Order parameters in lanthanum gallate lightly doped with manganese and paramagnetic resonance

The Cr³⁺ centers have been revealed, transitions at room temperature have been identified, and spin Hamiltonian parameters have been determined for the Cr³⁺ and Fe³⁺ triclinic centers in lanthanum gallate lightly doped with manganese. The principal axes of the fourth-rank fine-structure tensor for the Fe³⁺ triclinic centers have been established and used to determine the order parameters, i.e., the angles of rotation of oxygen octahedra of lanthanum gallate with respect to the perovskite structure. The order parameter in the rhombohedral phase has been estimated.     

An intermediate temperature solid oxide fuel cell utilizing superior oxide ion conducting electrolyte, doubly doped LaGaO3 perovskite

LaGaO₃-based perovskite oxide doped with Sr and Mg exhibits high ionic conduction over a wide oxygen partial pressure. In this study, the stability of the LaGaO₃ based oxide was investigated. It became clear that LaGaO₃ based oxide is very stable for reduction and oxidation. SOFCs utilizing LaGaO₃-based perovskite type oxide for electrolyte were further studied for the decreased temperature solid oxide fuel cells. The power generation characteristics of cells were strongly affected by the electrode, both anode and cathode. It became clear that Ni and LnCoO₃ (Ln: rare earth) are suitable for anode and cathode, respectively. Rare earth cations in the Ln-site of Co-based perovskite cathode also have a great effect on the power generation characteristics. In particular, high power density could be attained in the temperature range from 973 to 1273 K by using doped SmCoO₃ for the cathode. The electrical conductivity of SmCoO₃ increases with increasing Sr amount doped for the Sm site and attained the maximum at Sm_0.5Sr_0.5CoO₃. The cathodic overpotential and the internal cell resistance exhibit almost opposite dependence on the amount of doped Sr. Consequently, the power density of the cell reaches a maximum when Sm_0.5Sr_0.5CoO₃ is used for cathode. On this cell, the maximum power density is as high as 0.58 W/cm² at 1073 K, although a 0.5 mm thick electrolyte is used. Therefore, this study reveals that the LaGaO₃ based oxide for electrolyte and the SmCoO₃ based oxide for cathode are promising for solid oxide fuel cells at intermediate temperature. Paper presented at the 97th Xiangshan Science Conference on New Solid State Fuel Cells, Xiangshan, Beijing, China, June, 14–17, 1998.     

Electrical conductivity of Co doped cuprous oxide

The solubility limit of metals in cuprous oxide is very low and it is therefore difficult to form solid solutions of metal oxides with cuprous oxide. In an on going research looking for such solid solutions and their properties we have prepared Co doped Cu₂O. We report here on measurements of the electrical conductivity of Co doped Cu₂O as a function of the oxygen partial pressure. It is found that Co doped material is an n-type semiconductor in the low oxygen partial pressure regime and p-type at higher oxygen pressures (while undoped Cu₂O is a p-type material throughout the whole existence regime). A point defect model is discussed. The ionic transference number is also measured and is found to be less than 2⋅10⁻⁴. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

High oxide ion conductivity in Fe and Mg doped LaGaO3 as the electrolyte of solid oxide fuel cells

La(Sr)Ga(Fe,Mg)O₃ exhibited the high oxide ion conductivity and the electrical power generating property of SOFC single cell using La_0.7Sr_0.3Ga_0.7Fe_0.2Mg_0.1O_3-δ (LSGFM) electrolyte was investigated in this study. The transport number of oxide ion is almost 0.8 in LSGFM and so open circuit potential (OCV) is as low as 0.8 V. OCV was strongly affected by anode materials and the highest OCV was achieved on Ni–Fe bimetallic anode. The extremely high power density was achieved by using LSGFM for electrolyte of SOFC. The maximum power densities of the cells can be elevated by coating with oxide ion conductor film at anode side. The maximum power density increased in the following order for coating film: LSGM > SDC > YSZ. The maximum power density of 197 and 100 mW/cm² can be achieved at 873 and 773 K, respectively, when LSGM film deposited on the anode side of LSGFM. Therefore, LSGFM can be used as electrolyte of SOFC operating at intermediate temperature.     

Dielectric relaxation and ac conductivity of double perovskite oxide Ho2ZnZrO6

Double perovskite oxide holmium zinc zirconate Ho₂ZnZrO₆ (HZZ) is synthesized by solid state reaction technique under a calcination temperature of 1100 °C. The crystal structure has been determined by powder X-ray diffraction, which shows monoclinic phase at room temperature. The variation of dielectric constant (ε′) and loss tangent (tan δ) with frequency is carried out assuming a distribution of relaxation times. The frequency corresponding to loss tangent peak is found to obey an Arrhenius law with activation energy of 89.7 meV. The frequency-dependant electrical data are analyzed in the framework of conductivity and electric modulus formalisms. Both these formalisms show qualitative similarities in relaxation times. The scaling behaviour of imaginary electric modulus shows the temperature-independent nature of the distribution of relaxation times. Nyquist plots are drawn to identify an equivalent circuit and to know the bulk and interface contributions.     

Investigations on thermoelectric power of lanthanum oxide doped ferroelectric sodium vanadate

The thermoelectric power of ferroelectric sodium vanadate doped with different concentrations of lanthanum oxide has been measured in the temperature range covering their transition temperatures. It has been observed that the thermoelectric power increases with temperature, attains maximum value and with further increase in the temperature decreases to zero, indicating Curie temperature of the respective samples; however, it changes the sign for higher temperature. The thermoelectric power of sodium vanadate increases to maximum with increase in doping concentration of lanthanum oxide from 0.025 to 0.1 mol%; however, it decreases for higher concentrations. Pure as well as lanthanum oxide doped sodium vanadate samples showp-type behaviour in the ferroelectric region andn-type behaviour in the paraelectric region.     

Cooperative up-conversion luminescence of ytterbium doped yttrium lanthanum oxide transparent ceramic

The up-conversion luminescence of Yb³⁺-doped yttrium lanthanum oxide transparent ceramic was investigated. It was ascribed to cooperative luminescence originated from the coupled states of the Yb³⁺ ion pairs. The proper doping of La₂O₃ can remove the cooperative luminescence of Yb³⁺ ion. But excessive La₂O₃ (at least 10 at.%) the cooperative up-conversion of Yb³⁺:Y₂O₃ is obtained again, and the intensity of up-conversion luminescence strengthens with the increase of La₂O₃ content.     

A study of oxygen ion conductivity in doped non-stoichiometric oxides

In doped non-stoichiometric oxides that show oxygen ion conductivity, association commonly takes place between the dopant cations and the compensating oxygen vacancies. The activation energy thus comprises two parts, a migration enthalpy and an association enthalpy. We have determined the effects of structure and host cation type on the migration enthalpies, and the effect of dopant cation size on the association enthalpies. This we did by a variety of methods including theoretical calculations and experiment. We have further reviewed the literature in order to verify our calculations and we conclude that size terms in the association enthalpies are the most important factor in the determination of the magnitude of oxygen ion conduction.     

Reduced conductivity and enhancement of Debye orientational polarization in lanthanum doped cobalt ferrite nanoparticles

In this work we have investigated the conductivity and dielectric properties of CoLa_xFe_2−xO₄ (x=0.0, 0.03, 0.05, and 0.07) nanoparticles synthesized by chemical co-precipitation route. X-ray diffraction analysis confirms the inverse spinal structure of nanoparticles with slight increase in the lattice constant as La concentration increases. Transmission electron microscopy shows spherical nanoparticles with sizes of ∼20 nm. Impedance spectroscopy of the samples was performed in the frequency range 20 Hz-2 MHz at room temperature. The resistance of the grains and grain boundaries was found to increase with lanthanum concentration while the AC conductivity of the samples was observed to decrease with increasing La concentration. Dipolar orientational polarization was found to play an important role in determining dielectric properties of the samples.     

Thermal conductivity of silver doped lanthanum manganites between 10 and 300 K

Thermal conductivity (λ) of nanocrystalline La_1−xAg_xMnO₃ (x=0.05, 0.15, 0.25, 0.3) pellets prepared by pyrophoric method is reported between 10 and 300 K. Magnitude of thermal conductivity has been found to be strongly influenced by monovalent (Ag) substitution at the La site. Silver doping in LaMnO₃ enhances T_C of the system to ∼299 K. Qualitative nature of the temperature variation of thermal conductivity of the silver substituted lanthanum manganites remains closely similar to that for divalent doped systems. Our analysis demonstrates that in La_1−xAg_xMnO₃ also, the mechanism of heat conduction is predominantly by phonons. The contribution of the electronic part is only ∼1% of the total λ. The spin wave contribution is also estimated close to T_C, which for all the samples lies within ∼2%. At temperatures below ∼100 K, the measured data have been analyzed using phonon relaxation time method and the strengths of the various phonon scattering processes have been estimated. Our analysis further suggests strong influence of phonon scattering by 2D like defects in the thermal conductivity of monovalent doped lanthanum manganites at low temperatures (<70 K) in the ferromagnetic region.     

Paramagnetic centers in two phases of manganese-doped lanthanum gallate

An EPR study of two phases of manganese-doped lanthanum gallate (with a first-order structural transition occurring at 430 K) has revealed Gd³⁺, Fe³⁺, and Mn⁴⁺ centers at room temperature and 438 K. The parameters of spin Hamiltonians are determined for the Gd³⁺, Fe³⁺, and Mn⁴⁺ rhombohedral centers in the high-temperature phase (with no other centers found here) and for the monoclinic center Gd³⁺ in the low-temperature phase. Both in the orthorhombic and in the rhombohedral phase, crystallographic twins (or ferroelastic domains) are observed.     

Nd3+离子掺杂氧化物玻璃的光谱性质

高温熔融法制备了69.5B2O3-20Li2O-(10-χ)CaO-χPbO-0.5Nd2O3(χ=1,3,5,7,mol%)和68.5Li2O-(29-φ)CaO-φAl2O3-2La2O3-0.5Nd2O3(φ=3,7,10,15,mol%)玻璃,测量了玻璃样品的吸收和发射光谱(800nm激光二极管激发),从吸收光谱出发,应用Judd-Ofelt理论获得了Nd3+光学跃起的强度参数。根据强度参数和发射光谱,计算了Nd3+离子4F3/2→4I11/2跃迁的荧光发射截面σe。结果显示,在B2O3-Li2O-CaO-PbO-Nd2O3系统中随着CaO的减少和PbO的增加,Nd3+离子的强度参数Ω2增大,表明样品的对称性降低;强度参数Ω6也增大,说明玻璃样品中Nd-O键的共价性和键强降低;同时,Nd3+离子4F3/2→4I11/2跃迁的荧光发射截面σe的大小和荧光强度都减小。在Li2O-CaO-Al2O3-La2O3-Nd2O3系统中,随着CaO的减少和Al2O3的增加,Nd3+离子的强度参数Ω2减小,说明样品的对称性增加;强度参数Ω6减小,说明玻璃样品中Nd-O键的共价性和键强增强;同时,Nd3+离子4F3/2→4I11/2跃迁的荧光发射截面的大小和荧光强度也都减小。     

Spectral properties of Ce3+ doped yttrium lanthanum oxide transparent ceramics

Ce3+-doped yttrium lanthanum oxide (Y0.9La0.1)2O3 transparent ceramics is fabricated with nanopowders and sintered in H2 atmosphere. The spectral properties of Ce:(Y0.9La0.1)2O3 transparent ceramics are investigated. There appear two characteristic absorption peaks of Ce3+ ions at 230 nm and 400 nm, separately. It is found that Ce3+ ions can efficiently produce emission at 384 nm from (Y0.9La0.1)2O3 transparent ceramic host, while the emission is completely quenched in Re2O3 (Re=Y, Lu, La) host materials.     

Study of oxygen ion transport in acceptor doped samarium cobalt oxide

Dense samples of the perovskite Sm_1−xSr_xCoO₃ (where x=0, 0.2, 0.4, 0.5 and 0.6) have been prepared. The samples were¹⁸O/¹⁶O isotopically exchanged at a variety of temperatures between 500°C and 900°C. Subsequent analysis of the diffusion profile using Secondary Ion Mass Spectrometry (SIMS) allowed the oxygen self-diffusion coefficient, D*, and surface exchange co-efficient, k, to be determined. From the temperature dependence of these parameters the activation energies for both processes were evaluated. The surface coverage of samarium, cobalt and oxygen in SmCoO₃ was determined from calibration samples using Low Energy Ion Scattering (LEIS). LEIS was used to determine the effect of strontium doping on the surface composition and the¹⁸O-concentration at the surface of a number of the¹⁸O-exchanged samples. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11 – 18 Sept. 1994.     

Mixed conducting perovskite-like ceramics on the base of lanthanum gallate

Ceramic perovskite solid solutions (La_0.9Sr_0.1)[(Ga_1−xM_x)_0.8Mg_0.2]O_3−y, 0 ≤ x ≤ 0.5, M = Fe, Ni, Cr (systems I–III) and brownmillerite solid solutions (La_0.2Sr_1.8)[Ga(Fe_1−xMg_x)]O_5−z, 0 ≤ x ≤ 0.5, (system IV) have been prepared. The samples have been studied by X-ray diffraction and electron microscopy methods, dielectric spectroscopy and permeability measurements. The correlation between the composition, unit cell parameter changes, electrical transport and oxygen permeation properties has been revealed. Introduction of transition metals (Fe, Ni, or Cr), substituting for gallium, ensures the enhancement of the electronic constituent of the conductivity in the perovskite systems I–III. Stabilization of the transition metal high valence states 4+ or 5+ has been suggested for compositions I and III. This leads to a unit cell volume contraction and provides a decrease in the concentration of oxygen vacancies. The oxygen permeability reaches its maximum values in compositions I–III with x ∼ 0.3. On the contrary, increasing concentration of the doping element with lower valence state (magnesium), substituting for iron, determines the expansion of the brownmillerite unit cell volume and provides an increase of the oxygen vacancy concentration, which in turn, favors the enhancement of oxygen permeability of composition IV.     

Oxygen ion conductivity of yttria-niobia mixed oxide with fluoride related structure

The oxygen ion conductivity of Y₂O₃---Nb₂O₅ with a fluorite-like structure was studied. Substitutional solid solutions of Nb₂ O₅ in Y₂O₃ lattice formed the defect fluorite phase and remarkably enhanced the oxygen ion conductivity. Doping with tetravalent cations, especially Ti⁴⁺ or Ce⁴⁺, in yttria-niobia oxide is effective in enhancing the oxygen ion conductivity. Although the n-type semiconducting property appeared below P_O2 = 10⁻¹⁸ atm at 1243 K, the yttria-niobia mixed oxide doped with Ce⁴⁺, Ti⁴⁺, and Zr⁴⁺ stably exhibited oxygen-ion conduction in the wide range of oxygen partial pressures studied.     

Mixed conductivity and oxygen permeability of doped Pr2NiO4-based oxide

Pr₂NiO₄-based oxide was studied as a new mixed electronic and oxide ionic conductor for the oxygen permeation membrane. It was found that Pr₂NiO₄ doped with Cu and Fe for Ni site exhibits the relatively high oxygen permeation rate. Doping second cation to Ni site is effective for improving the oxygen permeation rate and the trivalent cation seems to be effective for increasing the oxygen permeation rate. Among the examined cation, the highest oxygen permeation rate was obtained by doping 5 mol% Fe. The oxygen permeation rate was also significantly affected by the surface catalyst and the highest oxygen permeation rate of 80 μmol·min^− 1·cm^− 2 at 1273 K was achieved by using La_0.1Sr_0.9Co_0.9Fe_0.1O₃ for the surface catalyst. Since the electrical conductivity slightly decreased with decreasing P_O2 and it dropped significantly at P_O2 = 10^− 19 atm, chemical stability of Pr₂NiO₄-based oxide seems to be reasonably high. Application of this new mixed conductor for the oxygen permeation membrane under the CH₄ partial oxidation was also studied and it was confirmed that the oxygen permeation rate much improved under the CH₄ oxidation condition and this Pr₂NiO₄ can be used for the oxygen permeation membrane for the CH₄ partial oxidation.     

A new analytical device incorporating a nitrogen doped lanthanum metal oxide with reduced graphene oxide sheets for paracetamol sensing

The novel N-CeO₂ nanoparticles decorated on reduced graphene oxide (N-CeO₂@rGO) composite has been synthesized by sonochemical method. The characterization of as prepared nanocomposite was intensely performed by UV–Vis, FT-IR, EDX, FE-SEM, HR-TEM, XRD, and TGA analysis. The synthesized nanomaterial was further investigated for its selective and sensitive sensing of paracetamol (PM) based on a N-CeO₂@rGO modified glassy carbon electrode. A distinct and improved reversible redox peak of PM is obtained at N-CeO₂@rGO nanocomposite compared to the electrodes modified with N-CeO₂ and rGO. It displays a very good performance with a wide linear range of 0.05–0.600 μM, a very low detection limit of 0.0098 μM (S/N = 3), a high sensitivity of 268 μA µM⁻¹ cm⁻² and short response time (<3 s). Also, the fabricated sensor shows a good sensibleness for the detection of PM in various tablet samples.     

Magnetoresistance of lanthanum manganites with activation-type conductivity

The temperature dependence of the resistivity and magnetic moment of La_0.85Ba_0.15MnO₃ and La_0.85Sr_0.15MnO₃ manganite single crystals in magnetic fields up to 90 kOe is investigated. Analysis of the experimental results shows that the magnetoresistance of lanthanum manganites far from the Curie temperature T _C can be described quantitatively by the s-d model normally used for ferromagnets and taking into account only the exchange interaction between the spins of charge carriers and magnetic moments. These data also show that the features of lanthanum manganites responsible for colossal magnetoresistance (CMR) are manifested in a narrow temperature interval δT ≈ 20 K near T _C. Our results suggest a CMR mechanism analogous to the mechanism of giant magnetoresistance (GMR) observed in Fe/Cr-type multilayers with nanometer layer thickness. The nanostratification observed in lanthanum manganites and required for GMR can be described taking into account the spread in T _C in the CMR range δT.