Trace and surface analysis of ceramic layers of solid oxide fuel cells by mass spectrometry

For the trace analysis of impurities in thick ceramic layers of a solid oxide fuel cell (SOFC) sensitive solid-state mass spectrometric methods, such as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and radiofrequency glow discharge mass spectrometry (rf-GDMS) have been developed and used. In order to quantify the analytical results of LA-ICP-MS, the relative sensitivity coefficients of elements in a La_0.6Sr_0.35MnO₃ matrix have been determined using synthetic standards. Secondary ion mass spectrometry (SIMS) – as a surface analytical method – has been used to characterize the element distribution and diffusion profiles of matrix elements on the interface of a perovskite/Y-stabilized ZrO₂ layer. The application of different mass spectrometric methods for process control in the preparation of ceramic layers for the SOFC is described.     

Mass spectrometric analysis of ceramic components for solid oxide fuel cells

For the determination of trace impurities in ceramic components of solid oxide fuel cells (SOFCs), some mass spectrometric methods have been applied such as spark source mass spectrometry (SSMS), laser ionization mass spectrometry (LIMS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and inductively coupled plasma mass spectrometry (ICP-MS). Due to a lack of suitable standard reference materials for quantifying of analytical results on La _x Sr _y MnO₃ cathode material a matrix-matched synthetic standard-high purity initial compounds doped with trace elements-was prepared in order to determine the relative sensitivity coefficients in SSMS and LA-ICP-MS. Radiofrequency glow discharge mass spectrometry (rf-GDMS) was developed for trace analysis and depth profiling of thick non-conducting layers. Surface analytical techniques, such as secondary ion mass spectrometry (SIMS) and sputtered neutral mass spectrometry (SNMS), were used to determine the element distribution on surfaces (homogeneity) and the surface contaminants of SOFC ceramic layers.Dedicated to Professor Dr. rer. nat. Hubertus Nickel on the occasion of his 65th birthday     

Magnetocapacitance and impedance spectroscopy of Ba0.7Sr0.3TiO3/La0.67Sr0.33MnO3 and Ba0.8Sr0.2TiO3/La0.67Sr0.33MnO3 thin film heterostructures

The paper discuses synthesis of Ba_0.7Sr_0.3TiO₃/La_0.67Sr_0.33MnO₃ and Ba_0.8Sr_0.2TiO₃/La_0.67Sr_0.33MnO₃ thin film heterostructures by sol–gel (citrate gel route) method. The XRD spectra are determined for confirmation of crystalline phases of Ba_0.7Sr_0.3TiO₃, Ba_0.8Sr_0.2TiO₃ and La_0.67Sr_0.33MnO₃ thin films. The observed variation of Cp, tan δ, magnetocapacitance (Mc), real part of dielectric constant ε′, imaginary part of dielectric constant ε″as a function of frequency, magnetoresistance R(H) and magnetoimpedance Z(H) are presented in the paper. Further the observed impedance spectra as a function of frequency f is also presented in the paper. The observed variation of Mc is qualitatively correlated with the stress induced effect and magnetoresistasnce effect occurring simultaneously.     

Synthesis of rod-shaped La0.7Sr0.3MnO3 by a simple solid state ceramic route

The manganese oxides La_0.7Sr_0.3MnO₃ with rod shape have been synthesized by a simple solid state ceramic method. The morphology and magnetic properties of La_0.7Sr_0.3MnO₃ have been studied by XRD, SEM, TEM and VSM. The diameters of rod-shaped oxide were ranging from 180 nm to1.5 μm and the length was averaging 20 μm. The ratio of length to diameter could reach more than 35:1. The magnetic results showed that the Curie temperature of rod-shaped La_0.7Sr_0.3MnO₃ is far lower than single crystal.     

The Reactivity of Manganites in 18O Isotope Exchange Reactions

The effect of the structural properties and the oxidation state of Mn on the ¹⁸O isotope exchange behaviour of ternary manganites (La_1–xSr_xMnO₃, La_0.5Sr_1.5MnO₄ and SrMnO₃) has been studied. All types of ¹⁸O isotope exchange homomolecular, partially and completely heteromolecular) take place on the very active manganites with perovskite (LaMnO₃ and La_0.7Sr_0.3MnO₃) and perovskite-like (SrMnO₃) structure, but not on the less active K₂NiF₄-structure (La_0.5Sr_1.5MnO₄). The highest ¹⁸O exchange activity is observed for La_0.7Sr_0.3MnO₃, for which the completely heteromolecular ¹⁸O exchange starts to occur at 520 K, already, a T_on which is typical for excellent redox catalysts. The influence of the structural properties on the ¹⁸O exchange and oxygen diffusion behaviour of the manganites is much more pronounced than that of the Mn³⁺/Mn⁴⁺ ratio. The different reduction behaviour of the manganites with perovskite and K₂NiF₄-structure can be explained by means of the bond-valence model.This revised version was published online in November 2005 with corrections to the Cover Date.     

Exoemission near phase transitions of epitaxial films of manganites with colossal magnetic resistance

Intense exoemission near phase transitions of epitaxial films of the La_0.16Sr_0.84MnO₃ and La_0.35Pr_0.35Sr_0.3MnO₃, manganites, which exhibit the colossal magnetic resistance (CMR), is detected in a wide temperature range from 278 to 623 K including the Curie temperature. The role of the absorbed and lattice oxygen in the exoemission and CMR phenomena is discussed. The aftereffect of the magnetic field directed along the film plane on the intensity of photostimulated exoemission is discussed.     

PREPARATION AND CATALYTIC PERFORMANCE OF La0.5RE0.1Sr0.4MnO3 (RE: Y, Dy, Sm OR Ce) ULTRA-FINE PARTICLES in METHANE COMBUSTION

Ultra-fine particles of La_0.5RE_0.1Sr_0.4MnO₃ (RE: Y, Dy, Sm or Ce) with perovskite structure were prepared by the co-precipitation method, resulting in high surface area and good thermal stability catalysts (S_BET reached 45 and 16.5 m²/g, upon calcination at 700 and 1000^oC, respectively). The thermal stability of these ultra-fine particles was effectively improved with partial substitution of RE³⁺ (Y³⁺, Dy³⁺, or Sm³⁺) for La³⁺ in La_0.6Sr_0.4MnO₃. The catalysts exhibited high activity for the total combustion of methane. For the catalysts calcined at 1000^oC, La_0.5RE_0.1Sr_0.4MnO₃ (RE: Y or Dy) were much more active and showed much higher specific surface area than La_0.6Sr_0.4MnO₃.     

Reverse micellar synthesis and properties of nanocrystalline GMR materials (LaMnO3, La0.67Sr0.33MnO3 and La0.67Ca0.33MnO3): Ramifications of size considerations

Nanoparticles of complex manganites (viz. LaMnO₃, La_0.67Sr_0.33MnO₃ and La_0.67Ca{0.33}MnO₃) have been synthesized using the reverse micellar route. These manganites are prepared at 800‡C and the monophasic nature of all the oxides has been established by powder X-ray diffraction studies. TEM studies show an average grain size of 68, 80 and 50 nm for LaMnO₃, La_0.67Sr_0.33MnO₃ and La_0.67Ca{0.33}MnO₃respectively. Ferromagnetic ordering is observed at around 250 K for LaMnO₃, 350 K for La_0.67Sr_0.33MnO₃ and 200 K for La_0.67Ca{0.33}MnO₃. These Curie temperatures correspond well with those reported for bulk materials with similar composition.     

Nano-sized La0.8Sr0.2MnO3 as oxygen reduction catalyst in nonaqueous Li/O2 batteries

Nano-sized La_0.8Sr_0.2MnO₃ prepared by the polyethylene glycol assisting sol–gel method was applied as oxygen reduction catalyst in nonaqueous Li/O₂ batteries. The as-synthesized La_0.8Sr_0.2MnO₃ was characterized by X-ray diffraction (XRD), scanning electron microscopy, and Brunauer–Emmet–Teller measurements. The XRD results indicate that the sample possesses a pure perovskite-type crystal structure, even sintered at a temperature as low as 600 °C, whereas for solid-state reaction method it can only be synthesized above 1,200 °C. The as-prepared nano-sized La_0.8Sr_0.2MnO₃ has a specific surface area of 32 m² g⁻¹, which is much larger than the solid-state one (1 m² g⁻¹), and smaller particle size of about 100 nm. Electrochemical results show that the nano-sized La_0.8Sr_0.2MnO₃ has better catalytic activity for oxygen reduction, higher discharge plateau and specific capacity.     

Investigations on chemical interactions between alternate cathodes and lanthanum gallate electrolyte for Intermediate Temperature Solid Oxide Fuel Cell (ITSOFC)

The doped perovskite oxides such as La_0.65Sr_0.30MnO_3-δ (LSM), La_0.70Sr_0.30CoO_3-δ (LSC), La_0.65Sr_0.30FeO_3-δ (LSF), La_0.65Sr_0.30NiO_3-δ (LSN) and La_0.60Sr_0.40Co_0.20Fe_0.80O_3-δ (LSCF) are proposed as alternate cathode materials for solid oxide fuel cells working at reduced temperature (< 1073 K). The critical requirement for their applicability is their chemical compatibility in conjunction with an alternate solid electrolyte, La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-δ (LSGM) without any new phase formation. To understand the chemical reactivity between these two components, thoroughly mixed different cathode and LSGM electrolyte (1:1 by wt.) powders were pressed as circular components and subjected to annealing at 1573 K for 3 h in air. XRD and SEM were used for the characterization of the annealed samples. XRD measurements revealed that no new secondary phases were formed in LSM, LSC, and LSF with LSGM mixtures whereas LSN and LSCF with LSGM resulted in the formation of new secondary phases after high temperature treatment. The sintering shrinkage for all the components (cathode + electrolyte mixture) was also estimated. For comparison of data, the individual powders (cathode/electrolyte) were also compacted and studied in the same manner. The obtained results are discussed keeping in view the requirements that the candidate cathode material must meet out with respect to its chemical compatibility to qualify for the LSGM based ITSOFC systems at 1073 K.     

Magnetic poly(glycidyl methacrylate)-based microspheres prepared by suspension polymerization in the presence of modified La0.75Sr0.25MnO3 nanoparticles

With the aim of preparing new magnetic poly(glycidyl methacrylate) (PGMA) microspheres suitable for magnetic separation, La_0.75Sr_0.25MnO₃ nanoparticles were selected as a core material. In order to improve their compatibility with PGMA, the surface of the nanoparticles was treated with penta(methylethylene glycol) phosphate methacrylate (PMGPMA) as a stabilizer. Subsequently, the nanoparticles were encapsulated by the suspension polymerization of glycidyl methacrylate (GMA) resulting in a relatively homogeneous distribution of La_0.75Sr_0.25MnO₃ nanoparticle aggregates inside the polymer microspheres. Microspheres in the size range of a hundred micrometers with a broad particle size distribution were obtained. PMGPMA can be considered to be an efficient compatibilizer between La_0.75Sr_0.25MnO₃ nanoparticles and PGMA. Both PMGPMA-coated La_0.75Sr_0.25MnO₃ nanoparticles and magnetic PGMA microspheres were characterized in terms of morphology, particle size, composition and magnetic properties by the appropriate methods, such as X-ray diffraction, FTIR spectroscopy, thermogravimetric analysis (TGA), transmission electron microscopy (TEM), light microscopy and SQUID magnetometry.     

The synthesis and complex anion-vacancy ordered structure of La0.33Sr0.67MnO2.42

The low-temperature topotactic reduction of La_0.33Sr_0.67MnO₃ with NaH results in the formation of La_0.33Sr_0.67MnO_2.42. A combination of neutron powder and electron diffraction data show that La_0.33Sr_0.67MnO_2.42 adopts a novel anion-vacancy ordered structure with a 6-layer OOTOOT' stacking sequence of the ‘octahedral’ and tetrahedral layers (Pcmb, a=5.5804(1) Å, b=23.4104(7) Å, c=11.2441(3) Å). A significant concentration of anion vacancies at the anion site, which links neighbouring ‘octahedral’ layers means that only 25% of the ‘octahedral’ manganese coordination sites actually have 6-fold MnO₆ coordination, the remainder being MnO₅ square-based pyramidal sites. The chains of cooperatively twisted apex-linked MnO₄ tetrahedra adopt an ordered -L-R-L-R- arrangement within each tetrahedral layer. This is the first published example of a fully refined structure of this type which exhibits such intralayer ordering of the twisted tetrahedral chains. The rationale behind the contrasting structures of La_0.33Sr_0.67MnO_2.42 and other previously reported reduced La_1−xSr_xMnO_3−y phases is discussed.     

A conductive oxide as an O2 evolution anode for the electrolytic reduction of metal oxides

The feasibility of applying the conductive oxide, La_0.33Sr_0.67MnO₃, as an O₂ evolution electrode in an electrochemical system was investigated. The La_0.33Sr_0.67MnO₃ anode was able to electrochemically reduce UO₂ to metallic U in a Li₂O-containing LiCl molten salt electrolyte with O₂ evolution. Although the La_0.33Sr_0.67MnO₃ anode remained stable during the reaction, its long-term stability should be further investigated.     

Electrochemical characteristics of cathodes based on perovskites modified by ceria

A system consisting of a solid oxide electrolyte of the Ce_0.9Gd_0.1O_{2 − x} (CGO) composition in contact with a two-layer cathode based on a nonstoichiometric composition (La_0.8Sr_0.2)_0.95MnO_{3 ± δ} (LSM1) and a stoichiometric perovskite La_0.8Sr_0.2MnO_{3 ± δ} (LSM2) is prepared by the tape-casting process. It was shown that the best electrochemical characteristics are achieved for a three-layer system LSM2/{CGO-LSM1}/CGO sintered at 1410°C. The use of Ce-modified perovskites La_0.8Sr_0.2MnO_{3 ± δ} and La_0.6Sr_0.6CoO_{3 ± δ} as the collector layer of two-layer electrodes allows the electrochemical characteristics at moderately high temperatures (600–750°C) to be improved.     

Magnetic properties of quasi-two-dimensional La1−xSr1+xMnO4 and the evolution of itinerant electron ferromagnetism in the SrO · (La1−xSrxMnO3)n system

Quasi-two-dimensional oxides of the La_1−xSr_1+xMnO₄ system, possessing the K₂NiF₄ structure, show no evidence for ferromagnetic ordering in contrast to the corresponding three-dimensional La_1−xSr_xMnO₃ perovskites. Instead, there is an increasing tendency toward antiferromagnetic ordering with increasingx in La_1−xSr_1+xMnO₄. Furthermore, these oxides are relatively high-resistivity materials over the entire compositional range. Substitution of Ba for Sr in La_0.5Sr_1.5MnO₄ decreases the ferromagnetic interaction. Increasing the number of perovskite layers in SrO · (La_1−xSr_xMnO₃)_n causes an increase in electrical conductivity as well as ferromagnetic interaction. The oxide becomes a highly conducting ferromagnet whenn ≥ 2.     

Microstructure and electrical properties of lead zirconate titanate thin films deposited by sol-gel method on La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript>/SiO<Subscript>2</Subscript>/Si substrate

(La_0.7Sr_0.3)MnO₃ thin films were deposited on SiO₂/Si substrates by a metal-organic decomposition (MOD) method, and then Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films were grown on (La_0.7Sr_0.3)MnO₃-coated SiO₂/Si substrates by a sol-gel method. The effects of annealing temperature on the crystalline phases, microstructures and electrical properties of the PZT films were investigated. X-ray diffraction analysis results indicated that the PZT films with a perovskite single phase could be obtained by annealing at 650°C. The dielectric constant and the remnant polarization of the PZT films increased with increasing annealing temperature. The remnant polarization and the coercive field of the films annealed at 650°C were 18.3 μC/cm² and 35.5 kV/cm, respectively, whereas the dielectric constant and loss value measured at 1 kHz were approximately 1100 and 0.81, respectively.     

钙铝石涂层对整体型钙钛矿氧化物催化剂活性和热稳定性的影响

 采用固相反应法合成了钙铝石材料 12SrO•7Al2O3, 并以此作为涂层制备了堇青石蜂窝陶瓷型 La0.8Sr0.2MnO3 整体催化剂, 在不同温度 (850~1 050 oC) 下对该催化剂进行了热处理, 并采用 N2 吸附-脱附、X 射线衍射和扫描电镜等手段对其进行了表征, 考察了其催化甲基丙烯酸甲酯燃烧反应的活性. 结果表明, 12SrO•7Al2O3 作为涂层明显改善了整体催化剂的热稳定性, 在 850 oC 下焙烧 6 h 后, 含有 12SrO•7Al2O3 涂层的整体催化剂在 260 oC 即可将甲基丙烯酸甲酯完全转化. 12SrO•7Al2O3 涂层可避免 La0.8Sr0.2MnO3 活性组分与堇青石的接触, 减轻了活性组分在催化剂表面的烧结, 有利于保持 La0.8Sr0.2MnO3 活性组分的晶体结构和分散度, 提高整体催化剂的活性和热稳定性.     

Preparation of La0.75Sr0.25MnO3 Nano-Phase Powders and Films from Alkoxide Precursors

The first purely alkoxide-based sol-gel route to nano-phase powders and thin films of perovskite La_0.75Sr_0.25MnO₃ is described. The phase and microstructure evolution on heat treatment of free gel films to form the target nano-phase oxide were investigated by TGA, IR spectroscopy, powder XRD, SEM and TEM-EDS. The xerogel consisted of a hydrated oxo-carbonate, without remaining alkoxo groups or solvent. Heating at 5°C·min^–1 decomposed the carbonate groups and yielded the pure perovskite La_0.75Sr_0.25MnO₃ at 760°C. The cell dimensions were virtually unchanged from the first observation of perovskite at 680°C, to 1000°C, 4 h. The monoclinic cell of La_0.75Sr_0.25MnO₃ obtained at 1000°C, 4 h, had the dimensions a = 5.475(1), b = 5.504(2), c = 7.771(1) Å, = 90.50(2), fitting the literature data quite well. Crack-free, homogenous, 150 nm thick La_0.75Sr_0.25MnO₃ films were prepared by spin-coating Si/SiO₂/TiO₂/Pt and polycrystalline -Al₂O₃ substrates with a 0.6 M alkoxide solution, followed by heating at 5°C·min^–1 to 800°C, 30 min.     

Direct Observation of Oxygen Dissociation on Non‐Stoichiometric Metal Oxide Catalysts

Oxygen dissociation on metal oxides is a key reaction step, limiting the efficiency of numerous technologies. The complexity of the multi‐step oxygen reduction reaction (ORR) makes it difficult to investigate the oxygen dissociation step independently. Direct observation of the oxygen dissociation process is described, quantitatively, on perovskites La_0.6Sr_0.4Co_0.2Fe_0.8O_3‐δ and (La_0.8Sr_0.2)_0.95MnO_3±δ, using gas‐phase isotope‐exchange with a 1:1 ¹⁶O₂:¹⁸O₂ ratio. Oxygen transport mechanisms between gas–surface reactions and surface–bulk exchange are deconvoluted. Our findings show that regardless of participation of lattice oxygen, La_0.6Sr_0.4Co_0.2Fe_0.8O_3‐δ is better at oxygen dissociation than (La_0.8Sr_0.2)_0.95MnO_3±δ. Heteroexchange, involving lattice oxygen, dominates on La_0.6Sr_0.4Co_0.2Fe_0.8O_3‐δ. In contrast, (La_0.8Sr_0.2)_0.95MnO_3±δ shows both homoexchange and heteroexchange, with the latter only happening above 600 °C. Using a 1:1 isotope mixture, a simple method is presented for separation of the oxygen dissociation step from the overall ORR.     

Synthesis and structural characterization of LaxSr1−xMnO2.6+δ (0.1<x<0.4) compounds displaying compressed octahedral coordination of Mn

La_xSr_1−xMnO_2.6+δ (x=0.1-0.4) compounds have been obtained by low-temperature annealing of stoichiometric materials in hydrogen. La_0.1Sr_0.9MnO_2.6+δ (δ=0.15) and La_0.3Sr_0.7MnO_2.6, tetragonal (P4/m), and La_0.2Sr_0.8MnO_2.6, pseudo-tetragonal monoclinic (P2/m), structures are isostructural with oxygen-vacancy-ordered Sr₅Mn₅O₁₃ (, c≈a_P). La_0.4Sr_0.6MnO_2.6 shows cubic perovskite structure with disordered oxygen vacancies. In the vacancy-ordered (La_xSr_1−x)₅Mn₅O₁₃ phases four out of five Mn cations are Mn³⁺ and show a typical Jahn-Teller elongated pyramidal coordination while the fifth one Mn^(4−5x)+, in octahedral environment, shows decreasing formal charge from Mn⁴⁺ (x=0) to Mn^2.5+x=0.3. This unusual selective doping of the octahedral site produces structural strain due to increasing size of the Mn^(4−5x)+ and, in the case of (La_0.2Sr_0.8)₅Mn₅O₁₃, the unusual compressed octahedral arrangement of oxygen atoms around it. The coordination geometry implies that either the d_x²-y² orbital is occupied, which would be a rare example of inverted occupancy of e_g orbitals in manganites, or that disordered Mn³⁺ apically elongated MnO₆ octahedra are present with normal electronic configuration , and the observed bond distances are the average of the long and intermediate in-plane Mn-O bonds. Several structural features favor the second case.