Solid oxide fuel cells (SOFCs) are devices that allow direct conversion of chemical to electrical energy through an electrochemical reaction in a cleaner and more efficient way than conventional processes (eg. gas turbines). They are characterized by the use of a solid oxide material as the electrolyte. Yttria-stabilised zirconia
(YSZ) has traditionally been used in SOFCs electrolytes at temperatures in the range of 850-1000 °C. Recent research is being focused on the development of new materials with increased ionic conductivity at intermediate temperatures (500-800ºC) as alternative materials to YSZ. Rare earth silicates with an apatite-type structure,
such as doped lanthanum oxides of general formula La10(MO4)6O2, where M = Ge, Co, Si, Al, or P, are among these materials. The major limitation associated with the manufacture of these materials is their poor sinterability, which requires high sintering temperatures (1600ºC).
La9.33Si2Ge4O26 oxyapatite powders were synthesized at room temperature through mechanical alloying of La2O3, GeO2 and SiO2 precursor powders with different particle sizes as well as crystal structure in the case of silica powder (crystalline/amorphous). The mechanical alloyed mixtures were subsequently sintered by microwave heating at 1350 C for 1 h in order to obtain dense and homogeneous materials. All sintered materials consisted of the target apatite phase although minor amounts of secondary phases (e.g.La4GeO8) were also present only in samples obtained from micrometric SiO2 powders with a crystalline structure. The microstructure of the materials obtained from nanometric SiO2 with an amorphous structure was found to be more homogenous than the ones obtained from micrometric/crystalline silica. The mechanical behavior of the samples was slightly dependent on the particle size of the precursors and on the SiO2 crystallinity.
A well crystallized powder sample of sodium holmium orthosilicate oxyapatite, Na2.27Ho7.73(SiO4)6O0.72, was obtained after mechanical milling and thermal treatment at 1123 K. Crystal structure analysis was performed from the results of Rietveld refinement of the synchrotron diffraction data. As in other rare-earth orthosilicate apatites, sodium cations appear located sharing with holmium the 4f Wyckoff position at the center of a tricapped trigonal prism. In its turn, holmium almost fully occupies the 6h position at the center of a seven-coordinated pentagonal bipyramid. A small quantity of Na atoms was found at this site. No vacancies are present in the two independent crystallographic sites available for Ho and Na atoms.
Chlorapatite can be considered a potential biomaterial for orthopaedic applications. Its use as plasma-sprayed coating could be of interest considering its thermal properties and particularly its ability to melt without decomposition unlike hydroxyapatite. Chlorapatite (ClA) was synthesized by a high-temperature ion exchange reaction starting from commercial stoichiometric hydroxyapatites (HA). The ClA powder showed similar characteristics as the original industrial HA powder, and was obtained in the monoclinic form. The HA and ClA powders were plasma-sprayed using a low-energy plasma spraying system with identical processing parameters. The coatings were characterized by physical-chemical methods, i.e. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy, including distribution mapping of the main phases detected such as amorphous calcium phosphate (ACP), oxyapatite (OA), and HA or ClA. The unexpected formation of oxyapatite in ClA coatings was assigned to a side reaction with contaminating oxygenated species (O2, H2O). ClA coatings exhibited characteristics different from HA, showing a lower content of oxyapatite and amorphous phase. Although their adhesion strength was found to be lower than that of HA coatings...
Fonte: Royal Society of ChemistryPublicador: Royal Society of Chemistry
Tipo: Artigo de Revista Científica
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The crystal chemistry and oxygen conductivity of vanadium-doped apatites of nominal composition [La 8AE 2][Ge 6-xV x]O 26+x/2 (AE = Ca, Sr, Ba; 0 ≤ x ≤ 1.5) were studied to establish their potential as intermediate temperature solid oxide fuel cell (S
Pramana, Stevin S; Baikie, Tom; Kendrick, Emma; Schreyer, Martin K; Slater, Peter R; White, Timothy
Fonte: ElsevierPublicador: Elsevier
Tipo: Artigo de Revista Científica
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Calcium (La10-xCaxGe6O27-x/2, 0 ≤ x ≤ 2.57) and barium (La10-xBaxGe6O27-x/2, 0 ≤ nominal x ≤ 3) doped lanthanum germanate apatites were synthesized by high temperature solid-state sintering. The lattice parameters obtained from Rietveld refinement
A family of lanthanide silicates adopts an oxyapatite-like structure with structural formula Ln9.33∎0.67(SiO4)6O2 (Ln 4 La, Sm, Nd, Gd, ∎ = vacancy). The enthalpies of solution, DHS, for these materials and their corresponding binary oxides were determined by high-temperature oxide melt solution calorimetry using molten 2PbO·B2O3 at 1078 K. These data were used to complete thermodynamic cycles to calculate
enthalpies of formation from the oxides, ΔHs f-oxides (kJ/mol): La9.33∎0.67(SiO4)6O2 = −776.3 ± 17.9, Nd9.33∎0.67(SiO4)6O2 = −760.4 ± 31.9, Sm9.33∎0.67(SiO4)6O2 = −590.3 ± 18.6, and Gd9.33∎0.67(SiO4)6O2 = −446.9 ± 21.9. Reference data were used to calculate the standard enthalpies of formation from the elements, ΔH0 f (kJ/mol): La9.33∎0.67(SiO4)6O2 = −14611.0 ± 19.4, Nd9.33∎0.67(SiO4)6O2 = −14661.5 ± 32.2, Sm9.33∎0.67(SiO4)6O2 = −14561.7 ± 20.8, and Gd9.33∎0.67(SiO4)6O2 = −14402.7 ± 28.2. The formation enthalpies become more endothermic as the ionic radius of the lanthanide ion decreases.
Mechanical properties of La9.33Si2Ge4O26 prepared by mechanical alloying and subsequent sintering at 1300–1400 °C for 1 h were evaluated. Hardness and Young's modulus values in the range 7.3–9.6 GPa and 106–135 GPa, respectively, were obtained from nanohardness tests. The fracture toughness values derived from the Palmqvist method varied between 3.5 and 3.9 MPa m1/2 from classical microindentation test with an indentation load of 9.8 N. Yield stress (σy) was determined by inverse analysis from microhardness tests. The maximum value of σy (1829 MPa) was obtained for the sample sintered at 1400 °C showing the highest density (5.42 g/cm3).
In this work, microwave hybrid sintering at 1300 and 1350 °C was carried out for densification of La9.33Si2Ge4O26 mechanically alloyed powder with apatite structure. The pellets sintered at these two temperatures present the same structure (apatite) with relative densities of 92 and 96%, respectively. Mechanical analysis performed on sintered materials revealed the following results: hardness of 7.1 and 8.0 GPa, Young's modulus of 122 and 133 GPa, yield strength of 1807 and 2073 MPa and fracture toughness of 1.5 and 1.0 MPa m1/2, respectively.
Apatite-type rare earth based oxides, such as R-doped lanthanum oxides of general formula La9.33(RO4)6O2 with R = Ge, Si, exhibit high ionic conductivity and low activation energy at moderate temperatures, when compared to the yttria-stabilized zirconia electrolyte making them potential materials to be used in the range 500–700 °C, for intermediate temperature solid oxide fuel cells (IT-SOFCs). In this study, dense oxyapatite-based La9.33Si2Ge4O26 electrolytes have been successfully prepared either by electrical sintering at 1400 °C or microwave hybrid sintering at 1350 °C for 1 h from La2O3, SiO2 and GeO2 powders dry milled at 350 rpm for 15 h in a planetary ball mill. The densification behaviour of the apatite-type phase synthesized by mechanical alloying was found to be dependent on the grade of SiO2 used: either pre-milled quartz powder or amorphous nanosized fumed silica. The influence of the silica type on the La9.33Si2Ge4O26 integrity was assessed by dynamic Young's modulus, microhardness and indentation fracture toughness measurements. A good correlation between the degree of densification (as observed by SEM/EDS) and the resulting mechanical properties could be established. Pre-milling of quartz powder has favoured higher densification rates to be attained suggesting that both Fe content...