Preparation of Silica-Coated Lanthanum–Strontium Manganite Particles with Designable Curie Point, for Application in Hyperthermia Treatments

Silica-coated lanthanum–strontium manganite particles with La_0.76Sr_0.24MnO_3+δ stoichiometric formula, exhibiting Curie temperature at ∼40°C, were prepared by using a traditional solid-state method of synthesis of magnetic ceramic particles, followed by milling and a low-temperature coating procedure in an aqueous alcoholic alkali medium. The properties of the obtained material establish it as a potential candidate for self-regulated power-absorbing and temperature-controlling materials in hyperthermia treatments. Moreover, core-comprising LaSr–manganites with different stoichiometries, ranging from La_0.5Sr_0.5MnO_3+δ to LaMnO_3+δ, were synthesized, with magnetic and structural properties examined thereof. Herein reported findings can potentially be used in the preparation of silica-coated magnetic particles with designable Curie temperature, offering a wide range of possibilities of adapting the material to practical instrumental setups in drug delivery and hyperthermia treatments.     

Low-Temperature Synthesis and Properties of LaMnO3±d and La0.67R0.33MnO3±d (R = Ca, Sr, Ba) from Citrate Precursors

LaMn_{1− y} ³⁺Mn _y ⁴⁺O_3±d and La_0.67R_0.33Mn_{1− y} ³⁺Mn _y ⁴⁺O_3±d (R = Ca, Sr, Ba) phases were synthesized at 350°C by using very reactive, amorphous precursors obtained from the stoichiometric citrate solutions. The chemical process was optimized with respect to the solution concentration, pH, and additives. The precursor reactions were investigated as a function of the cation stoichiometry and the additive by simultaneous thermal and thermogravimetric analysis and X-ray diffraction. The reaction pathway was found to be independent of the cation stoichiometry, but related to the acid or base additive. The annealing temperature was systematically increased in the 350–1200°C interval and the La_0.67Sr_0.33MnO_3±d properties (i.e., crystal sizes, Mn average valence, Curie temperature, magnetization, magnetic susceptibility) were measured and found to vary consistently as a function of it.     

Reactions between Strontium-Substituted Lanthanum Manganite and Yttria-Stabilized Zirconia: I, Powder Samples

Sintered submicrometer powder mixtures of strontium-substituted lanthanum manganite and yttria-stabilized zirconia have been studied in order to investigate the chemical stability of these materials as respectively electrode and electrolyte in solid oxide fuel cells. Formation of secondary phases was observed after 1 h heat treatment at 1350°C and more than 13 h at 1200°C. La₂Zr₂O₇ was formed in mixtures with LaMnO₃ at 1350°C, while SrZrO₃ was formed in mixtures containing La_0.6Sr_0.4MnO₃ or La_0.4Sr_0.6MnO₃. Only minor amounts of secondary phases were observed in mixtures with La_0.7Sr_0.3MnO₃. Chemical analysis revealed considerable interdiffusion between the primary phases as well as A-site deficiency of LaMnO₃ and La_0.7Sr_0.3MnO₃ when exposed to cubic zirconia. The oxidative/reductive nature of the chemical reaction between strontium-substituted lanthanum manganite and yttria-stabilized zirconia is discussed in relation to the Sr content in LSM. The lattice parameter of cubic zirconia was observed to be quite sensitive to the interdiffusion and is an excellent tool for investigating reactions on heterophase interfaces involving stabilized zirconia.     

Chemical Preparation of Pure and Strontium- and/or Magnesium-Doped Lanthanum Gallate Powders

Powder compositions of LaGaO₃, La_0.9Sr_0.1GaO_2.95, and La_0.8Sr_0.2Ga_0.83Mg_0.17O_2.815 were prepared via a Pechini-type process that uses citric acid and ethylene glycol. The calcination behavior of the precursor powders of the above-mentioned phases was studied in the temperature range of 200°–1400°C in an air atmosphere. Characterization of the powder samples were performed using several processes, including X-ray diffractometry, thermogravimetry/differential thermal analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, inductively coupled plasma–atomic emission spectroscopy, and carbon and nitrogen analyses.     

Electrical Conduction Behavior of La1+xSr1−xGa3O7–δ Melilite-Type Ceramics

Ceramics of the melilite-type compound La_{1+ x} Sr_{1− x} Ga₃O_7−δ were prepared by conventional ceramic processing. Samples prepared represented the entire homogeneity region of the phase (i.e., x =−0.15 to 0.60). Electrochemical characterization under variable temperature and atmospheric conditions in the vicinity of air entailed four-point direct-current conductivity measurements and electromotive force measurements. La_{1+ x} Sr_{1− x} Ga₃O_7−δ samples exhibited a p -type behavior with generally increased conductivity with increased substitution of lanthanum for strontium, which reached a saturation value of ∼10⁻¹ S·cm⁻¹ at 950°C.     

Thermal Expansion Behavior of Titanium-Doped La(Sr)CrO3 Solid Oxide Fuel Cell Interconnects

La_0.8Sr_0.2Cr_0.9Ti_0.1O₃ perovskite has been designed as an interconnect material in high-temperature solid oxide fuel cells (SOFCs) because of its thermal expansion compatibility in both oxidizing and reducing atmospheres. La_0.8Sr_0.2Cr_0.9Ti_0.1O₃ shows a single phase with a hexagonal unit cell of a = 5.459(1) Å, c = 13.507(2) Å, Z = 6 and a space group of R -3 C . Average linear thermal expansion coefficients of this material in the temperature range from 50° to 1000°C were 10.4 × 10⁻⁶/°C in air, 10.5 × 10⁻⁶/°C under a He–H₂ atmosphere (oxygen partial pressure of 4 × 10⁻¹⁵ atm at 1000°C), and 10.9 × 10⁻⁶/°C in a H₂ atmosphere (oxygen partial pressure of 4 × 10⁻¹⁹ atm at 1000°C). La_0.8Sr_0.2Cr_0.9Ti_0.1O₃ perovskite with a linear thermal expansion in both oxidizing and reducing environments is a promising candidate material for an SOFC interconnect. However, there still remains an air-sintering problem to be solved in using this material as an SOFC interconnect.     

La(Sr)FeO3 SOFC Cathodes with Marginal Copper Doping

(La_0.8Sr_0.2)_0.98Fe_0.98Cu_0.02O_3−δ can be sintered directly onto YSZ (without the need for a protective ceria interlayer). Though subject to an extended "burn-in" period (∼200 h), anode-supported YSZ cells using the Cu-doped LSF achieve power densities ranging from 1.3 to 1.7 W/cm² at 750°C and 0.7 V. These cells have also demonstrated 500 h of stable performance. The results are somewhat surprising given that XRD indicates an interaction between (La_0.8Sr_0.2)_0.98Fe_0.98-Cu_0.02O_3−δ and YSZ resulting in the formation of strontium zirconate and/or monoclinic zirconia. The amount and type of reaction product was found to be dependent on cathode and electrolyte powder precalcination temperatures.     

Preparation of Yttria-Stabilized Zirconia Thin Films on Strontium-Doped LaMnO3 Cathode Substrates via Electrophoretic Deposition for Solid Oxide Fuel Cells

A yttria-stabilized zirconia (YSZ) thin film on an La_0.8Sr_0.2MnO₃ porous cathode substrate was prepared, using electrophoretic deposition (EPD) to fabricate a solid oxide fuel cell (SOFC). The electrical conductivity of an La_0.8Sr_0.2MnO₃ substrate is satisfactorily high at room temperature; therefore, YSZ powder could be deposited electrophoretically onto an La_0.8Sr_0.2MnO₃ substrate without any extra surface treatment, such as a metal coating. Successive repetition of EPD and sintering was required to obtain a film without gas leakage, because of the thermal expansion coefficient mismatch between the YSZ and the La_0.8Sr_0.2MnO₃ substrate. On the other hand, the electromotive force of the oxygen concentration in the cell that used YSZ film prepared via EPD increased and attained the theoretical value when the number of deposition and calcination cycles was increased. Six or more successive repetitions were required to obtain a YSZ film without gas leakage. A planar-type SOFC was fabricated, using nickel as the anode and YSZ film (∼10 μm thick) that had been deposited onto the La_0.8Sr_0.2MnO₃ substrate as the electrolyte and cathode. The cell exhibited an open circuit voltage of 1.0 V and a maximum power density of 1.5 W/cm². Thus, the EPD method could be used as a colloidal process to prepare YSZ thin-film electrolytes for SOFCs.     

Homogeneity Region of Strontium- and Magnesium-Containing LaGaO3 at Temperatures between 1100° and 1500°C in Air

Phase stability studies were performed within the quasi-ternary system LaGaO₃-SrGaO_2.5-"LaMgO_2.5". Emphasis was cast on the temperature dependence of the homogeneity region of La_{1− x} Sr _x Ga_{1− y} Mg _y O_3−δ perovskite solid solutions. Isothermal sections were determined at 1100°, 1250°, 1400°, and 1500°C in a static air atmosphere. The single-phase homogeneity region was found to considerably diminish with decreasing temperature, indicating a reduction of the solid solubility of Sr and Mg, and below 1100°C the doped perovskite becomes unstable. Consequently, the cubic perovskite phase was found to exist only at elevated temperatures and for high Sr and Mg amounts. Sample preparation was performed by the mixed-oxide process as well as by a modified combustion synthesis.     

Two-Dimensional Modeling of Self-Propagating High-Temperature Synthesis of Strontium-Doped Lanthanum Manganate

A two-dimensional finite element model is developed to study the reaction kinetics and heat transfer during the self-propagating high-temperature synthesis of La_0.6Sr_0.4MnO₃, a cathode and interconnect material used in solid oxide fuel cells. The activation energy of La_0.6Sr_0.4MnO₃ formation was calculated from experimental temperature history. The calculated spatial-temporal temperature profile, heat generation rate, reaction conversion, and flow pattern of surrounding gas during the reaction are reported in this work. Hot spots are found at the corner near the ignition point shortly after the ignition. The model provided a simple and reliable way to design a large-scale production of La_0.6Sr_0.4MnO₃.     

Reactions between Strontium-Substituted Lanthanum Manganite and Yttria-Stabilized Zirconia: II, Diffusion Couples

Formation of secondary phases and diffusion of cations in diffusion couples of yttria-stabilized zirconia and lanthanum manganite substituted with 0 to 60 mol% strontium have been studied by scanning electron microscopy and energy dispersive X-ray spectroscopy. Only the primary phases were observed after 120 h at 1200°C, while formation of secondary phases was identified already after 1 h heat treatment at 1350°C. The phase composition of the reaction layer altered from La₂Zr₂O₇ to SrZrO₃ at increasing Sr content in La _x Sr_{1- x} MnO₃. The thickness of the reaction layer was increasing with heat treatment time. In diffusion couples of La_0.4Sr_0.6MnO₃ formation of manganese oxide was observed in the perovskite layer after 1 h heat treatment at 1350°C, while isolated grains of SrZrO₃ relatively deep inside the zirconia were observed after longer heat treatment time. Diffusion of Mn into zirconia was observed preferenced along grain boundaries in the early stage of the interface reaction.     

Enhanced Shrinkage of Lanthanum Strontium Manganite (La0.90Sr0.10MnO3+δ) Resulting from Thermal and Oxygen Partial Pressure Cycling

Exposure of (La_0.90Sr_0.10)_0.98MnO_3+δ (LSM-10) to repeated oxygen partial pressure cycles (air/10 ppm O₂) resulted in enhanced densification rates, similar to behavior shown previously due to thermal cycling. Shrinkage rates in the temperature range 700°–1000°C were orders of magnitude higher than Makipirtti–Meng model estimations based on stepwise isothermal dilatometry results at a high temperature. A maximum in enhanced shrinkage due to oxygen partial pressure cycling occurred at 900°C. Shrinkage was the greatest when LSM-10 bars that were first equilibrated in air were exposed to gas flows of lower oxygen fugacity than in the reverse direction. The former creates transient cation and oxygen vacancies well above the equilibrium concentration, resulting in enhanced mobility. These vacancies annihilate as Schottky equilibria are reestablished, whereas the latter condition does not lead to excess vacancy concentrations.     

30 kbar Phase Equilibria of the La2O3–SrO–CuO System at 950°C

Phase equilibria of the La₂O₃–SrO–CuO system have been determined at 950°C at 30 kbar (3 GPa). Stable phases at the apexes of the ternary phase diagram are CuO, La₂O₃, and SrO. Stable intermediate phases are La₂, CuO₄ and La₂Cu₂O₅ in the LaO_1.5–CuO binary and Sr₂CuO₃, SrCuO₂, and Sr₁₄Cu₂₄O₄₁ in the CuO–SrO binary. The La_{2– x} Sr _x -CuO_4–δ solid solution is stable for 0.00 is ≤ x ≤ 1.29, the La_{2– x} Sr_{1+ x} Cu₂O_6+δ solid solution is stable for 0.03 ≤ x ≤0.20, the La_{2– x} Sr _x Cu₂O_5–δ solid solution is stable for 0.00 ≤ x ≤1.08, and the La _x Sr_{14– x} Cu₂₄O₄₁ solid solution is stable for 0.00 ≤ x ≤ 6.15. The 30 kbar phase diagram differs from the 1 atm (0.1 MPa) and 10 kbar (1 GPa) results principally in the absence of La_{1– x} Sr_{2+ x} Cu₂O_5.5+δ as a stable phase and the extended range of the La_{2– x} Sr _x Cu₂O_5–δ solid solution at 30 kbar.     

Structural Analysis of a New Layered Compound: La0.05Sr0.95MnO3

We have found a new phase of La_0.05Sr_0.95MnO₃ with a 30-layer rhombohedral structure by using electron microscopy. The lattice constants were hexagonal axes of a = 0.5444 nm and c = 6.7582 nm. Both weak and strong intensities appeared in selected area diffraction (SAD) patterns. The strong intensities were caused by the periodicity of 15 (Sr,La)O₃ layers that had a new stacking sequence of (cchch)₃. However, the weak intensities indicated that the 15-layer structure has modulation along the c -direction that is twice as long as that of the structure indicated by the strong intensities. We concluded that the modulation of the 30-layer structure was produced by the introduction of two kinds of oxygen octahedra, Mn³⁺O₆ and Mn⁴⁺O₆.     

Phase Equilibria of the La2O3-SrO-CuO System at 950°C and 10 kbar

Phase equilibria of the La₂O₃-SrO-CuO system have been determined at 950°C and 10 kbar (1 GPa). Stable phases at the apices of the ternary phase diagram are CuO, La₂O₃, and SrO. Stable intermediate phases are La₂CuO₄ in the LaO_1.5-CuO binary and Sr₂CuO₃, SrCuO₂, and Sr₁₄Cu₂₄O₄₁ in the CuO-SrO binary. The La_2-xSr _x CuO_4-δ solid solution is stable where 0.0 ≤ x ≤ 1.3, the La_2-xSr_1+xCu₂O_6+δ solid solution is stable where 0.0 ≤ x ≤ 0.2, the La_8-xSr _x Cu₈O_20-δ solid solution is stable where 1.3 ≤ x ≤ 2.7, the La _x Sr_14-x-Cu₂₄O₄₁ solid solution is stable where 0 ≤ x ≤ 6, and the La_1+xSr_2-xCu₂O_5.5+δ phase is stable where 0.04 ≤ x ≤ 0.16. The La₂O₃-SrO-CuO phase diagram at 950°C and 10 kbar is almost identical to that determined by other authors at 950°C and 1 atm, in terms of phase stability and solid-solution ranges.     

Oxidation Resistance Coating of LSM and LSCF on SOFC Metallic Interconnects by the Aerosol Deposition Process

Conductive La_0.8Sr_0.2MnO₃ (LSM) and La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) layers with a thickness of ∼10 μm were deposited on ferritic stainless steel (SS) by the aerosol deposition method, for use as an oxidation resistance-coating layer in the metallic interconnector of a solid oxide fuel cell. The coated layers were fairly dense without pores or cracks, and maintained good adhesion even after oxidation at 800°C for 100 h. The surface of the bare SS after annealing at 800°C for 100 h was covered with Cr₂O₃ and Fe₃O₄ oxide scales, and the electrical conductivity was sharply decreased. However, the LSM- and LSCF-coated SSs showed a surface microstructure with almost no oxidation and maintained good electrical conductivity after annealing at 800°C for 100 h. The area-specific resistance (ASR) of LSM- and LSCF-coated alloys after 100 h of oxidation at 800°C was 20.6 and 11.7 mΩ·cm², respectively.     

Novel Design of Microchanneled Tubular Solid Oxide Fuel Cells and Synthesis Using a Multipass Extrusion Process

A novel, microchanneled tubular solid oxide fuel cell was fabricated using a multipass extrusion process, with an outside diameter of 2.7 mm that contained 61 cells. Cell materials used in this work were 8 mol% yttria-stabilized zirconia (8YSZ), La_0.8Sr_0.2MnO₃ (LSM), and NiO–8YSZ (50:50 vol%) as electrolyte, cathode, and anode, respectively. Three stages of heat-treatment processes were applied, at 700°C in N₂ condition, at 1000°C in air, and then sintered at 1300°C for 2 h, respectively. The X-ray diffraction analysis confirmed that no reaction phases appeared after sintering. The microstructures of anode and cathode were fairly porous while the electrolyte had a dense microstructure (relative density >96%). The thickness of electrolyte, anode, and cathode were 20, 30, and 40 μm, respectively, and the diameter of the continuous channels was 150 μm.     

Thin Yttrium-Stabilized Zirconia Electrolyte Solid Oxide Fuel Cells by Centrifugal Casting

A centrifugal casting technique was developed for depositing thin 8-mol%-yttrium-stabilized zirconia (YSZ) electrolyte layers on porous NiO-YSZ anode substrates. After the bilayers were cosintered at 1400°C, dense pinhole-free YSZ coatings with thicknesses of ∼25 μm were obtained, while the Ni-YSZ retained porosity. After La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF)-Ce_0.9Gd_0.1O_1.95 (GDC) or La_0.8Sr_0.2MnO₃ (LSM)-YSZ cathodes were deposited, single SOFCs produced near-theoretical open-circuit voltages and power densities of ∼1 W/cm² at 800°C. Impedance spectra measured during cell tests showed that polarization resistances accounted for ∼70%–80% of the total cell resistance.     

Structure and Magnetic Properties of La0.7Ca0.3MnO3−δ for (3 −δ) < 3.0

Annealing studies were conducted on bulk La_0.7Ca_0.3MnO_3−δ to determine the sensitivity of its structural and magnetic properties to oxygenation conditions. Standard bulk sintering conditions, thin-film annealing conditions for obtaining good magnetoresistive properties, and a reducing anneal, which corresponded to the onset of phase decomposition, were conducted. The main phase formed was a face-centered (fcc) pseudocubic double-perovskite structure, with cell parameters of a ∼ 2 a _p∼ 0.772 nm, where a _p is the single-perovskite cubic cell parameter. A minor superstructure—body-centered pseudotetragonal, with lattice parameters of c = 4 a _p and a =√2 a _p—was observed in samples with (3 −δ) < 3. A maximum of 20% of the superstructure was formed using the most-reducing conditions. The superstructure had a lower critical temperature than the main phase and depressed ferromagnetic order.     

Mechanism of Reaction between Lanthanum Manganite and Yttria-Stabilized Zirconia

The reaction of La_{1- x} Ca _x MnO₃ ( x = 0, 0.1, 0.2) with ZrO₂-8 mol% Y₂O₃ (YSZ) has been investigated at temperatures ranging from 1300° to 1425°C in air. Substitution of Ca for La in LaMnO₃ depresses the reactivity with YSZ. A layer of La₂Zr₂O₇ is formed at the La_{1- x} Ca _x MnO₃/YSZ interface after an induction period, and its formation is accelerated when the La_{1- x} Ca _x MnO₃ phase is porous. The reaction proceeds by unidirectional diffusion of La, Mn, and/or Ca ions, mainly Mn ions, into YSZ. The diffusion coefficients of La and Mn ions in YSZ, which are estimated using a LaMnO₃/single-crystal YSZ couple, are much lower than that of oxygen ion. From the experimental data, a reaction mechanism is proposed.