Sub-Riemannian Curvature in Contact Geometry

We compare different notions of curvature on contact sub-Riemannian manifolds. In particular, we introduce canonical curvatures as the coefficients of the sub-Riemannian Jacobi equation. The main result is that all these coefficients are encoded in the asymptotic expansion of the horizontal derivatives of the sub-Riemannian distance. We explicitly compute their expressions in terms of the standard tensors of contact geometry. As an application of these results, we obtain a sub-Riemannian version of the Bonnet–Myers theorem that applies to any contact manifold.     

Holderian Weak Invariance Principle for Stationary Mixing Sequences

We provide some sufficient mixing conditions on a strictly stationary sequence in order to guarantee the weak invariance principle in Hölder spaces. Strong mixing and \(\rho \)-mixing conditions are investigated as well as \(\tau \)-dependent sequences. The main tools are deviation inequalities for mixing sequences.     

Uniaxial Modeling of Multivariant Shape-Memory Materials with Internal Sublooping using Dissipation Functions

Models for the macroscopic behavior of Shape Memory Materials can be conveniently constructed within the Ziegler–Green–Naghdi framework where all the constitutive information is encoded in two ingredients: the free energy and the dissipation function. In a previous work, we have proposed various expressions for the basic functions suitable to model pseudoelasticity with complete transformations cycles. In this work we consider additional effects due to Martensite reorientation and to transformation reversal prior to transformation completion. The new constitutive model allows for the modeling of a variety of effects including: shape memory associated with thermally induced transformation, internal pseudoelastic subloops and the determination of limit cycles associated with repetitive stress cycling.     

Models for one-variant shape memory materials based on dissipation functions

Some simple models for the macroscopic behavior of shape memory materials whose microstructure can be described as a mixture of two phases are derived on the basis of a free energy and a dissipation function. Keeping a common expression for the free energy, each model is based on a different expression for the dissipation function. Temperature-induced as well as isothermal, adiabatic and convective stress-induced transformations are studied. Attention is paid to closed form solutions, comparison among the models and parameter identification.     

Opening the Pandora's jar of molecule‐to‐material conversion in chemical vapor deposition: Insights from theory

First‐principles modeling can be a powerful tool for the understanding and optimization of bottom‐up processes for nanomaterials fabrication, such as chemical vapor deposition (CVD), a key technology for the development of advanced systems and devices. Molecule‐to‐material conversion by CVD involves complex chemical phenomena, which are often obscure and still largely unexplored. A proper modeling would require high level of accuracy, large sized models and should include both temperature effects and statistical sampling of reactive events. By presenting a few selected examples, this perspective surveys such problems and discusses currently available approaches for their solution. Possible strategies for future advances in the field are also highlighted. © 2013 Wiley Periodicals, Inc.     

Interaction between inner and outer layer in drag-reduced turbulent flows

Effects of wall-based skin-friction drag reduction strategies on the statistical properties of large-scale motions in moderate Reynolds number turbulent flows have been investigated by exploiting Direct Numerical Simulation of turbulent channels. To educe large scales, a new efficient parallel distributed memory algorithm has been implemented which delivers data-driven modes of increasing characteristic lengthscales: the Fast and Adaptive Bidimensional Empirical Mode Decomposition (FABEMD). The influence of wall-based skin friction reduction on large scales is studied by comparing single point statistics, such as r.m.s. fluctuations, and two-point statistics, as cross-correlation functions in controlled and uncontrolled channel flow fields at constant friction Reynolds number. The traditional way of observing large-scale footprinting at the wall, as cross-correlation of the streamwise velocity components at different wall distances, has been found to be unreliable when comparing drag-reduced flows, due to the arbitrary choice of a reference plane in the logarithmic layer. A more sound way of observing the footprinting via the correlation of the streamwise velocity with the friction velocity is addressed and shows an increase of the footprinting in drag-reduced flows. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Coke formation during the methanol-to-olefin conversion: in situ microspectroscopy on individual H-ZSM-5 crystals with different Brønsted acidity

Coke formation during the methanol‐to‐olefin (MTO) conversion has been studied at the single‐particle level with in situ UV/Vis and confocal fluorescence microscopy. For this purpose, large H‐ZSM‐5 crystals differing in their Si/Al molar ratio have been investigated. During MTO, performed at 623 and 773 K, three major UV/Vis bands assigned to different carbonaceous deposits and their precursors are observed. The absorption at 420 nm, assigned to methyl‐substituted aromatic compounds, initiates the buildup of the optically active coke species. With time‐on‐stream, these carbonaceous compounds expand in size, resulting in the gradual development of a second absorption band at around 500 nm. An additional broad absorption band in the 600 nm region indicates the enhanced formation of extended carbonaceous compounds that form as the reaction temperature is raised. Overall, the rate of coke formation decreases with decreasing aluminum content. Analysis of the reaction kinetics indicates that an increased Brønsted acid site density facilitates the formation of larger coke species and enhances their formation rate. The use of multiple excitation wavelengths in confocal fluorescence microscopy enables the localization of coke compounds with different molecular dimensions in an individual H‐ZSM‐5 crystal. It demonstrates that small coke species evenly spread throughout the entire H‐ZSM‐5 crystal, whereas extended coke deposits primarily form near the crystal edges and surfaces. Polarization‐dependent UV/Vis spectroscopy measurements illustrate that extended coke species are predominantly formed in the straight channels of H‐ZSM‐5. In addition, at higher temperatures, fast deactivation leads to the formation of large aromatic compounds within channel intersections and at the external zeolite surface, where the lack of spatial restrictions allows the formation of graphite‐like coke.     

The porosity, acidity, and reactivity of dealuminated zeolite ZSM-5 at the single particle level: the influence of the zeolite architecture

A combination of atomic force microscopy (AFM), high‐resolution scanning electron microscopy (HR‐SEM), focused‐ion‐beam scanning electron microscopy (FIB‐SEM), X‐ray photoelectron spectroscopy (XPS), confocal fluorescence microscopy (CFM), and UV/Vis and synchrotron‐based IR microspectroscopy was used to investigate the dealumination processes of zeolite ZSM‐5 at the individual crystal level. It was shown that steaming has a significant impact on the porosity, acidity, and reactivity of the zeolite materials. The catalytic performance, tested by the styrene oligomerization and methanol‐to‐olefin reactions, led to the conclusion that mild steaming conditions resulted in greatly enhanced acidity and reactivity of dealuminated zeolite ZSM‐5. Interestingly, only residual surface mesoporosity was generated in the mildly steamed ZSM‐5 zeolite, leading to rapid crystal coloration and coking upon catalytic testing and indicating an enhanced deactivation of the zeolites. In contrast, harsh steaming conditions generated 5–50 nm mesopores, extensively improving the accessibility of the zeolites. However, severe dealumination decreased the strength of the Brønsted acid sites, causing a depletion of the overall acidity, which resulted in a major drop in catalytic activity.     

Hyperbranched anatase TiO2 nanocrystals: nonaqueous synthesis, growth mechanism, and exploitation in dye-sensitized solar cells

A colloidal crystal-splitting growth regime has been accessed, in which TiO(2) nanocrystals, selectively trapped in the metastable anatase phase, can evolve to anisotropic shapes with tunable hyperbranched topologies over a broad size interval. The synthetic strategy relies on a nonaqueous sol-gel route involving programmed activation of aminolysis and pyrolysis of titanium carboxylate complexes in hot surfactant media via a simple multi-injection reactant delivery technique. Detailed investigations indicate that the branched objects initially formed upon the aminolysis reaction possess a strained monocrystalline skeleton, while their corresponding larger derivatives grown in the subsequent pyrolysis stage accommodate additional arms crystallographically decoupled from the lattice underneath. The complex evolution of the nanoarchitectures is rationalized within the frame of complementary mechanistic arguments. Thermodynamic pathways, determined by the shape-directing effect of the anatase structure and free-energy changes accompanying branching and anisotropic development, are considered to interplay with kinetic processes, related to diffusion-limited, spatially inhomogeneous monomer fluxes, lattice symmetry breaking at transient Ti(5)O(5) domains, and surfactant-induced stabilization. Finally, as a proof of functionality, the fabrication of dye-sensitized solar cells based on thin-film photoelectrodes that incorporate networked branched nanocrystals with intact crystal structure and geometric features is demonstrated. An energy conversion efficiency of 6.2% has been achieved with standard device configuration, which significantly overcomes the best performance ever approached with previously documented prototypes of split TiO(2) nanostructures. Analysis of the relevant photovoltaic parameters reveals that the utilized branched building blocks indeed offer light-harvesting and charge-collecting properties that can overwhelm detrimental electron losses due to recombination and trapping events.     

Modular engineering of H-bonded supramolecular polymers for reversible functionalization of carbon nanotubes

A H-bond-driven, noncovalent, reversible solubilization/functionalization of multiwalled carbon nanotubes (MWCNTs) in apolar organic solvents (CHCl(3), CH(2)Cl(2), and toluene) has been accomplished through a dynamic combination of self-assembly and self-organization processes leading to the formation of supramolecular polymers, which enfold around the outer wall of the MWCNTs. To this end, a library of phenylacetylene molecular scaffolds with complementary recognition sites at their extremities has been synthesized. They exhibit triple parallel H-bonds between the NH-N-NH (DAD) functions of 2,6-di(acetylamino)pyridine and the CO-NH-CO (ADA) imidic groups of uracil derivatives. These residues are placed at 180° relative to each other (linear systems) or at 60°/120° (angular modules), in order to tune their ability of wrapping around MWCNTs. Molecular Dynamics (MD) simulations showed that the formation of the hybrid assembly MWCNT?[X?Y](n) (where X = 1a or 1b -DAD- and Y = 2, 3, or 4 -ADA-) is attributed to π-π and CH-π interactions between the graphitic walls of the carbon materials and the oligophenyleneethynylene polymer backbones along with its alkyl groups, respectively. Addition of polar or protic solvents, such as DMSO or MeOH, causes the disruption of the H-bonds with partial detachment of the polymer from the CNTs, followed by precipitation. Taking advantage of the chromophoric and luminescence properties of the molecular subunits, the solubilization/precipitation processes have been monitored by UV-vis absorption and luminescence spectroscopies. All hybrid MWCNTs-polymer materials have been also structurally characterized via thermogravimetric analysis (TGA), transmission electron microscopy (TEM), atomic force microscopy (AFM), scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS).