Thermo-physical properties of as deposited and aged thermal barrier coatings (TBC) for gas turbines: State-of-the art and advanced TBCs

In the perspective of fuelling the future generations of gas turbines by hydrogen rich syngas, the evaluation of the effect of a higher water vapour content into the flue gases on the TBC used, or potentially usable, is a need. For this purpose YPSZ APS TBC with two different microstructures have been exposed for 500?h at different temperatures in the range 1000?°C–1250?°C either in air and air +20% vol. H₂O. The comparison between the different testing conditions has been performed in terms of sintering kinetics and phase stability, as evaluated by thermal diffusivity measurements and Synchrotron X-Rays diffraction, respectively. Furthermore the characterisation of thermal properties of two innovative TBCs (GZO-YPSZ and YAG) potentially able to withstand the CMAS attack and erosive environments, respectively, has been carried out.No clear evidence of a different behaviour of TBC has been observed, at least in the considered aging time and temperature range.     

Surface decorated platinum carbonyl clusters

Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt(13)(CO)(12){Cd(5)(μ-Br)(5)Br(2)(dmf)(3)}(2)](2-) (1), [Pt(19)(CO)(17){Cd(5)(μ-Br)(5)Br(3)(Me(2)CO)(2)}{Cd(5)(μ-Br)(5)Br(Me(2)CO)(4)}](2-) (2), [H(2)Pt(26)(CO)(20)(CdBr)(12)](8-) (3) and [H(4)Pt(26)(CO)(20)(CdBr)(12)(PtBr)(x)](6-) (4) (x = 0-2), have been obtained from the reactions between [Pt(3n)(CO)(6n)](2-) (n = 2-6) and CdBr(2)·H(2)O in dmf at 120 °C. The structures of these molecular clusters with diameters of 1.5-2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt-CO cores decorated on the surface by Cd-Br motifs, whereas 3 and 4 display a cubic close packed Pt(26)Cd(12) metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au-thiolate nanoclusters.     

Oxidative post-treatments for enhanced corrosion resistance of aluminium electrodeposited from ionic liquids

In this paper we report the results of a study on the corrosion properties of carbon steel (UNI Fe360B) coated with a thin aluminium layer electrodeposited from ionic liquids and subsequently post-treated in an oxidizing environment. Two different types of treatments were investigated: thermal oxidation in air and electrochemical anodization. We found that heat treatments provided only a modest improvement of the anticorrosion properties while the electrochemical treatment produced a significant improvement.     

Effects of grain refinement on the microstructure,mechanical properties and reliability of AlSi7Cu3Mg gravity die cast cylinder heads

The effects of grain refinement on the microstructure and mechanical properties of a secondary AlSi7-Cu3Mg gravity die cast cylinder head are reported. Metallographic and image analysis techniques have been used to quantitatively examine the macro- and microstructural changes occurring with the addition of grain-refining agent. The results indicate that the AlTi5B1 addition produces a fine and uniform grain structure throughout the casting; this effect is more pronounced in the slowly solidified regions. The initial contents of Ti and B, which are present as impurity elements in the supplied secondary alloy ingots, are not sufficient to produce effective grain refinement. Under the present casting conditions, the combined addition of AlTi5B1 and Sr does not produce any reciprocal interaction or effect on primary α-Al and eutectic solidification. Grain refinement improves the mechanical properties of the as-cast AlSi7Cu3Mg alloy and produces higher Weibull moduli, thus increasing the reliability of the casting. For automotive structural components, this could be considered an increase in safety.     

Advanced testing procedures for high performance coatings

In the first part of this work, an integrated approach incorporating electrochemical (electrochemical impedance spectroscopy), calorimetric (differential scanning calorimetry), mechanical (dynamic mechanical thermal analysis), and infrared spectroscopy (Fourier transform infrared spectroscopy) techniques was used to characterize some organic coatings from the automotive industry. Comparison of the results obtained with different techniques allows not only a higher precision in the evaluation of natural or artificial degradation, which is very difficult to obtain using traditional techniques, but also better data interpretation and, therefore, the possibility of understanding the different degradation mechanisms. In the second part, some preliminary results concerning the comparison of salt spray exposure and EIS measurements are discussed. The statistical analysis of the results showed that the degradation mechanism in the two cases is completely different and, therefore, the information which is obtained with the two testing approaches is also different. With EIS measurements obtained in immersion, it is possible to monitor, in particular, the barrier properties of the coatings, which are dominated by the presence of defects. In the case of salt spray (without scratch), the main property to be measured is the loss of adhesion which causes blister formation. Presented at the 77th Annual Meeting of the Federation of Societies for Coatings Technology, on October 18–22, 1999, in Dallas, TX. Dept. of Materials Engineering, Via Mesiano 77, Trento, Italy. e-mail: Flavio.Deflorian@ing.unitn.it; Stefano.Rossi@ing.unitn.it; Bonora@ing.unitn.it. Dept. ICMMPM, Via Eudossiana, Rome, Italy. e-mail: Lorenzo.Fedrizzi@ing.unitn.it.     

ON THE RETRIEVAL OF URBAN AEROSOL MASS CONCENTRATION BY A 532 AND 1064 nm LIDAR

Based on the hypothesis of a monomodal, lognormal size distribution, the uncertainty affecting the humid-mass retrieval from LIDAR data was estimated by considering our ignorance of the distribution width to be a source of error. The mass to backscatter ratio and its uncertainty were computed for six accumulation-mode aerosol models as a function of the backscatter angstrom coefficient (α) and of the relative humidity (RH). A mass to backscatter uncertainty of less than ±30% was obtained for all six models. We computed the mass and simulated the expected LIDAR backscatter at 532 and 1064 nm for a test data set of 14 “real-world” multimodal size distributions obtained from the literature. The possible presence of 0–20%–50% water-insoluble compounds in each aerosol mode was assumed. An urban-type accumulation mode and 10 different coarse mode compositions were considered, including dust-like aerosols. The aerosol mass concentration was derived by fitting the simulated LIDAR data at 532 and 1064 nm with a monomodal distribution of urban aerosols of “unknown” width. The relative over- or underestimation of the mass with respect to the real aerosol mass was expressed in terms of α and RH for the 10 coarse aerosol types. The LIDAR-derived mass turned out to be underestimated by 0 – 15% in the case of (NH₄)₂SO₄, NaCl, maritime, and H₂SO₄ coarse aerosols. In the case coarse dust aerosols, the range of underestimation was wider (0–30%). Absorbing aerosols showed a maximum underestimation of 40–50%.     

An experimental investigation of Fischer–Tropsch synthesis over washcoated metallic structured supports

In principle, the application of monolithic catalysts to the Fischer–Tropsch synthesis can solve many of the problems related to the classical Fischer–Tropsch reactors, in particular concerning the necessity to operate with short diffusion distances and low pressure drops, preferably according to the ideal plug-flow behavior, while still maintaining a reasonable inventory of catalytic material in the reactor volume.The preparation of prototype cobalt-based catalysts, washcoated onto metallic structured supports with different geometries, is described herein, together with the evaluation of the catalytic properties of such systems in the Fischer–Tropsch synthesis at industrially relevant process conditions (220–235 °C, 20 bar, 2.1  mol_H2/mol_CO,  5000 cm³(STP)_CO+H2/h/g_cat). Comparative tests with the same catalyst in the powdered form were also carried out at the same process conditions.It was found that the structured catalysts maintained the activity and the selectivity of the original powdered catalyst, provided that the washcoat thickness is sufficiently thin.