In situ CCVD synthesis of carbon nanotubes within a commercial ceramic foam

Consolidated nanocomposite foams containing a large quantity of carbon nanotubes (CNTs) within millimetre-sized pores are prepared for the first time. A commercial ceramic foam is impregnated by a 60 g L21 slurry of a (Mg(12x)(Co0.75Mo0.25)xO solid solution (x = 0.01, 0.05, 0.1 and 0.2) powder in ethanol. Three successive impregnations led to deposits several tens of mm thick, with a good coverage of the commercial-ceramic pore walls but without closing the pores. The materials were submitted to a CCVD treatment in H2–CH4 atmosphere in order to synthesise the CNTs. When using attrition-milled powders, the carbon is mostly in the form of nanofibres or disordered carbon rather than CNTs. Using non-milled powders produces a less-compact deposit of catalytic material with a higher adherence to the walls of the ceramic foam. After CCVD, the carbon is mostly in the form of high-quality CNTs, as when using powder beds, their quantity being 2.5 times higher. The so-obtained consolidated nanocomposite materials show a multi-scale pore structuration

An Ice-Structuring Mechanism for Zirconium Acetate

International audienceThe control of ice nucleation and growth is critical in many natural and engineering situations. However, very few compounds are able to interact directly with the surface of ice crystals. Ice-structuring proteins, found in certain fish, plants, and insects, bind to the surface of ice, thereby controlling their growth. We recently revealed the icestructuring properties of zirconium acetate, which are similar to those of ice-structuring proteins. Because zirconium acetate is a salt and therefore different from proteins having icestructuring properties, its ice-structuring mechanism remains unelucidated. Here we investigate this ice-structuring mechanism through the role of the concentration of zirconium acetate and the ice crystal growth velocity. We then explore other compounds presenting similar functional groups (acetate, hydroxyl, or carboxylic groups). On the basis of these results, we propose that zirconium acetate adopts a hydroxy-bridged polymer structure that can bind to the surface of the ice crystals through hydrogen bonding, thereby slowing down the ice crystal growth

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

Structural study of metastable tetragonal YSZ powders produced via a sol-gel route

Sol-gel yttria stabilized zirconia (YSZ) is investigated in this paper. The final aim is to process YSZ powders into stable slurries in order to prepare thick coatings for thermal barrier to be applied on hot turboengine components. In fact, this system is well-known for its excellent thermomechanical resistance at elevated temperatures but the relationship between these performances and the structural and microstructural characteristics of these materials is not fully understood. This paper reports a preliminary study concerning recent progress on the structural properties control of YSZ powders synthesized by solâ��gel process and the main advantages of this process compared to conventional methods. As a first step towards this understanding, structural investigations of ZrO2 doped with various xmol%YO1.5 coatings, have been performed using X-ray diffraction, structural Rietveld refinement, Raman spectra analysis and transmission electron microscopy. The evolution of the crystallographic structure of YSZ powders after air annealing at various temperatures 1100 °C, 1200 °C and 1400 °C was studied to well understand the conditions of the formation of desired metastable tetragonal phase (t). Then, this work should allow to correlate chemical and thermomechanical parameters as YSZ formulation and sol-gel elaboration conditions, temperature and t phase performances

Morphology and structure of YSZ powders: Comparison between xerogel and aerogel

Yttria-stabilized zirconia (YSZ) fine powders were prepared via sol–gel route in order to shape thermal barrier coatings (TBCs) from these powders. The main objective is to develop new undirectional coatings to allow best thermo-mechanical accommodations compared to conventional processes. To reach this aim, powders have to be able first to be highly dispersed into a sol (non-agglomeration, high specific surface area, etc.) and second to crystallize in the required metastable phase t0. Two routes have been used to dry gels: the conventional way which consists of simple evaporation of the solvent is compared to drying in supercritical conditions. Both YSZ powders after calcination at 950 8C of xerogel (Ex-xero-YSZ powder) and aerogel (Ex-aero-YSZ powder) crystallize in the tetragonal form. N2 adsorption/desorption analysis of the Ex-xero-YSZ powder indicates an Sw of 2.8 m2/g. For the Ex-aero-YSZ powder, the Sw (26 m2/g) is much higher than of Ex-xero-YSZ, leading to a better sintering capability. This high Sw is correlated to the small crystallite size (26 nm) and the alveolar morphology of Ex-aero-YSZ powders compared to Exxero-powder (49 nm). By reducing particles size and increasing the Sw of the powders, supercritical drying appears as a promising way to prepare stable slurries or loaded sols from fine YSZ particles for TBC applications. Indeed, after preparing nanometric powders, they are dispersed into a sol before shaping on superalloys substrates. After thermal treatment at 950 8C for 2 h which corresponds to the working temperature of TBC, the final aim will be to prepare ceramic YSZ coatings

Ice Shaping Properties, Similar to That of Antifreeze Proteins, of a Zirconium Acetate Complex

The control of the growth morphologies of ice crystals is a critical issue in fields as diverse as biomineralization, medicine, biology, civil or food engineering. Such control can be achieved through the ice-shaping properties of specific compounds. The development of synthetic ice-shaping compounds is inspired by the natural occurrence of such properties exhibited by antifreeze proteins. We reveal how a particular zirconium acetate complex is exhibiting ice-shaping properties very similar to that of antifreeze proteins, albeit being a radically different compound. We use these properties as a bioinspired approach to template unique faceted pores in cellular materials. These results suggest that ice-structuring properties are not exclusive to long organic molecules and should broaden the field of investigations and applications of such substances

Synthesis of Yttria Stabilized Zirconia by sol–gel route: Influence of experimental parameters and large scale production

This paper develops an advance in the field of new synthesis techniques for functional materials like Yttria Stabilized Zirconia (YSZ) used as sensors, thermal barriers or electrolytes for high-temperature fuel cells. In recent years, sol–gel routes were developed to prepare, by suitable chemical modifications, submicronic based materials with a controlled morphology, which conventional solid state chemistry paths are unable to provide. Wet chemistry methods provide interesting alternative routes because mixing of species occurs on the atomic scale. In this paper, ultrafine powders were prepared by a novel wet chemistry method based on the sol–gel process. One of the advantages of this method is to decrease the crystallization temperature in comparison to the conventional ones, allowing the synthesis of reactive powders with nanometric particles size. 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 and additives). Pure phases of YSZ were obtained and the characteristics of these powders investigated (crystallographic study, morphology, phase composition, etc.). Also, our optimised synthesis was applied to large scale elaboration by increasing the quantity of precursors. This study underlines the interest of the sol–gel process both to control the morphology of oxides and to prepare large amounts of high purity powders for an eventual industrialization process

Erosion and high temperature oxidation resistance of new coatings fabricated by a sol-gel route for a TBC application.

This paper examines the erosion and cyclic oxidation performance of novel thermal barrier coatings produced via the sol-gel route. The ceramic top coat, with a thickness of 5- 25µm, was deposited via a sol-gel route onto standard MCrAlY and PtAl bond coats. In both the erosion and the cyclic oxidation tests it was found that the bond coat had a profound affect on the results. The erosion of the sol-gel coatings were compared to standard EB PVD and PS TBCs and were found to be significantly higher. The effect of aging (100hr at 1100°C) on the erosion rates was also evaluated and was found to increase the erosion rates. The information obtained from the erosion and cyclic oxidation tests have highlighted the need to develop and optimise the parameters for producing thicker coatings

Elaboration of Sol-Gel Coatings from Aerogels and Xerogels of Doped Zirconia for TBC Applications

Thermal Barrier Coatings (TBCs) are used as insulators on hot section components to reduce operating temperatures in aircraft engines and industrial gas turbine. The TBC system consists of two layers: the ceramic top coat traditionally Yttria Stabilized Zirconia (YSZ) with a low conductivity, and the bond coat generally MCrAlY, M=Ni and/or Cr or Co or Pd or Pt modified aluminides. In the industry, two dry-route processes used to deposit TBCs give quite different microstructures of coatings. In one hand, coatings resulted by plasma spraying (PS) present a lamellar microstruture with a low thermal conductivity in the range from 0.7 to 0.9 Wm−1K−1. In the other hand, Electron Beam Physical Vapour Deposition (EBPVD) coatings with columnar microstruture coatings present the best mechanical performances but perpendicular orientation of the columns makes their thermal conductivity twice higher compared to PS coatings. The present study proposes the elaboration of zirconia coatings via the sol-gel route combined with dip-coating process. It is a versatile process able to produce either thin ceramic coatings or thick deposits. The main advantage of this method is to decrease the crystallization temperature, much lower than conventional processes. Moreover, the sol-gel process is a nondirectional deposition technique, which is very different to the physical methods described above. Doped zirconia have been chosen to constitute isolating multilayers coatings. Sol formulation, slurries stability but also dip-coating conditions have been optimized in order to obtain homogeneous layers on nickel based superalloys substrates