Silver ion dynamics in silver borate glasses: spectra and multiple-time correlation functions from 109Ag-NMR

The motion of silver ions in (AgI)x-(Ag2O-B2O3)1-x glasses with AgI concentrations of x=0.5 and 0.7 was studied using 109Ag-NMR. The NMR spectra were analyzed in terms of a superposition of two different contributions. These are associated with Ag ions, which hop on vastly different time scales. The existence of dynamic heterogeneity, i.e. the existence of slow and of fast contributions to the hopping dynamics was directly demonstrated using a four-time stimulated-echo experiment. The results are compatible with an intrinsically exponential response. From measurements of the spectra and of two-time correlation functions a Gaussian distribution of energy barriers, hindering the ionic motion, could be mapped out.     

Evolution of particle-scale dynamics in an aging clay suspension

Multispeckle x-ray photon correlation spectroscopy was employed to characterize the slow dynamics of a suspension of highly charged, nanometer-sized disks. At wave vectors q corresponding to interparticle length scales, the dynamic structure factor follows a form f(q,t) approximately exp([-(t/tau)(beta)], where beta approximately 1.5. The relaxation time tau increases with the sample age t(a) approximately as tau approximately t(1.8)(a) and decreases with q as tau approximately q(-1). Such behavior is consistent with models that describe the dynamics in disordered elastic media in terms of strain from random, local structural rearrangements. The measured amplitude of f(q,t) varies with q in a manner that implies caged particle motion. The decrease in the range of this motion and an increase in suspension conductivity with increasing t(a) indicate a growth in interparticle repulsion as the mechanism for internal stress development implied by these models.     

Effects of various types of molecular dynamics on 1D and 2D (2)H NMR studied by random walk simulations

By carrying out random walk simulations we systematically study the effects of various types of complex molecular dynamics on (2)H NMR experiments in solids. More precisely, we calculate one-dimensional (1D) (2)H NMR spectra and the results of two dimensional (2D) (2)H NMR experiments in time domain, taking into account isotropic as well as highly restricted motions which involve rotational jumps about different finite angles. Although the dynamical models are chosen to mimic the primary and secondary relaxation in supercooled liquids and glasses, we do not intend to describe experimental results quantitatively but rather to show general effects appearing for complex reorientations. We carefully investigate whether 2D (2)H NMR in time domain, which was originally designed to measure correlation times of ultraslow motions (tau >/= 1 ms), can be used to obtain shorter tau, too. It is demonstrated that an extension of the time window to tau >/= 10 &mgr;s is possible when dealing with exponential relaxation, but that it will fail if there is a distribution of correlation times G(lgtau). Vice versa, we show that 1D (2)H NMR spectra, usually recorded to look at dynamics with tau in the microsecond regime, are also applicable for studying ultraslow motions provided that the loss of correlation is achieved step by step. Therefore, it is useful to carry out 1D and 2D NMR experiments simultaneously in order to reveal the mechanism of complex molecular motions. In addition, we demonstrate that highly restricted dynamics can be clearly observed in 1D spectra and in 2D NMR in time domain if long solid-echo delays and large evolution times are applied, respectively. Finally, unexpected observations are described which appear in the latter experiment when considering very broad distributions G(lgtau). Because of these effects, time scale and geometry of a considered motion cannot be extracted from a straightforward analysis of experimental results. Copyright 2000 Academic Press.     

Neutron scattering from elemental silver

Differential neutron elastic-scattering cross sections of elemental silver were measured from 1.5 → 10 MeV at scattering angles distributed between ≈17° and 160°. Cross sections for ten inelastically scattered neutron groups were determined, corresponding to observed excitations of 328 ± 13, 419 ± 50, 748 ± 25, 908 ± 26, 1150 ± 38, 1286 ± 25, 1507 ± 20, 1623 ± 30, 1835 ± 20, and 1944 ± 26 keV, all of which were composites of contributions from the two isotopes ¹⁰⁷Ag and ¹⁰⁹Ag. The experimental results were interpreted in terms of the spherical-optical and rotational and vibrational coupled-channels models.     

Isotope effect in the Knight shift of silver

The Knight shifts of the silver isotopes ¹⁰⁷Ag and ¹⁰⁹Ag were determined with high accuracy. Between these shifts there is a difference ΔK = K¹⁰⁷ - K¹⁰⁹ = ?(17.1 ± 1.1) ppm. The relative isotope effect ΔK/K is not in agreement with the hyperfine structure anomaly ¹⁰⁷Δ¹⁰⁹.     

电感耦合等离子体质谱法测定铜矿区20种植物中的金银

采用灰化-王水处理试样,选取103 Rh和203 Tl作为测定107 Ag、109 Ag和197 Au的内标元素,建立了电感耦合等离子体质谱法测定铜矿区栓皮栎等20种植物中金和银的方法。所建立方法用于不同矿区植物样品的分析,相对标准偏差(n=5)为9.05%～0.85%,加标回收率在93.6%～101.6%之间,Au和Ag检出限分别为0.048和1.06ng.g-1。该方法简便、准确,适用于铜矿区植物中金和银的测定。测定结果表明,矿区中金和银含量因不同植物而存在较大差异,变动范围为Au:0.18～0.99ng.g-1,Ag:282～2 150ng.g-1,其中凤尾蕨、芒萁和长叶实蕨中Ag具备地球化学异常特征,可作为找矿有效指示的植物。     

Investigation of the catalysis and SERS properties of flower-like and hierarchical silver microcrystals

Noble metal nano/microstructures have attracted considerable attention because of their unique properties and their various applications. Controlling the shape of noble metal nano/microstructures is a promising strategy to tailor their physical and chemical properties for various applications in fields such as biological labeling and imaging, catalysis, and sensing. Among various specific structures, flower-like and hierarchical silver nano/microstructures have attracted increasing interest because exploration of these novel nano/microstructures with unusual optical properties can provide new perspectives into the rational design of novel materials. It is significantly more challenging to develop facile and effective solution approaches for systematic manipulation of the shape of Ag nano/microstructures. In this article, we revisited the ascorbic acid reduction method to prepare flower-like silver microcrystal with plate petals and hierarchical Ag microcrystal on a large scale and in high purity. Ascorbic acid plays two roles of a reducing agent and a crystal growth regulator. Therefore, the molar ratio of ascorbic acid and silver nitrate is critical to the formation of Ag microcrystal. The controlling of the two different Ag microstructures can be achieved by adjusting the molar ratio of the reactants in aqueous medium at room temperature. The as-prepared Ag microcrystals were characterized by transmission electron microscopy, scanning electron microscopy, and X-ray diffraction. The flower-like Ag microcrystal with plate petals and hierarchical Ag microcrystal with nanoscale sharp tips and gaps could exhibit high catalytic activity and strong surface-enhanced Raman spectroscopy (SERS) activity due to the high surface area and the local electromagnetic field intensity enhancement, respectively. The potential application of the as-prepared Ag microcrystals in catalysis and SERS was investigated, which revealed that these two kinds of Ag microcrystals exhibit high catalytic activities to the NaBH₄-catalyzed reduction of 4-nitrophenol and significant SERS effect to 4-aminothiophenol molecular due to their nanoscale sharp tips and gaps. Therefore, the flower-like Ag microcrystal and hierarchical Ag microcrystal investigated here could be promising candidates for single particle catalyst and SERS.     

A new neutron monitor with silver activation

A moderator-type neutron monitor has been developed, which registers delayed beta rays from neutron-induced silver activation and which is able to measure dose equivalent in pulsed fields with peak dose rates of several thousand Sv h^?1. The monitor uses four silicon diodes in the centre of a polyethylene moderator, 30 cm in diameter. Two of the diodes are covered by natural silver foils and two of them by tin foils. The latter are used to subtract photon-induced pulses. For registering signals, a pulse height threshold is set at 662 keV, which minimizes the effect of ¹³⁷Cs and lower energy radiation and – in addition – enhances the detection of beta rays from the shorter half-life silver isotope ¹¹⁰Ag (25 s) as compared to the longer half-life isotope ¹⁰⁸Ag (144 s). The results of measurements in neutron and photon calibration fields, of MCNPX neutron response calculations and of first measurements in a high-intensity pulsed field at the PSI accelerator are shown.     

Diffusion measurements with the aid of nutation spin echoes appearing after two inhomogeneous radiofrequency pulses in inhomogeneous magnetic fields

Nutation echoes are generated by radiofrequency (RF) pulses with an inhomogeneous amplitude, B(1) = B(1)(r), in inhomogeneous magnetic fields, B(0) = B(0)(r). The two gradients of strengths G(1) and G(0), respectively, must be aligned in parallel for a maximum echo signal. After two RF pulses, two echoes appear at times tau(a) = 2 tau(1) + tau(2) + (G(1)/G(0))tau(1) and tau(b) = 2 tau(1) + tau(2) + 2(G(1)/G(0))tau(1), where tau(1) is the RF pulse duration and tau(2) the interpulse interval. It is shown that these echoes can favorably be employed for the determination of self-diffusion coefficients even in the poor experimental situation one often faces in low-resolution or low-field NMR. The signal intensity is comparable to that of ordinary Hahn echoes. Diffusion coefficients and spin-lattice relaxation times can be evaluated from the same experimental data set if both nutation echoes are recorded. Test experiments are in good agreement with literature data. Applications of the technique to "inside out" NMR, well logging NMR, surface coil NMR, toroid cavity NMR, etc., are suggested.     

Background gradient suppression in stimulated echo NMR diffusion studies using magic pulsed field gradient ratios

By evaluating the spin echo attenuation for a generalized 13-interval PFG NMR sequence consisting of pulsed field gradients with four different effective intensities (F(p/r) and G(p/r)), magic pulsed field gradient (MPFG) ratios for the prepare (G(p)/F(p)) and the read (G(r)/F(r)) interval are derived, which suppress the cross term between background field gradients and the pulsed field gradients even in the cases where the background field gradients may change during the z-store interval of the pulse sequence. These MPFG ratios depend only on the timing of the pulsed gradients in the pulse sequence and allow a convenient experimental approach to background gradient suppression in NMR diffusion studies with heterogeneous systems, where the local properties of the (internal) background gradients are often unknown. If the pulsed field gradients are centered in the tau-intervals between the pi and pi/2 rf pulses, these two MPFG ratios coincide to eta=G(p/r)/F(p/r)=1-8/[1+(1/3)(delta/tau)(2)]. Since the width of the pulsed field gradients (delta) is bounded by 0< or =delta< or =tau, eta can only be in the range of 5< or =-eta< or =7. The predicted suppression of the unwanted cross terms is demonstrated experimentally using time-dependent external gradients which are controlled in the NMR experiment as well as spatially dependent internal background gradients generated by the magnetic properties of the sample itself. The theoretical and experimental results confirm and extend the approach of Sun et al. (J. Magn. Reson. 161 (2003) 168), who recently introduced a 13-interval type PFG NMR sequence with two asymmetric pulsed magnetic field gradients suitable to suppress unwanted cross terms with spatially dependent background field gradients.     

Functionalization of carbon nanotubes with silver clusters

In this paper, an advanced method of one-step functionalization of single and multi walled carbon nanotubes (SWCNTs and MWCNTs) using γ-irradiation was described. Two synthesis procedures, related with different reduction species, were employed. For the first time, poly(vinyl alcohol) PVA is successfully utilized as a source to reduce silver (Ag) metal ions without having any additional reducing agents to obtain Ag nanoparticles on CNTs. The decoration of carbon nanotubes with Ag nanoparticles takes place through anchoring of (PVA) on nanotube's surface. Optical properties of as-prepared samples and mechanism responsible for the functionalization of carbon nanotubes were investigated using UV-vis and FTIR spectroscopy, respectively. Decorated carbon nanotubes were visualized using microscopic techniques: transmission electron microscopy and scanning tunneling microscopy. Also, the presence of Ag on the nanotubes was confirmed using energy dispersive X-ray spectroscopy. This simple and effective method of making a carbon nanotube type of composites is of interest not only for an application in various areas of technology and biology, but for investigation of the potential of radiation technology for nanoengineering of materials.     

Synthesis of biomacromolecule-stabilized silver nanoparticles and their surface-enhanced Raman scattering properties

In this work, water soluble silver nanoparticles stabilized by biomacromolecule, were produced through using an aqueous solution of silver nitrate with Bovine Serum Albumin (BSA) under different reducing agents (such as sodium borohydride, hydrazine, N,N-dimethyl formamide) at the room temperature, where BSA provided the main function to form monodispersed silver nanoparticles. UV–vis spectroscopy, Fluorescence spectra, TEM and HR-TEM are used to characterize the BSA-capped silver nanoparticles under different condition. The results show that the formed silver nanoparticles have different size and morphology under the three different reducing agents. Moreover, the fluorescence intensity of BSA was drastically quenched in presence of Ag nanoparticles from the results of fluorescence spectra. Furthermore, the surface-enhanced Raman scattering effects of the formed silver nanoparticles were also displayed and we made a comparison under three different reducing agents.     

Extraction of silver from a refractory silver ore by sono-cyanidation

In this study, effect of ultrasound on silver extraction from a refractory silver ore containing both native silver and various silver sulphide minerals was investigated. Main effects and interaction effects of pulp density, ultrasonic frequency, cyanide concentration, air flow rate and agitation speed on the extraction rate of silver were studied by a two-level fractional factorial experimental design. A few additional cyanidation tests were also conducted to verify the findings of the designed experiments.It was found that the overall extraction yield was varied from 67% to 90% depending on the operating conditions used in the sono-cyanidation tests (48 h). However, it was varied from 63% to 80% by same operating conditions used in the direct cyanidation tests at the same cyanidation time. It was observed that an increase in the ultrasonic frequency has a negligible effect on the silver recovery. More importantly, it was determined that there were insignificant differences between the 24-h sono-cyanidation results and the 48-h direct cyanidation results for each cyanidation conditions. This finding, which is very important from the cyanidation practice standpoint, indicates that the cyanidation time can be reduced up to 50%, or the capacity of an operating silver extraction plant can be increased up to 100% by the sono-cyanidation by the refractory silver ores. In order to describe the rate of silver dissolution in the cyanide solutions, the experimental data were analysed using shrinking core models. It was found that there is a good fit between the experimental data and the models, indicating the rate of silver dissolution in cyanide can be described by a two-stage, porous layer diffusion controlled, shrinking core model.     

Peptide internal motions on nanosecond time scale derived from direct fitting of (13)C and (15)N NMR spectral density functions

NMR relaxation-derived spectral densities provide information on molecular and internal motions occurring on the picosecond to nanosecond time scales. Using (13)C and (15)N NMR relaxation parameters [T(1), T(2), and NOE] acquired at four Larmor frequencies (for (13)C: 62.5, 125, 150, and 200 MHz), spectral densities J(0), J(omega(C)), J(omega(H)), J(omega(H) + omega(C)), J(omega(H) - omega(C)), J(omega(N)), J(omega(H) + omega(N)), and J(omega(H) - omega(N)) were derived as a function of frequency for (15)NH, (13)C(alpha)H, and (13)C(beta)H(3) groups of an alanine residue in an alpha-helix-forming peptide. This extensive relaxation data set has allowed derivation of highly defined (13)C and (15)N spectral density maps. Using Monte Carlo minimization, these maps were fit to a spectral density function of three Lorentzian terms having six motional parameters: tau(0), tau(1), tau(2), c(0), c(1), and c(2), where tau(0), tau(1) and tau(2) are correlation times for overall tumbling and for slower and faster internal motions, and c(0), c(1), and c(2) are their weighting coefficients. Analysis of the high-frequency portion of these maps was particularly informative, especially when deriving motional parameters of the side-chain methyl group for which the order parameter is very small and overall tumbling motions do not dominate the spectral density function. Overall correlation times, tau(0), are found to be in nanosecond range, consistent with values determined using the Lipari-Szabo model-free approach. Internal motional correlation times range from picoseconds for methyl group rotation to nanoseconds for backbone N-H, C(alpha)-H, and C(alpha)-C(beta) bond motions. General application of this approach will allow greater insight into the internal motions in peptides and proteins.     

A field emission study of silver on rhenium

Field emission measurements of the change in average work function ?f of rhenium with adsorbed silver indicate that a rhenium-silver dipole forms with silver positive, of moment μ₀=5.2±1.5 ×10^?30 C m and polarizability $\text{α=29±12}\text{A}\text{?}{}^3$. Measurement of the rate of thermal desorption yields a mean binding energy of 2.31 ± 0.04 eV for sub-monolayer silver and 2.69±0.04 eV for a 2.5 monolayer deposit. Changes in work function induced by adsorption of silver on low-index rhenium plane surfaces are characterised by the formation of well-defined states and in this, silver resembles gold. These states are thought to result from a relatively large difference between the binding energy of adatoms on the low-index planes and on the surrounding surfaces, and this differnce is maintained when the surfaces are covered with silver. At the lowest coverage, silver is believed to be absent from all four observed planes and the measured rise in work function is thought to be apparent and to result from a decrease in field strength on the plane due to extension of the plane area by surrounding adsorbed silver. The structures adopted by silver overlayers are not known, but it is argued that on (101?0) and (101?1?) the final state at high coverage has the Ag(111) surface structure. On (112?0) and (112?2?) the silver layer at high coverage is thought to have either Ag(110) or Ag(100) surface structure. The structures of intermediate states found on all four low-index planes remain unkown. Field emission spectroscopy shows that emission from clean (101?0) is free-electron like and confirms earlier observations that emission from (202?1) is not. Spectroscopy also reveals a feature in the spectrum from silver on (101?0) which may be identified with a known surface state on Ag(111), thus providing some support for the assignment of Ag(111) to the surface structure of thick silver layers (> 3 monolayers) on (101?0).     

Structure/transport relationships in silver-based oxide glasses: 1-D and 2-D NMR information

AgI-doped silver oxide glasses are of interest both for their possible applications in electrochemical devices, and as a model system to study the transport/structure relationships in ionic glasses. Here we summarize the information given by 1-D and 2-D solid-state NMR measurements on both the cations dynamics and short (and medium) range structure of several glassy systems. Emphasis is given to understand how AgI enters into the glass matrix. A new and careful analysis of our previously reported 109Ag 1-D data shows that the glass matrix plays a relevant role in determining the efficiency of carriers formation, as well as their mobility. Finally, as an example of a modern 2-D NMR application to these materials, we report the first 11B and 17O Multiple Quantum MAS study on a glass of the system AgI:Ag2O:2B2O2, which confirms the nearly complete absence of non-bridging oxygens (NBOs) in the silver diborate composition.     

In situ nucleation and growth of silver nanoparticles in membrane materials: a controllable roughened SERS substrate with high reproducibility

A controllable roughened silver surface with high surface‐enhanced Raman scattering (SERS) activity and high reproducibility has been developed in this study. This silver surface was prepared by silver nucleation in polyelectrolyte multilayers (PEMs) and silver‐enlarged growth. First, the small Ag nuclei were synthesized by NaBH₄ in situ reduction of Ag ions on a surface of PEMs. Then the small Ag nuclei formed were effectively enlarged by using a mixture of commercially available reagents named Li Silver . The optical properties and morphologies of the silver substrates have been investigated by ultraviolet–visible (UV–vis) spectroscopy and atomic force microscopy (AFM). The UV–vis and AFM results revealed that the small Ag nuclei separately appeared on the PEMs after NaBH₄ in situ reduction. The size of the enlarged Ag nanoparticles can be easily controlled with the immersing cycle in Li Silver. 4‐Mercaptopyridine (4‐MPY) and Rhodamine 6G (R6G) have been used as Raman probes to evaluate the properties of the new SERS substrates. It has been found that the enhancement factor of R6G reached ∼10⁹ after treatment in Li Silver. Reproducibility has been investigated using the SERS signal intensity at 1094 cm⁻¹ of 4‐MPY. Signals collected over multiple spots within the same substrate resulted in a relative standard deviation (RSD) of 6.38%, while an RSD of 10.33% was measured in signals collected from different substrates. Copyright © 2008 John Wiley & Sons, Ltd.     

Simulating dislocation movement through a composite ensemble of forest dislocations and point obstacles

Simulation has been applied to NaCl-lattice crystals to examine the effects from the strength and relative concentration of point obstacles on sliding-dislocation movement through a composite ensemble of forest dislocations and point obstacles. The range in the parameter = _cr ^p /_cr=1.5–2.5, corresponds to the threshold value * of the proportion of forest dislocations in the composite ensemble above which the point obstacles affect the motion of the sliding dislocations through the composite ensemble, where _cr and _cr ^p are correspondingly the critical stresses for the passage of sliding dislocations through the one-component ensembles of forest dislocations and point obstacles in the composite. The sum of the squares of _cr ^f and _cr corresponds best to the square of the total stress for the passage of sliding dislocations through the composite ensemble.Kaluga Branch, N. É. Bauman Moscow State Technical University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 105–111, September, 1993.     

Size-dependent nonlinear optical properties and thermal lens in silver nanoparticles

We have investigated the nonlinear response of the silver nanoparticle samples in a low-power regime of electromagnetic field based on nonlocal thermo-optic models. In this work, the experimental investigation of the thermo-optic nonlinear response of Ag colloids containing different size of silver nanoparticles is reported. The colloidal nanoparticle samples were synthesized by nanosecond pulsed laser ablation of Ag bulk in acetone. The sample containing Ag was characterized by linear absorption spectroscopy and transmission electron microscopy. Using the z-scan technique, the behavior of thermal nonlinear refractive index of colloid was studied at different concentrations of silver nanoparticles. Observation of asymmetrical configurations of the z-scan data indicates that nonlinear refraction occurring in the Ag samples is related to the thermo-optical process. The optical limiting here is due to nonlinear refraction of the samples arising from thermal lens formation under low-power CW excitation. When the laser power is low, the self-defocusing effect is mainly dominated by surface plasmon resonance effect. Results show that with increasing concentration of nanoparticles in acetone, the nonlinear refractive index increases while the threshold power of optical limiting decreases.     

Transparent chromatic electrode using the mixture of silver nanowire and silver nanoprism

In this research, we studied a chromatic transparent silver nanowire (Ag NW) electrode using a silver nanoprism (Ag NP). Ag NW and Ag NP were produced using a chemical synthesis method (polyol method) and deposited on substrate via spray method.The Ag NW electrode showed a more than 80% transmittance and no or low conductivity without high temperature annealing process. In the case of applying an annealing process, a 13 Ω/□ sheet resistance was measured.The electrode, which consisted of a mixture of Ag NW and Ag NP, showed a reduced transmittance of about 70%. However, by applying Ag NPs to a conventional bare Ag NW electrode, we were able to add a chromatic characteristic to the transparent electrode; this addition was induced by the localized surface plasmon resonance (LSPR) and the low sheet resistance, even though no annealing process was applied.