooling and a thermostabilization system. The temperature of the target, close to 22 K is fixed with an accuracy of 0.1 K. This revised version was published online in August 2006 with corrections to the Cover Date.     

Formation and its mechanism of copper metal layers at surface by annealing in reduced atmosphere in CuO–Li2O–Nb2O5–SiO2 glass

A trace amount (0.5 mol%) of CuO-doped 40Li₂O–32Nb₂O₅–28SiO₂ glass (mol%) exhibits the formation of copper metal layers at the glass surface by annealing at temperatures (530 °C) below the glass transition temperature (544 °C) in the reduced atmosphere of 7% H₂–93%Ar. The coordination state of copper ions is examined from optical absorption and Fourier transform infrared (FT-IR) spectrum measurements, indicating the formation of Si–OH and Si–H bonds due to the diffusion of hydrogen into the inside of the glass and the reduction of Cu⁺ and Cu²⁺ ions. The mechanism of the formation of copper metals at the surface is proposed, in which the key points are the reduction of Cu²⁺ to Cu⁺ ions due to the hydrogen and the migration of Cu⁺ ions in the interior of the glass to the surface. The first finding on copper metal layers at the glass surface might have a potential for practical applications such as electrodes in glass.     

Determination and analysis of opiates in complex mixtures by surface-ionization mass spectrometry

The results of studies of the analytical opportunities of surface-ionization mass spectrometry (SIMS) for high-sensitivity and selective detection and analysis of opiate mixtures—natural opium, crude heroin, and narcotic analgesic omnopon—are presented. The experiments were carried out using an MX-1320 chemical mass spectrometer modernized for studying surface ionization (SI). It was ascertained that the opiate mixtures are ionized by highly efficient surface ionization. The bands of M⁺ (for papaverine), (M-H)⁺, (M-H-2nH)⁺, (M-R)⁺, and (M-R-2nH)⁺ ions, where M is a molecule, H is a hydrogen atom, R is a radical, are observed in the mass spectra; they are the sum of the SI mass spectra of components of the mixtures. The series of bands of ions with m/z of 144 and 146 that is characteristic of SI-morphinelike molecules is the main one in the mass spectrum of crude heroin, while for omnopon and natural opium this series is the main at low temperatures of a thermionic emitter (up to ∼900 K). At high temperatures of the thermionic emitter, the band series with m/z of 218 and 220 is the main series. Studies of natural opium, crude heroin, and omnopon have shown that the SIMS method allows analyzing mixtures without preliminary chromatographic separation thereof. The study also contains the results of comparative analyses of opiate mixtures by SIMS and chromate- and mass spectrometry (HP-6890) with electronic ionization.     

New states in heavy Cd isotopes and evidence for weakening of the N = 82 shell structure

A chemically selective laser ion source has been used in a β-decay study of heavy Ag isotopes into even-even Cd nuclides. Gamma-spectroscopic techniques in time-resolving event-by-event and multiscaling modes have permitted the identification of the first 2⁺ and 4⁺ levels in ¹²⁶Cd₇₈, ¹²⁸Cd₈₀, and tentatively the 2⁺ state in ¹³⁰Cd₈₂. From a comparison of these new states in ₄₈Cd with the E(2⁺) and E(4⁺)/E(2⁺) level systematics of ₄₆Pd and ₅₂Te isotopes and several recent model predictions, possible evidence for a weakening of the spherical N = 82 neutron-shell below double-magic ¹³²Sn is obtained. Received: 13 July 2000 / Accepted: 12 October 2000     

NMR EVIDENCE OF HYDROGEN BOND IN 1-ETHYL-3-METHYLIMIDAZOLIUM-TETRAFLUOROBORATE ROOM TEMPERATURE IONIC LIQUID

The 1-ethyl-3-methylimidazolium-tetrafluoroborate (EMI-BF₄) room-temperature molten salt was investigated with NMR techniques. Diffusion coefficients measured at temperatures ranging from 300 to 360 K indicate phase-change occurred in the vicinity of 333 K, which is supported by ¹¹B quadrupolar relaxation rates. Combined with the sizes of diffusion particles obtained form the Stokes-Einstein equation, this phase change is ascribed to that the diffusion particle is transformed from “discrete ion-pair” to “individual ion” at temperatures above 335 K due to decomposition of the EMI-BF₄ ion pair. Analysis of the ¹³C dipole-dipole relaxation rates identifies the formation of hydrogen bond(C2H…F) between the counter ions, EMI⁺ and BF₄ ^?. That the values of viscosity in EMI-BF₄ are higher than those in EMI-AlCl₄ at corresponding temperatures is therefore understood according to the viscosity approach employed to investigate the H-bonding in molten salts     

Defect annealing in the hexagonal close packed heavy rare earth metals Gd,Tb, Dy,Ho, Er,Tm and Lu after electron irradiation at low temperatures

The recovery spectra of the heavy rare earths Gd, Tb, Dy, Ho, Er and Tm were determined after irradiation with electrons at low temperatures. In the cases of Er and Tm, strong thermal cycling phenomena were observed and attributed to hydrogen atoms changing configurations and interacting with the magnetic structure of the metal. After elimination of these effects in Er and Tm, all the spectra—together with those of the earlier treated Lu—had rather similar form: several close-pair peaks followed by a broad complex substage resembling the stage I _D in f.c.c metals and attributed to long-range interstitial migration. A correlation is found between the temperature of the maximum of this substage (normalized to the melting temperature) and the c/a-ratio of the metals.     

Kinetics and thermodynamics of the Li/Li+ couple in tetrahydrofuran at low temperatures (195–295 K)

Kinetic and thermodynamic (formal potential) data relating to the synthetically useful Li/Li⁺ couple in tetrahydrofuran (THF) solvent at a range of temperatures (196–295 K) are reported. Formal potentials, have been measured versus the standard reference electrode, in THF. At 295 K the following data have been obtained using a mathematical model to simulate the electro‐deposition (metal deposition and growth kinetics) processes of lithium (Li) on a platinum microelectrode; a of ?3.48 ± 0.005 V, = ?9.2 (±0.5) × 10^?4 V K^?1, the standard electrochemical rate constant, k₀ = 1 (± 0.1) × 10^?4 cm s^?1, transfer coefficient, α = 0.57 ± 0.03 and diffusion coefficient, D = 8.7 ± 0.1 × 10^?6 cm² s^?1. Copyright © 2007 John Wiley & Sons, Ltd.     

Enhanced superconductivity in zirconium after H(D) implantation

Zirconium foils (superconducting transition atT _c =0.7 K) were implanted at liquid helium temperatures with hydrogen, deuterium and helium. In all cases a remarkable increase ofT _c was observed. Implantation of the inert He atoms leads only to the introduction of lattice defects, which is known to increaseT _c of Zr. However, the implanted H and D atoms exert an additional influence on the superconducting behavior based on a change of the electronic properties and an increase of the electron-phonon coupling. Introduction of lattice defects seems to account for theT _c increase to 1.49 K after He implantation, whereasT _c is even more enhanced by implantation of the hydrogen isotopes. The maximum values forT _c are 3.14 K for H and 4.65 K for D implantation. The concentration necessary to produce a saturation inT _c for both isotopes is H(D)/Zr0.13. The remarkably highT _c for the heavier isotope corresponds to an extreme inverse isotope effect. A smaller inverse isotope effect was found earlier in the Pd –H(D) system, where it could be explained by anharmonic effects.Dedicated to Prof. Dr. W. Buckel on the occasion of his 60th birthday     

Lattice atom displacements produced near the end of implanted μ+ tracks

Spin rotation experiments with implanted μ⁺ projectiles are a convenient method for extending studies of the isotope effect for hydrogen diffusion in metals to very light mass. In the present letter information is presented which allows a determination of the mean free path for vacancy production by μ⁺ particles slowing down in C (graphite), Al, V, Fe, Ni, Cu, Nd, Pd, and Ta targets. Also given is the excess distance traveled by the μ⁺ after its energy is reduced below the threshold necessary for vacancy production in these materials.     

Isomeric states in proton-unbound 187, 189Bi isotopes

Prompt and delayed gamma-ray spectroscopy of very neutron-deficient bismuth isotopes ^{187, 189}Bi has been performed using the Recoil Decay Tagging (RTD) method. The isomeric i _13/2 states have been identified and their lifetimes have been measured. The systematics of these long-lived M2 isomers has been extended to the proton-unbound isotopes. The general behaviour of single-proton states is discussed within the systematics and interpreted within the shell-model framework. Received: 2 May 2002 / Accepted: 3 June 2002 / Published online: 19 November 2002 RID="a" ID="a"e-mail: wkorten@cea.fr RID="b" ID="b"Present address: GANIL, Caen, France. RID="c" ID="c"Present address: Radiation and Nuclear Safety Authority, P.O. Box 14, FIN-00881 Helsinki. Communicated by D. Schwalm     

Hydrogen on W(100): temperature dependence of LEED and angle-resolved ESD

For hydrogen adsorption on W(100), the evolution of the c(2 × 2) LEED intensities and of the H⁺ ESD signal with H coverage have been investigated for various adsorption and annealing temperatures. Striking changes have been found for the half-order LEED intensities in the temperature range 140–360 K, in agreement with other workers, where the H⁺ signal showed only minor differences. The maxima of the LEED and the ESD intensities, however, occurred at the same exposure throughout this range (≈25% of saturation coverage). A temperature dependent variation of the height of the H⁺ maximum was observed which was reversible up to the desorption temperature of the β₂ hydrogen phase. The H⁺ ESDIAD lobe was found to have a polar FWHM of about 21°, independent of temperature between 140 and 450 K, and without any azimuthal dependence. These results provide evidence for the assumption that the observable H⁺ ions desorb from reconstructed sites. The number of these sites depends on temperature and hydrogen coverage, as shown by the change of the H⁺ current with these parameters. The transition from H on reconstructed to H on unreconstructed sites is of the order-order type; the energy difference between the two different adsorbate situations is about 135 meV/site at the quarter coverage. The consistency of the results and conclusions with a bridge-site model for H adsorption is shown. Elastic interactions lead to agglomeration of adsorbed H. The azimuthal isotropy of the ESDIAD lobes is interpreted by a superposition of emission from various types of bridge-sites which smear out the anisotropy expected for individual bridge-sites.     

Influence of impurities on muon diffusion in copper

We present new results on the positive muon (μ⁺) linewidth in “pure” and doped copper samples. These and previously published data are analysed within the framework of the quantum theory of diffusion. This analysis shows that for $\text{T}\text{? 10}\text{K}$ the linewidth is dominated by the effect of the remaining interstitial impurities in the “pure” sample.The analysis also indicates that the narrowing of the μ⁺ linewidth is due to an incoherent process even below 0.5 K and that coherent diffusion does not occur in the Cu-samples studied so far. We comment on the main differences between muon diffusion in Cu- and Al-samples. The model presented should be applicable to other metals as well.