Characterization and Oxidation of Magnetron Sputtered Fe-Al Intermetallic Alloys

Fe-Al intermetallic alloys have been considered as protective materials against corrosion. We have studied the properties of such intermetallic coatings Fe _x Al_1?x (x ≤ 0.5) on the aluminum-rich side and their oxidation behaviour. The samples were prepared using rf-magnetron sputtering. The composition and layer thickness were determined by Rutherford Backscattering Spectrometry (RBS) and high-resolution scanning electron microscopy (HRSEM). Conversion Electron Mössbauer Spectroscopy (CEMS) and X-Ray Diffraction (XRD) were applied for phase analysis. We report here on the oxidation of such coatings.     

Optimization of a conversion electron Mössbauer spectroscopy gas flow He/CH4 proportional counter

A new detector for CEMS has been built and optimized with respect to the statistical quality of spectra obtained. The optimization has been performed by measuring Mößbauer and pulse height spectra at in- and off-resonance. Single channel analyzer settings were calculated by a new optimization routine. A comparison of different detector designs has been performed using the statistical utility rate of spectra obtained from a stainless steel foil. A procedure for determining optimal operating parameters for ICEMS gas flow proportional counters is proposed.     

Geometric aspects influencing N-NTB transition - implication of intramolecular torsion

Herein we report a comprehensive study on novel carbonyl- and ethenyl-linked symmetric dimers that combine synthesis, mesomorphic properties and molecular modelling. The study has been focused on the impact of geometry imposed by the linkage group on the incidence of the twist-bend nematic (N_TB) phase. Comparison of the mesomorphic properties of these two series complemented with computational studies of conformational space around the linkage group points molecular curvature and intramolecular torsion plays important role in the appearance of the N_TB phase and can be regarded as the basic structural requirements for design of new twist-bend nematogen materials.     

High-temperature oxidation behaviour of low-entropy alloy to medium- and high-entropy alloys

The high-temperature oxidation behaviour of CoCrNi, CoCrNiMn, and CoCrNiMnFe equimolar alloys was investigated. All three alloys have a single-phase face-centred cubic structure. Thermogravimetric analyses (TGA) were conducted at temperatures ranging from 800 to 1000 °C for 24 h in dry air. The kinetic curves of the oxidation were measured by TGA, and the microstructure and chemical element distribution in different regions of the specimens were analysed. The oxidation kinetics of the three alloys followed the two-stage parabolic rate law, with rate constants generally increasing with increasing temperature. CoCrNi displayed the highest resistance to oxidation, followed by CoCrNiMnFe and CoCrNiMn exhibiting the least resistance to oxidation. The addition of Mn to CoCrNi increased the oxidation rate. The oxidation resistance of CoCrNiMn was enhanced by the addition of Fe. Less Mn Content and the formation of more Cr₂O₃ were responsible for the reduction in the oxidation rates of CoCrNiMnFe. The calculated activation energies of CoCrNiMn and CoCrNiMnFe at 800, 850 and 900 °C were 108 and 137 kJ mol^?1, respectively, and are comparable to that of Mn diffusion in Mn oxides. The diffusion of Mn through the oxides at 800–900 °C is considered to be the rate-limiting process. The intense diffusion of Cr at 1000 °C contributed to the formation of CrMn_1.5O₄ spinel with Mn in the outer layer of CoCrNiMn and Cr₂O₃ in the outer layer of CoCrNiMn.     

On the core of the minimum cost steiner tree game in networks

A cost allocation problem arising from the Steiner Tree (ST) problem in networks is analyzed. This cost allocation problem is formulated as a cost cooperative game in characteristic function form, referred to as theST-game. The class ofST games generalizes the class of minimum cost spanning tree games which were used in the literature to analyze a variety of cost allocation problems. In general, the core of anST-game may be empty. We construct an efficient Core Heuristic to compute a good lower bound on the maximum fraction of the total cost that can be distributed among users while satisfying the core constraints. Based on the Core Heuristic, we also provide a sufficient condition for a givenST not to be optimal for the linear programming relaxation of an integer programming formulation of theST problem. The Core Heuristic was implemented and tested on 76 data sets from the literature (Wong's, Aneja's and Beasley's Steiner tree problems). Core points were found for 69 of these cases, and points close to the core were computed in the others.     

A high-temperature structure for Ta2O5 with modulations by TiO2 substitution

Solid solutions in the series (1−x)Ta₂O₅−xTiO₂ with x=0.0-0.1 were prepared by high-temperature ceramic processing methods, and the crystal structure was determined at room temperature by transmission electron microscopy, electron diffraction and high-resolution lattice imaging. A structural model is proposed for the oxygen-deficient tantalum oxide (Ta₂O₅) phase with high TiO₂ doping level (x=0.08). The model is based on edge sharing of an oxygen octahedron-hexagonal bi-pyramid-octahedron molecular building block unit that repeats four times per unit cell. Electron diffraction reveals a monoclinic distortion from a pseudo-tetragonal model structure that is modulated primarily along 〈110〉. The modulation length varies with increasing TiO₂ content. Furthermore, by quantitative HREM analysis and matching of lattice images by simulation, it is shown that the modulation is associated with small ionic displacements in specific lattice planes that coincide with Ta ions in the model structure coordinated by oxygen hexagonal bi-pyramids. Based on this evidence, it is suggested that the modulation comes from a replacement of Ta with Ti ions, and the loss of inversion symmetry in the modulated structure is related to the dielectric properties of the material.     

Hydrolysis of the Peptide Bond in N-Acetylated L-Methionylglycine Catalyzed by Various Palladium(II) Complexes: Dependence of the Hydrolytic Reactions on the Nature of the Chelate Ligand in cis-[Pd( L)(H 2O) 2] 21 Complexes

Hydrolytic reactions between various palladium(II) complexes of the type cis-[Pd(L)(H₂O)₂]²⁺ in which L is ethylenediamine (en), 1,2-propylenediamine (1,2-pn), isobutylenediamine (ibn), 1,2-diaminocyclohexane (1,2-dach), N-methylethylenediamine (Meen), N,N,N,N-tetramethylethylenediamine (Me₄en), S-methyl L-cysteine (MeS-L-HCys), L-methionine (L-HMet), and 2,5-dithiahexane (dth) and dipeptide N-acetylated L-methionylglycine (MeCOMet-Gly) were studied by ¹H NMR spectroscopy. The reactions were carried out in the pH range 2.0–2.5 and at 50°C. In all these reactions, palladium(II) complex bound to a methionine residue effects the regioselective cleavage of the amide bond involving the carboxylic group of methionine. We found that the rate of hydrolysis and mechanism of this reaction are strongly dependent from the nature of the chelate ligand L in palladium(II) complexes of the type cis-[Pd(L)(H₂O)₂]²⁺.     

Asymptotic Formulas for Thermography Based Recovery of Anomalies

We start from a realistic half space model for thermal imaging, which we then use to develop a mathematical asymptotic analysis well suited for the design of reconstruction algorithms. We seek to reconstruct thermal anomalies only through their rough features. With this way our proposed algorithms are stable against measurement noise and geometry perturbations. Based on rigorous asymptotic estimates, we first obtain an approximation for the temperature profile which we then use to design nonit-erative detection algorithms. We show on numerical simulations evidence that they are accurate and robust. Moreover, we provide a mathematical model for ultrasonic temperature imaging, which is an important technique in cancerous tissue ablation therapy.AMS subject classifications: 35R20, 35B30     

Complexation of molybdenum(V) with glycolic acid: an unusual orientation of glycolato ligand in {Mo2O4}2+ complexes

(PyH)5[Mo(V)OCl4(H2O)]3Cl2 and (PyH)n[Mo(V)OBr4]n reacted with glycolic acid (H2glyc) or its half-neutralized ion (Hglyc(-)) to afford a series of novel glycolato complexes based on the {Mo(V)2O4}2+ structural core: (PyH)3[Mo2O4Cl4(Hglyc)]. (1)/ 2CH 3CN (1), (PyH) 3[Mo 2O 4Br 4(Hglyc)].Pr(i)OH(2), (PyH)2[Mo2O4(glyc) 2Py 2] (3), (PyH) 4[Mo 4O 8Cl 4(glyc) 2].2EtOH (4), and [Mo 4O 8(glyc) 2Py 4] (5) (Py = pyridine, C 5H 5N; PyH(+) = pyridinium cation, C 5H 5NH (+) and glyc (2-) = a doubly ionized glycolate, (-)OCH 2COO (-)). The compounds were fully characterized by X-ray crystallography and infrared spectroscopy. The Hglyc (-) ion binds to the {Mo 2O 4} (2+) core through a carboxylate end in a bidentate bridging manner, whereas the glyc (2-) ion adopts a chelating bidentate coordination through a deprotonated hydroxyl group and a monodentate carboxylate. The orientations of glyc (2-) ions in 3- 5 are such that the alkoxyl oxygen atoms occupy the sites opposite the multiply bonded oxides. {(C6H5) 4P}[Mo(VI)O 2(glyc)(Hglyc)] ( 6), an oxidized complex, features a reversed orientation of the glyc(2-) ion. The theoretical DFT calculations on the [Mo(V)2O4(glyc) 2Py 2](2-) and [Mo(VI)O2(glyc)2](2-) ions confirm that binding of glycolate with the alkoxyl oxygen to the site opposite the MoO bond is energetically more favorable in {Mo(V)2O4}(2+) species, whereas a reversed orientation of the ligand is preferred in Mo(VI) complexes. An explanation based on the orbital analysis is put forward.     

Hyperbolic conservation laws with vanishing nonlinear diffusion and linear dispersion in heterogeneous media

We analyze family of solutions to multidimensional scalar conservation law, with flux depending on the time and space explicitly, regularized with vanishing diffusion and dispersion terms. Under a condition on the balance between diffusion and dispersion parameters, we prove that the family of solutions is precompact in L¹_loc{L^1_{\rm loc}}. Our proof is based on the methodology developed in Sazhenkov (Sibirsk Math Zh 47(2):431–454, 2006), which is in turn based on Panov’s extension (Panov and Yu in Mat Sb 185(2):87–106, 1994) of Tartar’s H-measures (Tartar in Proc R Soc Edinb Sect A 115(3–4):193–230, 1990), or Gerard’s micro-local defect measures (Gerard Commun Partial Differ Equ 16(11):1761–1794, 1991). This is new approach for the diffusion–dispersion limit problems. Previous results were restricted to scalar conservation laws with flux depending only on the state variable.