Comparison of Two Unsteady Intermittency Models for Bypass Transition Prediction on a Turbine Blade Profile

The present paper evaluates two unsteady transition modelling approaches: the prescribed unsteady intermittency method PUIM, developed at Cambridge University and the dynamic unsteady intermittency method developed at Ghent University. The methods are validated against experimental data for the N3-60 steam turbine stator profile for steady and for unsteady inlet flow conditions. The characteristic features of the test case are moderately high Reynolds number and high inlet turbulence intensity, which causes bypass transition. The tested models rely both on the intermittency parameter and are unsteady approaches. In the prescribed method, the time-dependent intermittency distribution is obtained from integral relations. In the dynamic method, the intermittency distribution follows from time-dependent differential equations. For unsteady computations, self-similar wake profiles are prescribed at the inlet of the computational domain. Joint validation of the prescribed and the dynamic unsteady intermittency models against experimental data shows that both methods are able to reproduce the global features of the periodical evolution of the boundary layer under the influence of a periodically impinging wake. The overall quality of the dynamic method is better than that of the prescribed method.     

Multianalytical Study of Patina Formed on Archaeological Metal Objects from Bliesbruck-Reinheim

 Patinas naturally formed on archaeological bronze alloys were characterized using light microscopy (LM), micro energy dispersive X-ray fluorescence analysis (μ-EDXRF), time of flight secondary ion mass spectrometry (TOF-SIMS) and scanning electron microscopy in combination with energy dispersive X-ray microanalysis (SEM/EDX). The examinations carried out on cross-sections of samples have shown that in all samples the copper content in the corrosion layer is lower than in the bulk, while an increase of tin and lead could be observed. Two different types of corrosion were found: first type, a corrosion formation leading to a three layer structure was observed on lead bronze. The outer layer consists mainly of Cu(II) compounds and soil material, followed by a fragmented layer of cuprous oxide and the surface layer of the alloy, where a depletion of copper and an enrichment of tin and high amounts of Cl could be detected. The second type of corrosion is characterized by a two layer structure on the tin bronze sample consisting of an outer layer with copper containing corrosion products and a layer with cracks, which reveals a depletion of copper whereas tin and lead are enriched. Also high amounts of Si were detected in this surface layer.     

Balancing Ligand Flexibility versus Rigidity for the Stepwise Self-Assembly of M12L24 via M6L12 Metal–Organic Cages

Non-covalent interactions are important for directing protein folding across multiple intermediates and can even provide access to multiple stable structures with different properties and functions. Herein, we describe an approach for mimicking this behavior in the self-assembly of metal–organic cages. Two ligands, the bend angles of which are controlled by non-covalent interactions and one ligand lacking the above-mentioned interactions, were synthesized and used for self-assembly with Pd²⁺. As these weak interactions are easily broken, the bend angles have a controlled flexibility giving access to M₂( L1 )₄, M₆( L2 )₁₂, and M₁₂( L2 )₂₄ cages. By controlling the self-assembly conditions this process can be directed in a stepwise fashion. Additionally, the multiple endohedral hydrogen-bonding sites on the ligand were found to play a role in the binding and discrimination of neutral guests.     

Transformations of Gibbs measures

We study local transformations of Gibbs measures. We establish sufficient conditions for the quasilocality of the images and obtain results on the existence and continuity properties of their relative energies. General results are illustrated by simple examples. Received: 11 November 1997 / Revised version: 20 February 1998     

Generalized quadrangles admitting PSL(2,q) × PSL(2,q)

In this paper, we classify the generalized quadrangles of order (s,t), s ≠ 1 ≠ t, which admit the natural action of PSL(2,s) × PSL(2,s) on a subGQ of order (s,1). This generalizes a recent result of J. De Kaey and H. Van Maldeghem 3 , by whom the classification was obtained for the case s = t. © 2005 Wiley Periodicals, Inc. J Combin Designs.     

On the problem of spacetime symmetries in the theory of supergravity. III. Superspace formalism

The study of the problem of defining, in the theory of supergravity, the notion of a spacetime symmetry is continued. The connection with the formalism of superspace is explicitly considered, and the geometrical significance of the definition given in Parts I and II of this series of papers is emphasized.     

Capturing the Genesis of an Active Fischer–Tropsch Synthesis Catalyst with Operando X‐ray Nanospectroscopy

A state‐of‐the‐art operando spectroscopic technique is applied to Co/TiO₂ catalysts, which account for nearly half of the world's transportation fuels produced by Fischer–Tropsch catalysis. This allows determination of, at a spatial resolution of approximately 50 nm, the interdependence of formed hydrocarbon species in the inorganic catalyst. Observed trends show intra‐ and interparticular heterogeneities previously believed not to occur in particles under 200 μm. These heterogeneities are strongly dependent on changes in H₂/CO ratio, but also on changes thereby induced on the Co and Ti valence states. We have captured the genesis of an active FTS particle over its propagation to steady‐state operation, in which microgradients lead to the gradual saturation of the Co/TiO₂ catalyst surface with long chain hydrocarbons (i.e., organic film formation).     

Recycling of homogeneous hydrogenation catalysts by dialysis coupled catalysis

Although transition-metal complexes are very attractive as homogeneous catalysts in fine chemistry, their high prices often limit their applications. A means to recycle those catalysts would solve this problem and would simultaneously facilitate the downstream purification of the product. This is now realized in a new concept in which homogeneous catalysis is coupled to dialysis. The advantages of homogeneous catalysis (off-the-shelf catalysts, high activities and selectivities) are thus combined with those of heterogeneous catalysis (easy catalyst separation from product solution, reuse of catalyst, and possibility for continuous operation). Since the heart of the process is the membrane, self-prepared membranes were preferred as they allow a better control and understanding of the separation characteristics. Rhodamine B was used as a probe molecule to define the working conditions of the membrane. The concept is proven to work for two relevant chiral reactions: a hydrogenation with Ru-BINAP and a hydrogen transfer reaction with Ru-TsDPEN [BINAP=(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine); TsDPEN= tosyl-N,N'-diphenyl-1,2-ethanediamine].     

Some new C2-symmetric bicyclo[2.2.1]heptadiene ligands: synthesis and catalytic activity in rhodium(I)-catalyzed asymmetric 1,4- and 1,2-additions

C₂-Symmetric bicyclo[2.2.1]hepta-2,5-dienes with various substituents (R=Bn, i-Bu, c-Hex, allyl) are prepared starting from the corresponding enantiomerically pure bis-triflate (R=OTf). These chiral ligands are tested and compared in rhodium(I)-catalyzed 1,4- and 1,2-addition of phenylboronic acid to cyclic enones and aryl aldehydes, respectively. Some interesting reactivity and selectivity effects due to the introduction of sterically demanding or olefinic substituents are reported. Moreover, remarkably high catalytic activity is observed for the rhodium(I)-catalyzed 1,2-addition.