Effect of synthetic route on sintering behaviour, phase purity and conductivity of Sr- and Mg-doped LaGaO3 perovskites

La1-xSrxGa1-yMgyO3-d (LSGM) powders containing different amounts of Sr2+ and Mg2+ were prepared from precursors synthesised by either Pechini or citrate sol-gel method and by subsequent calcination at 1400 °C. Some powders were also submitted to further 10 h firing at 1500 °C. All as-calcined powders contained small amounts of Sr- and Ga-containing phases (namely SrLaGa3O7 and SrLaGaO4), as detected by X-Ray Diffraction (XRD). The relative amounts of these phases depended on x and y, i.e. the dopants’ levels. Nevertheless, powders prepared by the citrate method exhibited systematically higher phase purity than those obtained by the Pechini process. Calcined powders were then sintered at 1500 °C (10 h) in air and the degree of sintering was assessed by scanning electron microscopy (SEM). Phase composition of sintered pellets was different from that of powders. In fact, sintered pellets showed the presence of MgO, as detected by SEM, and of lesser amounts of SrLaGa3O7. Both these phases were less abundant in materials sintered using powders prepared by citrate method, thus suggesting that Pechini method does not represent the best wet chemical process for manufacturing. The conductivity of sintered pellets was measured by impedance spectroscopy in the 600–800 °C interval. Conductivity values of LSGM materials were affected by secondary phase segregation and, therefore, depended on both composition and sol-gel method synthetic route

Sol–gel synthesis and characterization of Co-doped LSGM perovskites

One of the major requirements for the development and commercialization of low-cost SOFCs is the reduction in the operating temperature. One of the methods to reach this aim is the use of solid electrolytes which exhibit superior ionic conductivity at intermediate temperatures (IT, T < 800 °C). Among these ionic conductors, doped LaGaO3 materials show high oxide ionic conductivity in the 600–800 °C range. These perovskites are usually prepared by time- and energy-consuming solid state reaction. In this paper, La0.8Sr0.2Ga0.8Mg0.2O2.8 (LSGM) and La0.8Sr0.20Ga0.8Mg0.2−xCoxO3−δ (LSGMC) powders containing different amounts of Co (x = 0.05, 0.085 and 0.10) were prepared from precursors synthesised by citrate sol–gel method. The precursors were calcined at 1000 °C (10 h) and dense high-purity pellets were obtained by pressing (300 MPa) and sintering in air at 1475 °C (5, 10 and 20 h). Sintered pellets of LSGM and LSGMC contained very small amounts (<1%) of SrLaGa3O7 and SrLaGaO4, respectively, as detected by X-ray diffraction (XRD) and by the combined use of scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The data clearly showed the feasibility of sol–gel methods to produce Co-doped LSGM perovskite type oxides

Diamond nucleation from the gas phase onto cold-worked Co-cemented tungsten carbide

Co-cemented tungsten carbide (WC–Co) substrates with fine (1 μm) and coarse (6 μm) grain size were sintered using 6 wt.% Co as a binder. The as-sintered samples were ground to the final geometry (10×10×3 mm3). After the grinding treatment, the full width at half maximum (FWHM) of the WC X-ray diffraction (XRD) peaks indicated a high level of strain in a few micrometers thick surface layer, according to the penetration depth of Cu Kα radiation. The as-ground substrates were submitted to a two-step etching procedure with Murakami's solution, to roughen the surface, and 10 s acid wash to etch surface cobalt out. The Murakami's etching time was varied between 1 and 20 min. Fine- and coarse-grained substrates submitted to different chemical etching times were characterized by scanning electron microscopy and XRD, and then submitted to short diamond nucleation runs in a Hot Filament Chemical Vapour Deposition reactor. Both FWHM of WC peaks and diamond nucleation density decreased by increasing the Murakami's etching duration, providing that the etched layer did not exceed 2 μm thickness. When a layer thicker than a couple of micrometers was removed by etching, diamond nucleation density was very low and no more dependent on etching time. This occurrence suggested that diamond nucleation density correlates well with the amount of residual strain at the substrate surface and can be tailored by a suitable control of strain-related defects produced by mechanical treatments

Dry turning of alumina/aluminum composites with CVD diamond coated Co-cemented tungsten carbide tools

Triangular (TPGN 160308) WC-6 wt.%Co inserts having different average grain sizes (1 and 3 µm) were submitted to surface roughening either by wet etching with Murakami's reagent or by a heat treatment in the hot filament chemical vapour deposition (HFCVD) reactor. The heat treatment was performed in a monohydrogen-rich atmosphere at substrate temperatures as high as 1000 degrees C. Scanning electron microscopy and energy-dispersive spectroscopy showed that this pre-treatment led to surface roughening of the as-ground inserts and to a lower surface Co concentration. Prior to deposition, all inserts were etched with an acid solution of hydrogen peroxide. Diamond coatings were deposited by HFCVD. The coated inserts were tested by dry machining of aluminum-matrix composite (Al-10%Al2O3) bars. Turning test results indicated that a proper combination of substrate pretreatment and microstructure can significantly improve tool life

Quantitative determination of the adhesive fracture toughness of CVD diamond to WC-Co cemented carbide

Well-separated diamond particles were nucleated and grown by hot filament chemical vapor deposition (HFCVD) onto WC-Co cemented carbide pretreated by Murakami's reagent and H2O2 + H2SO4 solution. The adhesive strength of diamond particles to WC-Co cemented carbide was quantitatively determined in terms of interface toughness by directly applying an external load to the CVD diamond particles. From the measurement of the maximum load required to scratch off the particles, we determined that the adhesive toughness was 14 J/m(2). This value is more than twice as high as that of CVD diamond on smooth silicon substrate and comparable to the cleavage fracture energy of diamond. The newly developed procedure will allow to check the effectiveness of substrate surface pretreatments for further improving the adhesion level of diamond films on WC-Co. (C) 2000 Elsevier Science S.A. All rights reserved

Tailoring phase stability and electrical conductivity of Sr0.02La0.98Nb1–xTaxO4 for intermediate temperature fuel cell proton conducting electrolytes

Sr0.02La0.98Nb1–-xTaxO4 (SLNT, with x=0.1, 0.2, and 0.4) proton conducting oxides were synthesized by solid state reaction for application as electrolyte in solid oxide fuel cells operating below 600 °C. Dense pellets were obtained after sintering at 1600 °C for 5 h achieving a larger average grain size with increasing the tantalum content. Dilatometric measurements were used to obtain the SLNT expansion coefficient as a function of tantalum content (x), and it was found that the phase transition temperature increased with increasing the tantalum content, being T=561, 634, and 802 °C for x=0.1, 0.2, and 0.4, respectively. The electrical conductivity of SLNT was measured by electrochemical impedance spectroscopy as a function of temperature and tantalum concentration under wet (pH2O of about 0.03 atm) Ar atmosphere. At each temperature, the conductivity decreased with increasing the tantalum content, at 600 °C being 2.68×10−4, 3.14×10−5, and 5.41×10−6 Scm−1 for the x=0.1, 0.2, and 0.4 compositions, respectively. SLNT with x=0.2 shows a good compromise between proton conductivity and the requirement of avoiding detrimental phase transitions for application as a thin-film electrolyte below 600 °C

Strontium and iron-doped barium cobaltite prepared by solution combustion synthesis: exploring a mixed-fuel approach for tailored intermediate temperature solid oxide fuel cell cathode materials

Ba0.5Sr0.5Co0.8Fe0.2O3–δ (BSCF) powders were prepared by solution combustion synthesis using single and double fuels. The effect of the fuel mixture on the main properties of this well-known solid oxide fuel cell cathode material with high oxygen ion and electronic conduction was investigated in detail. Results showed that the fuel mixture significantly affected the area-specific resistance of the BSCF cathode materials, by controlling the oxygen deficiency and stabilizing the Co2+ oxidation state. It was demonstrated that high fuel-to-metal cations molar ratios and high reducing power of the combustion fuel mixture are mainly responsible for the decreasing of the area-specific resistance of BSCF cathode materials. Moreover, a new metastable monoclinic phase with Ba0.5Sr0.5CO3 composition was discovered in the as-burned BSCF powders, enlarging the existing information on the BSCF phase formation mechanis

Determinación mediante ensayos térmicos del CO₂ absorbido por morteros de cemento

El CO₂ atmosférico ingresa por la red de capilares del hormigón o de los morteros interconectados con el exterior, originando la carbonatación, en especial del hidróxido de calcio formado durante la hidratación del cemento. Cuando se desea conocer el CO₂ absorbido, por ejemplo en estudios de sustentabilidad del hormigón, resulta necesario evaluar el porcentaje fijado mediante técnicas disponibles en laboratorio. En este trabajo se analiza la cantidad de CO₂ absorbida por morteros de cemento portland normal y con distintas razones a/c mediante ensayos térmicos (análisis termogravimétrico y pérdida gradual por calcinación). Los morteros fueron carbonatados empleando un método acelerado con una concentración de CO₂ de 4% en volumen (40.000 ppm) y temperatura y humedad controladas. Las experiencias se realizaron sobre morteros carbonatados durante tiempos diferenciales (48 y 96 h), a fin que el COV fijado alcance mayor profundidad. Se analiza en los estudios realizados la fiabilidad de las técnicas empleadas y los errores relativos que se comenten cuando se las emplean.Atmospheric CO₂ enters the capillary network of concrete or mortars interconnected with the outside, causing carbonation, especially calcium hydroxide formed during hydration of the cement. When you want to know the CO₂ absorbed, for example in concrete sustainability studies, it is necessary to evaluate the percentage set by techniques available in the laboratory. In this paper we analyze the amount of CO₂ absorbed by normal portland cement mortars with different rationales a / c by thermal tests (thermogravimetric analysis and gradual loss of ignition). The mortars were carbonated using an accelerated method with a COV concentration of 4% by volume (40,000 ppm) and temperature and humidity. The experiments were performed on carbonated mortars during differential times (48 and 96 h) To reach the CO₂ fixed depth. Is analyzed in studies the reliability of the techniques used and the relative errors that are committed when they are used

Sol–gel synthesis, X-ray photoelectron spectroscopy and electrical conductivity of Co-doped (La, Sr)(Ga, Mg)O3−δ perovskites

La0.8Sr0.2Ga0.8Mg0.2−xCoxO3−δ (LSGMC) powders containing different amounts of Co (x = 0.05 and 0.085) were prepared by a citrate sol–gel method. The powders were used to prepare highly phase-pure LSGMC sintered pellets with controlled composition and fractional densities larger than 95%. For the first time, LSGMC materials were subjected to X-ray photoelectron spectroscopy (XPS) characterization. XPS data confirmed the presence of the dopants in the material and allowed to identify two different chemical states for Sr2+ and oxygen, both related to the oxygen-deficient perovskite structure of LSGMC. The conductivity of LSGMC sintered pellets containing different amounts of Co ions in the B sites of the perovskite lattice was assessed by electrochemical impedance spectroscopy (EIS) in the 250–750 °C temperature range. Conductivity values and apparent activation energies were in good agreement with previously published data referring to materials with same composition, but prepared by solid-state route. Therefore, the physicochemical and electrochemical characterization clearly demonstrated the ability of sol–gel methods to produce high-purity Co-doped LSGM perovskites, which represent promising solid electrolytes for intermediate-temperature SOFCs