Antiferromagnetic phase transition in garnet-type AgCa2Co2V3O12 and AgCa2Ni2V3O12

Antiferromagnetic phase transition in two vanadium garnets AgCa₂Co₂V₃O₁₂ and AgCa₂Ni₂V₃O₁₂ has been found and investigated extensively. The heat capacity exhibits sharp peak due to the antiferromagnetic order with the Néel temperature T_N=6.39 K for AgCa₂Co₂V₃O₁₂ and 7.21 K for AgCa₂Ni₂V₃O₁₂, respectively. The magnetic susceptibilities exhibit broad maximum, and these T_N correspond to the inflection points of the magnetic susceptibility χ a little lower than T(χ_max). The magnetic entropy changes from zero to 20 K per mol Co²⁺ and Ni²⁺ ions are 5.31 J K⁻¹ mol-Co²⁺-ion⁻¹ and 6.85 J K⁻¹ mol-Ni²⁺-ion⁻¹, indicating S=1/2 for Co²⁺ ion and S=1 for Ni²⁺ ion. The magnetic susceptibility of AgCa₂Ni₂V₃O₁₂ shows the Curie-Weiss behavior between 20 and 350 K with the effective magnetic moment μ_eff=3.23 μ_B Ni²⁺-ion⁻¹ and the Weiss constant θ=−16.4 K (antiferromagnetic sign). Nevertheless, the simple Curie-Weiss law cannot be applicable for AgCa₂Co₂V₃O₁₂. The complex temperature dependence of magnetic susceptibility has been interpreted within the framework of Tanabe-Sugano energy diagram, which is analyzed on the basis of crystalline electric field. The ground state is the spin doublet state ²E(t₂⁶e) and the first excited state is spin quartet state ⁴T₁(t₂⁵e²) which locates extremely close to the ground state. The low spin state S=1/2 for Co²⁺ ion is verified experimentally at least below 20 K which is in agreement with the result of the heat capacity.     

Synthesis and crystallographic studies of garnet-type AgCa2Mn2V3O12 and NaPb2Mn2V3O12

High-purity powder specimens of AgCa₂Mn₂V₃O₁₂ and NaPb₂Mn₂V₃O₁₂ have been successfully synthesized by solid-state chemical reaction. The Rietveld refinements from X-ray powder diffraction data verified that these compounds have the garnet-type structure (space group , No. 230) with the lattice constant of a=12.596(2) Å for AgCa₂Mn₂V₃O₁₂ and a=12.876(2) Å for NaPb₂Mn₂V₃O₁₂. Calculation of the bond valence sum supported that Mn is divalent and V is pentavalent in these garnets. Estimation of the quadratic elongation and the bond angle variance showed that the distortions of the MnO₆ octahedra and the VO₄ tetrahedra are significantly suppressed. Our new results of AgCa₂Mn₂V₃O₁₂ and NaPb₂Mn₂V₃O₁₂ are compared to those of AgCa₂M₂V₃O₁₂ and NaPb₂M₂V₃O₁₂ (M=Mg, Co, Ni, Zn).     

Synthesis and crystallographic studies of garnet-related lithium-ion conductors Li6CaLa2Ta2O12 and Li6BaLa2Ta2O12

High-purity specimens of Li₆CaLa₂Ta₂O₁₂ and Li₆BaLa₂Ta₂O₁₂ have been successfully synthesized by solid-state reactions. The analytical chemical compositions of these samples were in good agreement with the nominal compositions of Li₆CaLa₂Ta₂O₁₂ and Li₆BaLa₂Ta₂O₁₂. The Rietveld refinements verified that these compounds have the garnet-type framework structure with the lattice constants of a = 12.725(2) Å for Li₆CaLa₂Ta₂O₁₂ and a = 13.001(4) Å for Li₆BaLa₂Ta₂O₁₂. All of the diffraction peaks of X-ray powder diffraction patterns were well indexed on the basis of cubic symmetry with space group Ia-3d. To make a search for Li sites, the electron density distributions were precisely examined by using the maximum entropy method. Li⁺ ions occupy partially two types of crystallographic site in these compounds: (i) tetrahedral 24d sites, and (ii) distorted octahedral 96h sites, the latter of which are the vacant sites of the ideal garnet-type structure. The present Li₆CaLa₂Ta₂O₁₂ and Li₆BaLa₂Ta₂O₁₂ samples exhibit the conductivity σ = 2.2 × 10^? 6 S cm^? 1 at 27 °C (E_a = 0.50 eV) and σ = 1.3 × 10^? 5 S cm^? 1 at 25 °C (E_a = 0.44 eV), respectively.     

Synthesis and electrochemical characterization of M2Mn3O8 (M = Ca,Cu) compounds and derivatives

M₂Mn₃O₈ (M = Ca²⁺, Cu²⁺) compounds were synthesized and characterized in lithium cells. The M²⁺ cations, which reside in the van der Waals gaps between adjacent sheets of Mn₃O₈⁴⁻, may be replaced chemically (by ion-exchange) or electrochemically with Li. More than 7 Li⁺/Cu₂Mn₃O₈ may be inserted electrochemically, with concomitant reduction of Cu²⁺ to Cu metal, but less Li can be inserted into Ca₂Mn₃O₈. In the case of Cu²⁺, this process is partially reversible when the cell is charged above 3.5 V vs. Li, but intercalation of Cu⁺ rather than Cu²⁺ and Li⁺/Cu⁺ exchange occurs during the subsequent discharge. If the cell potential is kept below 3.4 V, the Li in excess of 4 Li⁺/Cu₂Mn₃O₈ can be cycled reversibly. The unusual mobility of + 2 cations in a layered structure has important implications both for the design of cathodes for Li batteries and for new systems that could be based on M²⁺ intercalation compounds.     

Photoluminescence of Lu3Al5O12:Bi and Y3Al5O12:Bi single crystalline films

Single crystalline films of Lu₃Al₅O₁₂:Bi and Y₃Al₅O₁₂:Bi have been studied at 4.2–450 K by the time-resolved luminescence spectroscopy method. Their emission spectrum consists of two types of bands with strongly different characteristics. The ultraviolet band consists of two components, arising from the electronic transitions which correspond to the ³P₁ → ¹S₀ and ³P₀ → ¹S₀ transitions in a free Bi³⁺ ion. At T < 80 K, mainly the lower-energy component with the decay time ～10^?3 s is observed, arising from the metastable ³P₀ level. At T > 150 K, the higher-energy component prevails, arising from the thermally populated emitting ³P₁ level. The visible emission spectrum consists of two dominant strongly overlapped broad bands with large Stokes shifts. At 4.2 K, their decay times are ～10^?5 s and ～10^?4 s and decrease with increasing temperature. Both of the visible emission bands are assumed to be of an exciton origin. The lower-energy band is ascribed to an exciton, localized near a single Bi³⁺ ion. The higher-energy band, showing a stronger intensity dependence on the Bi³⁺ content, is assumed to arise from an exciton, localized near a dimer Bi³⁺ center. The structure of the corresponding excited states is considered, and the processes, taking place in these states, are discussed.     

Interfacial reactions of Ba2YCu3O6+z with coated conductor buffer layer,LaMnO3

Chemical interactions between the Ba₂YCu₃O_6+x superconductor and the LaMnO₃ buffer layers employed in coated conductors have been investigated experimentally by determining the phases formed in the Ba₂YCu₃O_6+x–LaMnO₃ system. The Ba₂YCu₃O_6+x–LaMnO₃ join within the BaO–(Y₂O₃–La₂O₃)–MnO₂–CuO_x multi-component system is non-binary. At 810 °C (p_O2 = 100 Pa) and at 950 °C in purified air, four phases are consistently present along the join, namely, Ba_2?x(La_1+x?yY_y)Cu₃O_6+z, Ba(Y_2?xLa_x)CuO₅, (La_1?xY_x)MnO₃, (La,Y)Mn₂O₅. The crystal chemistry and crystallography of Ba(Y_2?xLa_x)CuO₅ and (La_1?xY_x)Mn₂O₅ were studied using the X-ray Rietveld refinement technique. The Y-rich and La-rich solid solution limits for Ba(Y_2?xLa_x)CuO₅ are Ba(Y_1.8La_0.2)CuO₅ and Ba(Y_0.1La_1.9)CuO₅, respectively. The structure of Ba(Y_1.8La_0.2)CuO₅ is Pnma (No. 62), a = 12.2161(5) Å, b = 5.6690(2) Å, c = 7.1468(3) Å, V = 494.94(4) Å³, and D_x = 6.29 g cm^?3. YMn₂O₅ and LaMn₂O₅ do not form solid solution at 810 °C (p_O2 = 100 Pa) or at 950 °C (in air). The structure of YMn₂O₅ was confirmed to be Pbam (No. 55), a = 7.27832(14) Å, b = 8.46707(14) Å, c = 5.66495(10) Å, and V = 349.108(14) Å³. A reference X-ray pattern was prepared for YMn₂O₅.     

Synthesis and visible light photocatalysis water splitting property of chromium-doped Bi4Ti3O12

Photocatalysts Bi₄Ti_3 ? xCr_xO₁₂(x = 0.00, 0.06, 0.15, 0.30, 0.40, and 0.50) with perovskite structure were synthesized by sol–gel method and their electronic structures and photocatalytic activities were investigated. The Bi₄Ti_2.6Cr_0.4O₁₂ photocatalyst exhibited the highest performance of H₂ evolution in methanol aqueous solution (58.1 μmol h^? 1 g^? 1) under visible light irradiation (λ > 400 nm) without a co-catalyst, whereas no H₂ evolution is observed for Bi₄Ti₃O₁₂ under the same conditions. The UV–vis spectra indicated that the Bi₄Ti_2.6Cr_0.4O₁₂ had strong photoabsorption in the visible light region. The results of density functional theory (DFT) calculation illuminate that the conduction bands of Bi₄Ti₃O₁₂ are mainly attributable to the Ti 3d + Bi 6p orbitals, and the valence bands are composed of O 2p + Bi 6s hybrid orbitals, while the conduction bands of chromium-doped Bi₄Ti₃O₁₂ are mainly attributable to the Ti 3d + Bi 2p + Cr 3d orbitals, and the O 2p + Cr 3d hybrid obitals are the main contribution to the valence band.     

Low-temperature investigations of the open-framework material HfMgMo3O12

The A₂Mo₃O₁₂ family, where A³⁺ is a large trivalent cation, can show interesting thermal properties such as negative thermal expansion. One member of this family, HfMgMo₃O₁₂, where the two A³⁺ cations have been replaced by Hf⁴⁺ and Mg²⁺, has been shown to have a low positive coefficient of thermal expansion above room temperature. This property makes HfMgMo₃O₁₂ an attractive candidate as a component for solid solutions with near-zero thermal expansion. However, its properties below room temperature were unexplored. In this work we report the phase transition from orthorhombic Pnma to monoclinic P2₁/a at T～175 K with an enthalpy change of 0.27 kJ mol^?1. Relaxation calorimetry, from 5 K to 300 K, show only the small anomaly associated with this transition. The thermal conductivity, determined from 2 K to 300 K, was low, but not as low as some other materials exhibiting negative thermal expansion. Analysis of the low-temperature heat capacity indicates the presence of low-energy phonon modes in HfMgMo₃O₁₂, consistent with the low thermal conductivity. The upper bound of the Young's modulus, estimated from the effective Debye temperature derived from the low-temperature heat capacity, is 20 GPa, a relatively low value due to the flexibility of the framework structure.     

White-light generation through Ce3+/Mn2+-codoped and Eu2+-doped Ba1.2Ca0.8SiO4 T-phase phosphors

Hexagonal Ba_1.20Ca_0.8?2x?ySiO₄:xCe³⁺,xLi⁺,yMn²⁺ phosphors exhibit two emission bands peaking near 400 and 600 nm from the allowed f–d transition of Ce³⁺ ions and the forbidden ⁴T₁–⁶A₁ transition of Mn²⁺ ions, respectively. The strong interaction between Ce³⁺/Mn²⁺ ions is investigated in terms of energy transfer, crystal field effect, and microstructure by varying their concentrations. They show a higher quenching temperature of 250 °C than that of a commercially used (Ba,Sr)₂SiO₄:Eu²⁺ phosphor (150 °C). Finally, mixtures of these phosphors with green-emissive Ba_1.20Ca_0.70SiO₄:0.10Eu²⁺ are tested and yielded correlated color temperatures from 3500 to 7000 K, and color rendering indices up to 95%.     

Phase dependent photoluminescence and energy transfer in Ca2P2O7: Eu2+, Mn2+ phosphors for white LEDs

α- and β-Ca₂P₂O₇: Eu²⁺, Mn²⁺ phosphors were prepared by solid-state reaction. Phase transition from tetragonal (β-phase) to monoclinic (α-phase) is performed. A strong orange emission of Mn²⁺ is observed in both α-and β-Ca₂P₂O₇: Eu²⁺, Mn²⁺ upon near ultraviolet (UV) excitation through energy transfer from Eu²⁺ to Mn²⁺. The transfer efficiencies for various Mn²⁺ concentrations are estimated based on lifetime measurements of the fluorescence of Eu²⁺ in the two phases. The photoluminescence excitation spectra of α-Ca₂P₂O₇: Eu²⁺, Mn²⁺ can cover 400 nm of the near-UV range, denoting its potential use as a phosphor with intense orange component for white light emitting diodes (LEDs).     

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.     

M/Li+(M = Mg2+, Zn2+, and Mn2+) ion-exchange on lithium ion-conducting perovskite-type oxides and their properties

Lithium ions of perovskite-type lithium ion conductor La_0.55Li_0.35TiO₃ were replaced by divalent Mg²⁺, Zn²⁺, and Mn²⁺ ions in an ion-exchange reaction using molten chlorides. The polycrystalline Mg-exchanged and Zn-exchanged samples are solid electrolytes for divalent Mg²⁺ and Zn²⁺ ions, whose dc ionic conductivities (σ = 2.0 × 10^− 6 S cm^− 1 at 558 K for the Mg-exchanged sample, La_0.56(2)Li_0.02(1)Mg_0.16(1)TiO_3.01(2) and σ = 1.7 × 10^− 6 S cm^− 1 at 708 K for the Zn-exchanged samples, La_0.55(1)Li_0.0037(2)Zn_0.15(1)TiO_2.98(2)) were compared to those of the known highest Mg²⁺ and Zn²⁺ inorganic solid electrolytes. The Mn-exchanged sample, then, showed paramagnetic behavior in the temperature range of 2 to 300 K. The Mn ions in the exchanged sample are divalent and the spin configuration is in high spin state (S = 5/2).     

Proton conduction of Ba6Mn24O48 tunnel manganite

A protonated Ba₆Mn₂₄O₄₈ phase with an original tunnel crystal structure and mixed-valent manganese has been prepared in the form of powders and millimeter-long fibrous crystals (whiskers). A combined study either by impedance spectroscopy or transport measurements revealed that the Ba₆Mn₂₄O₄₈ phase demonstrates mixed conductivity with both proton and electronic components reaching ～ 10^? 3 Ω^? 1?cm^? 1 at room temperature.     

High temperature protonic conduction in Sr-doped LaP3O9

Electrical conduction of Sr-doped LaP₃O₉ ([Sr]/{[La] + [Sr]} = 2–10 mol%) was investigated under 0.4–5 kPa of p(H₂O) and 0.01–100 kPa of p(O₂) or 0.3–3 kPa of p(H₂) at 573–973 K. Sr-doped LaP₃O₉ showed apparent H/D isotope effect on conductivity regardless of the Sr-doping level under both H₂O/O₂ oxidizing and H₂/H₂O reducing conditions at investigated temperatures. Conductivities of the material were almost independent of p(O₂) and p(H₂O). These results demonstrated that the Sr-doped LaP₃O₉ exhibited protonic conduction under wide ranges of p(O₂), p(H₂O) and temperature. The conductivity of the Sr-doped LaP₃O₉ increased with increasing Sr concentration up to its solubility limit, ca. 3 mol%, while the further Sr-doping slightly degraded the conductivity. These indicate that Sr²⁺ substitution for La³⁺ leads to proton dissolution into the material and induced protonic conduction. Conductivities of the 3 mol% Sr-doped sample were 2 × 10^- 6–5 × 10^− 4 S cm^− 1 at 573–973 K.     

Structural and magnetic ordering in La0.6Ca0.4MnO3

The structural and magnetic ordering in La_0.6Ca_0.4MnO₃ has been studied by neutron powder diffraction as a function of temperature between 15 and 300 K. The para-ferromagnetic transition at T∼250 K is accompanied by significant structural distortions in the form of octahedral Mn–O₆ rotations. At 15 K, the total refined ferromagnetic moment on the Mn site was obtained as 3.1 μ_B, in reasonable agreement with the total expected average moment of mixed Mn³⁺/Mn⁴⁺ matrix.     

Defect equilibria and partial molar properties of (La,Sr)(Co,Fe)O3−δ

The oxygen nonstoichiometry δ of La_1−xSr_xCo_1−yFe_yO_3−δ (x = 0.6 and y = 0.2, 0.4) was investigated by thermogravimetry in the range 703 ≤ T/°C ≤ 903 and 1E−5 < pO₂/atm < 1. The oxygen deficit increases with increasing T and decreasing pO₂. Electronic conductivities σ were measured as a function of pO₂ in the range 1E−5 < pO₂/atm < 1 at 700 ≤ T/°C ≤ 900. At constant T, a p-type pO₂-dependence of σ is observed. Oxygen nonstoichiometry data are analyzed with regard to the enthalpy and entropy of oxidation ΔH_ox^θ and ΔS_ox^θ, as well as to the partial molar enthalpy and entropy of oxygen with respect to the standard state of oxygen (pO₂^θ = 1 atm), (h_O − H_O^θ) and (s_O − S_O^θ), respectively. For 2.67 ≤ (3 − δ) ≤ 2.79, (h_O − H_O^θ) decreases with increasing δ, while (s_O − S_O^θ) is constant within the limits of error. Defect chemical modelling was performed by an ideal solution model under consideration of three different valence states for B-site ions (Co or Fe). The dependence of σ on δ is modelled, using calculated defect concentrations as functions of δ. Deviations from the ideal behaviour suggest an immobilization of n-type charge carriers by oxygen vacancies.     

The studies on structural and thermal properties of delithiated LixNi1/3Co1/3Mn1/3O2 (0 < x ≤ 1) as a cathode material in lithium ion batteries

The structural and thermal properties of the delithiated Li_xNi_1/3Co_1/3Mn_1/3O₂ (0 < x ≤ 1) material have been investigated by using diffraction and thermoanalytical techniques such as XRD and TG-DSC methods. XRD result shows that the delithiated materials maintain the O3-type structure with defined stoichiometric number at the range of 0.24 < x ≤ 1, exhibiting good crystal structural stability. The cobalt and nickel ions in the delithiated materials change their valence state (i.e. Co³⁺ to Co⁴⁺ and Ni³⁺ to Ni⁴⁺) when x < 0.49; the irreversible changes of the transformation may affect the first cycle of charge–discharge efficiency of the materials. A comparison of the results of TG-DSC with TPD-MS shows that the irreversible change of oxygen species during the delithiation process of Li_xNi_1/3Co_1/3Mn_1/3O₂ have great influence on the structural and thermal stability and reversibility of the materials.     

Current controlled negative differential resistance behavior in Co2FeO2BO3 and Fe3O2BO3 single crystals

I–V curves showing negative differential resistance (NDR) are reported for single crystals of Co₂FeO₂BO₃ at 315 K and 290 K and for Fe₃O₂BO₃ at 300 K, 260 K and 220 K. Resistivity measurements are presented for both systems, parallel and perpendicular to the c axis, in the range 315–120 K. The high hysteretic behavior of the I–V curves in Co₂FeO₂BO₃ around room temperature is discussed and the heat dissipated is estimated, suggesting an increase in the sample temperature of almost 22 K for the I–V curve at 315 K and a dominant contribution of Joule self-heating for the observed NDR. In contrast, insignificant hysteresis is observed on the I–V curves of Fe₃O₂BO₃ around room temperature. The depinning of charge order domains is suggested as the main contribution to the NDR phenomenon for Fe₃O₂BO₃. The high reproducibility of the NDR in the Fe₃O₂BO₃ single crystal allows its use as a low frequency oscillator, as it is demonstrated.     

DFT study of carbon monoxide adsorption on α-Al2O3(0001)

The adsorption of CO on α-Al₂O₃(0001) was studied using the DFT-GGA computational method and on α-Al₂O₃ powder experimentally by Infra red spectroscopy. The core and valence level regions of α-Al₂O₃(0001) single crystal surface were also studied experimentally. Ar ions sputtering of the surface results in a slight but reproducible decrease in the XPS O2p lines in the valence band regions due to preferential removal of surface (and near surface) O atoms. Core level XPS O1s and Al2p further confirmed oxygen depletion with an associated surface stoichiometry close to Al₂O_2.9. The adsorption energy of CO was computed and found equal to 0.52 eV for θ = 0.25, it decreased to 0.42 eV at θ = 1. The IR frequency of νCO was also computed and in all cases it was blue shifted with respect to gas phase CO. The shift, Δν, decreased with increasing coverage where it was found equal to 56 cm^? 1 for θ = 0.25 and decreased to 30 cm^? 1 for θ = 1. Structural analyses indicated that the change in the adsorption energy and the associated frequency shift is due to surface relaxation upon adsorption. Experimentally the adsorption of CO gave rise to one main IR peak at 2154 cm^? 1 at 0.3 Torr and above. Two far smaller peaks are also seen at lower pressures of 0.03–0.2 Torr at 2189 and 2178 cm^? 1. The isosteric heat of adsorption was computed for the IR band at 2154 cm^? 1 and was found equal to 0.2 eV which did not change with coverage in the investigated range up to θ = 0.6.     

On the rate constants of OH + HO2 and HO2 + HO2: A comprehensive study of H2O2 thermal decomposition using multi-species laser absorption

Hydrogen peroxide (H₂O₂) and hydroperoxy (HO₂) reactions present in the H₂O₂ thermal decomposition system are important in combustion kinetics. H₂O₂ thermal decomposition has been studied behind reflected shock waves using H₂O and OH diagnostics in previous studies (Hong et al. (2009) [9] and Hong et al. (2010) [6,8]) to determine the rate constants of two major reactions: H₂O₂ + M → 2OH + M (k₁) and OH + H₂O₂ → H₂O + HO₂ (k₂). With the addition of a third diagnostic for HO₂ at 227 nm, the H₂O₂ thermal decomposition system can be comprehensively characterized for the first time. Specifically, the rate constants of two remaining major reactions in the system, OH + HO₂ → H₂O + O₂ (k₃) and HO₂ + HO₂ → H₂O₂ + O₂ (k₄) can be determined with high-fidelity.No strong temperature dependency was found between 1072 and 1283 K for the rate constant of OH + HO₂ → H₂O + O₂, which can be expressed by the combination of two Arrhenius forms: k₃ = 7.0 × 10¹² exp(550/T) + 4.5 × 10¹⁴ exp(?5500/T) [cm³ mol^?1 s^?1]. The rate constants of reaction HO₂ + HO₂ → H₂O₂ + O₂ determined agree very well with those reported by Kappel et al. (2002) [5]; the recommendation therefore remains unchanged: k₄ = 1.0 × 10¹⁴ exp(?5556/T) + 1.9 × 10¹¹⁺exp(709/T) [cm³ mol^?1 s^?1]. All the tests were performed near 1.7 atm.