Synthesis, structure and magnetic properties of tetrakis-μ-carboxylato-bis(dodecylnicotinato)dicopper(II) complexes; crystal and molecular structure of the decyl carboxylate derivative

Dodecylnicotinate bis-adducts of binuclear copper carboxylates, of the general formula Cu2(O2CCn-1H2n-1)4(C 5H4NCOOC12H25)2, were synthesized for n = 10, 12, 14, 16, 18 and 20, and their crystal structure, thermal behavior and magnetic properties studied. The molecular structure of the decyl derivative has been determined from single-crystal X-ray diffraction data. The dimer is centrosymmetric with the CuII ions in a square-pyramidal coordination with four O-alkyl O atoms [average d(Cu - O) 1.960 (6) Å] in the basal plane and the nicotine N atom at apical positions [d(Cu - N) 2.183 (3) Å]. The copper ions, 2.615 (1) Å apart, are bridged by four O-alkyl carboxylate groups. Both the n = 20 and n = 18 homologues exhibit lamellar phases, which can be related to the supramolecular arrangement found in the n = 10 derivative. The magnetic behavior of the decyl and octadecyl dimers was studied in the 2-300 K temperature range. They exhibit a strong intramolecular antiferromagnetic interaction (Cu-Cu superexchange coupling constant J = -347 cm-1 for the decyl derivative), which can be attributed to a large overlap of the metal 3d orbitals and the oxygen lone pair orbitals of the linking carboxylate groups.Fil: Rusjan, Marcia. Universidad Nacional de General Sarmiento; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Chaia, Zulema. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Piro, Oscar Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; ArgentinaFil: Guillon, Daniel. Universite Paul Verlaine-Metz. Institut de Physique, Chimie et Materiaux; FranciaFil: Cukiernik, Fabio Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad Nacional de General Sarmiento; Argentin

Columnar Thermal Barrier Coatings Manufactured by Novel Laser Cladding Process

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Converting Nondeterministic Two-Way Automata into Small Deterministic Linear-Time Machines

In 1978 Sakoda and Sipser raised the question of the cost, in terms of size of representations, of the transformation of two-way and one-way nondeterministic automata into equivalent two-way deterministic automata. Despite all the attempts, the question has been answered only for particular cases (e.g., restrictions of the class of simulated automata or of the class of simulating automata). However the problem remains open in the general case, the best-known upper bound being exponential. We present a new approach in which unrestricted nondeterministic finite automata are simulated by deterministic models extending two-way deterministic finite automata, paying a polynomial increase of size only. Indeed, we study the costs of the conversions of nondeterministic finite automata into some variants of one-tape deterministic Turing machines working in linear time, namely Hennie machines, weight-reducing Turing machines, and weight-reducing Hennie machines. All these variants are known to share the same computational power: they characterize the class of regular languages

Superior performance of plasma sprayed YSZ thermal barrier coatings with oxide dispersion strengthened bond coats

Advanced thermal barrier coatings are essential to increase the efficiency of next-generation gas turbine engines. Different materials and process technologies give the possibility to extend the lifetime of TBCs. One limiting factor of the TBC lifetime is the growth of the TGO during thermal exposure resulting in a accelerated crack growth at the top coat- bond coat interface. The oxidation resistance and the temperature of the bond coat are key factors influencing the TGO growth rate. Oxide dispersion strengthened (ODS) bond coats have a slower oxygen scale growth during thermal exposure in comparison to standard bond coats. In previous studies TBC systems with an additional thin ODS bond coat on top of a standard bond coat showed a higher thermal cycling performance. These studies used Inconel 738 and Amdry 386 as substrate and bond coat material, respectively. This study investigates in the thermal cycling performance of the ODS bond coat TBC systems combined with a different substrate ERBO 1 and bond coat material Amdry 995. TBC systems with the new material combination show high cycling lifetimes and superior performance in comparison to previous samples. Samples were tested by a cyclic burner rig facility. Surface was heated by a gas burner to 1400°C while the backside is cooled by pressurized air to 1050°C. One cycle consists of 5 min heating followed by 2 min cooling. Cross sections of the samples were analyzed by SEM and laser microscope. The lifetime of the samples was evaluated especially with respect to diffusion processes, material properties, and bond coat temperature. ODS powders with higher aluminum oxide additions were produced by high energy milling to fit the CTE of the ODS bond coat to the one of the top coat. This will reduce the initial crack formation on the top a wavy top coat - bond coat interface and increase lifetime. The advanced bond coats were applied by low pressure plasma spraying, the standard YSZ top coat by atmospheric plasma spraying. The performance was evaluated by a gas burner rig test

Factors influencing the performance of zirconia based thermal barrier coatings

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Development of environmental barrier coatings for Al2O3/Al2O3 CMCs with improved Adhesion by texturing with laser ablation

Al2O3 /Al2O3 ceramic matrix composites (CMC) are candidate materials for high-temperature applications such as gas turbines. As water vapor corrosion of oxide/oxide CMC is a major issue, the application of suitable environmental barrier coatings (EBC) is inevitable. Besides the gas tightness a good adhesion of the EBC is a crucial aspect for providing an effective barrier against the combustion atmosphere. Due to the brittleness of the ceramic matrix conventional surface treatments like grinding and sandblasting fail to increase roughness without causing damage to the substrate. Therefore there is a need for new methods of surface preparation of CMCs. This work examines the suitability of surface preparation with laser ablation for use prior to air plasma spraying (APS) on an oxide/oxide-CMC. Laser ablation allows controlling of the surface’s structure and roughness. The effects of different laser parameters on the alumina surface were examined and a variety of different structures, for example a honeycomb or a cauliflower like structure, were prepared. The laser treated surfaces were coated with potential EBC-candidates, such as Y2O3 and Gd2Zr2O7 and the impact of laser textures on the coating adhesion was examined. Evaluation of the coated samples was done by pull-off adhesion testing and thermal cycling. Results indicate that laser pretreatment helps to increase the adhesion strength of the EBC-system

Thermally sprayed protective coatings under demanding load conditions

Materials in turbines are facing increasingly demanding conditions under operation. This is due to their diversifying field of application as e.g. in interplay with renewable energy sources. Each set of loading conditions, in terms of e.g. operation temperature, start/stop-frequency or contaminants present in the combustion atmosphere, shows a specific footprint of degradation pathways. Understanding and performance data are available for many individual degradation footprints as to date materials and coatings are developed in respect to each one of that kind of loading scenarios. Less often, materials are assessed at a wider range of conditions where changes and interplay of degradation modes can be observed. Today’s demand for design of material systems for flexible or volatile conditions of operation requires to consider the wider range of operation regimes including complex sequences of loading phases adding up to the overall degradation. Performance and degradation modes of APS TBC systems (both single layer YSZ as well as a double layer of YSZ plus Gd2Zr2O7) were studied under various conditions in cyclic testing. This includes scenarios with isothermal and gradient testing as well as sequential vs simultaneous loading with CMAS. Results are evaluated with respect to changes of (coexisting) degradation modes and spallation lifetime. Applicability of some modeling tools is discussed for lifetime prediction. Complete affiliations: 1) Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), 52425 Jülich, Germany 2) Jülich Aachen Research Alliance: JARA-Energ