Study of cation tracer diffusion in NaF

Cation tracer diffusion coefficients were measured in pure NaF crystals in the intrinsic ionic conductivity range (876–970 °C). The results can be rationalized satisfactorily in terms of contributions to the observed Na tracer diffusivities arising from both free vacancies and neutral vacancy pairs, the latter contribution amounting to about 53 per cent of the total Na diffusion at the highest measuring temperature. The best-fit defect parameters derived in an earlier conductivity study [21] from this laboratory on similar NaF crystals give for the free vacancy contribution D_v^*(Na) = 4·25 exp (?2·21 eV/kT) cm²s^?1. A combination of these D_v^*(Na) values with the present diffusion data yields for the vacancy-pair contribution D_p^*(Na) = 1·15 × 10⁸exp (?4·04 eV/kT) cm²s^?1. Comparison of the present findings with published values of the anion tracer diffusion coefficient in NaF showed that D_p^* (F) is 2·3 to 4·4 times larger than D_p^*(Na) over the temperature range of our observations, the difference between the two contributions increasing with decreasing temperature. When approximate account is taken of the temperature-dependence of the two pair correlation factors, this last result indicates that the anion jumps into the vacancy pair occur with a higher frequency, and increasingly so at lower temperatures, than do those involving the cations.     

Oxygen diffusion studies on (Y2O3)2(Sc2O3)9(ZrO2)89

The oxygen tracer diffusion coefficient (D?) has been measured for 9 mol% scandia 2 mol% yttria co-doped zirconia solid solution, (Y₂O₃)₂(Sc₂O₃)₉(ZrO₂)₈₉, using isotopic exchange and line scanning by Secondary Ion Mass Spectrometry, as a function of temperature. The values of the tracer diffusion coefficient are in the range of 10^? 8–10^? 7 cm² s^? 1 and the Arrhenius activation energy was calculated to be 0.9 eV; both valid in the temperature range of 600–900 °C. Electrical conductivity measurements were carried out using 2-probe and 4-probe AC impedance spectroscopy, and a 4-point DC method at various temperatures. There is a good agreement between the measured tracer diffusion coefficients (D?, Ea = 0.9 eV) and the diffusion coefficients calculated from the DC total conductivity data (D_σ, Ea = 1.0 eV), the latter calculated using the Nernst–Einstein relationship.     

Diffusion and conductivity properties of cerium niobate

The tracer diffusion coefficient (D⁎) and the surface exchange coefficient (k⁎) provide vital information for materials used in high temperature electrochemical devices (e.g. solid oxide fuel cells or oxygen permeation membranes). These values were established for the high temperature tetragonal scheelite structured CeNbO_4+δ (monoclinic fergusonite at room temperature), which is of interest due to its wide range of oxygen stoichiometries varying from stoichiometric CeNbO₄ to CeNbO_4.33. Measurements of D⁎ and k⁎ were performed by the isotopic exchange/line scan technique with SIMS (secondary ion mass spectrometry) used to determine ¹⁸O stable isotope depth distribution. This process was carried out between temperatures of 1073 K and 1173 K at 500 mbar of ¹⁶O/¹⁸O. These measurements were then correlated with oxide ion conductivity data previously determined from four probe d.c. and e.m.f. measurements using the Nernst–Einstein relation.     

Impact of MoO3 concentration,frequency and temperature on the dielectric properties of zinc phosphate glasses

Phosphate glasses with the chemical composition of 47P₂O₅–24ZnO-(29-x)Na₂O-xMoO₃, x = 0, 2, 4, 6, 8 and 10, have been prepared using the melt quenching technique. Dielectric properties of these phosphate glasses are carried out in the frequency range from 1 to 100 kHz at different temperatures. Dielectric parameters such as dielectric constant ε′, dielectric loss ε′′ and ac conductivity of the investigated glasses have been evaluated. The dependences of these dielectric parameters on frequency, composition and temperature have been discussed. It is found that dielectric constant decreases with increasing frequency due to the reduction of space-charge polarization and dipole polarization. The dependence of ac conductivity on the MoO₃ content indicates a competition between electronic and ionic conduction. The temperature dependence of the dielectric parameters reveals a rising trend of the dielectric parameters with temperature. This rising trend is indicated due to the increase of the amplitude of the thermal vibration of the charge carriers which facilitates the electron hopping and drifting of the mobile ions. The linear trend of the ln(σ_ac)-1000/T plot indicates that ac conductivity of the investigated glasses is thermally-activated transport process and follows the Arrhenius equation. The activation energy and its composition dependence have been reported.     

Electrical conductivity and tracer diffusion in sodium germanate glasses

Measurements of the electrical conductivity using ac complex impedance techniques and the tracer diffusion coefficient of ²²Na have been performed in a series of (x)Na₂O(1?x) GeO₂ glasses (where 0.0006 ? x ? 0.156). The compositional form of the Haven ratios, calculated from these data, have been interpreted in terms of a single defect model which considers a number of distinctly different jump frequencies for the alkali ion; the magnitude of these different jump frequencies is determined by the proximity of the diffusing alkali ion to a charge-compensating center within the glass network. Attractive interactions between the positive alkali ions and the negative charge-compensating centers cause successive jump directions of the alkali ions to become correlated. In the sodium germanate glasses the negatively-charged centers probably correspond to the six-fold coordinated sites formed upon addition of alkali oxide to GeO₂. These negatively-charged trapping centers correspond to non-bridging oxygen sites in alkali silicate glasses.     

On the thermal conductivity of glasses

We estimate the numerical contribution of the interaction between like defects in glasses for the linewidth (? T^?1₂) obtained in acoustical experiments. This interaction gives origin to a diffusion process with a very large diffusion constant (D = 10^?5 cm² sec^?1). The thermal conductivity due to this diffusion process is calculated. Its temperature dependence is also obtained.     

Investigation of proton diffusion in Nafion®117 membrane by electrical conductivity and NMR

The proton dynamics in Nafion ^®117 is investigated by comparison of the diffusion coefficient D_NMR estimated from PFG-NMR with that of D_σ estimated from electrical conductivity. At high water content region, D_σ is about two times higher than D_NMR as a result of Grotthuss mechanism. At low water content region, D_σ and D_NMR are in good agreement with each other. Both of the diffusion coefficients decrease steeply at low water content region. It can be explained as a result of the percolation transition due to the isolation of ion clusters, which is suggested by the recent small angle X-ray scattering data.     

The relationship between chemical and tracer diffusion coefficients of aliovalent ions in an ionic lattice

The theoretical model developed by Lidiard was extended to describe the relationship between the chemical and tracer diffusion coefficients of aliovalent ions in an ionic lattice.It is shown that the relationship between the chemical diffusion coefficient, D, and the tracer diffusion coefficient, D¹, is D = 2D¹ if the migration of dimers is the principal mechanism of transport and for the migration of trimers D = 3D¹ if the concentration of impurity ion is relatively small. These relationships are valid regardless of the charge of the aliovalent or lattice ions.The chemical diffusion coefficients of Cr³⁺ in Cr-doped MgO were determined for three different temperatures, 1656, 1717 and 1768K, and for the concentration region 2.5×10^?2?2.8×10^?1 mole% Cr₂O₃. Using previously determined values for the tracer diffusion coefficient of ⁵¹Cr in Cr-doped MgO it was found that for the temperature and concentration region investigated D = (2.00±0.17)D¹ which indicates that diffusion proceeds primarily by the migration of dimers.     

Chromium tracer diffusion in NiO crystals

Diffusion of ⁵¹Cr in NiO single crystals in air has been studied by the tracer-sectioning technique. In the temperature range 1192–1642°C, the diffusion coefficient can be expressed by the Arrhenius expression D=D_oexp(-Q/RT), with D_o=(8·6±1·2)×10^?3 cm²/sec and Q=67·4±1·1 kcal/mole. The use of a high specific-activity tracer and a special configuration for the diffusion anneal prevented the self-dopling effect found by Seltzer and the evaporation of chromium from the sample surface. The present results, in conjunction with published results on nickel self-diffusion in NiO and interdiffusion in the NiO?Cr₂O₃ system, are used to determine a chromium ion-vacancy binding energy of about 5 kcal/mole in pure NiO.     

Mechanical damage and thermal effect induced by ultrasonic treatment in olive leaf tissue. Impact on polyphenols recovery

The influence of ultrasound treatment (US) on cellular damage of olive leaf tissue was studied. Mechanical damage and thermal effect of US were characterized. The level of tissue damage was defined by the diffusivity disintegration index Z_D based on the diffusivity of solutes extracted from olive leaves differently treated. The Arrhenius form using the temperature dependences of the thermal treatment time within the temperature interval 20–90 °C was observed for the thermal process. The corresponding activation energy ΔUT was estimated as 57 kJ/mol. The temperature dependences of electrical conductivity were measured for extracts of intact and maximally treated olive leaves. Then the diffusivity disintegration index Z_D and total phenolic compounds recovery for three studied US powers were calculated (100, 200, and 400 W). The results evidenced that the mechanically stimulated damage in olive leaf tissue can occur even at a low US power of 100 W if treatment time is long enough (t = 3.5 h). The US treatment noticeably accelerated the diffusion process mechanically in addition to its thermal effect. Trials in aqueous solution revealed the dependence of polyphenols extraction on damage level with respect to the US power applied.     

Effect of iron doping on the characterization and transport properties of calcium phosphate glassy semiconductors

X-ray diffraction (XRD), differential scanning calorimeter (DSC), density (d) and dc conductivity (σ) of the glasses in Fe₂O₃-CaO-P₂O₅ system were reported. The dc conductivity in the temperature range 303-453 K was measured. The overall features of these XRD curves confirm the amorphous nature of the present samples. The density of glasses increases from 2.750 to 2.892 g/cm³ with increasing Fe₂O₃ content as a result of a strengthening of cross-linking within glass network. The glass temperature values (T_g) of the present glasses were larger than those of tellurite glasses. This indicates a higher thermal stability of the glass in the present system. The glasses had conductivities ranging from 10⁻⁹ to 10⁻⁵ Sm⁻¹ at temperatures from 303 to 453 K. Electrical conduction of the glasses was confirmed to be due to non-adiabatic small polaron hopping and the conduction was primarily determined by hopping carrier mobility.     

Electrical conduction and dielectric properties of vanadium phosphate glasses doped with lithium

AC conductivity and dielectric studies on vanadium phosphate glasses doped with lithium have been carried out in the frequency range 0.2-100 kHz and temperature range 290-493 K. The frequency dependence of the conductivity at higher frequencies in glasses obeys a power relationship, σ_ac=Aω^s. The obtained values of the power s lie in the range 0.5≤s≤1 for both undoped and doped with low lithium content which confirms the electron hopping between V⁴⁺ and V⁵⁺ ions. For doped glasses with high lithium content, the values of s≤0.5 which confirm the domination of ionic conductivity. The study of frequency dependence of both dielectric constant and dielectric loss showed a decrease with increasing frequency while they increase with increasing temperature. The results have been explained on the basis of frequency assistance of electron hopping besides the ionic polarization of the glasses. The bulk conductivity increases with increasing temperature whereas decreases with increasing lithium content which means a reduction of the V⁵⁺.     

Anomalous behaviour of the diffusion coefficient in interacting adsorbates

Langevin simulations provide an effective way to study collective effects of Brownian particles immersed in a two-dimensional periodic potential. In this paper, we concentrate essentially on the behaviour of the tracer (D_Tr) and collective diffusion coefficients (D_C) as function of friction (Γ). Our simulations show that in the high friction limit, the two physical quantities D_Tr and D_C present qualitatively the same behaviour, for both coupled and decoupled substrate potentials. However, for the low friction regime, and especially for the coupled potential case, an anomalous diffusion behaviour is found where D_Tr∼Γ^-σ_Tr and D_C∼Γ^-σ_C, with σ_Tr<σ_C<1. We also found that in the case of weak dynamical coupling between the adparticles and the substrate, the exponents are not universal and rather depend on the potentials. Moreover, changes in the inter-particle potentials may reverse the behaviour to a normal one.     

Dielectric properties and relaxation behavior of [TMA]2Zn0.5Cu0.5Cl4 compound

The [TMA]₂Zn_0.5Cu_0.5Cl₄ hybrid material was prepared and its dielectric spectra were measured in the 10⁻¹ Hz-10⁶ Hz frequency range and 200-305 K temperature interval. The dielectric permittivity showed a ferroelectric-paraelectric phase transition at 293 K. Double relaxation peaks are observed in the imaginary part of the electrical modulus, suggesting the presence of grain and grain boundary in the sample. The frequency dependent conductivity was interpreted in term of Jonscher's law: σ(ω)=σ_dc+Aωⁿ. The temperature dependent of the dc conductivity (σ_dc) was well described by the Arrhenius equation: σ_dcT=σ_o×exp(−E_a/kT).     

Structural and lithium ion transport studies in borophosphate glasses

Lithium ion transport process and glass network modification upon the variation of network modifier (M) to former (F) ratio (M/F) in 30% LiBO₂–70% [(M Li₂O–F P₂O₅)] glasses have been investigated. The glasses with different M/F ratios (0.42–1.0) were prepared by melt quenching technique and characterized by X-ray diffraction (XRD), differential scanning calorimetry (DSC), Raman and impedance spectroscopy techniques. The glass transition temperature, T_g increased with increasing M/F ratio suggesting an increase in overall connectivity of the network structure. Dc conductivity showed an enhancement of three orders of magnitude with increasing M/F. The observed increase in T_g and dc conductivity with modifier concentration has been explained on the basis of the competition between network breaking/forming events, leading to an increase in overall connectivity of the network and the formation of continuous channels for ion migration. Ac conductivity data were analyzed by fitting the data to Almond-West type power law equation, σ′(ω) = σ(0) + Aωⁿ. The power law exponent, n, was found to be temperature dependent and exhibited a minimum, n_min. The observation of n_min has been explained in the light of diffusion controlled relaxation (DCR) model. Furthermore, the scaling of both ac conductivity and electrical modulus data showed an excellent collapse on to a single master curve indicating that there is a good time–temperature superposition and that conduction mechanism remains unchanged in this glass system.     

Measurement of optical dephasing of Eu3+ and Pr3+ doped silicate glasses by spectral holeburning

Long-lived spectral holeburning has been observed in Eu³⁺ and Pr³⁺ doped silicate glasses, and used to measure homogeneous linewidths (φ_h). In the case of Eu³⁺, holes are burned by optical pumping of nuclear quadrupole levels, and our low temperature measurement of φ_h shows that the previously determined T^1.8 temperature dependence holds down to at least 1.6 K. On the other hand, in Pr³⁺ doped glass, holes are burned by optically induced local lattice rearrangements. In contrast to previously studied inorganic glasses, we find a linear temperature dependence of φ_h for the ³H₄ ? ¹D₂ transition from 1.6 K to 20 K. This was confirmed by picosecond accumulated grating photon echoes. Current theories of dephasing in glasses do not predict these temperature dependences. Holeburning has also been observed in Pr³⁺ doped BeF₂ and phosphate glasses and Nd³⁺ doped silicate glass and thus appears to be a rather general phenomenon in inorganic glasses, as has been found for molecules in organic glasses.     

Transport processes in heavy metal fluoride glasses

Na self-diffusion, Li self-diffusion, Na⁺–Li⁺ ion exchange, electrical conductivity, and mechanical relaxation have been studied below T_g on glasses of the system ZrF₄–BaF₂–LaF₃–AF (A=Na, Li), with A=10, 20, 30 mol%. Compared to the transport mechanism in alkali-containing silicate glasses, the mechanisms in these non-oxide glasses are anomalous. Thus the self-diffusion coefficient of Na decreases with increasing NaF content, whereas that of Li increases with increasing LiF content. Both the electrical conductivity and the Na⁺–Li⁺ ion exchange reach a minimum at ≈ 20 mol% LiF, and the mechanical relaxation shows one peak for the 20 and 30 mol% LiF-glasses and two peaks for the glass with 10 mol% LiF, evidencing both a contribution of F⁻ and Li⁺ ions to the transport. Moreover, the presence of the three partially interacting mobile species F⁻, Na⁺, Li⁺ obviously leads to an anionic–cationic mixed ion effect. Applying the Nernst–Einstein equation to the Li⁺ transport in LiF-containing glasses shows that its mechanism is dissimilar to that in oxide glasses. Calculated short jump distances possibly can be interpreted as an Li⁺ movement via energetically suitable sites near F⁻ ions. Likewise the Nernst–Planck model, successfully applied to the ionic transport in mixed alkali silicate glasses, obviously does also not hold for the present heavy metal fluoride glasses.     

Thermal diffusivity of MORB-composition rocks to 15 GPa: implications for triggering of deep seismicity

We have measured the thermal diffusivity of eclogite and majorite with a model MORB composition at pressures of 3 and 15 GPa, respectively. Both phase assemblages show inverse dependences of their thermal diffusivities on temperature: D _eclogite=9(10)×10^?10+7(1)×10^?4/T(K) m ²/s and D _majorite=6.2(5)×10^?7+3.0(5)×10^?4/T(K) m ²/s. The values for majorite are in good agreement with previous measurements for other garnets and are considerably lower than thermal diffusivities of wadsleyite and ringwoodite, which are the main components of the mantle transition zone. We discuss the implications of the low thermal conductivity of subducted oceanic crust in the transition zone for the triggering of deep seismicity.     

Calculation of the energy dependence of the fusion cross section and total cross sections for peripheral reactions on the basis of an analysis of data on elastic heavy-ion scattering: Strongly bound ions

A method is proposed for calculating the energy dependence of the fusion cross section (in general, the sum of the cross sections for complete and incomplete fusion, quasifission, and reactions of deep-inelastic scattering) σ _F (E) and the total cross section for peripheral (or quasielastic) reactions, σ _D (E). The method is based on an analysis of a limited set of angular distributions for the elastic scattering in a given pair of nuclei. The predictive power of the method is illustrated by considering the ¹⁶O + ²⁰⁸Pb, ¹⁶O + ⁴⁰Ca, and ¹⁶O + ²⁸Si systems. For each of these systems, the calculations were performed at energies in the range extending from subbarrier values to those exceeding the barrier height substantially. The results of the calculations are found to be in good agreement with relevant experimental data, whereby the reliability of the method is confirmed. By virtue of this, it is proposed to employ the method to study the energy dependences σ _F (E) and σ _D (E) in collisions involving unstable nuclei, for which it is difficult to determine experimentally the above dependences because of a low intensity of secondary beams.     

Diffusion of 22Na in Cd-doped silver bromide and silver chloride

The diffusion coefficients of ²²Na tracer in zone-refined, CdBr₂-doped, polycrystalline AgBr were measured. An approach is developed to calculate the intrinsic concentration of Frenkel defects in AgBr and AgCl based on the ²²Na diffusion data. The theory is based on the usual assumptions of random walk and electroneutrality.