Quantitative and high mass ToF-SIMS studies of siloxane segregation in hydrogel polymers using cryogenic sample handling techniques

This paper examines the capabilities of cryogenic sample handling to examine composition and structure of hydrogel materials where siloxane components are central to the analysis. XPS analysis of multicomponent polymers with cryogenic sample handling following exposure to aqueous environments has revealed the composition and kinetics of near surface reorganization for siloxane and fluorocarbon containing polymers. In this study we report results from a ToF-SIMS protocol for cryogenic sample handling applied to the analysis of surface changes upon hydration/dehydration of hydrogel polymers. Comparison of results from angle dependent XPS and ToF-SIMS are discussed for a range of commercial soft contact lens materials. Both methods detected changes in surface chemistry between the hydrated (frozen) and dehydrated surfaces. Analysis of the hydrated surfaces detected polymer components indicative of the commercial formulation as well as ice clusters. Analysis of the dehydrated materials detected changes in surface chemistry relative to the hydrated surface in addition to loss of water due to sample dehydration. A quantitative standard additions method for ToF-SIMS data was used to determine submonolayer amounts of PDMS impurities at the surface of the hydrogels. ToF-SIMS analysis of a series of seven poly (allyl methacrylate-g-dimethylsiloxane), AMA-g-DMS, graft copolymers in the hydrated state revealed high mass oligomeric ion distributions for systems with bulk PDMS content greater than 25 wt.%. This marks the first time that detection of high mass oligomeric ion distributions from hydrated (frozen) surfaces has been reported. Analysis of the dehydrated surface detected formation of high mass oligomeric ion distributions for systems with PDMS bulk content greater than 15 wt.%, but only detected these ion distributions in wet (frozen) samples when the bulk concentration was greater than 25 wt.%.     

Gas-phase thermal decomposition of peroxy-N-butyryl nitrate

The gas-phase thermal decomposition rate of peroxy-n-butyryl nitrate (n-C₃H₇C(O)OONO₂, PnBN) has been measured at ambient temperature (296 K) and 1 atm of air relative to that of peroxyacetyl nitrate (CH₃C(O)OONO₂, PAN) using mixtures of PAN (14–19 ppb), PnBN (22–46 ppb), and nitric oxide (1.35–1.90 ppm). The PnBN/PAN decomposition rate ratio was 0.773 ± 0.030. This ratio, together with a literature value of 3.0 × 10^?4 s^?1 for the thermal decomposition rate of PAN at 296 K, yields a PnBN thermal decomposition rate of (2.32 ± 0.09) × 10^?4 s^?1. The results are briefly discussed by comparison with data for other peroxyacyl nitrates and with respect to the atmospheric persistence of PnBN. © 1994 John Wiley & Sons, Inc.     

Decay of confined,two-dimensional,spatially periodic arrays of vortices: A numerical investigation

The disarrangement of a perturbed lattice of vortices was studied numerically. The basic state is an exponentially decaying, exact solution of the Navier-Stokes equations. Square arrays of vortices with even numbers of vortex cells along each side were perturbed and their evolution was investigated. Whether the energy in the perturbation grows somewhat before it decays or decays monotonically depends on the initial strength of the vortices of the basic state, the extent of lateral confinement and the structure of the perturbation. The critical condition for temporally local instability, i.e. the critical amplitude of the basic state that must be exceeded to allow energy transfer from the basic state to the perturbation, is discussed. In the strongly confined case of a square lattice of four vortices the appearance of enchancement of global rotation is the result of energy transfer from the basic state to a temporally local unstable mode. Energy is transferred from the basic state to larger-scaled structures (inverse cascade) only if the scales of the larger structures are inherently contained in the initial structure of the perturbation. The initial structure of the double array of vortices is not maintained except for a very special form of perturbation. The facts that large scales decay more slowly than small scales and that, when non-linearities are sufficiently strong, energy is transferred from one scale to another explain the differences in the disarrangement process for different initial strengths of the vortices of the basic state. The stronger vortices, i.e. the vortices perturbed in a manner that increases their strength, tend to dominate the weaker vortices. The pairing and subsequent merging (or capture) of vortices of like sense into larger-scale vortices are described in terms of peaks in the evolution of the square root of the palinstrophy divided by the enstrophy.     

Modélisation du champ des vitesses de l'urine dans un bolus urétéralModelling of urine flow in an ureteral bolus

Urine transport is made from the kidney to the bladder through the ureter by isolated pockets called bolus. To determine the urine flow in a bolus, we use an adherence condition on the interface urine/wall. It gives us an infinite linear system verified by a set of parameters. An iterative and convergent algorithm allows us to solve this system and to determine analytically the components of the velocity vector in the bolus. To cite this article: A. Vogel et al., C. R. Mecanique 332 (2004).     

Effect of nanotube functionalization on the properties of single‐walled carbon nanotube/polyurethane composites

A commercially available aliphatic thermoplastic polyurethane formulated with a methylene bis(cyclohexyl) diisocyanate hard segment and a poly(tetramethylene oxide) soft segment and chain‐extended with 1,4‐butanediol was dissolved in dimethylformamide and mixed with dispersed single‐walled carbon nanotubes. The properties of composites made with unfunctionalized nanotubes were compared with the properties of composites made with nanotubes functionalized to contain hydroxyl groups. Functionalization almost eliminated the conductivity of the tubes according to the conductivity of the composites above the percolation threshold. In most cases, functionalized and unfunctionalized tubes yielded composites with statistically identical mechanical properties. However, composites made with functionalized tubes did have a slightly higher modulus in the rubbery plateau region at higher nanotube fractions. Small‐angle X‐ray scattering patterns indicated that the dispersion reached a plateau in the unfunctionalized composites that was consistent with the plateau in the rubbery plateau region. The room‐temperature modulus and tensile strength increase was proportionally higher than almost all increases seen previously in thermoplastic polyurethanes; however, the increase was still an order of magnitude below what has been reported for the best nanotube–polymer systems. Nanotube addition increased the hard‐segment glass transition temperature slightly, whereas the soft‐segment glass transition was so diffuse that no conclusions could be drawn. Unfunctionalized tubes suppressed the crystallization of the hard segment; whereas functionalized tubes had no effect. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 490–501, 2007     

New data on the ternary fission of 252Cf from the Gammasphere facility

Ternary fission of ²⁵²Cf was studied at Gammasphere using eight ΔE×E particle telescopes. Helium, beryllium, boron, and carbon light charged particles (LCPs) emitted with kinetic energy more than 9, 21, 26, and 32 MeV, respectively, were identified. The 3368-keV γ transition from the first 2⁺ excited state in ¹⁰Be was found and the population probability ratio N(2⁺)/N(0⁺) = 0.160 ± 0.025 was estimated. No evidence was found for 3368-keV γ rays emitted from a triple molecular state. For the first time, charge distributions are obtained for ternary fission fragments emitted with helium, beryllium, and carbon LCPs.     

Bending loss measurement using a fiber cavity ringdown scheme

A novel sensitive technique for the determination of losses in fiber cavities is presented. The method is based on the cavity ringdown scheme implemented in silica-based single-mode fibers. Bending losses of fiber cavities of different lengths have been measured showing all an oscillating behavior with respect to the curvature radius of the fiber as predicted by a theoretical model. The best minimum detectable absorbance per cavity pass achieved by this new method is 1.72×10⁻³ dB within a 10 m-long cavity. This limit suffices well for an accurate determination of optical bending losses even in bend-insensitive fibers. Furthermore, the comparison of the measured bending losses with a theoretical model allows the extraction of different fiber parameters. Good agreement has been found between the experimentally derived parameters and literature data.     

Optimization for pattern classification using biased random search techniques

We demonstrate how optimization problems arise in the field of pattern classification, in particular in using piecewise-linear classification and classification based on an optimal linear separator. We motivate the need in this area for a general purpose optimization approach. We discuss ALOPEX, a biased random search approach, from the point of view of this need. While ALOPEX itself failed to fulfil our need, a newly-introduced generalization of it (iterated ALOPEX) was found to be appropriate for the optimization problems of our particular concern. We conclude the paper with a brief critical evaluation of this approach as compared to our original aims.     

Un théorème de type Beurling–Lax dans la boule unitéA Beurling–Lax type theorem in the unit ball

We prove a Beurling–Lax theorem for a family of reproducing kernel Hilbert spaces of functions analytic in an open subset of the unit ball containing the origin. The spaces under consideration are characterized by functions called Schur multipliers. Using the theory of linear relations in Pontryagin spaces we also give coisometric realizations of Schur multipliers. To cite this article: D. Alpay et al., C. R. Acad. Sci. Paris, Ser. I 334 (2002) 349–354.     

Coloring mixed hypertrees

A mixed hypergraph is a triple (V,C,D) where V is its vertex set and C and D are families of subsets of V, called C-edges and D-edges, respectively. For a proper coloring, we require that each C-edge contains two vertices with the same color and each D-edge contains two vertices with different colors. The feasible set of a mixed hypergraph is the set of all k's for which there exists a proper coloring using exactly k colors. A hypergraph is a hypertree if there exists a tree such that the edges of the hypergraph induce connected subgraphs of the tree.We prove that feasible sets of mixed hypertrees are gap-free, i.e., intervals of integers, and we show that this is not true for precolored mixed hypertrees. The problem to decide whether a mixed hypertree can be colored by k colors is NP-complete in general; we investigate complexity of various restrictions of this problem and we characterize their complexity in most of the cases.