Multifunctional ToF-SIMS: combinatorial mapping of gradient energy substrates

We present a simple method for chemical modification of chlorosilane self-assembled monolayers (SAMs) on Si surfaces by exposure to a gradient of UV-ozone radiation to create stable substrates with a range of contact angles (θ_H2O≈5–95°) and surface energies on a single substrate. These gradient energy substrates are developed to potentially generate libraries for combinatorial studies of thin film phenomenology, where a systematic variation of interfacial surface energy represents one of the significant parameters along one axis. The graded oxidation process presents a systematic variation of surface chemical composition. We have utilized contact angle measurements and time-of-flight secondary ion mass spectrometry (ToF-SIMS) to investigate this variation for a series of ions, among which are SiCH₃⁺, SiOH⁺ and COOH⁻. We show that the macroscopic measurements of surface free energy/contact angle correlate with the detailed analysis of surface chemistry (as assessed by ToF-SIMS) on these test substrates.     

Tight-binding method modelling of photonic crystal waveguides

We present here a tight-binding-like modelling of two-dimensional (2D) photonic crystals (PCs). Adopted from solid-state physics, the concept of generalized Wannier functions is used to construct a localized state basis that allows a parameter-free ab initio study of defects in PCs. We demonstrate here for a 2D triangular lattice of dielectric rods in air, the existence of this localized basis and the possibility to study large scale complex dielectric structures deviating from periodicity. Specific numerical simulations on a split waveguide embedded in this triangular lattice are performed, and they demonstrate the superiority of this method over plane wave based techniques.     

3D molecular imaging SIMS

Thin monolayer and bilayer films of spin cast poly(methyl methacrylate) (PMMA), poly(2-hydroxyethyl methacrylate) (PHEMA), poly(lactic) acid (PLA) and PLA doped with several pharmaceuticals have been analyzed by dynamic SIMS using SF₅⁺ polyatomic primary ion bombardment. Each of these systems exhibited minimal primary beam-induced degradation under cluster ion bombardment allowing molecular depth profiles to be obtained through the film. By combing secondary ion imaging with depth profiling, three-dimensional molecular image depth profiles have been obtained from these systems. In another approach, bevel cross-sections are cut in the samples with the SF₅⁺ primary ion beam to produce a laterally magnified cross-section of the sample that does not contain the beam-induced damage that would be induced by conventional focussed ion beam (FIB) cross-sectioning. The bevel surface can then be examined using cluster SIMS imaging or other appropriate microanalysis technique.     

Fully adaptive multiresolution finite volume schemes for conservation laws

The use of multiresolution decompositions in the context of finite volume schemes for conservation laws was first proposed by A. Harten for the purpose of accelerating the evaluation of numerical fluxes through an adaptive computation. In this approach the solution is still represented at each time step on the finest grid, resulting in an inherent limitation of the potential gain in memory space and computational time. The present paper is concerned with the development and the numerical analysis of fully adaptive multiresolution schemes, in which the solution is represented and computed in a dynamically evolved adaptive grid. A crucial problem is then the accurate computation of the flux without the full knowledge of fine grid cell averages. Several solutions to this problem are proposed, analyzed, and compared in terms of accuracy and complexity.

     

Branch and win: OR tree search algorithms for solving combinatorial optimisation problems

Currently, most combinatorial optimisation problems have to be solved, if the optimum solution is sought, using general techniques to explore the space of feasible solutions and, more specifically, through exploratory enumerative procedures in trees and search graphs. We propose Branch and Win, a general formulation for understanding and synthesising the different tree search procedures that have been presented in the literature of operations research as well as in that of artificial intelligence. Several general ideas are also presented, whose application allows designing new hybrid search algorithms, in order to implement the procedure.     

Pressure-temperature phase diagrams of smectogenic 4'-alkyl-4-cyanobiphenyls (9CB, 10CB, 11CB and 12CB)

The pressure-temperature ( p - T ) phase diagrams for four smectogenic members of the 4'-alkyl-4-cyanobiphenyl homologous series ( n CB, n =9, 10, 11 and 12) over the temperature range 320-410 K and pressure range 0.1-300 MPa (3 kbar) were constructed using DTA. At 1 atm 9CB exhibits nematic and smectic A d phases, while the other members show only the smectic A d phase. However, at elevated pressures the clearing line splits in the case of 10CB and 11CB which indicates the induction of a nematic phase. It was found that the triple point, where the isotropic, nematic and smectic phases coexist, is strongly shifted to higher pressures with increasing chain length. This was interpreted as being caused by a loss of the rod-like shape of the molecules containing longer alkyl tails which explore a range of conformations. The slope of the clearing line, d T /d p , depends strongly on the length of the alkyl chain for the n CB series, but does not show a step-wise change between the nematogenic and smectogenic members.     

Behaviors of the positive temperature coefficient of resistance of poly(styrene‐co‐n‐butylacrylate) filled with Ni‐plated core‐shell polymeric particles

Conductive composite films of poly(styrene‐co‐n‐butylacrylate) copolymers filled with low‐density, Ni‐plated core‐shell polymeric particles were prepared and their behaviors of positive temperature coefficient of resistance (PTCR) were investigated. When the conductive fillers in the composite film were loaded beyond the critical volume, 10 up to 25 vol %, composite films exhibited a unique electrical resistant transition behavior, which the electrical resistance rapidly increased by several orders of magnitude at the critical temperature. The PTCR transition temperature, in general, occurred before the glass transition temperature of polymer matrix. Further increased the conductive filler loading to 30 vol %, the overpacked conduction paths were formed in the entire composite and the PTCR effects became blurred. While the composite film treated with thermal cycle several times from room temperature up to 120 °C, the electrical resistivity increased accompanied with the shift of the PTCR transition to lower temperature. The reason might have been caused by the formed interfacial cracks within the composite film. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 322–329, 2007     

Bis[3‐(trimethyl­silyl)prop­yl] ethyl­enebisphospho­nate,H2DTMSP[EBP]

The title compound (H₂DTMSP[EBP]), C₁₄H₃₆O₆P₂Si₂, was crystallized by the slow evaporation of a solution in a 20:1 mixture of pentane and acetone. The H₂DTMSP[EBP] mole­cule lies about an inversion center. In the solid state, the mol­ecule exists in an anti configuration, with the mol­ecular backbone C—C bond located on an inversion center. The compound exists in the solid state as hydrogen‐bonded infinite sheets in the ab plane, unlike the methyl­ene analogue, which exists as hydrogen‐bonded infinite chains, demonstrating an `even–odd' effect of the length of the backbone alkyl chain.     

Magnetic silica colloids for catalysis

Monodisperse magnetizable colloidal silica particles in a stable dispersion have been functionalized with a homogeneous catalyst: a PCP–pincer Pd-complex. In a proof-of-principle experiment we demonstrate the catalytic activity of the colloids in a C–C bond formation reaction. Advantages of the magnetic silica carriers are the large surface-to-volume ratio and the easy recovery by magnetic separation. After magnetic separation, the catalyst-loaded particles are readily redispersed for further use.     

Un théorème de Choquet-Deny pour les groupes moyennables

Résumé SoitG un groupe moyennable connexe, locallement compact, à base dénombrable. Soit une mesure positive sur les boréliens deG. Nous étudions les fonctions boréliennes positivesh vérifiant: g G, . Sous de bonnes hypothèses sur , nous obtenons, pour ces fonctions, une représentation intégrale à l'aide d'exponentielles.

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Summary LetG be a connected locally compact separable amenable group. Let be a positive measure on the Borel -field ofG. We study the positive Borel functionsh onG which satisfy: g G, . Under smooth assumptions on , we establish an integral representation of these functions in term of exponentials.