Application of recurrent radon precursors for forecasting large earthquakes (Mw > 6.0) near Antung,Taiwan

Radon anomalies in groundwater were recorded prior to three major earthquakes – (1) 2003 M_w = 6.8 Chengkung, (2) 2006 M_w = 6.1 Taitung, and (3) 2008 M_w = 5.4 Antung. The epicenters were located 24 km, 52 km, and 13 km, respectively, from the Antung radon-monitoring station. Prior to the three major earthquakes, radon decreased from background levels of 29.3 ± 1.7, 28.2 ± 2.1, and 27.2 ± 1.8 Bq dm^?3 to minima of 12.1 ± 0.3, 13.7 ± 0.3, and 17.8 ± 1.6 Bq dm^?3, respectively. Based on the radon precursory data, this paper correlates the observed radon minima with earthquake magnitude and precursory time. The correlations provide a possible means for forecasting local disastrous earthquakes in the southern segment of coastal range and longitudinal valley of eastern Taiwan.     

Concurrent concentration declines in groundwater-dissolved radon,methane and ethane precursory to 2011 MW 5.0 Chimei earthquake

Radon volatilization mechanism into the gas phase was hypothesized to explain the anomalous declines in groundwater radon precursory to three major earthquakes – (1) 2003 M_W = 6.8 Chengkung, (2) 2006 M_W = 6.1 Taitung, and (3) 2008 M_W = 5.4 Antung in Taiwan. The epicenters were located 24 km, 52 km, and 13 km from the Antung radon-monitoring well D1, respectively. To verify the mechanism of in situ volatilization, we monitored groundwater-dissolved ethane in addition to radon and methane at well D1 in the Antung hot spring since November 30, 2010. The mechanism of in situ radon volatilization has been corroborated by the simultaneous concentration declines in groundwater-dissolved radon, methane, and ethane precursory to the 2011 M_W 5.0 Chimei earthquake. The epicenter was located 32 km from the Antung radon-monitoring well D1. Observations at the Antung hot spring also suggest that radon is the best-choice tracer among the groundwater-dissolved gases for strain changes in the crust preceding an earthquake. On the southern segment of the Chihshang fault, the observed radon minima decrease as the earthquake magnitude increases.     

Preparation,thermal expansion,chemical compatibility,electrical conductivity and polarization of A2−αA′αMO4 (A = Pr,Sm; A′ = Sr; M = Mn,Ni; α = 0.3, 0.6) as a new cathode for SOFC

A_2−αA′_αMO₄ (A = Pr, Sm, A′ = Sr, M = Ni, Mn) with K₂NiF₄-type structure were synthesized by solid reaction. Their chemical stability, electrical conductivity and thermal expansion behavior as well as cathodic polarization were investigated in relation to the cathode of SOFC. The results showed that A_2−αA′_αMO₄ exhibited a low reactivity with yttria stabilized zirconia (YSZ) electrolyte. The thermal expansion coefficient (TEC) values were changed with the ionic radius of A. The specific conductivities of the nickelates were higher than those of manganites. While the nickelates showed a lower cathodic polarization in comparison with manganites.     

The experimental study of Ba 6pjnk |M| = 0, 1 autoionizing series

The spectra of the Ba 6pnk autoionizing Stark states with |M| = 0, 1, converging to the 6p_1/2⁺ and 6p_3/2⁺ ionization thresholds, are measured as a function of the electric field strength F. Several 6p_jnk Stark manifolds with n = 13–15 have been systematically studied in order to explore their characteristics of configuration interaction. Experimental results are analyzed by fitting them to the Lorentzian profile, from which the positions and widths are determined. Different spectroscopic properties between the Ba 6p_1/2nk and 6p_3/2nk autoionizing Stark states are investigated. Comparison between the Ba 6p_jnk autoionizing Stark states with |M| = 0 and those with |M| = 1 are made.     

Structure and conductivity investigations of alkaline earth substituted uranium oxide,U1 − xMxO2 ± δ (M = Mg,Ca, Sr) for solid oxide fuel cell applications

Alkaline earth substituted UO₂ (U_1 − xM_xO_2 ± δ; M = Mg, Ca, Sr; 0.1 ≤ x ≤ 0.525) with fluorite structure was synthesized in reducing atmosphere. Structure and conductivity properties of U_1 − xM_xO_2 ± δ fluorites were investigated for possible application in solid oxide fuel cells (SOFC). At room temperature and ambient atmosphere the materials are stable; however they decompose at an oxygen partial pressure p_O2 > 10^− 4 atm and temperatures higher than 600 °C. The total conductivity measured for the best conducting U_1 − xM_xO_2 ± δ material with M = Ca and x = 0.177 is as high as 3 S/cm at p_O2 < 10^− 4 atm at 600 °C. The relatively low ionic transference number (t_i∼0.02) is disadvantageous for potential use as electrolyte material for SOFC applications. The high conductivity and possible depolarization effects suggest potential use as anode materials in SOFC.     

Crystal growth and structural properties of the spinel-type Li1 + xMn2 − xO4 (x = 0.10, 0.14)

Single crystals of the lithium-rich lithium manganese oxide spinels Li_1 + xMn_2 − xO₄ with x = 0.10 and 0.14 have been successfully synthesized in high-temperature molten chlorides at 1023 K. The single-crystal X-ray diffraction study confirmed the cubic Fd3¯m space group and the lattice parameters of a = 8.2401(9) Å for x = 0.10 and a = 8.2273(10) Å for x = 0.14 at 300 K, respectively. The crystal structures have been refined to the conventional values R = 3.7% for x = 0.10 and R = 3.1% for x = 0.14, respectively. Low-temperature single-crystal X-ray diffraction experiments revealed that these single crystal samples showed no phase transition between 100 and 300 K. The electron-density distribution images in these compounds by the single-crystal MEM analysis clearly showed strong covalent bonding features between the Mn and O atoms due to the Mn–3d and O–2p interaction.     

Soft chemistry synthesis and characterizations of fully oxidized and reduced NdBaCo2O5+δ phases δ = 0, 1

The double ordered perovskites NdBaCo₂O₅ and NdBaCo₂O₆ were prepared by soft chemistry. The samples were characterized from a structural and chemical point of view, concomitantly with their physical properties. Upon reduction, NdBaCo₂O₅ is formed with a tetragonal unit cell (a = b = 3.94 Å, c = 7.57 Å) and presents an antiferromagnetic behavior. Upon oxidation, a complete stoichiometric ordered phase NdBaCo₂O₆ with a tetragonal unit cell (a = b = 3.88 Å, c = 7.63 Å) could be obtained with a ferromagnetic and a metallic behavior. Finally it is shown that these phases are able to reversibly catch and release oxygen, suggesting a high anionic conductivity.     

Synthesis and characterization of La4Ni3−xCoxO10±δ (0.0 ≤ x ≤ 3.0, Δx = 0.2) for solid oxide fuel cell cathodes

The cobalt-doped lanthanum–nickel oxide system, La₄Ni_(3−x)Co_xO_10±δ (0.0 ≤ x ≤ 3.0, Δx = 0.2), was investigated as possible cathode materials for intermediate-temperature solid-oxide fuel cells. X-ray diffraction shows the presence of two structural phases in the series belonging to Bmab for 0.0 ≤ x ≤ 0.2, 0.8 ≤ x ≤ 2.0 and 2.6 ≤ x ≤ 3.0 and Fmmm for 0.4 ≤ x ≤ 0.6 and 2.2 ≤ x ≤ 2.4. All compositions are oxygen-deficient (δ < 0). Electrical conductivity measurements show a systematic decrease in the conductivity as cobalt content increases from x = 0.0 to 2.0, and reverses for x > 2.0. AC impedance measurements of the x = 0.4 composition in symmetrical cells with LSGM as an electrolyte show improved electrode performance over the parent nickelate La₄Ni₃O_9.78. Long-term thermal stability studies show the x = 0.4 composition to be more stable than the x = 3.0 phase after annealing at 1173 K in air for 1 week making this material a viable candidate for cathodes in solid oxide fuel cells.     

Synthesis of ammonia at atmospheric pressure with Ce0.8M0.2O2−δ (M = La,Y, Gd,Sm) and their proton conduction at intermediate temperature

Ionic conduction in fluorite-type structure oxide ceramics Ce_0.8M_0.2O_2−δ (M = La, Y, Gd, Sm) at temperature 400–800 °C was systematically studied under wet hydrogen/dry nitrogen atmosphere. On the sintered complex oxides as solid electrolyte, ammonia was synthesized from nitrogen and hydrogen at atmospheric pressure in the solid states proton conducting cell reactor by electrochemical methods, which directly evidenced the protonic conduction in those oxides at intermediate temperature. The rate of evolution of ammonia in Ce_0.8M_0.2O_2−δ (M = La, Y, Gd, Sm) is up to 7.2 × 10^− 9, 7.5 × 10^− 9, 7.7 × 10^− 9, 8.2 × 10^− 9 mol s^− 1 cm^− 2, respectively.     

Electrode reaction of Sr1−xLaxCo0.8Fe0.2O3−δ with x = 0.1 and 0.6 on Ce0.9Gd0.1O1.95 at 600 ≤ T ≤ 800 °C

The electrode reaction of the perovskite phases Sr_1−xLa_xCo_0.8Fe_0.2O_3−δ (x = 0.1 and 0.6) on Ce_0.9Gd_0.1O_1.95 has been investigated by impedance spectroscopy in the temperature range 600 ≤ T ≤ 800 °C. Thick porous electrodes (t ∼ 20 μm) were sprayed on Ce_0.9Gd_0.1O_1.95 and ac impedance spectra were recorded on symmetrical cells at the equilibrium. The analysis of the complex impedance diagrams clearly indicates the presence of two contributions. The low frequency one was assigned to the gas phase oxygen diffusion through the porous electrode and a finite length diffusion (Warburg) impedance was used to describe the high frequency (HF) data. The polarization resistance of the HF impedance contribution (R_w) is higher for x = 0.1 while the activation energy of R_w is higher for x = 0.6. The variations of R_w versus the La content, temperature and thickness indicate that the Warburg-type impedance contains information of both bulk oxygen diffusion and surface processes.     

Synthesis and characterization of layered Li1−x(Ni0.5Co0.5)1−yFeyO2(0 ≤ (1 − x) ≤ 1 and 0 ≤ y ≤ 0.2) cathodes

Layered Li(Ni_0.5Co_0.5)_1−yFe_yO₂ cathodes with 0 ≤ y ≤ 0.2 have been synthesized by firing the coprecipitated hydroxides of the transition metals and lithium hydroxide at 700 °C and characterized as cathode materials for lithium ion batteries to various cutoff charge voltages (up to 4.5 V). While the y = 0.05 sample shows an improvement in capacity, cyclability, and rate capability, those with y = 0.1 and 0.2 exhibit a decline in electrochemical performance compared to the y = 0 sample. Structural characterization of the chemically delithiated Li_1−x(Ni_0.5Co_0.5)_1−yFe_yO₂ samples indicates that the initial O3 structure is maintained down to a lithium content (1 − x) ≈ 0.3. For (1 − x) < 0.3, while a P3 type phase is formed for the y = 0 sample, an O1 type phase is formed for the y = 0.05, 0.1 and 0.2 samples. Monitoring the average oxidation state of the transition metal ions with lithium contents (1 − x) reveals that the system is chemically more stable down to a lower lithium content (1 − x) ≈ 0.3 compared to the Li_1−xCoO₂ system. The improved structural and chemical stabilities appear to lead to better cyclability to higher cutoff charge voltages compared to that found before with the LiCoO₂ system.     

Structural,XPS and impedance analysis of LixCoVO4 (x = 0.8, 1.0, 1.2)

Lithium cobalt vanadate Li_xCoVO₄ (x = 0.8; 1.0; 1.2) has been prepared by a solid state reaction method. The XRD analysis confirms the formation of the sample. A new peak has been observed for Li_1.0CoVO₄ and for Li_1.2CoVO₄ indicating the formation of a new phase. The XPS analysis indicates the reduction in the oxidation of vanadium and oxygen with the addition of Li in Li_xCoVO₄ (x = 0.8, 1.0, 1.2). The impedance analysis gives the conductivity value as 2.46 × 10^− 5, 6.16 × 10^− 5, 9 × 10^− 5 Ω^− 1 cm^− 1 for Li_xCoVO₄ (x = 0.8; 1.0; 1.2), all at 623 K. The similarity in the bulk activation energy (E_a) and the activation enthalpy for migration of ions (E_ω) indicate that the conduction in Li_1.2CoVO₄ has been due to hopping mechanism.     

Defect interactions in La0.3Sr0.7Fe(M′)O3−δ (M′ = Al,Ga) perovskites: Atomistic simulations and analysis of p(O2)-T-δ diagrams

Atomistic modelling showed that a key factor affecting the p(O₂) dependencies of point defect chemical potentials in perovskite-type La_0.3Sr_0.7Fe_1−xM′_xO_3−δ (M′ = Ga, Al; x = 0–0.4) under oxidizing conditions, relates to the coulombic repulsion between oxygen vacancies and/or electron holes. The configurations of A- and B-site cations with stable oxidation states have no essential influence on energetics of the mobile charge carriers, whereas the electrons formed due to iron disproportionation are expected to form defect pair clusters with oxygen vacancies. These results were used to develop thermodynamic models, adequately describing the p(O₂)-T-δ diagrams of La_0.3Sr_0.7Fe(M′)O_3−δ determined by the coulometric titration technique at 923–1223 K in the oxygen partial pressure range from 1 × 10^− 5 to 0.5 atm. The thermodynamic functions governing the oxygen intercalation process were found independent of the defect concentration. Doping with aluminum and gallium leads to increasing oxygen deficiency and induces substantial changes in the behavior of iron cations, increasing the tendencies to disproportionation and hole localization. Despite similar oxygen nonstoichiometry in the Al- and Ga-substituted ferrites at a given dopant content, the latter tendency is more pronounced in the case of aluminum-containing perovskites.     

BaT2As2 single crystals (T = Fe,Co, Ni) and superconductivity upon Co-doping

The crystal structure and physical properties of BaFe₂As₂, BaCo₂As₂, and BaNi₂As₂ single crystals are surveyed. BaFe₂As₂ gives a magnetic and structural transition at T_N = 132(1) K, BaCo₂As₂ is a paramagnetic metal, while BaNi₂As₂ has a structural phase transition at T₀ = 131 K, followed by superconductivity below T_c = 0.69 K. The bulk superconductivity in Co-doped BaFe₂As₂ below T_c = 22 K is demonstrated by resistivity, magnetic susceptibility, and specific heat data. In contrast to the cuprates, the Fe-based system appears to tolerate considerable disorder in the transition metal layers. First principles calculations for BaFe_1.84Co_0.16As₂ indicate the inter-band scattering due to Co is weak.     

Oxygen non-stoichiometry and electrical conductivity of Pr2−xSrxNiO4±δ with x = 0–0.5

Oxygen non-stoichiometry and electrical conductivity of the Pr_2−xSr_xNiO_4±δ series with x = 0.0–0.5 were investigated in Ar/O₂ (pO₂ = 2.5 to 21 000 Pa) within a temperature range of 20–1000 °C. The equilibrium values of oxygen non-stoichiometry and electrical conductivity of these nickelates were determined as functions of temperature and oxygen partial pressure (pO₂). The nickelates with x = 0–0.5 appear to be p-type semiconductors in the investigated temperature and pO₂ ranges. The nickelates with x = 0.3–0.5 show very feebly marked pO₂ dependencies of the conductivity. Pr_1.7Sr_0.3NiO_4±δ shows the anomalies of the conductivity versus oxygen partial pressure which can be related to the orthorhombic–tetragonal crystal structure transformations. The conductivity of the Pr_2−xSr_xNiO_4±δ samples correlates with the average oxidation state of the nickel cations. The samples with x = 0.5 have the highest nickel oxidation state (≈ 2.5+), the highest [Ni³⁺]/[Ni²⁺] ratio close to 1 and show the highest conductivity (≈ 120 S/cm) in the whole pO₂ and temperature ranges investigated.     

Novel olivine and spinel LiMAsO4 (M = 3d-metal) as positive electrode materials in lithium cells

New olivines LiMAsO₄ (M = Mn, Fe, Co, and Ni) have been tested as positive electrode in lithium cells. Under the used experimental conditions we did not succeed to remove lithium ions from LiFeAsO₄, LiMnAsO₄ or LiNiAsO₄. More work is needed in order to verify whether the lack of electrochemical activity is intrinsic to these materials, or it is due to kinetical limitations such as particle size and poor conductivity. On the contrary lithium ions could be reversibly deinserted/inserted from/into LiCoAsO₄ at average voltages of 4.8 and 4.6 V respectively; the delithiated compound maintaining the olivine structural framework.The high pressure polymorph of LiMAsO₄ (M = Fe, Co, Ni) crystallizing with the spinel structure did not show any electrochemical activity potentially useful in rechargeable lithium batteries.     

Oxygen adsorption and surface segregation in (2 1 1) surfaces of Pt(shell)/M(core) and Pt3M (M = Co,Ir) alloys

Density functional theory is used to study oxygen adsorption and its effect on surface segregation in (2 1 1) surfaces of Pt(shell)/M(core) and Pt₃M (M = Co, Ir) alloys. It is found that the most energetically favorable oxygen adsorption site is the bridge site over and parallel to the (1 0 0) step. Surface segregation phenomena is observed in Pt₃Co, Pt₃Ir and Pt/Co(core) systems. The Pt/Ir(core) structure was the only one, among the studied systems, that showed antisegregation behavior even in presence of oxygen adsorbed.     

(p, ρ, T) and (ps, ρs,Ts) properties,and apparent molar volumes Vϕ of LiI (aq) at T = 298.15 to 398.15 K and at pressures up to p = 60 MPa

(p, ρ, T) and (p_s, ρ_s, T_s) properties, and apparent molar volumes V_ϕ of LiI (aq) at T = 298.15 to 398.15 K, at pressures up to p = 60 MPa were reported, and apparent molar volumes at infinite dilution V_ϕ⁰ have been evaluated. An empirical correlation for density of lithium iodide (aq) with pressure, temperature and molality was derived. The experiments were carried out at molalities m = 0.11053, 0.32532, 0.70013, 1.40459, 2.95059, and 4.88147 mol kg^− 1 of lithium iodide.     

Ionic and electronic conductivities,stability and thermal expansion of La10 − x(Si,Al)6O26 ± δ solid electrolytes

Apatite-type La_10 − xSi_6 − yAl_yO_{27 − 3x/2 − y/2} (x = 0–0.33; y = 0.5–1.5) exhibit predominant oxygen ionic conductivity in a wide range of oxygen partial pressures. The conductivity of silicates containing 26.50–26.75 oxygen atoms per formula unit is comparable to that of gadolinia-doped ceria at 770–870 K. The average thermal expansion coefficients are (8.7–10.8) × 10^− 6 K^− 1 at 373–1273 K. At temperatures above 1100 K, silicon oxide volatilization from the surface layers of apatite ceramics and a moderate degradation of the ionic transport with time are observed under reducing conditions, thus limiting the operation temperature of Si-containing solid electrolytes.     

A comparative study of the Ruddlesden-Popper series,Lan+1NinO3n+1 (n = 1, 2 and 3), for solid-oxide fuel-cell cathode applications

A comparative investigation of the much-studied La₂NiO_4+δ (n = 1) phase and the higher-order Ruddlesden-Popper phases, La_n+1Ni_nO_3n+1 (n = 2 and 3), has been undertaken to determine their suitability as cathodes for intermediate-temperature solid-oxide fuel cells. As n is increased, a structural phase transition is observed from tetragonal I4/mmm in the hyperstoichiometric La₂NiO_4.15 (n = 1) to orthorhombic Fmmm in the oxygen-deficient phases, La₃Ni₂O_6.95 (n = 2) and La₄Ni₃O_9.78 (n = 3). High temperature d.c. electrical conductivity measurements reveal a dramatic increase in overall values from n = 1, 2 to 3 with metallic behavior observed for La₄Ni₃O_9.78. Impedance spectroscopy measurements on symmetrical cells with La_0.9Sr_0.10Ga_0.80Mg_0.20O_3−δ (LSGM-9182) as the electrolyte show a systematic improvement in the electrode performance from La₂NiO_4.15 to La₄Ni₃O_9.78 with ∼ 1 Ω cm² observed at 1073 K for the latter. Long-term thermal stability tests show no impurity formation when La₃Ni₂O_6.95 and La₄Ni₃O_9.78 are heated at 1123 K for 2 weeks in air, in contrast to previously reported data for La₂NiO_4.15. The relative thermal expansion coefficients of La₃Ni₂O_6.95 and La₄Ni₃O_9.78 were found to be similar at ∼ 13.2 × 10^− 6 K^− 1 from 348 K to 1173 K in air compared to 13.8 × 10^− 6 K^− 1 for La₂NiO_4.15. Taken together, these observations suggest favourable use for the n = 2 and 3 phases as cathodes in intermediate-temperature solid-oxide fuel cells when compared to the much-studied La₂NiO_4+δ (n = 1) phase.