XUV spectroscopic characterization of warm dense aluminum plasmas generated by the free-electron-laser FLASH

We report on experiments aimed at the generation and characterization of solid density plasmas at the free-electron laser FLASH in Hamburg. Aluminum samples were irradiated with XUV pulses at 13.5 nm wavelength (92 eV photon energy). The pulses with duration of a few tens of femtoseconds and pulse energy up to 100 mu J are focused to intensities ranging between 10(13) and 10(17) W/cm(2). We investigate the absorption and temporal evolution of the sample under irradiation by use of XUV and optical spectroscopy. We discuss the origin of saturable absorption, radiative decay, bremsstrahlung and atomic and ionic line emission. Our experimental results are in good agreement with simulations.

Exploring the free energy surfaces of clusters using reconnaissance metadynamics

A new approach is proposed for exploring the low-energy structures of small to medium-sized aggregates of atoms and molecules. This approach uses the recently proposed reconnaissance metadynamics method [G. A. Tribello, M. Ceriotti, and M. Parrinello. Proc. Natl. Acad. Sci. U.S.A. 107(41), 17509 (2010)] in tandem with collective variables that describe the average structure of the coordination sphere around the atoms/molecules. We demonstrate this method on both Lennard-Jones and water clusters and show how it is able to quickly find the global minimum in the potential energy surface, while exploring the finite temperature free energy surface. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3628676]

Electronic, structural, and reactive properties of ultrathin aluminum oxide films on Pt(111)

Low-energy electron diffraction, X-ray photoelectron spectroscopy, high-resolution electron energy-loss spectroscopy, scanning tunneling microscopy, and temperature-programmed reaction spectrometry results are reported for the structural and reactive behavior of alumina films grown on Pt(111) as a function of thickness and oxidation temperature. Submonolayer Al films undergo compete oxidation at 300 K, annealing at 1100 K resulting in formation of somewhat distorted crystalline gamma-alumina, Thicker deposits require 800 K oxidation to produce Al2O3, and these too undergo crystallization at 800 K, yielding islands of apparently undistorted gamma-alumina on the Pt(111) surface. Oxidation of a p(2 x 2) Pt3Al surface alloy occurs only at>800 K, resulting in Al extraction, These alumina films on Pt(lll) markedly increase the coverage of adsorbed SO4 resulting from SO2 chemisorption onto oxygen-precovered surfaces. This results in enhanced propane uptake and subsequent reactivity relative to SO4/Pt(111). A bifunctional mechanism is proposed to account for our observations, and the relevance of these to an understanding of the corresponding dispersed systems is discussed.

Theoretical and FE analysis of ultrasonic welding of aluminum alloy 3003

Ultrasonic welding (consolidation) process is a rapid manufacturing process that is used to join thin layers of metal at low temperature and low energy consumption. Experimental results have shown that ultrasonic welding is a combination of both surface (friction) and volume (plasticity) softening effects. In the presented work, an attempt has been made to simulate the ultrasonic welding of metals by taking into account these effects (surface and volume). A phenomenological material model has been proposed, which incorporates these two effects (i.e., surface and volume). The thermal softening due to friction and ultrasonic (acoustic) softening has been included in the proposed material model. For surface effects, a friction law with variable coefficient of friction that is dependent on contact pressure, slip, temperature, and number of cycles has been derived from experimental friction tests. The results of the thermomechanical analyses of ultrasonic welding of aluminum alloy have been presented. The goal of this work is to study the effects of ultrasonic welding process parameters, such as applied load, amplitude of ultrasonic oscillation, and velocity of welding sonotrode on the friction work at the weld interface. The change in the friction work at the weld interface has been explained on the basis of softening (thermal and acoustic) of the specimen during the ultrasonic welding process. In the end, a comparison between experimental and simulated results has been presented, showing a good agreement. Copyright © 2009 by ASME.

In situ FTIR spectroscopy studies on electrochemical redox processes of high nuclearity osmium carbonyl clusters

The electrochemical redox processes of two high nuclearity osmium carbonyl clusters [(PhP)N[OsC(CO) ]·PPN (1) and Os(CO) (6) have been studied by electrochemical in situ FTIR. The five oxidation states of 1, i.e., [OsC(CO)], have been characterized. There are no significant structural changes for these species. Hence, the ability of this decanuclear cluster to act as an electron reservoir has been demonstrated. The structural rearrangement associated with the two-electron reduction of bicapped tetrahedral 6 to octahedral dianion [Os(CO)] and [Os(CO)] tetraanion has also been investigated. © 1996 American Chemical Society.

Hybrid Polyoxovanadates: Anion-Influenced Formation of Nanoscopic Cages and Supramolecular Assemblies of Asymmetric Clusters

Organoarsonate-functionalized polyoxovanadates form upon the reduction of vanadates(V) in aqueous systems, whereby the underlying condensation reactions are influenced by the nature of the employed acid. In the presence of Cl− ions that derive from hydrochloric acid, a tetradecanuclear cage [VIV14O16(OH)8(O3AsC6H4-4-NH2)10]4– is obtained. When nitric acid is used, a condensed, decanuclear complex [V10O18(O3AsC6H4-4-NH2)7(DMF)2]5– forms. The latter organizes into a hexagonal packing arrangement in the solid state.

Self-assembly of hybrid organic–inorganic polyoxovanadates: functionalised mixed-valent clusters and molecular cages’

Herein we report the intra- and inter-molecular assembly of a {V5O9} subunit. This mixed-valent structural motif can be stabilised as [V5O9(L1–3)4]5−/9− (1–3) by a range of organoarsonate ligands (L1–L3) whose secondary functionalities influence its packing arrangement within the crystal structures. Variation of the reaction conditions results in the dodecanuclear cage structure [V12O14(OH)4(L1)10]4− (4) where two modified convex building units are linked via two dimeric {O4VIV(OH)2VIVO4} moieties. Bi-functional phosphonate ligands, L4–L6 allow the intramolecular connectivity of the {V5O9} subunit to give hybrid capsules [V10O18(L4–6)4]10− (5–7). The dimensions of the electrophilic cavities of the capsular entities are determined by the incorporated ligand type. Mass spectrometry experiments confirm the stability of the complexes in solution. We investigate and model the temperature-dependent magnetic properties of representative complexes 1, 4, 6 and 7 and provide preliminary cell-viability studies of three different cancer cell lines with respect to Na8H2[6]·36H2O and Na8H2[7]·2DMF·29H2O.

Hybrid Organic–Inorganic Polyoxometalates: Functionalization of VIV/ VV Nanosized Clusters to Produce Molecular Capsules

Functionalization of polyoxovanadate clusters using phosphonate and arsonate ligands results in molecular capsules (see structure; green V, purple P, red O, black C). Through the use of extended homologous ligands, these hybrid organic-inorganic capsules can be successively elongated into tubular molecules.

Microstructure and microtexture evolution of aluminum alloy 3003 under ultrasonic welding process for embedding SiC fibre

Ultrasonic welding process can be used for bonding metal foils which is the fundament of ultrasonic consolidation (UC). UC process can be used to embed reinforcement fibres such as SiC fibres within an aluminum matrix materials. In this research we are investigating the phenomena occurring in the microstructure of the parts during ultrasonic welding process to obtain better understanding about how and why the process works. High-resolution electron backscatter diffraction (EBSD) is used to study the effects of the vibration on the evolution of microstructure in AA3003. The inverse pole figures (IPF) and the correlated misorientation angle distribution of the mentioned samples are obtained. The characteristics of the crystallographic orientation, the grain structure and the grain boundary are analyzed to find the effect of ultrasonic vibration on the microstructure and microtexture of the bond. The ultrasonic vibration will lead to exceptional refinement of grains to a micron level along the bond area and affect the crystallographic orientation. Ultrasonic vibration results in a very weak texture. Plastic flow occurs in the grain after welding process and there is additional plastic flow around the fibre which leads to the fibre embedding. © 2009 Editorial Board of CHINA WELDING.

Tailoring ionic liquid catalysts: structure, acidity and catalytic activity of protonic ionic liquids based on anionic clusters, [(HSO4)(H2SO4)x]− (x = 0, 1, or 2)

Aiming at inexpensive Brønsted-acidic ionic liquids, suitable for industrial-scale catalysis, a family of protonic ionic liquids based on nitrogen bases and sulfuric acid has been developed. Variation of the molar ratio of sulfuric acid, χH2SO4, was used to tune acidity. The liquid structure was studied using 1H NMR and IR spectroscopies, revealing the existence of hydrogen-bonded clusters, [(HSO4)(H2SO4)]−, for χH2SO4 > 0.50. Acidity, quantified by Gutmann Acceptor Number (AN), was found to be closely related to the liquid structure. The ionic liquids were employed as acid catalysts in a model reaction; Fischer esterification of acetic acid with 1-butanol. The reaction rate depended on two factors; for χH2SO4 > 0.50, the key parameter was acidity (expressed as AN value), while for χH2SO4 > 0.50 it was the mass transport (solubility of starting materials in the ionic liquid phase). Building on this insight, the ionic liquid catalyst and reaction conditions have been chosen. Conversion values of over 95% were achieved under exceptionally mild conditions, and using an inexpensive ionic liquid, which could be recycled up to eight times without diminution in conversion or selectivity. It has been demonstrated how structural studies can underpin rational design and development of an ionic liquid catalyst, and in turn lead to a both greener and economically viable process.