Measurement of diffusion coefficients in polystyrene using xenon-129 NMR

A sample of polystyrene beads, 18 μm in diameter, has been sealed in an NMR tube under 10 atm of xenon gas. Two dimensional,¹²⁹Xe NMR spectra show cross peaks between the resonances corresponding to xenon in the free gas and the sorbed state, indicating that appreciable exchange occurs during the mixing time of the NMR experiment. Selective saturation of the free gas resonance attenuates the integrated intensity of the sorbed xenon resonance as a function of saturation time, thus allowing the accurate measurement of the exchange rates between the gas and the sorbed states. A model has been developed using a slightly modified form of Crank’s treatment of diffusion in a sphere which allows for the accurate determination of the diffusion coefficient for xenon in the sorbed state. The diffusion coefficient for xenon in polystyrene at 25°C is determined to be 2.9·10^?9 cm²/s.     

129Xe NMR study of the homogeneity and the size distribution of small sodium metal particles in NaY zeolite

NaY zeolite samples loaded with sodium metal by vapor phase deposition have been investigated using¹²⁹Xe NMR spectroscopy. At low sodium concentration, the¹²⁹Xe NMR spectrum showed three resonance lines which clearly indicate the existence of distinct domains in the zeolite sample. Such an observation suggests that the diffusion of the xenon atoms into each domain only occurs with respect to the NMR time scale (2.9 ms). As the sodium concentration increases, observation of a single broad line indicate a macroscopic homogenization of the system. The shift of this line is explained in part due to a paramagnetic interaction between the xenon atoms and the unpaired electrons of particles containing an odd number of sodium atoms. The linewidth is due to the distribution of the local magnetic fields partially averaged by the rapid motion of the xenon atoms and to the statistical distribution of the sodium particles in the supercage cavities. The paramagnetic interaction vanishes with the oxidation of the sample leading to a narrowing and a shift of the line to higher magnetic fields.     

129Xe NMR studies of the dynamics of xenon in siliceous ZSM-12 zeolite

The adsorption of xenon in siliceous zeolite ZSM-12 has been studied by static, magic angle spinning and 2D-EXSY¹²⁹Xe NMR. Anisotropic lines were observed with parameters dependent on the Xe loading and the temperature of the experiment. The observed dependence of the isotropic chemical shift is at variance with the predictions of the mean-free-path model, which casts further doubt on the applicability of this model to the interpretation of Xe NMR data in porous systems. Based on the continuous changes of anisotropic parameters with the loading, we conclude that there are several adsorption sites for xenon in the pores. A qualitative model for the distribution and rapid exchange of the xenon atoms between several sites is discussed. The observed lines arise from a dynamic average of the chemical shift tensors for the different types of site weighted by their populations. 2D-EXSY spectra show two kinds of slow exchange of Xe: (a) particle to particle and, (b) particle to interparticle gas phase.     

Application of129Xe 2D-EXSY NMR to intra- and interparticle exchange in zeolites

2D-EXSY NMR methods were used to explore diffusion between different domains in zeolites on two very different length scales. Measurements were made on xenon-containing samples consisting of a mixture of NaX and NaY zeolite particles which give distinct resonance lines. The cross peaks observed were interpreted in terms of interparticle exchange, and exchange rates were measured as a function of particle size. This kind of experiment with a length scale of microns to mm should be useful in model studies of diffusion in packed catalyst beds. Measurements also were made to study exchange on a much smaller length scale between the main-channel and side-pocket sites in samples of microcrystalline Na-mordenite. Exchange rates and site occupancies were measured as a function of temperature, yielding activation energies for xenon desorption and intersite diffusion. Also, information was obtained on the distribution of inequivalent side-pocket sites which leads to the large xenon NMR linewidths for this type of site.     

Xenon-131 surface sensitive imaging of aerogels in liquid xenon near the critical point

In recent years, optically pumped xenon-129 has received a great deal of attention as a contrast agent in gas-phase imaging. This report is about the other NMR active xenon isotope (i.e., xenon-131, S = 32) which exhibits distinctive features for imaging applications in material sciences that are not obtainable from xenon-129 (S = (1/2)). The spin dynamics of xenon-131 in gas and liquid phases is largely determined by quadrupolar interactions which depend strongly on the surface of the surrounding materials. This leads to a surface dependent dispersion of relaxation rates, which can be substantial for this isotope. The dephasing of the coherence due to quadrupolar interactions may be used to yield surface specific contrast for imaging. Although optical pumping is not practical for this isotope because of its fast quadrupolar relaxation, a high spin density of liquid xenon close to the critical point (289 K) overcomes the sensitivity problems of xenon-131. We report the first xenon-131 magnetic resonance images and have tested this technique on various meso-porous aerogels as host structures. Aerogels of different densities and changing levels of hydration can clearly be distinguished from the images obtained.     

Xenon porometry: a novel method for the derivation of pore size distributions

Xenon porometry is a novel method used for characterizing porous materials by the (129)Xe nuclear magnetic resonance of xenon gas. With the method, the diffusion of gas is slowed down by immersing the material in a medium, which can be in liquid or solid state during measurements. Because of slow diffusion, the signal of a xenon atom is characteristic of the properties of only one pore, and the composite signal of all atoms represents the distribution of properties. The method is especially applicable for determining pore size distribution because the chemical shifts of two different xenon signals (one from liquid and the other from gas pockets in solid) are dependent on pore size. Therefore, the shapes of these signals represent pore size distribution function. In addition, the porosity of the material can be determined by comparing the intensities of two signals. This article focuses on describing xenon signals observed from gas pockets in a solid medium, which has turned out to be most convenient for pore size determination.     

Collision-induced diffusion and vacancy migration in alkanethiol monolayers on Au(1 1 1)

Scanning tunneling microscopy is used to characterize the collision-induced migration of molecules within well-ordered octanethiol and nonanethiol self-assembled monolayers. A seeded molecular beam is used to create xenon atoms with a kinetic energy of 1.3 eV, and collisions with these atoms cause measurable changes in alkanethiol monolayer surface structure. Migration rates are calculated and compared for molecules in close-packed domains, at domain-boundary defects, and along the perimeter of vacancy-island defects. The number of nearest-neighbor molecules (within the 5 Å lattice distance) is strongly predictive of molecular stability with respect to xenon bombardment, and the overall dependence of stability on nearest neighbors is well fit by a simple exponential curve. The incident direction of the molecular beam is not observed to influence the direction of molecular motion; however, in some cases, migration correlates strongly to surface lattice directions. Finally, there is no evidence that substrate restructuring or gold-atom diffusion accompanies alkanethiol migration under these non-equilibrium conditions.     

A129Xe NMR study of highly cadmium-exchanged zeolite Y

The adsorption isotherms of carbon monoxide and xenon as well as the¹²⁹Xe NMR chemical shifts of xenon in highly (68 and 87%) cadmium-exchanged zeolite NaY were measured. The complete set of experimental data can quantitatively be reproduced with a model that considers localized adsorption of both adsorbate molecules on cadmium and sodium cation sites in the supercages. The concentrations of the supercage cadmium cations as well as their characteristics like adsorption constants for Xe and CO and¹²⁹Xe NMR chemical shifts were determined.     

129Xe and131Xe NMR of xenon on silica surfaces at 77 K

Little is known about¹²⁹Xe NMR spectral features and spin-lattice relaxation behavior, and the dynamics of xenon atoms, for xenon adsorbed on solid surfaces at cryogenic temperatures (≤77 K), where exchange with gas-phase atoms is not a significant complication. We report¹²⁹Xe NMR experiments at 9,4 T that provide such information for xenon adsorbed onto the hydroxylated surface of a number of microporous silica samples at 77 K. A convenient design for these cryogenic experiments is described. Dynamics of surface-adsorbed xenon atoms on the time scale of seconds can be observed by¹²⁹Xe NMR hole-burning experiments; much slower dynamics occurring over hours and days are evidenced from changes with time of the¹²⁹Xe NMR chemical shifts. The peak maxima occur in the region ca. 180–316 ppm, considerably downfield of¹²⁹Xe shifts previously reported on surfaces at higher temperatures, and closer to the shift of xenon bulk solid (316.4±1 ppm). The¹²⁹Xe spin-lattice relaxation timesT ₁ range over five orders of magnitude; possible explanations for both nonexponential relaxation behavior and extremely shortT ₁ values (35 ms) are discussed. Preliminary¹³¹Xe and¹H NMR results are presented, as well as a method for greatly increasing the sensitivity of¹²⁹Xe NMR detection at low temperatures by using closely-spaced trains of rf pulses.     

超极化气体氙-129的低场NMR测量

在自旋交换光泵过程中,多种参数可能会影响到最终可获得的超极化气体氙-129核自旋极化度.通过低场(0.002 T)核磁共振(NMR)系统研究了连续流动工作模式的自旋交换光泵过程,当混合工作气体流量为0.3 SLPM和0.5 SLPM时,实验测量得到最佳光泵泡工作温度;对于同位素富集和自然丰度的氙-129气体,核自旋极化度的建立时间分别为15 min和22 min.由于混合工作气体的压力以及组分会导致铷原子吸收线的频移和展宽,并且影响到其线型,实验通过低场NMR系统测量确定了用于自旋交换光泵的最佳激光工作波长.低场NMR测量为获得具有高核自旋极化度的超极化气体氙-129,并且能够用于人体肺部MRI研究提供了实验依据.     

The scattering and transmission of elastic waves in quasi-two-dimensional planar waveguides with linear defect boundaries

The influence of linear defect boundaries on the transmission and scattering of elastic waves in quasi-two-dimensional wave-guides is studied using the matching method. A linear defect boundary separating two wave-guide crystalline lattice domains is characterised here by a linear chain of defect masses and by modified elastic constants in the boundary, different from their values in the bulk of the domains. In particular a square lattice is considered to model the domains of the two-dimensional planar wave-guide containing the linear defect. The reflection and transmission probabilities, and the total transmission probabilities are calculated numerically and presented for the scattering processes in a variety of cases. We show that the interaction between the localised modes introduced by the defect boundary and the propagating modes of the system leads to Fano resonances. These resonances shift to higher (lower) frequencies for smaller (larger) defect masses, and for the same mass as function of the angle of the incident wave. Other spectral features shown to exist are due to interference effects especially at oblique incidence and when modifying the boundary elastic constants. Received 8 November 1999 and Received in final form 14 January 2000     

Pore-Structure Determinations of Silica Aerogels byXe NMR Spectroscopy and Imaging

Silica aerogels represent a new class of open-pore materials with pore dimensions on a scale of tens of nanometers, and are thus classified as mesoporous materials. In this work, we show that the combination of NMR spectroscopy and chemical-shift selective magnetic resonance imaging (MRI) can resolve some of the important aspects of the structure of silica aerogels. The use of xenon as a gaseous probe in combination with spatially resolved NMR techniques is demonstrated to be a powerful, new approach for characterizing the average pore structure and steady-state spatial distributions of xenon atoms in different physicochemical environments. Furthermore, dynamic NMR magnetization transfer experiments and pulsed-field gradient (PFG) measurements have been used to characterize exchange processes and diffusive motion of xenon in samples at equilibrium. In particular, this new NMR approach offers unique information and insights into the nanoscopic pore structure and microscopic morphology of aerogels and the dynamical behavior of occluded adsorbates. MRI provides spatially resolved information on the nature of the flaw regions found in these materials. Pseudo-first-order rate constants for magnetization transfer among the bulk and occluded xenon phases indicate xenon-exchange rate constants on the order of 1 s⁻¹for specimens having volumes of 0.03 cm³. PFG diffusion measurements show evidence of anisotropic diffusion for xenon occluded within aerogels, with nominal self-diffusivity coefficients on the order ofD= 10⁻³cm²/s.     

Analysis of porosity in porous silicon using hyperpolarized 129Xe two-dimensional exchange experiments

The porosity in porous silicon was characterized using hyperpolarized (HP) xenon as a probe. HP xenon under conditions of continuous flow allows for the rapid acquisition of xenon NMR spectra that can be used to characterize a variety of materials. Two-dimensional exchange spectroscopy (EXSY) (129)Xe NMR experiments using HP xenon were performed to obtain exchange pathways and rates of xenon mobility between pores of different dimensions within the structure of porous silicon and to the gas phase above the sample. Pore sizes are estimated from chemical shift information and a model for pore geometry is presented.     

Observation of micropores in hard-carbon using Xe NMR porosimetry

The existence of micropores and the change of surface structure in pitch-based hard-carbon in xenon atmosphere were demonstrated using ¹²⁹Xe NMR. For high-pressure (4.0 MPa) ¹²⁹Xe NMR measurements, the hard-carbon samples in Xe gas showed three peaks at 27, 34 and 210 ppm. The last was attributed to the xenon in micropores (<1 nm) in hard-carbon particles. The NMR spectrum of a sample evacuated at 773 K and exposed to 0.1 MPa Xe gas at 773 K for 24 h showed two peaks at 29 and 128 ppm, which were attributed, respectively, to the xenon atoms adsorbed in the large pores (probably mesopores) and micropores of hard-carbon. With increasing annealing time in Xe gas at 773 K, both peaks shifted and merged into one peak at 50 ppm. The diffusion of adsorbed xenon atoms is very slow, probably because the transfer of molecules or atoms among micropores in hard-carbon does not occur readily. Many micropores are isolated from the outer surface. For that reason, xenon atoms are thought to be adsorbed only by micropores near the surface, which are easily accessible from the surrounding space.     

Combined nuclear-molecular resonance inelastic scattering of x rays

We report on theoretical and experimental studies of nuclear inelastic scattering in a molecular crystal, whose atoms experience both molecular and lattice vibrations. In this case scattering proceeds as combined nuclear-molecular resonance inelastic scattering. The lattice vibrations give rise to inelastic scattering around the molecular resonances with an energy dependence identical to that around the nuclear resonance. The incoherent nature of the scattering in the molecular resonances results in a proper balance of elastic and inelastic components, which has important implications for studies of heterogeneous systems.     

Counting atoms using interaction blockade in an optical superlattice

We report on the observation of an interaction blockade effect for ultracold atoms in optical lattices, analogous to the Coulomb blockade observed in mesoscopic solid state systems. When the lattice sites are converted into biased double wells, we detect a discrete set of steps in the well population for increasing bias potentials. These correspond to tunneling resonances where the atom number on each side of the barrier changes one by one. This allows us to count and control the number of atoms within a given well. By evaluating the amplitude of the different plateaus, we can fully determine the number distribution of the atoms in the lattice, which we demonstrate for the case of a superfluid and Mott insulating regime of 87Rb.     

1H and 129Xe NMR absorption line shapes in the presence of highly polarized and concentrated xenon solutions in high magnetic field

The presence of highly concentrated dissolved laser-polarized xenon (approximately 1mol/L, polarization up to 0.2) induces numerous effects on proton and xenon NMR spectra. We show that the proton signal enhancements due to (129)Xe-(1)H cross-relaxation (SPINOE) and overall shifts of the proton resonances due to the average dipolar shift created by the intense xenon magnetization are correlated. Protons behave as very useful sensors of the xenon magnetization. Indeed the xenon resonances exhibit many features such as superimposition of narrow lines on the main resonance due to clustering effects, or such as a polarization-dependent line broadening that is tentatively assigned to the effects of temperature fluctuations that decorrelate some distant dipolar field effects from local interactions, transforming xenon spins from "like" to "unlike" spins. These spectral features make difficult the determination of the average dipolar field by means of the xenon resonance but have interesting consequences on the heteronuclear polarization transfer experiment in Hartmann-Hahn conditions (SPIDER).     

Diffusion of hydrogen in heterogeneous systems

The effective long-range long-time tracer diffusivity D_eff for interstitial diffusion of hydrogen through heterogeneous systems was studied theoretically for model systems consisting of isolated grains of material G embedded in a matrix of material M. Different solubilities of hydrogen in these two materials as well as different diffusivities are allowed for. Additionally, modified diffusion barriers at the phase boundaries were included in the diffusion model. The effect of different sizes, arrangements, and forms of the grains was also considered. D_eff was determined by Monte Carlo (MC) simulations on simple lattice models of the systems described above. An equilibrium distribution of hydrogen atoms among the two constituent materials was assumed. Our main interest was focused on whether and how D_eff may be related to mesoscopic or macroscopic quantities characterizing the heterogeneous system and its constituent materials, such as the volume fractions of the two materials, the fraction of lattice sites in the immediate vicinity of the phase boundary, the hydrogen concentrations c_G and c_M in the grains and in the matrix and the respective hydrogen diffusivities D_G(c_G) and D_M(c_M). In order to obtain good estimates for these relations in terms of analytic formulas, we attempted to model a heterogeneous system by a network of diffusion elements connected in series and in parallel, in analogy to an electric network. The properties of the basic connections, in parallel and in series, were studied on layered structures, for which analytic expressions for D_eff could be derived. The network formulas for different grain–matrix systems were tested by comparing with results of MC simulations. In general, the network formulas describe the corresponding MC results for D_eff fairly well. It was found that differences in the hydrogen solubilities in the two phases as well as modified energy barriers at the phase boundaries may have dramatic effects on D_eff. Received: 19 September 2000 / Accepted: 6 November 2000 / Published online: 9 February 2001     

T1-relaxation of 129Xe on metal single crystal surfaces-multilayer experiments on iridium and monolayer considerations

The surface of a typical laboratory single crystal has about 10(15) surface atoms or adsorption sites, respectively, and is thus far out of reach for conventional NMR experiments using thermal polarization. It should however be in reach for NMR of adsorbed laser polarized (hyperpolarized) 129Xe, which is produced by spin transfer from optically pumped rubidium. With multilayer experiments of xenon adsorbed on an iridium surface we do not only demonstrate that monolayer sensitivity has been obtained, we also show that such surface experiments can be performed under ultra high vacuum conditions with the crystal being mounted in a typical surface analysis chamber on a manipulator with far-reaching sample heating and cooling abilities. With only four spectra summed up we present an NMR signal from at most 4x10(14) atoms of 129Xe, four layers of naturally abundant xenon, respectively. The fact that no monolayer signal has been measured so far is explained by a fast Korringa relaxation due to the Fermi contact interaction of the 129Xe nuclei with the electrons of the metal substrate. T(1)-relaxation times in the order of several ms have been calculated using all electron density functional theory for several metal substrates.