In-situ SAXS studies of the morphological changes of an alumina-zirconia-silicate ceramic during its formation

D Le Messurier, R Winter, CM Martin; J Appl Cryst 39 (2006) 589 Sponsorship: EPSRC, CCLRC, Pilkington

Locating hexagonal and cubic phases in boron nitride using wavelength-selective optically detected x-ray absorption spectroscopy

Locating hexagonal and cubic phases in boron nitride using wavelength-selective optically detected x-ray absorption spectroscopy, D.A. Evans, A.R. Vearey-Roberts, N.R.J. Poolton Appl Phys Lett 89, (2006) 161107

Two-electron QED contributions to the ground-state binding energy in He-like Kr34+ ions

The two-electron QED contributions to the ground-state binding energy of Kr34+ ions have been determined in two independent experiments performed with electron beam ion traps (EBIT) in Heidelberg (HD) and Tokyo (BT, Belfast-Tokyo collaboration). X rays arising from radiative recombination (RR) of free electrons to the ground state of initially bare Kr36+ and hydrogenlike Kr35+ ions were observed as a function of the interacting electron energy. The K edge absorption by thin Eu and W foils provided fixed photon energy references used to measure the difference in binding energy Delta E-2e between the H- and He-like Kr ions (Kr35+ and Kr34+, respectively). The two values agree well, yielding a final result of Delta E-2e=641.8 +/- 1.7 eV, confirming recent results of rigorous QED calculations. This accuracy is just of the order required to access screened radiative QED contributions.

Electronic structures and bonding properties of chlorine-treated nitrogenated carbon nanotubes: X-ray absorption and scanning photoelectron microscopy studies

The electronic and bonding properties of nitrogenated carbon nanotubes (N-CNTs) exposed to chlorine plasma were investigated using C and N K-edge x-ray absorption near-edge structure (XANES) and scanning photoelectron microscopy (SPEM). The C and N K-edge XANES spectra of chlorine-treated N-CNTs consistently reveal the formation of pyridinelike N-CNTs by the observation of 1s ->pi(*)(e(2u)) antibonding and 1s ->pi(*)(b(2g)) bonding states. The valence-band photoemission spectra obtained from SPEM images indicate that chlorination of the nanotubes enhances the C-N bonding. First-principles calculations of the partial densities of states in conjunction with C K-edge XANES data identify the presence of C-Cl bonding in chlorine treated N-CNTs. (C) 2007 American Institute of Physics.

TiK alpha radiography of Cu-doped plastic microshell implosions via spherically bent crystal imaging

We show that short pulse laser generated Ti K alpha radiation can be used effectively as a backlighter for radiographic imaging. This method of x-ray radiography features high temporal and spatial resolution, high signal to noise ratio, and monochromatic imaging. We present here the Ti K alpha backlit images of six-beam driven spherical implosions of thin-walled 500-mu m Cu-doped deuterated plastic (CD) shells and of similar implosions with an included hollow gold cone. These radiographic results were used to define conditions for the diagnosis of fast ignition relevant electron transport within imploded Cu-doped coned CD shells. (c) 2005 American Institute of Physics.

Bright quasi-phase-matched soft-x-ray harmonic radiation from argon ions

Selective enhancement (> 10(3)) of harmonics extending to the water window (similar to 4 nm) generated in an argon gas filled straight bore capillary waveguide is demonstrated. This enhancement is in good agreement with modeling which indicates that multimode quasi-phase-matching is achieved by rapid axial intensity modulations caused by beating between the fundamental and higher-order capillary modes. Substantial pulse energies (> 10 nJ per pulse per harmonic order) at wavelengths beyond the carbon K edge (similar to 4.37 nm, similar to 284 eV) up to similar to 360 eV are observed from argon ions for the first time.

M-L band x-rays (3-3.5 KeV) from palladium coated targets for isochoric radiative heating of thin foil samples

We describe experiments designed to produce a bright M-L band x-ray source in the 3-3.5 keV region. Palladium targets irradiated with a 10(15) W cm(-2) laser pulse have previously been shown to convert up to similar to 2% of the laser energy into M-L band x-rays with similar pulse duration to that of the incident laser. This x-ray emission is further characterized here, including pulse duration and source size measurements, and a higher conversion efficiency than previously achieved is demonstrated (similar to 4%) using more energetic and longer duration laser pulses (200 ps). The emission near the aluminium K-edge (1.465-1.550 keV) is also reported for similar conditions, along with the successful suppression of such lower band x-rays using a CH coating on the rear side of the target. The possibility of using the source to radiatively heat a thin aluminium foil sample to uniform warm dense matter conditions is discussed.

Evolution of an Archean greenstone belt in the Stormy Lake - Kawashegamuk Lake area (stratigraphy, structure and geochemistry) - Western Wabigoon Subprovince, Northwest Ontario /

330 km 2 of the easter-n part of the Archean Manitou Lakes - Stormy Lake metavolcanic - metasedimentary belt have been mapped and sampled. A large number of rocks ~.vere analyzed for the major and trace constituents including the rare-earth elements (REE). The Stormy Lake - Kawashegamuk Lake area may be subdivided into four major lithological groups of supracrustal rocks 1) A north-facing mafic assemblage, consisting of pillowed tholeiitic basalts and gabbro sills characterized by flat REE profiles, is exposed in the south part of the map area and belongs to a 8000 m thick homoclinal assemblage outside the map area. Felsic pyroclastic rocks believed to have been issued from a large central vent conformably overlie the tholeiites. 2) A dominantly epiclastic group facing to the north consists of terrestrial deposits interpreted to be an alluvial fan deposit ; a submarine facies is represented by turbiditic sediments. 3) The northeastern part of the study area consists of volcanic rocks belonging to two mafic - felsic cycles facing to the southuest ; andesitic flows with fractionated REE patterns make up a large part of the upper cycle, whereas the lower cycle has a stronger chemical polarity being represented by tholeiitic flows, with flat REE, which a r e succeeded by dacitic and rhyolitic pyroclasti cs. iii 4) A thick monotonous succession of tholeiitic pillmled basalt f lows and gabbro sills with flat REE represent the youngest supracrustal rocks. TIle entire belt underwent folding, faulting and granitic plutonism during a tectono-thermal event around 2700 Ma ago. Rocks exposed in the map area were subjected to regional greenschist facies metamorphism, but higher metamorphic grades are present near late granitic intrusions. Geochemical studies have been useful in 1) distinguishing the various rock units ; 2) relating volcanic and intrusive rocks 3) studying the significance of chemical changes due to post magmatic processes 4) determining the petrogenesis of the major volcanic rock types. In doing so, two major volcanic suites have been recognized : a) a tholeiitic suite, mostly represented by mafic rocks, was derived from partial melting of upper mantle material depleted in Ti, K and the light REE ; b) a calc-alkalic suite which evolved from partial melting of amphibolite in the lower crust. The more differentiated magma types have been produced by a multistage process involving partial melting and fractional crystallization to yield a continuum of compos i t i ons ranging from basaltic andesite to rhyolite. A model for the development of the eastern part of the Manitou Lakes - Stormy Lake belt has been proposed.

The adsorption and stability of sulfur containing amino acids on Cu{531}

The adsorption of L-CySteine and L-methionine amino acids on a chiral Cu{5 3 1} surface was investigated with high resolution X-ray photoelectron spectroscopy (XPS) and carbon K-edge near edge X-ray absorption fine structure (NEXAFS) Spectroscopy using synchrotron radiation. XPS shows that at 300 K L-cysteine adsorbs through two oxygen, a nitrogen and a sulfur atom, in a four point 'quadrangular footprint', whereas L-methionine adsorbs through only two oxygen and a nitrogen atom in a 'triangular footprint'. NEWS was used to clarify the adsorption geometry of both molecules, which suggests a binding orientation to the top layer and second layer atoms in two different orientations associated with adsorption sites on {1 1 0} and {3 1 1} microfacets; of the Cu{5 3 1} surface. (C) 2009 Elsevier B.V. All rights reserved.

Enantiospecific adsorption of alanine on the chiral Cu{531} surface

We have studied enantiospecific differences in the adsorption of (S)- and (R)-alanine on Cu{531}R using low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy, and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. At saturation coverage, alanine adsorbs as alaninate forming a p(1 4) superstructure. LEED shows a significantly higher degree of long-range order for the S than for the R enantiomer. Also carbon K-edge NEXAFS spectra show differences between (S)- and (R)-alanine in the variations of the ð resonance when the linear polarization vector is rotated within the surface plane. This indicates differences in the local adsorption geometries of the molecules, most likely caused by the interaction between the methyl group and the metal surface and/or intermolecular hydrogen bonds. Comparison with model calculations and additional information from LEED and photoelectron spectroscopy suggest that both enantiomers of alaninate adsorb in two different orientations associated with triangular adsorption sites on {110} and {311} microfacets of the Cu{531} surface. The experimental data are ambiguous as to the exact difference between the local geometries of the two enantiomers. In one of two models that fit the data equally well, significantly more (R)-alaninate molecules are adsorbed on {110} sites than on {311} sites whereas for (S)-alaninate the numbers are equal. The enantiospecific differences found in these experiments are much more pronounced than those reported from other ultrahigh vacuum techniques applied to similar systems.

Vertex splitting and connectivity augmentation in hypergraphs

We consider problems of splitting and connectivity augmentation in hypergraphs. In a hypergraph G = (V +s, E), to split two edges su, sv, is to replace them with a single edge uv. We are interested in doing this in such a way as to preserve a defined level of connectivity in V . The splitting technique is often used as a way of adding new edges into a graph or hypergraph, so as to augment the connectivity to some prescribed level. We begin by providing a short history of work done in this area. Then several preliminary results are given in a general form so that they may be used to tackle several problems. We then analyse the hypergraphs G = (V + s, E) for which there is no split preserving the local-edge-connectivity present in V. We provide two structural theorems, one of which implies a slight extension to Mader’s classical splitting theorem. We also provide a characterisation of the hypergraphs for which there is no such “good” split and a splitting result concerned with a specialisation of the local-connectivity function. We then use our splitting results to provide an upper bound on the smallest number of size-two edges we must add to any given hypergraph to ensure that in the resulting hypergraph we have λ(x, y) ≥ r(x, y) for all x, y in V, where r is an integer valued, symmetric requirement function on V*V. This is the so called “local-edge-connectivity augmentation problem” for hypergraphs. We also provide an extension to a Theorem of Szigeti, about augmenting to satisfy a requirement r, but using hyperedges. Next, in a result born of collaborative work with Zoltán Király from Budapest, we show that the local-connectivity augmentation problem is NP-complete for hypergraphs. Lastly we concern ourselves with an augmentation problem that includes a locational constraint. The premise is that we are given a hypergraph H = (V,E) with a bipartition P = {P1, P2} of V and asked to augment it with size-two edges, so that the result is k-edge-connected, and has no new edge contained in some P(i). We consider the splitting technique and describe the obstacles that prevent us forming “good” splits. From this we deduce results about which hypergraphs have a complete Pk-split. This leads to a minimax result on the optimal number of edges required and a polynomial algorithm to provide an optimal augmentation.

The adsorption geometry and chemical state of lysine on Cu{110}

Chemisorbed layers of lysine adsorbed on Cu{110} have been studied using X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. XPS indicates that the majority (70%) of the molecules in the saturated layer at room temperature (coverage 0.27 ML) are in their zwitterionic state with no preferential molecular orientation. After annealing to 420 K a less densely packed layer is formed (0.14 ML), which shows a strong angular dependence in the characteristic π-resonance of oxygen K edge NEXAFS and no indication of zwitterions in XPS. These experimental results are best compatible with molecules bound to the substrate through the oxygen atoms of the (deprotonated) carboxylate group and the two amino groups involving Cu atoms in three different close packed rows. This μ4 bonding arrangement with an additional bond through the !-amino group is different from geometries previously suggested for lysine on Cu{110}.

Observing the in situ chiral modification of Ni nanoparticles using scanning transmission X-ray microspectroscopy

Enantioselective heterogeneous hydrogenation of Cdouble bond; length as m-dashO bonds is of great potential importance in the synthesis of chirally pure products for the pharmaceutical and fine chemical industries. One of the most widely studied examples of such a reaction is the hydrogenation of β-ketoesters and β-diketoesters over Ni-based catalysts in the presence of a chiral modifier. Here we use scanning transmission X-ray microscopy combined with near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) to investigate the adsorption of the chiral modifier, namely (R,R)-tartaric acid, onto individual nickel nanoparticles. The C K-edge spectra strongly suggest that tartaric acid deposited onto the nanoparticle surfaces from aqueous solutions undergoes a keto-enol tautomerisation. Furthermore, we are able to interrogate the Ni L2,3-edge resonances of individual metal nanoparticles which, combined with X-ray diffraction (XRD) patterns showed them to consist of a pure nickel phase rather than the more thermodynamically stable bulk nickel oxide. Importantly, there appears to be no “particle size effect” on the adsorption mode of the tartaric acid in the particle size range ~ 90–~ 300 nm.

Asymmetric Ramsey Properties of Random Graphs Involving Cliques

Consider the following problem: Forgiven graphs G and F(1),..., F(k), find a coloring of the edges of G with k colors such that G does not contain F; in color i. Rodl and Rucinski studied this problem for the random graph G,,, in the symmetric case when k is fixed and F(1) = ... = F(k) = F. They proved that such a coloring exists asymptotically almost surely (a.a.s.) provided that p <= bn(-beta) for some constants b = b(F,k) and beta = beta(F). This result is essentially best possible because for p >= Bn(-beta), where B = B(F, k) is a large constant, such an edge-coloring does not exist. Kohayakawa and Kreuter conjectured a threshold function n(-beta(F1,..., Fk)) for arbitrary F(1), ..., F(k). In this article we address the case when F(1),..., F(k) are cliques of different sizes and propose an algorithm that a.a.s. finds a valid k-edge-coloring of G(n,p) with p <= bn(-beta) for some constant b = b(F(1),..., F(k)), where beta = beta(F(1),..., F(k)) as conjectured. With a few exceptions, this algorithm also works in the general symmetric case. We also show that there exists a constant B = B(F,,..., Fk) such that for p >= Bn(-beta) the random graph G(n,p) a.a.s. does not have a valid k-edge-coloring provided the so-called KLR-conjecture holds. (C) 2008 Wiley Periodicals, Inc. Random Struct. Alg., 34, 419-453, 2009

Oxidation of anilinium ions intercalated in montmorillonite clay by electrochemical route

Resonance Raman, FTIR, X-ray diffraction, UV-vis-NIR, electron paramagnetic resonance, X-ray absorption at Si K-edge and electron microscopy were employed for characterizing the products formed through electrochemical oxidation of intercalated anilinium ions inside the cationic montmorillonite (MMT) clay. The layer silicate structure was not affected by the anilinium oxidation between the layers. The intercalated products present only an electronic absorption band at 400 nm, very low conductivity (ca. 10(-7) S cm(-1)) and their Raman spectrum displays bands, with high relative intensities, assigned to the benzidine dication, indicating that this product was formed in high amount. Nevertheless, bands that can be correlated to phenazine-like segments and 1,4-phenylenediamine repeat units (PANI like segments) are also observed. The very low EPR signal indicates that diamagnetic species are predominant. All results are compared to those obtained by anilinium-MMT chemically oxidized by persulfate and the differences are pointed out. (C) 2008 Elsevier B.V. All rights reserved.