Potentiometric CO2 - sensors with ion - conducting glasses as solid electrolytes

Alkali-ion conducting glasses/glass ceramics of the system Me₂O-A1₂O₃-SiO₂ (Me=Li, Na) were applied as solid electrolytes in potentiometric gas sensors to detect CO₂ in the presence of O₂ at increased temperatures. The corresponding Me-Carbonates were utilized as auxiliary electrodes. Sensors using the direct Au-glass contact as a kind of reference electrode (type I), as well as symmetrical sensors with carbonate phase at the reference and measuring electrode (type II - for comparative measurements) were manufactured. By applying Au as electrode metal, the theoretically expected EMF difference and the observed EMF difference of both sensor types agree quite well with the expected values according to the Nernst equation between 500 and 600 °C (over four orders of magnitude of CO₂ partial pressure (10⁻⁵ – 10⁻¹ bar) at constant O₂ partial pressure (2.1×10⁻¹ bar)). A long time stability of 120 days for sensors of type I with Li glasses has been observed, although evaporation of carbonate phase (Li₂CO₃) was detected under the conditions of sensor application. Sensors of type I (with Li₂CO₃) show thermodynamically unexpected cross-sensitivities to H₂O. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Investigations of electronic minority charge carrier conductivity in La0.9Sr0.1Ga0.8Mg0.2O2.85

The perovskite structured material LaGaO₃ doped with 10 mol-% strontium and 20 mol-% magnesium was prepared by two different wet-chemical synthesis routes. The total conductivity was measured in air and under an oxygen partial pressure of 10⁻²⁰ bar. There was a decrease by 10 % in 4 days when the atmosphere was changed from air to 10⁻²⁰ bar. This process is reversible. Hebb-Wagner measurements resulted in values for the electronic minority charge carrier conductivities in pure oxygen of log σ_h [S/cm]=−4.02 and log σ_e [S/cm]=−15.5 for the holes and electrons, respectively, at 600 °C. In the partial pressure range 10⁻³ bar≤p(O₂)≤1 bar, a slope of +1/4 was observed for d(log (σ_h)) / d(log (p(O₂)) at T=600, 650 and 700 °C. That is in agreement with the assumption of a large number of oxygen vacancies. The diffusion coefficient of the holes was evaluated from the relaxation curves to be 1.1*10⁻⁷ cm²/s at 600 °C. Degradation effects were observed under highly reducing conditions which are attributed to the formation of gallium-platinum alloys and the loss of gallium oxide if O₂ is available in the gas phase. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Spectral components that form UV absorption spectrum of Ce3+ and Ce(IV) valence states in matrix of photothermorefractive glasses

We have measured the UV absorption spectra of photothermorefractive glasses of the system Na₂O-ZnO-Al₂O₃-NaF-SiO₂ doped by cerium oxide in the range of (2.8–5.0) × 10⁴ cm⁻¹ (360–200 nm). The spectra have been processed by the method of dispersion analysis based on the analytical convolution model for the complex dielectric function of glasses. We show that the absorption band centered at 3.3 × 10⁴ cm⁻¹ (∼303 nm) that is attributed to the transition 2F _5/2 → 5d in the Ce³⁺ ion, is an envelope of three spectral components. The broad absorption range (3.5–4.7) × 10⁴ cm⁻¹ (200–270 nm) that is commonly interpreted as a charge transfer band of the Ce(IV) valence state, is an envelope of at least three spectral components.     

Structure property correlation in lithium borophosphate glasses

To investigate the influence of cation mobility variation due to the mixed glass former effect, 0.45Li₂O-(0.55 − x) P₂O₅−x B₂O₃ glasses (0 ≤; x ≤ 0.55) are studied keeping the molar ratio of Li₂O/(P₂O₅ + B₂O₃) constant. Addition of B₂O₃ into lithium phosphate glasses increases the glass transition temperature (T _g) and number density, decreases the molar volume, and generally renders the glasses more fragile. The glass system has been characterised experimentally by XRD, XPS and impedance studies and studied computationally by constant volume molecular dynamics (MD) simulations and bond valence (BV) method to identify the structural variation with increasing the B₂O₃ content, its consequence for Li⁺ ion mobility, as well as the distribution of bridging and non-bridging oxygen atoms. These studies indicate the increase of P-O-B bonds (up to Y = [B₂O₃]/([B₂O₃] + [P₂O₅]) ≈ 0.5 and B-O-B bonds, as well as the decrease of P-O-P bonds and non-bridging oxygens (NBOs) with rising B₂O₃ content. The system with Y ≈ 0.5 exhibits maximum ionic conductivity, 1.0 × 10⁻⁷ S cm⁻¹, with activation energy 0.63 V. Findings are rationalised by a model of structure evolution with varying B₂O₃ content Y and an empirical model quantifying the effect of the various structural building blocks on the ionic conductivity in this mixed glass former system.     

EPR studies of Cu2+ and V4+ ions in phosphate glasses

Two lead-phosphate glass systems doped with both copper and vanadium ions in different ratios were studied by EPR (electron paramagnetic resonance) method. EPR spectra and parameters (g_‖ = 2.44, g_⊥ = 2.08 andA _‖ = 117.6 · 10⁻⁴ cm⁻¹) obtained for x(CuO · V₂O₅)(l−x)[2P₂O₅ · PbO] glasses withx ≤ 10 mol% suggest a tetrahedral (Td) coordination of Cu²⁺ ions and not a tetragonally elongated octahedron as has been assumed in previous works. The ground state of the paramagnetic electron is thed _xy copper orbital with a 4p_z contribution of 6%. For 20 ≤x ≤ 40 mol% a broad line (ΔB = 307 G) characteristic for clustered ions appears atg = 2.18. The V⁴⁺ ions are evidenced only in the spectra of x(CuO · 2V₂O₅)(1 −x)[2P₂O₅ · PbO] glasses and the resonance parameters suggest a pentacoordinated C_4v local symmetry for these ions. The hyperfine structures characteristic for Cu²⁺ and V⁴⁺ ions disappear for 10 ≤x ≤ 40 mol% due to the mixed exchange Cu²⁺−V⁴⁺ pair formation in these glasses.     

Preparation of sol-gel method P2O5-Al2O3-SiO2 glasses and their characterization

Nanostructures P₂O₅-Al₂O₃-SiO₂ glasses were prepared by sol-gel method. The glasses were characterized by XRD, FTIR and TG/DTA methods. The average pore size of the glass was less than 3 nm as measured by N₂ adsorption — desorption method. The thermal stability was measured as a function of decomposition temperature and weight loss calculations. Proton conductivities of all samples increased with an increase in relative humidity (40–90 %), indicating that continuous paths suitable for proton conduction were developed when glasses heat treated at 300 °C due to the adsorption of water. The temperature dependence of the conductivity for all compositions increases with increasing temperature in the range 30–90 °C with relative humidity 70 %. The overall conductivity was in the range 10⁻⁴–10⁻³ S/cm for compositions.     

Ion transport studies in zinc/cadmium halide doped silver phosphate glasses

A number of samples of silver phosphate glasses Ag₂O−P₂O₅−Zn/CdX₂ (X=Cl, Br or I) with 1, 5, 10 and 20 mol-% zinc or cadmium halides have been prepared. Control samples of undoped silver phosphate glasses were also prepared. These glasses were characterized by elemental analysis, X-ray diffraction, IR spectra, differential scanning calorimetry, transference number measurements and electrical conductivity studies. These glasses were found to be essentially ionic conductors. The undoped silver phosphate glass (Ag₂O−P₂O₅) has a low σ value in comparison to the doped ones. The conductivity (σ) in the doped glasses increases substantially with increasing concentration of dopant salts Zn/or CdX₂ and as the anions of the dopants are changed from Cl⁻ to I⁻. It is found that the σ values of the ZnX₂ doped glasses are slightly greater than those of the CdX₂ doped ones, and the silver phosphate glasses doped with (20 mol-%) Zn/CdI₂ yielded maximum conductivity. The results have been discussed and explained on the basis of changes in the structure of the glass matrix by the addition of dopant ions of different sizes, IR spectra and thermal studies.     

Fluorescent Method for the Determination of Sulfide Anion with ZnS:Mn Quantum Dots

Water-soluble Mn²⁺-doped ZnS quantum dots (QDs) were prepared using mercaptoacetic acid as the stabilizer. The optical properties and structure features were characterized by X-Ray, absorption spectrum, IR spectrum and fluorescence spectrum. In pH 7.8 Tris-HCl buffer, the QDs emitted strong fluorescence peaked at 590 nm with excitation wavelength at 300 nm. The presence of sulfide anion resulted in the quenching of fluorescence and the intensity decrease was proportional to the S²⁻ concentration. The linear range was from 2.5 × 10⁻⁶ to 3.8 × 10⁻⁵ mol L⁻¹ with detection limit as 1.5 × 10⁻⁷ mol L⁻¹. Most anions such as F⁻, Cl⁻, Br⁻, I⁻, CH₃CO₂ ⁻, ClO₄ ⁻, CO₃ ²⁻, NO₂ ⁻, NO₃ ⁻, S₂O₃ ²⁻, SO₃ ²⁻ and SO₄ ²⁻ did not interfere with the determination. Thus a highly selective assay was proposed and applied to the determination of S²⁻ in discharged water with the recovery of ca. 103%.     

The rate constants of singlet oxygen collision-induced emission at 634 and 703 nm wavelengths

Absolute spectral luminosity from an O₂–O₂(a)-H₂O gas flow formed by a chemical singlet oxygen generator was measured at 600–800 and 1230–1310 nm wavelengths. The results were used to determine the rate constants for O₂(a, 0) + O₂(a, 0) → O₂(X, 0) + O₂(X, 0) + hν (λ = 634 nm) and O₂(a, 0) + O₂(a, 0) → O₂(X, 1) + O₂(X, 0) + hν (λ = 703 nm) collision-induced emission ((6.72 ± 0.8) × 10⁻²³ and (7.17 ± 0.8) × 10⁻²³ cm³/s, respectively).     

CW CO2-laser annealing of arsenic implanted silicon

CW CO₂-laser annealing of arsenic implanted silicon was investigated in comparison with thermal annealing. Ion channeling, ellipsometry, and Hall effect measurements were performed to characterize the annealed layers and a correlation among the different methods was made. The laser annealing was done with power densities of 100 to 640 W cm⁻² for 1 to 20 s. It was found that the lattice disorder produced during implantation can be completely annealed out by laser annealing with a power density of 500 W cm⁻² and the arsenic atoms are brought on lattice sites up to 96±2%. The maximum sheet carrier concentration of 6×10¹⁵ cm⁻² was obtained for 1×10¹⁶ cm⁻² implantation after laser annealing, which was up to 33% higher than that after thermal annealing at 600 to 900°C for 30 min.     

Europium-sensitized Chemiluminescence of System Tetracycline–H<Subscript>2</Subscript>O<Subscript>2</Subscript>–Fe(II)/(III) and Its Application to the Determination of Tetracycline

Chemiluminescence (CL) of the reaction system tetracycline–H₂O₂–Fe(II)/(III)–Eu(III) was used for the determination of tetracycline hydrochloride in water, pharmaceutical preparations, and honey. The CL spectrum registered for this system shows emission bands typical of Eu(III) ions, with a maximum at λ ∼ 600 nm, corresponding to the electronic transitions of ⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂. A strong chemiluminescence intensity characteristic of europium(III) ions in the system tetracycline–H₂O₂–Fe(II)/(III)–Eu(III), as contrasted to the emission of the system tetracycline–H₂O₂–Fe(II)/(III) without Eu(III), proves that the Eu(III) ion plays the role of a chemiluminescence sensitizer, accompanying tetracycline oxidation in the Fenton system (H₂O₂–Fe(II)/(III)). A linear dependence was observed for the integrated CL light intensity on the tetracycline concentration in the range of 2 × 10⁻⁷ to 3 × 10⁻⁵ mol l⁻¹ with the detection limit of 5 × 10⁻⁸ mol l⁻¹ in aqueous solution.     

Study of Enhanced Chemiluminescence of Diperiodatocuprate (III) on 1,10-Phenanthroline/Hydrogen Peroxide/Cetyltrimethylammonium Bromide System

In the paper, a chemiluminescence (CL) system was developed based on the catalytical effect of diperiodatocuprate (III) (DPC) on the 1,10-phenanthroline (phen)/hydrogen peroxide (H₂O₂) in the presence of cetyltrimethylammonium bromide (CTAB). The effects of experimental conditions were investigated. Meanwhile the increase of CL intensity of the DPC/phen/H₂O₂/CTAB system is proportional to the concentration of phen in the range of low concentration. The linear range of the calibration curve is 5.0 × 10⁻⁹–1.0 × 10⁻⁶ mol L⁻¹, and the corresponding detection limit is 1.9 × 10⁻⁹ mol L⁻¹. The effects of phenolic compounds (PCs) on the system were investigated. Hydroquinone was used as an example to investigate the application of the CL system to the determination of PCs. The quenched CL intensity is linearly related to the logarithm of concentration of hydroquinone. The linear range of the calibration curve is 2.5 × 10⁻⁹–1.0 × 10⁻⁵ g mL⁻¹, and the corresponding detection limit is 1.8 × 10⁻⁹ g mL⁻¹. This phen and hydroquinone can be synchronously determined. The method was applied to the determination of hydroquinone in water samples and the recoveries were from 92% to 106%.     

Structure,thermal properties,conductivity and electrochemical stability of di-urethanesil hybrids doped with LiCF<Subscript>3</Subscript>SO<Subscript>3</Subscript>

Variable chain length di-urethane cross-linked poly(oxyethylene) (POE)/siloxane hybrid networks were prepared by application of a sol-gel strategy. These materials, designated as di-urethanesils (represented as d-Ut(Y′), where Y′ indicates the average molecular weight of the polymer segment), were doped with lithium triflate (LiCF₃SO₃). The two host hybrid matrices used, d-Ut(300) and d-Ut(600), incorporate POE chains with approximately 6 and 13 (OCH₂CH₂) repeat units, respectively. All the samples studied, with compositions ∞ > n ≥ 1 (where n is the molar ratio of (OCH₂CH₂) repeat units per Li⁺), are entirely amorphous. The di-urethanesils are thermally stable up to at least 200 °C. At room temperature the conductivity maxima of the d-Ut(300)- and d-Ut(600)-based di-urethanesil families are located at n = 1 (approximately 2.0 × 10⁻⁶ and 7.4 × 10⁻⁵ Scm⁻¹, respectively). At about 100 °C, both these samples also exhibit the highest conductivity of the two electrolyte systems (approximately 1.6 × 10⁻⁴ and 1.0 × 10⁻³ Scm⁻¹, respectively). The d-Ut(600)-based xerogel with n = 1 displays excellent redox stability.     

Polarisation resistance of the O2, Au/O2− and H2-H2O, Au/O2− electrode systems

Gold electrodes with known contact geometries were studied using impedance spectroscopy. From these data it was possible to determine the specific polarisation conductivity per unit length of three-phase boundary (TPB). The values were found to be (3÷22)×10⁻⁴ S·cm⁻¹ dependent on the electrode history in pure oxygen at 977 °C and 2×10⁻⁶ S·cm⁻¹ at 977 °C in “pure” hydrogen (P_O2=10⁻²⁰ atm at 1001 °C). The results are compared with previous data obtained for platinum electrodes.     

Microstructure of Cu<Subscript>60</Subscript>Zr<Subscript>20</Subscript>Ti<Subscript>20</Subscript> bulk metallic glass rolled at different strain rates

The structural evolution of Cu₆₀Zr₂₀Ti₂₀ bulk metallic glass during rolling at different strain rates and cryogenic temperature was investigated by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and high-resolution transmission electron microscopy (HRTEM). It is revealed that the deformation-induced transformation is strongly dependent on the strain rate. At the lowest experimental strain rate of 1.0×10⁻⁴ s⁻¹, no phase transformation occurs until the highest deformation degree reaches 95%. In a strain rate range of 5.0×10⁻⁴−5.0×10⁻² s⁻¹, phase separation occurs in a high deformation degree. As the strain rate reaches 5.0×10⁻¹ s⁻¹, phase separation and nanocrystallization concur. The critical deformation degree for occurrence of phase transformation decreases with the strain rate increasing. Supported by the National Natural Science Foundation of China (Grant No. 50471016)     

Neutron diffraction studies of the negative thermal expansion in a layered indium selenide crystal

The neutron diffraction patterns have been analyzed for a layered single crystal and a powder of the γ-polytype of indium selenide in the temperature range 10–300 K. In the temperature range 10–50 K, the excitation of bending vibrations due to the charge density waves changes the phonon spectrum and gives rise to a negative thermal expansion in the plane of layers, i.e., α_‖c = −2.2 × 10⁻⁶ K⁻¹, which is characteristic of two-dimensional structures. The average (over the range T = 50–300 K) coefficients of thermal expansion along the principal crystallographic directions have been calculated: $ \bar \alpha _{ \bot c} $ \bar \alpha _{ \bot c} = 10.48 × 10⁻⁶ K⁻¹ and $ \bar \alpha _{\parallel c} $ \bar \alpha _{\parallel c} = 12.97 × 10⁻⁶ K⁻¹, which agree with the X-ray diffraction data previously obtained by the authors at T = 290 K.     

Pyrophosphate Selective Recognition in Aqueous Solution Based on Fluorescence Enhancement of a New Aluminium Complex

A novel and simple fluorescence enhancement method for selective pyrophosphate(PPi) sensing was proposed based on a 1:1 metal complex formation between bis(8-hydroxy quinoline-5-solphonat) chloride aluminum(III) (Al(QS)₂Cl), (L) and PPi in aqueous solution. The linear response range covers a concentration range of 1.6 × 10⁻⁷ to 1.0 × 10⁻⁵ mol/L of PPi and the detection limit of 2.3 × 10⁻⁸ mol/L. The association constant of L-PPi complex was calculated 2.6 × 10⁵ L/mol. L was found to show selectively and sensitively fluorescence enhancement toward PPi over than I₃^-, NO₃^-, CN⁻, CO₃²⁻, Br⁻, Cl⁻, F⁻, H₂PO4⁻ and SO₄²⁻, which was attributed to higher stability of inorganic complex between pyrophosphate and L.     

Electrical transport properties of CuWO4

The temperature dependence of the electrical conductivity, thermoelectric power and dielectric constant of the antiferromagnetic CuWO₄ have been studied in the temperature range 300–1000 K. The conductivity results can be summarised by the equations σ_I=6.31 × 10⁻³ exp (−0.29 eV/kT) ohm⁻¹ cm⁻¹ in the temperature range 300–600 K and σ_II=3.16 × 10⁵ exp (−1.48 eV/kT) ohm⁻¹ cm⁻¹ between 600 K and 1000 K. The thermoelectric power can be expressed byθ=[− 1.25 (10³/T) + 3.9] mV/K. Initially dielectric constant increases slowly but for high temperatures its increase is fast.     

The local structure and interactions between V4+ ions in soda-phosphate glasses

EPR investigation on xV₂O₅ · (100 −x)[2P₂O₅ · Na₂O] and xV₂O₅ · (100 −x)[P₂O₅ · mNa₂O] (m = 1.5 and 2) glass systems was performed. The changes observed in the EPR spectra of xV₂O₅× (100 −x)[2P₂O₅ · Na₂O] glasses with increasing content of vanadium oxide are explained supposing that these spectra consist of two superposed EPR signals, one with hyperfine structure typical for isolated ions and another one consisting of a broad line without hyperfine structure characteristic for clustered ions. The clustered V⁴⁺ ions are not evidenced at low V₂O₅ contents (x = 5 mol%). The EPR spectra of xV₂O₅ · (100 −x)[P₂O₅ · mNa₂O] glasses indicate a superposition of two or three hyperfine structures attributed to nonequivalent VO²⁺ centers. Spin Hamiltonian parameters (g, A), dipolar hyperfine coupling parameter (P) and Fermi contact interaction term (K) have been evaluated. The ratio between the number of clustered and isolated ions was also determined.     

Thermomechanical and conductivity studies of doped niobium titanates as possible current collector material in the SOFC anode

In the reducing atmosphere of the SOFC anode at operating temperatures of 800 °C and above Nb₂TiO₇ is reduced to Nb_1.33Ti_0.67O₄. This material displays very high electronic conductivity of >100 Scm⁻¹, suitable for use in such applications as a current collector. It has a low thermal expansion coefficient of 3 × 10⁻⁶ K⁻¹, however, which may cause problems due to mismatch with other SOFC components, e.g. YSZ. Doping with Fe₂O₃ successfully increased the thermal expansion to a maximum of 6 × 10⁻⁶ K⁻¹. A conductivity of 140 Scm⁻¹ at 900 °C in dry 5% H₂/Ar, with an activation energy of 0.18 eV, was achieved for the Nb_1.344Ti_0.642Fe_0.014O₄, making it suitable for the use as a current collector. Conductivity runs in wet 5%H₂/Ar showed lower conductivities of 15–18 Scm⁻¹ and lower activation energies of 0.08 − 0.09 eV. Single cell tests of Nb_1.33Ti_0.67O₄ showed power outputs of 5.5 − 7.2 mW·cm⁻² at 850 °C, lower than for Ni with 150 − 200 mW·cm⁻² at 850 °C, however, this material displayed much better stability at high temperatures than Ni. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.