Ionic conduction in dilute pseudo-binary systems CuBr–Cu2Se

Ionic conductivity, σ_i, of dilute pseudobinary alloys (CuBr)_1−x(Cu₂Se)_x (x≤0.1) in their γ-phase has been measured by an ac method. The increase of the ionic conductivity propertional to x has been observed, which is attributed to interstitial ions brought by Cu₂Se dissolved in CuBr. It is found that the temperature dependence of mobility of interstitial ions, μ, evaluated by the relation Δσ_i/x=kμ (k is a constant) is bent at the temperature corresponding to the extrinsic–intrinsic transition of the based material CuBr.     

Pipe-sphere model for enhancement of ionic conductivity in composite solid electrolytes

It is well-known that the ionic conductivity of a superionic conductor when dispersed with an insulator shows a remarkable enhancement. In this work we suggest that the contribution coming from grain-boundaries and dislocations is primarily responsible for this phenomenon in a number of cases. We propose a simple theoretical model for such composites and with the aid of the Effective Medium Theory (EMT) under self-consistent scheme we estimate the effective conductivity as a function of insulator volume fraction and particle size for four composites, namely CaF₂-Al₂O₃, CuCl-Al₂O₃, Sr(NO₃)₂-Al₂O₃ and SrCl₂-Al₂O₃. This model is applicable to composites where enhancement is observed for a very low insulator volume fraction and other prevalent models are inadequate. The results exhibit a good qualitative fit to the experimental data and all characterisitic experimental observations.     

隔环结构的Ne H2 CuBr激光放电管气体温度径向分布

针对溴化亚铜激光器中放电管径向温度不均匀现象，在工程设计中同时采用隔环结构放电管设计方案和溴化亚铜激光放电管充氢方案。对隔环结构及隔环结构同时充氢的CuBr激光放电管温度场进行了分析。利用简化的热流耗散泊松方程，给出了激光放电管内温度场分布的数学模型，获得了激光放电管气体温度场径向分布的解析表达式，明确了温度分布与输入电功率及缓冲气体热传导系数之间的关系，得到了与实验一致的结果，为该类激光器的实用化提供了理论分析依据。     

Transport in dispersed ionic conductors: Effect of insulating particle size

Dispersed ionic conductors are random mixtures of a solid salt, e.g. AgI, LiI, with fine particles of an insulating second phase, like Al₂O₃ or SiO₂. These composites can show a dramatic increase in ionic conductivity compared to the pure homogeneous system. Generally, this observation is attributed to an increased conductivity along the internal interface between the conducting salt and the insulating material. In this work a three-component random resistor network (RRN) model for dispersed ionic conductors is reviewed. In the model, the ionic conductor is represented by normally conducting bonds, the insulating material by non-conducting bonds and the interface between the two phases by highly conducting bonds. A special feature of the model is the existence of two critical concentrations of the insulating phase, p′_c and p″_c , for interface percolation and bulk conduction, respectively, where critical transport properties corresponding to conductor/superconductor and conductor/insulator networks are predicted. The model describes satisfactorily the dependence on composition of the conductivity and activation energy of dispersed ionic conductors. Furthermore, the observed effect on the conductivity of the size of dispersed particles can be described qualitatively well by a generalized version of the RRN model, which in addition predicts a sensitive dependence of the critical thresholds on particle size. Non-universality features in the critical exponents for the conductivity are also discussed within a continuum percolation analog of the model.     

Phase transitions and dynamics of superionic conductors

A Hamiltonian is constructed for superionic conductors taking into account the mutual interactions and transports of the mobile ions, and their interactions with the phonons of the cage. Under special conditions we recover the phenomenological results of Rice et al. and Huberman in regard to phase transitions. Two transition points are shown to be possible in the presence of the mutual interactions of cations (as observed in RbAg₄I₅ and CuBr). Structural phase transitions involving the cage when exist are found to occur at the same temperature at which the conductivity becomes critical, in agreement with experiments. Dynamical aspects of our Hamiltonian are also discussed. The collective modes of the phonon-cation system are calculated and used to explain the abrupt disappearance of certain modes above the critical temperature as observed in the Raman spectra of RbAg₄I₅, KAg₄I₅ and AgI. Our theory does contain the possibility that there is no soft mode with nonzero frequency, in accordance with the existing experimental situation. Our Hamiltonian is compared to others. The similarities between superionic conductors and other systems (Hubbard model, ferroelectrics, Jahn-Teller systems, molecular crystals) are emphasized.     

Stabilized high-temperature hexagonal phase in copper halide nanocrystals

Low-temperature (T = 4.2–77 K) absorption spectra of CuCl and CuBr nanocrystals in photochromic glass matrixes are studied. A fine structure of exciton absorption bands (Z₃ band for CuCl and Z₁₂ band for CuBr) is discovered and studied as a function of nanocrystal size. It is suggested that the high-energy part of the absorption band is due to the high-temperature hexagonal β phase being stabilized in very small samples; a transition to the stable cubic phase with increasing nanocrystal size is demonstrated.     

Application of SAXS to the study of particle-size-dependent thermal conductivity in silica nanofluids

Knowledge of the size and distribution of nanoparticles in solution is critical to understanding the observed enhancements in thermal conductivity and heat transfer of nanofluids. We have applied small-angle X-ray scattering (SAXS) to the characterization of SiO₂ nanoparticles (10–30 nm) uniformly dispersed in a water-based fluid using the Advanced Photon Source at Argonne National Laboratory. Size distributions for the suspended nanoparticles were derived by fitting experimental data to an established model. Thermal conductivity of the SiO₂ nanofluids was also measured, and the relation between the average particle size and the thermal conductivity enhancement was established. The experimental data contradict models based on fluid interfacial layers or Brownian motion but support the concept of thermal resistance at the liquid–particle interface.     

A composite theoretical model for the thermal conductivity of nanocrystalline materials

In order to study the thermal conductivity of nanocrystalline (NC) materials, a two-phase composite model consisting of grain interior (GI) regarded as an ordered crystal phase and plastically softer grain boundary-affected zone (GBAZ) phase was presented. The effects of GI and GBAZ on thermal conduction were considered, respectively. In this work, time independent Schrodinger’s wave equation (TISWE) was used to study the carriers’ transmission in a crystal particle, through which we can get the thermal conductivity of the GBAZ. The thermal conductivity of GI was calculated based on a kinetic theory. The whole effective grain thermal conductivity was simulated by a modified formula for composite materials. The results showed that as the grain size decreases to 80 nm, it has a strong size effect, and the thermal conductivity decreases with the decreasing of grain size.     

Electrical properties of A′Ca2Nb3O10 (A′=K, Rb, Cs) layered perovskite ceramics

The electrical conductivity properties of Dion-Jacobson type layered perovskites A′Ca₂Nb₃O₁₀ (A′=K, Rb, Cs) was investigated under different gas atmospheres. An increase in the electrical conductivity by about 2–5 orders in magnitude in both ammonia and hydrogen atmospheres is observed compared to air. Among the members of the series, the compound with the smallest size of the alkali ion, i.e. KCa₂Nb₃O₁₀, exhibits the highest conductivity. In air and hydrogen, a single activation energy value in the range 0.25 – 0.80 eV is observed, while in ammonia a sharp increase in the electrical conductivity is found at about 500 °C. The activation energy at low-temperatures (300–500 °C) is attributed to ionic motion and at higher temperatures (500–700 °C) to both defect formation and ionic motion. The unusual electrical conductivity behavior in ammonia is explained on the basis of the model developed for alkali halides. EMF measurements reveal that the layered perovskites are ionic (proton) conductors. The electrical conductivity changes as a function of the ammonia gas concentration; accordingly, layered perovskites appear to be useful solid electrolytes in galvanic cells for practical applications, e.g. for gas sensors. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Comparison of the interaction of Cl2 and Br2 with Cu(100)

The adsorption, reaction and etching of Cu(100) by Cl₂ was studied using temperature programmed desorption (TPD) and low energy electron diffraction (LEED), and the results were compared with recent results for Br₂. Although the general etching mechanism was the same for both gases (adsorption rate limited Cu halide formation followed by halide sublimation), significant differences between the behavior of Cl₂ and Br₂ were observed. The desorption of CuCl was characterized by a single zero order sublimation peak, independent of CuCl coverage, while limiting the CuBr coverage resulted in a desorption peak at temperatures lower than a prediction based on vapor pressure data of all known phases of CuBr. In addition, Cl₂ was found to be at least an order of magnitude less reactive than Br₂ towards halide formation. For both Cl₂ and Br₂, the halide formation rate reversibly decreased with increasing reaction temperature. However, for Br₂, but not Cl₂, annealing a chemisorbed halogen layer prior to further reaction irreversibly increased the halide formation rate. Structural differences between CuCl and CuBr on Cu(100) were also observed. For CuCl, LEED data suggested that highly faceted crystallites form at 325 K and remain stable until desorption, while LEED data for CuBr reveal a compressed epitaxial (111) layer that disorders below 400 K and then desorbs. The implications of these differences on etching and oxidation processes are discussed.     

A new thermal conductivity model for nanofluids

In a quiescent suspension, nanoparticles move randomly and thereby carry relatively large volumes of surrounding liquid with them. This micro-scale interaction may occur between hot and cold regions, resulting in a lower local temperature gradient for a given heat flux compared with the pure liquid case. Thus, as a result of Brownian motion, the effective thermal conductivity, k_eff, which is composed of the particles conventional static part and the Brownian motion part, increases to result in a lower temperature gradient for a given heat flux. To capture these transport phenomena, a new thermal conductivity model for nanofluids has been developed, which takes the effects of particle size, particle volume fraction and temperature dependence as well as properties of base liquid and particle phase into consideration by considering surrounding liquid traveling with randomly moving nanoparticles.The strong dependence of the effective thermal conductivity on temperature and material properties of both particle and carrier fluid was attributed to the long impact range of the interparticle potential, which influences the particle motion. In the new model, the impact of Brownian motion is more effective at higher temperatures, as also observed experimentally. Specifically, the new model was tested with simple thermal conduction cases, and demonstrated that for a given heat flux, the temperature gradient changes significantly due to a variable thermal conductivity which mainly depends on particle volume fraction, particle size, particle material and temperature. To improve the accuracy and versatility of the k_effmodel, more experimental data sets are needed.     

Microstructure — Property relationships in nanocrystalline oxide thin films

Results of studies of the preparation, structure and physical properties of nanocrystalline CeO₂, ZrO₂:16%Y (YSZ) and SrCeO₃:5%Yb oxide thin films are presented. A polymeric precursor spin coating technique has been used to obtain dense specimens with stable and uniform microstructure controlled in the grain size range of 1–400 nm. A variety of characterization techniques including X-ray diffraction, impedance spectroscopy, Raman scattering and optical absorption have been used for the evaluation of the microstructure-property relationships. Nanocrystalline specimens are characterized by enhanced electrical conductivity and different stoichiometry compared with microcrystalline materials. A direct comparison has been achieved between the conductivity and quantum confinement effects observed in optical measurements and correlated with a defect model. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Interfacial conductivity enhancement in alkali oxy-salts by second phase dispersion

In the search for the improvement the conduction properties of composite ceramics, we have found a conductivity enhancement by two orders of magnitude when ferroelectric PZT particles are dispersed into an NZS particle matrix. Ferroelectric BaTiO₃ particle dispersion has shown that the enhancement does not depend on the particle size, but depends on the magnitude of dielectric constant. An application of solid super acid particles such as ZrO₂ treated with sulfuric acid is another example to enhance the conductivity. Lithium compounds also have the effect to enhance the conductivities in other lithium ion conductor systems. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11 – 18 Sept. 1994     

Experimental Study of Nanofluid Convective Heat Transfer for Implementation of Dispersion Model Considering Non-Uniform Particle Distribution

Thermal dispersion model has been used here to simulate heat transfer of water–Al₂O₃ nanofluid. A new form for dispersion thermal conductivity has been introduced in which non-uniform concentration distribution is applied on the model. It was observed that the non-uniformity of concentration increases at greater Reynolds numbers and average concentrations. An experimental set-up was made, and an experimental study was conducted to find the empirical coefficient in the dispersion thermal conductivity. The obtained results show that the developed dispersion model is able to properly simulate heat transfer of the nanofluid and provides more accurate results in comparison with a homogenous model.     

Different conduction behaviors of grain boundaries in SiO2-containing 8YSZ and CGO20 electrolytes

Both doped zirconia and ceria have been widely recognized as promising electrolytes in solid oxide fuel cells (SOFC). Total conductivity is an important parameter to evaluate solid electrolytes. It is well know that the contribution to the total conductivity by grain boundaries is especially pronounced for SiO₂-contaminated electrolytes. In this study, we report on the different conduction behaviors of grain boundaries (GB) found in SiO₂-containing (impure) 8YSZ (8 mol% Y₂O₃-doped ZrO₂) and CGO20 (10 mol% Gd₂O₃-doped CeO₂) ceramics. In the grain size range (∼ 0.5–10 μm) studied, the GB conductivity of impure CGO20 ceramics constantly decreases with increasing grain size, in contrast to that observed in impure 8YSZ electrolytes whose GB conductivity increases almost linearly with grain size. It is also found that the variation in GB conductivity versus grain size is different from case to case, depending on the sintering/annealing conditions used to fabricate the ceramics. Two mechanisms were proposed to explain the GB behaviors of the impure 8YSZ and CGO20 ceramics. For doped ceria, the GB phases are supposed to be inert, which do not react with or dissolve into the matrix. Increasing sintering temperature leads to not only grain growth but also change in viscosity and wetting nature of the GB phases. These two factors promote further propagation of the GB phases along the grain boundaries, leading to an increased GB coverage fraction. For doped zirconia, however, the major factor dominating the GB conduction is the further dissolution of SiO₂ into zirconia lattice as a result of increase in sintering temperature or/and time. In addition, we will also evaluate and discuss the validities of the three models that are widely used to analyze the GB conduction in solid electrolytes.     

Temperature calibration for high-temperature MAS NMR to 913 K: 63Cu MAS NMR of CuBr and CuI, and 23Na MAS NMR of NaNbO3

The solid-state phase transitions of CuBr, CuI and NaNbO₃ can be readily observed using ⁶³Cu and ²³Na high-temperature magic-angle spinning nuclear magnetic resonance spectroscopy. Temperature has large, linear effects on the peak maximum of ⁶³Cu in each solid phase of CuBr and CuI, and there is large jump in shift across each phase transition. The ²³Na MAS NMR peak intensities and the line widths in NaNbO₃ also clearly show its high-temperature transition to the cubic phase. These data can be used to calibrate high-temperature MAS NMR probes up to 913 K, which is two hundred degrees higher than the commonly-used temperature calibration based on the chemical shift of ²⁰⁷Pb in Pb(NO₃)₂.     

Model for heat conduction in nanofluids

A comprehensive model has been proposed to account for the large enhancement of thermal conductivity in nanofluids and its strong temperature dependence, which the classical Maxwellian theory has been unable to explain. The dependence of thermal conductivity on particle size, concentration, and temperature has been taken care of simultaneously in our treatment. While the geometrical effect of an increase in surface area with a decrease in particle size, rationalized using a stationary particle model, accounts for the conductivity enhancement, a moving particle model developed from the Stokes-Einstein formula explains the temperature effect. Predictions from the combined model agree with the experimentally observed values of conductivity enhancement of nanofluids.     

Self-similar solutions of equations of the nonlinear Schrödinger type

Experimental data are presented for the temperature dependence of the conductivity of Cu: SiO₂ metal-insulator composite films containing 3-nm Cu granules. At low temperatures in the concentration range 17–33 vol % Cu, all of the conductivity curves have a temperature dependence of the form σ ∝ exp{ (T ₀/T)^1/2}, while at higher temperatures a transition is observed to an activational dependence. A numerical simulation of the conduction in a composite material shows that an explanation of the observed temperature dependence must include the Coulomb interaction and the presence of a rather large random potential. The simulation also yields the size dependence and temperature dependence of the mesoscopic scatter of the conductivities of composite conductors. It is shown that a self-selecting percolation channel of current flow is formed in the region of strong mesoscopic scatter.     

Dispersive effects and correction term in two-mode phonon conduction model for Ge

A complete analysis of the phonon conductivity κ, still lacking in the literature, is presented in the two-mode conduction model for Germanium. First a method is derived from which the correction term κ_c of the Callaway model is separated into its longitudinal and transverse parts and then the effects of strong phonon dispersion and the role of longitudinal and transverse phonons on κ_c are studied. For this purpose we have also proposed some new empirical expressions for the three phonon relaxation rates τ_3ph⁻¹'s which are valid in the entire temperature range. This improvised model, when applied simultaneously to the phonon conductivity data of both normal and enriched Ge, yields some new results. These are (i) κ_c neglected by the earlier workers in the two-mode phonon conduction model, gives a substantial contribution beyond the conductivity maximum and (ii) the longitudinal phonons are the major carriers of heat at high temperature.