Catalytic coatings on steel for low-temperature propane prereforming to solid oxide fuel cell (SOFC) application

Catalyst layers (4–20 lm) of rhodium (1 wt%) supported on alumina, titania, and ceria–zirconia (Ce0.5Zr0.5O2) were coated on stainless-steel corrugated sheets by dip-coating in very stable colloidal dispersions of nanoparticles in water. Catalytic performances were studied for low-temperature (6500 C) steam reforming of propane at a steam to carbon ratio equal to 3 and low contact time (0.01 s). The best catalytic activity for propane steam reforming was observed for titania and ceria–zirconia supports for which propane conversion started at 250 C and was more than three times better at 350 C than conversion measured on alumina catalyst. For all catalysts a first-order kinetics was found with respect to propane at 500 C. Addition of PEG 2000 in titania and ceria–zirconia sols eliminated the film cracking observed without additive with these supports. Besides, the PEG addition strongly expanded the porosity of the layers, so that full catalytic efficiency was maintained when the thickness of the ceria–zirconia and titania films was increased

Catalytic coatings on stainless steel prepared by sol–gel route

Stainless steel (flat and microstructured) substrates have been coated with sol–gel catalysts made up of metal nanoparticles (Rh, Ni, Pt) dispersed on alumina and alumina–ceria supports. The aluminum monohydroxyde (boehmite) sols were synthesized by hot hydrolysis/peptization of an aluminum alkoxide (Yoldas method). It is shown that the rheological properties of the sol, especially the thixotropy, play a key role on the homogeneity and the quality of the film deposited on the metal substrate. The catalyst layers have a very good adhesion, a thickness which can be easily controlled (in the range 0.1 to 10 μm), a large specific surface area and a good mechanical and thermal stability

Effect of cerium concentration on corrosion resistance and polymerization of hybrid sol–gel coating on martensitic stainless steel

Stainless steels are increasingly used in the aeronautics field for the manufacture of structural parts. One of them, the X13VD martensitic stainless steel (X12CrNiMoV12-3), known for its good mechanical properties, has a poor corrosion resistance in confined or severe environments. In the past years, Cr(VI) based pre-treatments have been currently used for corrosion protection of different metals, however, they are toxic and due to environmental regulations, they will be definitely banned in a near future. Alternatives to replace Cr(VI) show advantages and drawbacks considering key properties such as: corrosion resistance, adhesion of coatings, fatigue resistance, durability and reliability. However, some of their possible alternatives show high potential. In this paper, a process was developed to improve the corrosion resistance of the martensitic stainless steel. Organic–inorganic hybrid coatings with different cerium concentrations were deposited onto stainless steel by sol–gel process. Corrosion resistance of the coatings was evaluated by electrochemical impedance measurements and it has been proved that cerium concentration of 0.01 M into hybrid coating was an optimal content. Adhesion tests were also carried out by "nanoscratchtest" to characterize the coatings mechanical properties as a function of cerium concentration but results do not clearly show the influence of cerium for the coating adhesion toward the substrate. To try to correlate with the electrochemical properties, liquid 29Si NMR spectroscopy was then performed to investigate hydrolysis and condensation reactions of sol–gel process, and by this method, it was demonstrated that for higher cerium concentration (>0.01 M) there is a modification of the chemical structure of the sol–gel network

Sol–gel synthesis and characterization of barium (magnesium) aluminosilicate glass sealants for solid oxide fuel cells

Solid oxide fuel cells (SOFC) correspond to efficient energy conversion systems coupled with low emissions of pollutants. In the aim to fabricate high temperature planar SOFC, glass and glass-ceramic sealants are developed to associate several criteria and properties : high thermal expansion (11.0 to 12.0 ⋅ 10− 6 K− 1), high electrical resistance > 2 kΩ/cm2, good thermochemical compatibility with the other active materials of the fuel cell, and stability under H2 and H2O atmospheres at an operation temperature of 800 °C for a long time. According to these requirements, new BAS (BaO–Al2O3–SiO2) and BMAS (BaO–MgO–Al2O3–SiO2) glass-ceramic sealants have been developed by sol–gel route which is a non-conventional process for such applications. By this soft chemistry process, we anticipate a decrease in the glasses processing temperature due to a better homogeneity between cationic precursors in the mixture and a more important reactivity of materials. Experimental results in terms of thermomechanical properties, thermal expansion coefficient, crystalline phase content, and microstructure were discussed. In particular, the influence of the %BaO on the thermomechanical properties of glass-ceramics was described. Changes in properties of glass-ceramics were closely related to the microstructure. The influence of MgO on glass processing temperatures, on the structure and on the microstructure is evaluated in order to confirm that these glass-ceramics are promising candidates to SOFC applications. So, after performing a systematic investigation to the various systems, the properties of suitable glass were proposed

Development of new processes to protect zinc against corrosion, suitable for on-site use

Protection against corrosion of metals is well known as an important issue in numerous fields. In all cases, the improvement of durability of these metals has to be connected to the development of environmentally friendly processes. Sol–gel protective coatings have shown excellent chemical stability and enhanced corrosion resistance for zinc substrates. Further, the sol–gel method, used as technique of surface protection, showed the potential for the replacement of toxic pre-treatments. This paper highlights the recent developments and applications of silane based sol–gel coatings on zinc substrates. Then, the challenges for industrial transfer of the developed process are also discussed because this process presents a disadvantage for on-site use, which is the too time-consuming thermal treatment. So, the goal of this study was to determine the convenient experimental conditions to reduce the duration of heat treatment of the hybrid sol–gel layer, compatible with the severe industrial requirements, without reducing the protection against corrosion. To reach this objective, a correlation between the results of chemical analyses and the protection against corrosion efficiency was established

Evaluation of a sol–gel process for the synthesis of La1−xSrxMnO3+δ cathodic multilayers for solid oxide fuel cells

Solid oxide fuel cells (SOFCs) are electrical energy conversion devices with high efficiency and low pollution. In order to increase performances of SOFCs at intermediate temperature (700–800 °C) and to decrease materials cost, an alternative sol–gel synthesis method has been investigated to deposit La1−xSrxMnO3+δ (LSMx) as cathode thin films. Polycrystalline LSMx thin films were prepared by dip-coating using a polymeric solution. Lanthanum, strontium and manganese nitrates were used as raw materials. The viscosity of the solution was adjusted and the solution was deposited on polycrystalline ZrO2–8% Y2O3 ceramics. Prior to experiments, the substrate surface was eroded until a roughness of 20 nm and then cleaned with ethanol and dried. Film thicknesses were adjusted with the number of layers. Porosity and grain size of monolayers or multilayers were evaluated. Typical thickness of monolayer is 250 nm. A key parameter in the multilayer process was the intermediate calcination temperature (400, 700 or 1000 °C) of each further layer deposition. A correlation between this intermediate temperature and morphology, thickness and porosity was found; porosity is ranging from 3 to 40% and thickness can reach 1 micron for multilayers. Concerning electrochemical performances, the best results were obtained for LSM0.4 multilayers with an intermediate calcination temperature (called Ti) of 400 °C

Sol–gel processing and characterization of (RE-Y)-zirconia powders for thermal barrier coatings

The effect of doping on the structural, morphological and thermal properties of ZrO2–XO1.5 (X=Y, La, Sm, Er) solid solutions for thermal barrier (TBC) applications was investigated. Oxide powders of various compositions from 9.7 to 40 mol% XO1.5 (X=Y, La, Sm, Er) were synthesised by the sol–gel route. The structural analysis of the powders was performed using X-ray diffraction analysis coupled with Rietveld refinements and the measurement of their specific surface area with the BET method. For each rare earth dopant, the morphology of the powders varies from monoliths to agglomerates of thinner particles when the doping amount increases. In order to determine the specific heat, the thermal diffusivity at room temperature and the thermal expansion coefficient of some selected compositions, DSC, laser thermal diffusivity and hightemperature dilatometry measurements were performed on samples densified by Spark Plasma Sintering. Working thermal characterisation indicated that zirconia doped with 30 mol% SmO1.5 and ErO1.5 have better insulation properties and a lower thermal expansion coefficient than our reference YSZ ceramic. These various compositions are very promising for the elaboration of multilayer TBCs by the sol–gel process

Synthesis by sol–gel route of oxyapatite powders for dense ceramics : applications as electrolytes for solid oxide fuel cells

Solid oxide fuel cells have considerable interest in recent years, because of their high efficiency and environmentally friendly nature. Such systems required oxygen-conducting electrolytes and now the most common electrolyte is yttria stabilized zirconia (YSZ). This compound exhibits high oxide ion conductivity at elevated temperatures (850–1000 °C). However, this high working temperature causes problems in terms of materials selection and lifetime. One solution is to develop new oxide ions conductors exhibiting high oxide ion conductivity at intermediary temperatures (700–800 °C). Recent work has identified Ln10−xSi6O26±z (Ln = rare earths) as a good fast oxide ion conductor. Undoped and doped Ln10−xB6O26±z (B = Si or Ge) oxides are currently prepared by solid-state methods. In that work, we propose a sol–gel process to synthesize powders of La9.33Si6O26 type-silicated apatites. The main advantage is to decrease the crystallization temperature in ,comparison to the conventional methods, allowing the synthesis of reactive powders with nanometric particles size. These oxides are synthesized using silicon alkoxide and lanthanum nitride as precursors. In the litterature, no study refers to the synthesis of mixed oxides with silicon alcoxides. However, there are several studies on sol–gel synthesis of glasses with this precursor. In this study, several processing parameters have been investigated (the hydrolysis ratio, the concentration of metallic precursors in the sol and the role of organic compounds) in order to synthesize pure phases after the decomposition of the sols. Pure powders of La9.33Si6O26 type-silicated apatites are obtained at 800 °C. These powders were used to prepare ceramics. Several processing parameters as morphology of powders (agglomeration, particle sizes) and, heating profiles have been studied on the densification. Dense ceramics (90–95%) have been prepared at temperatures around 1400 °C. The used of sol–gel powders allow the decrease of the sintering temperature of about 200 °C

Relationship between mechanical properties and microstructure of yttria stabilized zirconia ceramics densified by Spark Plasma Sintering

Yttria stabilized zirconia ceramics are well known in the field of thermal barrier coatings due to their high ability to thermally insulate hot metallic parts of turbo-engines. The present work is focused on the mechanical properties and the fracture behavior of such materials shaped by Spark Plasma Sintering.1 Two types of powders have been used: i) the first one is a commercial powder made of micrometric spheroidal agglomerates of nano-crystallites (Tosoh), and ii) the second one is a home-made Sol-Gel powder 2 consisting of dense agglomerates of micrometric non-spherical crystallites. Both powders were shaped by Spark Plasma Sintering. The microstructures and mechanical properties of the various samples were characterized for different porosity rates and composition. The adjustment of several SPS processing parameters such as the temperature and the applied pressure allowed to obtain ceramics with a porosity in the range from 0 to 50 % vol. with oriented microstructure. Please click Additional Files below to see the full abstract

The sol–gel route: A versatile process for up-scaling the fabrication of gas-tight thin electrolyte layers

Sol–gel routes are often investigated and adapted to prepare, by suitable chemical modifications, submicronic powders and derived materials with controlled morphology, which cannot be obtained by conventional solid state chemistry paths. Wet chemistry methods provide attractive alternative routes because mixing of species occurs at the atomic scale. In this paper, ultrafine powders were prepared by a novel synthesis method based on the sol–gel process and were dispersed into suspensions before processing. This paper presents new developments for the preparation of functional materials like yttria-stabilized-zirconia (YSZ, 8% Y2O3) used as electrolyte for solid oxide fuel cells. YSZ thick films were coated onto porous Ni-YSZ substrates using a suspension with an optimized formulation deposited by either a dip-coating or a spin-coating process. The suspension composition is based on YSZ particles encapsulated by a zirconium alkoxide which was added with an alkoxide derived colloidal sol. The in situ growth of these colloids increases significantly the layer density after an appropriated heat treatment. The derived films were continuous, homogeneous and around 20 μm thick. The possible up-scaling of this process has been also considered and the suitable processing parameters were defined in order to obtain, at an industrial scale, homogeneous, crack-free, thick and adherent films after heat treatment at 1400 °C