Homogeneous functional Ni-P/ceramic nanocomposite coatings via stable dispersions in electroless nickel electrolytes

Stable nanoparticle dispersions in concentrated electrolytes are prerequisite for a variety of advanced nanocomposites prepared by deposition techniques. In this work we investigate the synthesis of electroless Ni-P/functional ceramic coatings from concentrated electrolytes containing functional nanoparticles such as TiO(2), α-Fe(2)O(3), ITO, and CeO(2). Stable nanoparticle dispersions in both low and high phosphorus electrolytes are achieved at plating temperatures (80-90 °C) by a generalized scheme employing comb-polyelectrolyte and antifreeze additives. Dispersion stability at room temperature is achieved in both low and high phosphorus EN media using anionic comb-polyelectrolyte surfactants with polyether side chain of 1100 g/mol. The optimal surfactant concentration is determined by zeta-potential and thermo-gravimetric analysis. Without additives the dispersions flocculate and sediment between 65 and 80 °C. Such phenomenon is believed to be associated with a critical flocculation temperature (CFT). The CFT is also weekly dependent on the particle type and the high ionic strength media. Addition of antifreeze additives such as propylene glycol and urea to the dispersions restores stability and increase the CFT for all particles. We estimate an average increase of the CFT by 1.5-2 °C per 1% additive for all particles and electrolytes. While the particle stabilization scheme is generalized in this work, the composite EN plating proved highly dependent on particle type. Baths containing ITO nanoparticles showed no plating reactions and those containing α-Fe(2)O(3) no nanoparticle co-deposition. In contrast, homogeneous Ni-P/TiO(2) and Ni-P/CeO(2) nanocomposites with up to 22 vol.% nanoparticles are produced. The possible application of the stabilization principles developed here for other functional nanocomposite systems is discussed.     

A Micromechanics Finite-Strain Constitutive Model of Fibrous Tissue

Biological tissues have unique mechanical properties due to the wavy fibrous collagen and elastin microstructure. In inflation, a vessel easily distends under low pressure but becomes stiffer when the fibers are straightened to take up the load. The current microstructural models of blood vessels assume affine deformation, i.e., the deformation of each fiber is assumed to be identical to the macroscopic deformation of the tissue. This uniform-field (UF) assumption leads to the macroscopic (or effective) strain energy of the tissue that is the volumetric sum of the contributions of the tissue components. Here, a micromechanics-based constitutive model of fibrous tissue is developed to remove the affine assumption and to take into consideration the heterogeneous interactions between the fibers and the ground substance. The development is based on the framework of a recently developed second-order homogenization theory, and takes into account the waviness, orientations and spatial distribution of the fibers, as well as the material nonlinearity at finite-strain deformation. In an illustrative simulation, the predictions of the macroscopic stress-strain relation and the statistical deformation of the fibers are compared to the UF model, as well as finite-element (FE) simulation. Our predictions agree well with the FE results, while the UF predictions significantly overestimate. The effects of fiber distribution and waviness on the macroscopic stress-strain relation are also investigated. The present mathematical model may serves as a foundation for native as well as for engineered tissues and biomaterials.     

Crystalline Conductance and Absolutely Continuous Spectrum of 1D Samples

We characterize the absolutely continuous spectrum of half-line one-dimensional Schrödinger operators in terms of the limiting behavior of the crystalline Landauer–Büttiker conductance of the associated finite samples.     

Probing microscopic architecture of opaque heterogeneous systems using double-pulsed-field-gradient NMR

Microarchitectural features of opaque porous media and biological tissues are of great importance in many scientific disciplines ranging from chemistry, material sciences, and geology to biology and medicine. Noninvasive characterization of coherently organized pores is rather straightforward since conventional diffusion magnetic resonance methods can detect anisotropy on a macroscopic scale; however, it remains extremely challenging to directly infer on microarchitectural features on the microscopic scale in heterogeneous porous media and biological cells that are comprised of randomly oriented compartments, a scenario widely encountered in Nature. Here, we show that the angular bipolar double-pulsed-field-gradient (bp-d-PFG) methodology is capable of reporting on unique microarchitectural features of highly heterogeneous systems. This was demonstrated on a toluene-in-water emulsion system, quartz sand, and even biological specimens such as yeast cells and isolated gray matter. We find that in the emulsion and yeast cells systems, the angular bp-d-PFG methodology uniquely revealed nearly an image of the pore space, since it conveyed direct microarchitectural information such as compartment shape and size. In two different quartz sand specimens, the angular bp-d-PFG experiments demonstrated the presence of randomly oriented anisotropic compartments. We also obtained unequivocal evidence that diffusion in interconnected interstices is restricted and therefore non-Gaussian. In biological contexts, the angular bp-d-PFG experiments could uniquely differentiate between spherical cells and randomly oriented compartments in gray matter tissue, information that could not be obtained by conventional NMR methods. The angular bp-d-PFG methodology also performs very well even when severe background gradients are present, as is often encountered in realistic systems. We conclude that this method seems to be the method of choice for characterizing the microstructure of porous media and biological cells noninvasively.     

Pore diameter mapping using double pulsed-field gradient MRI and its validation using a novel glass capillary array phantom

Double pulsed-field gradient (d-PFG) MRI can provide quantitative maps of microstructural quantities and features within porous media and tissues. We propose and describe a novel MRI phantom, consisting of wafers of highly ordered glass capillary arrays (GCA), and its use to validate and calibrate a d-PFG MRI method to measure and map the local pore diameter. Specifically, we employ d-PFG Spin-Echo Filtered MRI in conjunction with a recently introduced theoretical framework, to estimate a mean pore diameter in each voxel within the imaging volume. This simulation scheme accounts for all diffusion and imaging gradients within the diffusion weighted MRI (DWI) sequence, and admits the violation of the short gradient pulse approximation. These diameter maps agree well with pore sizes measured using both optical microscopy and single PFG diffusion diffraction NMR spectroscopy using the same phantom. Pixel-by-pixel analysis shows that the local pore diameter can be mapped precisely and accurately within a specimen using d-PFG MRI.     

Synthesis of poly(4‐vinylpyridine) by reverse atom transfer radical polymerization

Controlled radical polymerization of 4‐vinylpyridine (4VP) was achieved in a 50 vol % 1‐methyl‐2‐pyrrolidone/water solvent mixture using a 2,2′‐azobis(2,4‐dimethylpentanitrile) initiator and a CuCl₂/2,2′‐bipyridine catalyst–ligand complex, for an initial monomer concentration of [M]₀ = 2.32–3.24 M and a temperature range of 70–80 °C. Radical polymerization control was achieved at catalyst to initiator molar ratios in the range of 1.3:1 to 1.6:1. First‐order kinetics of the rate of polymerization (with respect to the monomer), linear increase of the number–average degree of polymerization with monomer conversion, and a polydispersity index in the range of 1.29–1.35 were indicative of controlled radical polymerization. The highest number–average degree of polymerization of 247 (number–average molecular weight = 26,000 g/mol) was achieved at a temperature of 70 °C, [M]₀ = 3.24 M and a catalyst to initiator molar ratio of 1.6:1. Over the temperature range studied (70–80 °C), the initiator efficiency increased from 50 to 64% whereas the apparent polymerization rate constant increased by about 60%. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5748–5758, 2007     

On Exiting After Voting

We consider the problem of a society whose members must choose from a finite set of alternatives. After knowing the chosen alternative, members may reconsider their membership by either staying or exiting. In turn, and as a consequence of the exit of some of its members, other members might now find undesirable to belong to the society as well. For general exit procedures we analyze the exit behavior of members after knowing the chosen alternative. For the case of monotonic preferences we propose, for each chosen alternative, an unambiguous and meaningful prediction of the subset of members that will exitWe thank Salvador Barberà, Carmen Beviá, David Cantala, Howard Petith, William Thomson, Marc Vorsatz, and Associate Editor, and two anonymous referees for their helpful comments and suggestions. The work of D. Berga is partially supported by Research Grants 9101100 from the Universitat de Girona, and also by AGL2001-2333-C02-01 and SEJ2004-03276 from the Spanish Ministry of Science and Technology and from the Spanish Ministry of Education and Science, respectively. The work of G. Bergantiñ os is partially supported by Research Grants BEC2002-04102-C02-01 from the Spanish Ministry of Science and Technology and PGIDIT03PXIC30002PN from the Xunta de Galicia. The work of J. Massó is partially supported by Research Grants BEC2002-02130 from the Spanish Ministry of Science and Technology and 2001SGR-00162 from the Generalitat de Catalunya. The work of D. Berga and J. Massó is also partially supported by the Barcelona Economics Program (CREA). The work of A. Neme is partially supported by Research Grant 319502 from the Universidad Nacional de San Luis     

Stability of spectral types for Jacobi matrices under decaying random perturbations

We study stability of spectral types for semi-infinite self-adjoint tridiagonal matrices under random decaying perturbations. We show that absolutely continuous spectrum associated with bounded eigenfunctions is stable under Hilbert-Schmidt random perturbations. We also obtain some results for singular spectral types.     

Glycerol as solvent and hydrogen donor in transfer hydrogenation-dehydrogenation reactions

Glycerol is employed successfully as a green solvent and hydrogen donor in catalytic transfer hydrogenation-dehydrogenation reactions. The glycerol donates hydrogen to various unsaturated organic compounds under mild reaction conditions and as a solvent, allows easy separation of products and catalyst recycling.