Computational modeling of cathodic limitations on localized corrosion of wetted SS 316L at room temperature

The ability of a SS 316L surface wetted with a thin electrolyte layer to serve as an effective cathode for an active localized corrosion site was studied computationally. The dependence of the total net cathodic current, I_net, supplied at the repassivation potential E_rp (of the anodic crevice) on relevant physical parameters including water layer thickness (WL), chloride concentration ([Cl⁻]) and length of cathode (Lc) were investigated using a three-level, full factorial design. The effects of kinetic parameters including the exchange current density (i_o,c) and Tafel slope (β_c) of oxygen reduction, the anodic passive current density (i_p) (on the cathodic surface), and E_rp were studied as well using three-level full factorial designs of [Cl⁻] and Lc with a fixed WL of 25 μm. The study found that all the three parameters WL, [Cl⁻] and Lc as well as the interactions of Lc × WL and Lc × [Cl⁻] had significant impact on I_net. A five-factor regression equation was obtained which fits the computation results reasonably well, but demonstrated that interactions are more complicated than can be explained with a simple linear model. Significant effects on I_net were found upon varying either i_o,c, β_c, or E_rp, whereas i_p in the studied range was found to have little impact. It was observed that I_net asymptotically approached maximum values (I_max) when Lc increased to critical minimum values. I_max can be used to determine the stability of coupled localized corrosion and the critical Lc provides important information for experimental design and corrosion protection.     

Low-Thermal-Conductivity Rare-Earth Zirconates for Potential Thermal-Barrier-Coating Applications

Rare-earth zirconates have been identified as a class of low-thermal-conductivity ceramics for possible use in thermal barrier coatings (TBCs) for gas-turbine engine applications. To document and compare the thermal conductivities of important rare-earth zirconates, we have measured the thermal conductivities of the following hot-pressed ceramics: (i) Gd₂Zr₂O₇ (pyrochlore phase), (ii) Gd₂Zr₂O₇ (fluorite phase), (iii) Gd_2.58Zr_1.57O₇ (fluorite phase), (iv) Nd₂Zr₂O₇ (pyrochlore phase), and (v) Sm₂Zr₂O₇ (pyrochlore phase). We have also measured the thermal conductivity of pressureless-sintered 7 wt% yttria-stabilized zirconia (7YSZ)—the commonly used composition in current TBCs. All rare-earth zirconates investigated here showed nearly identical thermal conductivities, all of which were ∼30% lower than the thermal conductivity of 7YSZ in the temperature range 25°–700°C. This finding is discussed qualitatively with reference to thermal-conductivity theory.     

In vivo aging of gutta‐percha dental cone

Gutta‐percha cone is the most widely used material for root canal filling. The in vivo aging of this cone focus on the degradation of its main organic component, trans‐1,4‐polyisoprene, was studied. Aged cones (25 samples) from 2 to 30 years of root canal filling were extracted from different patients in the occasion of retreatment by mechanical way. The information about the aging time was given by the patients. Gel‐permeation chromatography (GPC) and infrared spectroscopy (FTIR) were the analytical techniques used. Polyisoprene degrades with time of aging, but in a slow process. Decrease in polymer molar mass from 5.7 × 10⁵ to 1.7 × 10⁵ g/mol was observed in polyisoprene from cone after 30 years of root canal filling and inside a noninfected tooth. In tooth with caries and periodontal infection, the decrease in molar mass is higher (4.6 × 10⁴ g/mol in cone with 10 years of aging). The production of carbonyl and hydroxyl groups in the aged material indicates that the process is oxidative, even in closed teeth. In these cases, the oxygen could be provided from tissue fluid. The degradation mechanism is complex and depends on many factors, besides time of root canal filling. The dental problem caused by the aging could be the production and migration of cytotoxic substances to periodontal ligament and the reduction on the canal sealing property due to the polymer weight loss. Both of them could contribute to the root canal treatment failure. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:4082–4088, 2006     

Observability of linear systems with commensurate delays and unknown inputs

This paper investigates the observability analysis for linear time systems whose outputs are affected by unknown inputs. Three different definitions of observability are proposed. By introducing the Smith form and comparing the invariant factors, a sufficient condition is deduced for each proposed observability definition. Three examples are given for the purpose of highlighting the effectiveness of the proposed approach.     

Self-scaling cooperative discovery of service compositions in unstructured P2P networks

We propose an efficient technique for improving the performance of automatic and cooperative compositions in unstructured Peer-to-Peer networks during service discovery. The technique exploits a probabilistic forwarding algorithm that uses different sources of knowledge, such as network density and service grouping, to reduce the amount of messages exchanged in the network. The technique, analysed in several network configurations by using a simulator to observe resolution time, recall and message overhead, presents good performance especially in dense and large-scale service networks.     

Study of the NOχ reaction with reducing gases on Fe/ZrO2 catalyst

The Fe/ZrO₂ catalyst (1% Fe by weight) shows a strong adsorption capacity toward the nitric oxide (at room temperature the ratio NOFe is ca. 0.5) as a consequence of the formation of a highly dispersed iron phase after reduction at 500–773 K. Nitric oxide is adsorbed mainly as nitrosyl species on the reduced surface where the Fe²⁺ sites are prevailing, but it is easily oxidised by oxygen forming nitrito and nitrato species adsorbed on the support. However, in the presence of a reducing gas such as hydrogen, carbon monoxide, propane and ammonia at 473–573 K the Fe-nitrosyl species react producing nitrogen, nitrous oxide, carbon dioxide and water, as detected by FTIR and mass spectrometers. The results show that nitric oxide reduction is more facile with hydrogen containing molecules than with CO, probably due the co-operation of spillover effects. Experiments carried out with the same gases in the presence of oxygen show, however, a reduced dissociative activity of the surface iron sites toward the species NO_χ formed by NO oxidation and therefore the reactivity is shifted to higher temperatures.     

Mechanisms of hydrocarbon conversion reactions on heterogeneous catalysts: analogies with organometallic chemistry

Catalysis is central to most industrial processes for chemical manufacturing. As catalytic processes have become more complex and more demanding, selectivity has become the central issue in their design. Selectivity is defined by the relative rates of competing reaction pathways available to crucial intermediates, and can be controlled by subtle changes in the nature of the catalyst, the reactants, and/or the reaction conditions. In order to be able to do this in a systematic manner, a good understanding of the catalytic reaction mechanisms is needed. Here a connection is drawn between the key elementary steps comprising hydrocarbon conversion reactions on surfaces and those known to occur on discrete organometallic complexes. This way, the hydrogenation, dehydrogenation, hydrogenolysis, chain growth, and isomerization reactions typical in heterogeneous catalysis are redefined in terms of hydride elimination, oxidative addition, reductive elimination, migratory insertion, and 1, 2-shift elementary steps, among others. It is suggested that the knowledge already available from organometallic chemistry can be used to further advance the understanding of the surface science involved in heterogeneous catalysis. Thanks to the commonality of the chemistry involved, a better synergy could also be established between homogeneous and heterogeneous catalytic development. These ideas are discussed in this article in a critical and personal way.*Invited contribution to the special volume entitled The Interface between Heterogeneous and Homogeneous Catalysis, stemming from contributions at the recent International Symposium on Relations between Heterogeneous and Homogeneous Catalysis, and dedicated to the memory of Robert L. Burwell.     

Vessel Inspection: A Micro-Aerial Vehicle-based Approach

Vessel maintenance entails periodic visual inspections of the internal and external parts of the hull in order to detect the typical defective situations affecting metallic structures, such as coating breakdown, corrosion, cracks, etc. The main goal of project MINOAS is the automation of the inspection process, currently undertaken by human surveyors, by means of a fleet of robotic agents. This paper overviews an approach to the inspection problem based on an autonomous Micro Aerial Vehicle (MAV) which, as part of this fleet, is in charge of regularly supplying images that can teleport the surveyor from a base station to the areas of the hull to be inspected. The control software approach adopted for the MAV is fully described, with a special emphasis on the self-localization capabilities of the vehicle. Experimental results showing the suitability of the platform to the application are as well reported and discussed.     

Change detection by probabilistic segmentation from monocular view

We present a method for foreground/background video segmentation (change detection) in real-time that can be used, in applications such as background subtraction or analysis of surveillance cameras. Our approach implements a probabilistic segmentation based on the Quadratic Markov Measure Field models. This framework regularizes the likelihood of each pixel belonging to each one of the classes (background or foreground). We propose a new likelihood that takes into account two cases: the first one is when the background is static and the foreground might be static or moving (Static Background Subtraction), the second one is when the background is unstable and the foreground is moving (Unstable Background Subtraction). Moreover, our likelihood is robust to illumination changes, cast shadows and camouflage situations. We implement a parallel version of our algorithm in CUDA using a NVIDIA Graphics Processing Unit in order to fulfill real-time execution requirements.     

Agricultural use of three organic residues: effect on orange production and on properties of a soil of the ‘Comarca Costa de Huelva’ (SW Spain)

Disposal of urban, agricultural and industrial organic residues impliesan increasing problem because of all the economic and environmentalrepercussions involved. One of the most adequate ways of managing this problemis the agricultural use of these wastes as organic amendments. Three organicresidues (AC, olive mill waste water sludge compost; MWC, municipal solid wastecompost; and PS, paper mill sludge) were used in a 3-year field experimentinvolving orange production. The effect of their application on crop productionand on soil quality was investigated. Soil samples (0–20 cm depth)collected 11 months after the last soil amendment were analysed for: pH and EC,Kjeldahl-N, available-P, available-K, total organic carbon, humic substances,dehydrogenase, phosphatase, -glucosidase, urease andbenzoyl-argininamidehydrolysing protease (BAA-protease) activities. Generally, the application of the MWC and PSincreased orange yield when compared to control. Moreover, total organic carbonand humic substances significantly increased in soils treated with all theorganic amendments. Organic fertilisation increased the Kjeldahl-N andavailable-P contents of the soil. The application of the organic residues also causedsignificant increases in dehydrogenase, -glucosidase, urease andBAA-protease activities of the soil. Significant positive correlations (p <0.01) between these enzymatic activities and total organic carbon were foundforall treatments. Significant positive correlation between dehydrogenase, urease,-glucosidase, and BAA-protease and orange yield was also found. However,a clear inhibition of phosphatase activity was observed in soils treated withPS. The results indicate that the repeated application to the soil of moderateamounts of organic amendments has positive effects on the chemical andbiochemical properties of the soil, as well as on the orange yield.