Correlation between I-Ag distance and ionic conductivity in AgI fast-ion-conducting glasses

A large number of AgI-based fast-ion-conducting glasses have been investigated by K-iodine extended x-ray absorption fine structure spectroscopy (EXAFS) measurements at liquid nitrogen temperature. A general correlation between the I-Ag distance measured by EXAFS and the glass activation energy for dc ionic conductivity has been found out: glasses with longer I-Ag distances display higher ionic conductivity, independently from the chemical composition of their host glassy matrix. This behavior can be related to the progressive increase of the "pathway volume" for ionic conduction.     

The fractional ionic character of alkali and silver halide crystals

The fractional ionic character of alkali and silver halide crystals is defined in terms of the deviations from the additivity rule for polarizabilities of ions. The electronic polarizabilities of ions are calculated using an empirical relationship according to which the electronic polarizability of an ion can be assumed to be directly proportional to the cube of its radius. The calculated ionicities indicate that the alkali halides are nearly or more than 90% ionic and silver halides are much less ionic which is also evident from the Phillips ionicity scale.     

Anomalous electrical conductivity behavior at elevated pressure in the protic ionic liquid procainamide hydrochloride

Using broadband dielectric spectroscopy, we investigated the effect of hydrostatic pressure on the conductivity relaxation time τ{σ} of the supercooled protic ionic liquid, procainamide hydrochloride, a common pharmaceutical. The pressure dependence of τ{σ} exhibited anomalous behavior in the vicinity of the glass transition T{g}, manifested by abrupt changes in activation volume. This peculiar behavior, paralleling the change in temperature dependence of τ{σ} near T{g}, is a manifestation of the decoupling between electrical conductivity and structural relaxation. Although the latter effectively ceases in the glassy state, free ions retain their mobility but with a reduced sensitivity to thermodynamic changes. This is the first observation of decoupling of ion migration from structural relaxation in a glassy conductor by isothermal densification.     

Contributions from the indirect ionic interactions to the elastic constants in the rock-salt structure crystals

Under the harmonic approximation, the contributions from the indirect ionic interactions to the elastic constants are calculated for the alkali halide and silver halide crystals with the rock-salt structure. The coupling constants of the indirect ionic interactions are calculated by the self-consistent field treatment of the local density approximation and the spherical solid model. The calculated values of the coupling constants are large for the silver ion. The indirect ionic interaction significantly affects the elastic constants. It quantitatively explains the deviation from the Cauchy relation in alkali halide crystals. Moreover, it provides a clear account for the large values of the deviation from the Cauchy relation in AgCl and AgBr.     

Structure-conductivity relations in ion conducting glasses

The bond valence method has been applied to reverse Monte Carlo (RMC) produced structural models of a wide range of ion conducting glasses in order to elucidate the relation between the microscopic structure and the ionic conductivity. Our approach allows us to predict the ionic conductivity of the glasses directly from the “pathway volume” of the structural models and to investigate the nature of these low-dimensional conduction pathways. The pathways are defined to be the regions in the structural models where the valence mismatch for each mobile ions remains below a given threshold value. The results for the metal-halide doped glasses show the importance of including M⁺ sites with a high oxide coordination for the long range mobility, responsible for the dc conductivity. Thus, there are no long range migration pathways for M⁺ sites in an entire halide environment. Rather, the mobile ions are generally moving between sites with a local environment of both oxygens and halide ions, in contrast to earlier proposed “cluster models” where it has been assumed that cations associated with salt clusters are responsible for the high ionic conductivity. Finally, our bond valence approach provides a direct explanation for why the conductivity is favoured by highly polarizable anions and cations, since the pathway volume is related to the softness of the M⁺-X bond. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

Direct evidence for conduction pathways in a solid electrolyte

The emission of silver ions from the apex of an amorphous electrolyte tip has been investigated by field ion microscopy. The ion emission patterns show discrete nanometer-sized spots. We present evidence that they represent the termination of bulk ion conduction pathways at the solid-vacuum interface. The analysis of the signals from individual emission sites suggests the existence of a network of such pathways in the solid. Auto- and cross-correlation measurements of the currents from individual sites provide quantitative information on the microscopic dynamics of charge transport in solid electrolytes as well as on the lateral extent of the pathway network.     

Influence of pre-surface treatment on the morphology of silicon nanowires fabricated by metal-assisted etching

Herein we demonstrate an improved metal-assisted etching method to achieve highly dense and uniform silicon nanowire arrays. A pre-surface treatment was applied on a silicon wafer before the process of metal-assisted etching in silver nitrate and hydrogen fluoride solution. The treatment made silver ion continuously reduce on silver nuclei adherence on the silicon surface, leading to formation of dense silver nanoparticles. Silver nanoparticles acting as local redox centers cause the formation of dense silicon nanowire arrays. In contrast, an H-terminated silicon surface made silver ion reduce uniformly on the silicon surface to form silver flakes. The silicon nanowires fabricated with a pre-surface treatment reveals higher density than those fabricated without a pre-surface treatment. The volume fraction improves from 18 to 38%. This improvement reduces the solar-weighted reflectance to as low as 3.3% for silicon nanowires with a length of only 0.87 μm. In comparison, the silicon nanowires fabricated without a pre-surface treatment have to be as long as 1.812 μm to achieve the same reflectance.     

Kinetic aspects of the silver ion release from antimicrobial polyamide/silver nanocomposites

Spherical silver nanoparticles were grown in situ in different polyamides by a thermal reduction of silver acetate during melt processing of the polymers. Most of the particles have a diameter of about 20 nm. The absolute amount as well as the kinetics of the silver ion release from the various polyamide/silver nanocomposites differ strongly, although the filler content in all materials is the same (1.5 wt. %) and the morphologies of the silver particles are not very different. One result of the investigations was that the absolute amount of the long-term silver ion release increases exponentially with the maximum water absorption of the polymers used as matrix materials, because silver ions are formed from elemental silver particles in the presence of water, only. Moreover, it was also found that the long-term silver ion release increases with a growing diffusion coefficient of water in the polymer. The water absorption properties of the polymers govern the kinetics of the silver ion release, too: for strong hydrophilic polyamides like PA6 or PA6.6, which are plasticized by water, the silver ion release is a zero-order process. For nanocomposites with less hydrophilic polyamides like a cycloaliphatic polyamide or a P12 modified with polytetrahydrofurane (PA12-poly-THF), the silver ion release is governed by diffusion. As expected from the efficacy of the silver ion release, PA6, PA6.6, PA12 and PA12 modified with polytetrahydrofurane and a cycloaliphatic polyamide filled with 1.5 wt. % of silver nanoparticles are active against Escherichia coli. But, only nanocomposites with PA6, PA6.6 and P12-poly-THF as matrix materials are suitable as long-term biocidal materials. PACS 68.35.bm; 68.35.Fx; 68.37.Lp     

The effect of point defects on the ionic conductivity of RbAg4I5 solid electrolytes

Abstract

The effect has been studied of additive coloring on the magnitude of ion conductivity of RbAg₄I₅ crystals. It has been found that slight changes of silver stoichiometry of 10^?3 at.% can lead to considerable variations of the ionic conductivity Δ[sgrave]_i/[sgrave]_i ? 0.1. The dependence has been observed of the magnitude of ion conductivity on the ratio between the integral intensities of the main bands in the photoluminescence spectrum of the γ-phase of RbAg₄I₅ which associated with the luminescence centres containing vacancies and interstitials of silver cations.     

NASICON type ionic conductors for alkali ion sensing

NASICON type ionic conductors can be used as the sensitive membrane of alkali ion sensors. The main advantages compared to the classical glass electrodes are the better selectivity and lower impedance. The mechanism of response of this type of ionic sensors is presented. The sensitivity results from a direct ionic exchange between the ceramic electrolyte and the solution which has been characterized by impedance spectroscopy. The origin of the selectivity in the NASICON framework is discussed in terms of structural and ionic exchange properties. The performance characteristics of sodium and lithium ion sensing devices are presented. Examples of biomedical applications such as the measurement of sodium concentration in the crevicular fluid and the determination of lithium in artificial serum are described. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Optical and structural properties of CdS thin films grown by chemical bath deposition doped with Ag by ion exchange

In this work thin CdS films using glycine as a complexing agent were fabricated by chemical bath deposition and then doped with silver (Ag), by an ion exchange process with different concentrations of AgNO₃ solutions. The CdS films were immersed in silver solutions using different concentrations during 1 min for doping and after that the films were annealed at 200 °C during 20 min for dopant diffusion after the immersion on the AgNO₃ solutions. The aim of this research was to know the effects of different concentrations of Ag on the optical and structural properties of CdS thin films. The optical band gap of the doped films was determined by transmittance measurements, with the results of transmittance varying between 35% and 70% up to 450 nm in the electromagnetic spectra and the band gap varying between 2.31 and 2.51 eV depending of the silver content. X-ray photoelectron spectroscopy was used to study the influence of silver on the CdS:Ag films, as a function of the AgNO₃ solution concentration. The crystal structure of the thin CdS:Ag films was studied by the X-ray diffraction method and the film surface morphology was studied by atomic force microscopy. Using the ion exchange process, the CdS films’ structural, optical and electric characteristics were modified according to silver nitrate concentration used.     

High resolution magic angle spinning NMR studies of31P and11B in fast ion conducting AgI-Ag2O-P2O5 and AgI-Ag2O-B2O3 glasses

Silver iodide-based fast ion conducting glasses containing silver phosphate and silver borate have been studied. An attempt is made to identify the interaction between anions by studying the chemical shifts of³¹P and¹¹B atoms in high resolution (HR) magic angle spinning (MAS) NMR spectra. Variation in the chemical shifts of³¹P or¹¹B has been observed which is attributed to the change in the partial charge on the³¹P or¹¹B. This is indicative of the change in the electronegativity of the anion matrix as a whole. This in turn is interpreted as due to significant interaction among anions. The significance of such interaction to the concept of structural unpinning of silver ions in fast ion conducting glasses is discussed. Communication number 593 from Solid State and Structural Chemistry Unit     

Theory of electronic and ionic conductivity in particulate membrane ion selective electrode systems: All solid state silver sulfide electrode

In this paper, we have theoretically investigated the behavior of three figures of merit which might be used to characterize ion selective electrode membranes. This has been accomplished by extending the Smith-Anderson model for calculating the electronic conductivity of particulate membranes to the case of the all solid state silver sulfide electrode, one of the simplest such systems which can be treated. The transport number of Ag⁺ is found to be extremely sensitive to membrane composition. This result points to transport number as potentially the most useful figure of merit for ion selective membrane electrodes of this type.     

Calculation of the conductance and selectivity of an ion-selective potassium channel (IRK1) from simulation of atomic scale models

We present the equations and methodology for the theoretical prediction of the conductance, permeability and selectivity of a K⁺ channel on the basis of atomic scale models for it. The methodology involves the use of Langevin dynamics and activated trajectories in order to obtain translocation free energies, rate constants and transmission coefficients for an ion going through the channel. The models are for the Inward Rectifier K⁺ channel (IRK1) which is a member of a family of ion-selective K⁺ channels. The IRK1 channel is biologically important because of its role in cardiac pacemaker function. The models we use for the IRK1 channel are developed from a model of the Shaker voltage-gated K⁺ channel. We find that the theoretically predicted conductance is too low by three orders of magnitude. We attribute this underestimate to a specific structural defect in the model used. Perhaps our most significant result is that the computed conductance is tremendously sensitive to the structural details of the so-called ‘P-loop’ that lines the outer half of the permeation pathway of the channel. This sensitivity may be useful in future studies on ion channel proteins for which the structure is not known from X-ray crystallography. In addition, this sensitivity may help determine whether X-ray structures of these proteins correspond to open or closed conformations.     

用于检测水环境中银离子浓度的荧光适体传感器研究

银凭借其独特的性能,在医疗材料、摄影、电子、成像等行业中应用广泛。然而,银离子被列为最具毒性的重金属离子之一,会对环境以及人类的生命健康造成严重威胁。为了灵敏、特异性的检测水环境中的银离子浓度,利用纳米金的优良光学猝灭性以及双链核酸适体捕获银离子能力更强的优点,结合荧光能量共振转移原理,提出一种用于检测水环境中银离子浓度的荧光适体传感器。将修饰SH键的核酸适体与纳米金混合形成稳定的纳米结构,并加入标记有FAM的核酸适体,形成检测银离子浓度的工作溶液。当不存在银离子时由于不匹配碱基C-C之间的排斥力导致两条核酸适体不结合,反应体系中具有较强的荧光;当存在银离子时,双链核酸适体中不匹配的C-C能与银离子通过金属离子-碱基的相互作用形成稳定的C-Ag+-C碱基对,这种复合结构的产生会拉近纳米金和荧光基团之间的距离,使得荧光信号随着银离子浓度的增加而逐渐减弱。根据加入银离子前后荧光强度的变化可实现银离子浓度的检测。同时,为了提高传感器的灵敏性和稳定性,实验优化了工作溶液中纳米金与核酸适体的浓度比、氯化钠浓度、缓冲液的pH以及培养温度等参数。结果表明,当浓度为0.012 5 g·L-1的纳米金与5 μmol·L-1核酸适体的体积比为5∶1,NaCl浓度为260 mmol·L-1,缓冲液pH 7,培养温度为30 ℃时,工作溶液初始荧光强度最强,银离子检出限为10 nmol·L-1,相关系数为R2=0.99。此外,该传感器对银离子的浓度检测表现出较好的特异性,且具有操作简单、灵敏和不引入有毒溶剂等优点,在水环境中的银离子浓度检测领域有较好的应用前景。     

Aqueous Synthesis of Water-Soluble L-Cysteine-Modified Cadmium Sulfide Doped with Silver Ion/Zinc Sulfide Nanocrystals

The water-soluble silver ion-doped cadmium sulfide nanocrystals were synthesized by a co-precipitation technique in aqueous solution using L-cysteine as surface modifier, and then L-cysteine-modified cadmium sulfide doped with silver ion/zinc sulfide core/shell nanocrystals were prepared by zinc sulfide epitaxial coated on surface of silver ion-doped cadmium sulfide nanocrystals. The crystal structure, morphology, and spectral properties of cadmium sulfide doped with silver ion/zinc sulfide nanocrystals were characterized by X-ray power diffraction, transmission electron microscope, infrared spectrum, and photoluminescence spectrum. The results show that the photoluminescence quantum yield of cadmium sulfide doped with silver ion/zinc sulfide nanocrystals is improved greatly after doped with silver ion and coated with zinc sulfide shell. The cysteine modified on the surface of cadmium sulfide doped with silver ion/zinc sulfide nanocrystals renders the nanocrystals water-soluble and biocompatible.     

Two-dimensional 109Ag NMR and random-walk simulation studies of silver dynamics in glassy silver ion conductors

By applying one- and two-dimensional 109Ag NMR, we demonstrate that silver diffusion in silver iodide/silver phosphate glasses is governed by a very broad, continuous distribution of correlation times G(lg tau). As a consequence, over a wide temperature range, the 109Ag NMR spectra can be described by a weighted superposition of a Gaussian and a Lorentzian where these line-shape components result from the slow and the fast silver ions in G(lg tau), respectively. For the 109Ag NMR two-time correlation functions F2(t), measured as a stimulated echo, a very stretched decay to F2SS(t(m)) = 0 is observed. When fitting to a Kohlrausch function, exp[-(t/tau)beta], a stretching parameter beta approximately = 0.2 is found. The temperature dependence of the mean correlation time of silver dynamics is described by an Arrhenius law where the activation energy is consistent with the one reported for the dc conductivity sigma(dc). In addition, it is shown that the effect of complex dynamical processes on NMR multi-time correlation functions can easily be calculated when performing random-walk simulations for schematic models such as the random-barrier model and the random-energy model. Based on these models it is possible to simulate various NMR observables and the mean square displacement, thus revealing the information content of multi-dimensional NMR experiments on solid ion conductors.     

微波消解-原子吸收光谱法间接测定生物样品中的氯离子

微波消解样品,在中性介质中加入硝酸银,氯离子与银离子生成氯化银沉淀,采用火焰原子吸收光谱法测定溶液中剩余银的量,间接测出氯离子浓度。方法检出限为2.0μg/mL,回收率为96.0%—106.6%,相对标准偏差（RSD）为0.32%—2.72%。该方法具有良好的准确度和精密度。方法简便、快速,是测定生物样品中氯离子比较好的方法。     

Electron distribution in silver halides

Solid fast ion conductors such as silver halides and silver chalcogenides have been recently drawing attention, because of their unusually high ionic conductivity in the high-temperature phase at about 200°C. This peculiar property is of particular importance for both research field of codensed matter physics and practical application as solid state sensors. The information of the bonding nature relevant to the electron distribution is desirable, in order to obtain insights into their characteristic property of solid fast ion conductors. An attempt will be made in this paper to review the current information of the bonding nature of silver halides in terms of the electron density distribution. Thus, this paper is primarily concerned with some physical properties of silver halides including the characteristic features of the crystal structure and the phase diagram. The data of alkali halides are also described for comparison. The experimental results of the magnetic susceptibilities of silver halides are summarized from the phenomenological point of view. The magnetic susceptibilities of silver halides were found to be sensitive to the change of temperature and crystal structure. It implies that the valence electrons of silver halides are loosely bound by the ion core. The electron density distribution in Agl and AgBr is also discussed using the results by single crystal X-ray diffractometry and the following points are suggested; in AgBr, the deformation of the charge distribution in bromine ion is much larger than that of silver ion and the radial distribution of valence electrons in bromine ion is enlarged in comparison with that of free ion state. In Agl, charge accumulation is feasible only on the c-directed bond and the difference Fourier map on the (1 1 0) plane indicates the deficiency of electrons around the silver site.     

Formation of argentic clusters and small Ag nanoparticles in soda-lime silicate glass

The formation of argentic clusters and very small Ag nanoparticles of 0.5 to 2 nm size in commercial soda-lime glass silver-doped by Ag/Na ion exchange in a mixed nitrate melt has been studied by electron microscopy and EXAFS. Particles formation was induced already during the ion exchange procedure, or by subsequent ion irradiation with 1.5 MeV He⁺ or 3 MeV Au⁺. The presence of nanoparticles was also macroscopically revealed by their surface plasmon resonance. The structural characterization indicates that specific configurations of silver oxide-like structures, so-called argentic clusters, are involved in the initial stage of nanoparticles formation.