Sulphur containing mesogens. The mesophasic behaviour of di(4-alkyloxybenzoates) of 4,4′-dimercaptobiphenyl

Abstract

A homologous series of di(4-alkyloxybenzoates) of 4,4′-dimercaptobiphenyl: CH₃(CH₂) _n-1O?C₆H₄?COS?C₆H₄?C₆H₄?SOC?C₆H₄?O(CH₂) _n-1CH₃,n=1–7, has been synthesized and the thermotropic liquid-crystalline behaviour investigated. All compounds exhibit enantiotropic mesomorphism over a remarkable temperature range. While the mesophase thermal stability is moderately higher than that found for the corresponding oxygenated analogues, the smectic stability is definitely lower. In fact, all the compounds are nematic but smectic mesomorphism (S_C) is observed for n = 7. Compounds with n = 6 or 7 exhibit enantiotropic highly ordered smectic (or disordered crystal) phases, probably S_G in type.     

Overlapping Schwarz methods for Maxwell''s equations in three dimensions

Summary. A two-level overlapping Schwarz method is considered for a Nédélec finite element approximation of 3D Maxwell's equations. For a fixed relative overlap, the condition number of the method is bounded, independently of the mesh size of the triangulation and the number of subregions. Our results are obtained with the assumption that the coarse triangulation is quasi-uniform and, for the Dirichlet problem, that the domain is convex. Our work generalizes well–known results for conforming finite elements for second order elliptic scalar equations. Numerical results for one and two-level algorithms are also presented. Received November 11, 1997 / Revised version received May 26, 1999 / Published online June 21, 2000     

Domain decomposition preconditioners of Neumann-Neumann type for hp-approximations on boundary layer meshes in three dimensions

We develop and analyse Neumann–Neumann methods for hpfinite-element approximations of scalar elliptic problems ongeometrically refined boundary layer meshes in three dimensions.These are meshes that are highly anisotropic where the aspectratio typically grows exponentially with the polynomial degree.The condition number of our preconditioners is shown to be independentof the aspect ratio of the mesh and of potentially large jumpsof the coefficients. In addition, it only grows polylogarithmicallywith the polynomial degree, as in the case of p approximationson shape-regular meshes. This work generalizes our previousone on two-dimensional problems in Toselli & Vasseur (2003a,submitted to Numerische Mathematik, 2003c to appear in Comput.Methods Appl. Mech. Engng.) and the estimates derived here canbe employed to prove condition number bounds for certain typesof FETI methods.     

Dual-primal FETI algorithms for edge finite-element approximations in 3D

^** Email: toselli{at}sam.math.ethz.ch A family of dual-primal finite-element tearing and interconnectingmethods for edge-element approximations in 3D is proposed andanalysed. The key part of this work relies on the observationthat for these finite-element spaces there is a strong couplingbetween degrees of freedom associated with subdomain edges andfaces and a local change of basis is therefore necessary. Theprimal constraints are associated with subdomain edges. We proposethree methods. They ensure a condition number that is independentof the number of substructures and possibly large jumps of oneof the coefficients of the original problem, and only dependson the number of unknowns associated with a single substructure,as for the corresponding methods for continuous nodal elements.A polylogarithmic dependence is shown for two algorithms. Numericalresults validating our theoretical bounds are given.     

Perfluoropolyether-Silica Hybrids: Preparation and Surface Characterization

,-Triethoxysilane terminated perfluoropolyether-polycaprolactone block copolymers, TXCL(x)Si, were synthesised, characterised and subsequently reacted with tetraethoxysilane to prepare transparent organic-inorganic hybrid materials by using the sol–gel process. Surface characterization was carried out through contact angle measurements. All the materials investigated (independently on both the reaction time of the sol–gel reaction before coating application and the bulk organic-inorganic ratio) showed a strong hydrophobic character when compared with non-fluorinated and fully inorganic control materials. The highest water contact angles were obtained when TXCL(x)Si oligomer used for the preparation of the hybrid contained short hydrogenated polycaprolactone segments. In all cases, the surface tension values indicated that the very surface at the air-coating interface showed almost completely perfluoropolyether segments.     

An overlapping domain decomposition preconditioner for a class of discontinuous Galerkin approximations of advection-diffusion problems

We consider a scalar advection-diffusion problem and a recently proposed discontinuous Galerkin approximation, which employs discontinuous finite element spaces and suitable bilinear forms containing interface terms that ensure consistency. For the corresponding sparse, nonsymmetric linear system, we propose and study an additive, two-level overlapping Schwarz preconditioner, consisting of a coarse problem on a coarse triangulation and local solvers associated to a family of subdomains. This is a generalization of the corresponding overlapping method for approximations on continuous finite element spaces. Related to the lack of continuity of our approximation spaces, some interesting new features arise in our generalization, which have no analog in the conforming case. We prove an upper bound for the number of iterations obtained by using this preconditioner with GMRES, which is independent of the number of degrees of freedom of the original problem and the number of subdomains. The performance of the method is illustrated by several numerical experiments for different test problems using linear finite elements in two dimensions.

     

Effects of stratocumulus,cumulus, and cirrus clouds on the UV-B diffuse to global ratio: Experimental and modeling results

Broadband measurements of global and diffuse UV-B irradiance (280–315 nm) together with modeled and measured diffuse to global ratios (DGR) have been used to characterize the influence of different types of clouds on irradiance at the surface. Measurements were carried out during 2000–2001 in Córdoba City, Argentina. The Tropospheric Ultraviolet Visible (TUV) model was used to analyze the behavior of the modeled DGRs for different cloud optical depths and at different altitudes and solar zenith angles (SZA). Different cloud altitudes were also tested, although only the results for a cloud placed at 1.5–2.5 km of altitude are shown. A total of 16 day with stratocumulus, 12 with cumulus, and 16 with cirrus have been studied and compared among them and also against 21 clear sky days. Different behaviors were clearly detected and also differentiated through the analysis of the averages and the standard deviations of the DGRs: 1.02±0.06 for stratocumulus, 0.74±0.18 for cumulus, 0.63±0.12 for cirrus, and 0.60±0.13 for the clear sky days, respectively. Stratocumulus clouds showed a low variability in the DGR values, which were concentrated close to one at all SZAs. DGR values for cumulus clouds presented a large variability at all SZAs, mostly associated with the different optical depths. Finally, the closeness between the DGR values for cirrus clouds and the DGR values for clear days showed that these clouds generally do not strongly affect the UV-B irradiance at the surface at any SZA. In the opposite side, stratocumulus clouds were identified as those with the largest effects, at all SZAs, on the UV-B irradiance at the surface.     

Looking for a synergic effect between NHCs and chiral P-ligands

The issue of the added value of NHCs in asymmetric catalysis with respect to trusted chiral P-ligands was addressed: considering a prototypical asymmetric allylic alkylation reaction as a model, the association of a priori inhibiting and achiral NHCs with modular P-ligand resulted in enhancement of er up to 508% and increased rates.     

Design of surface properties of PET films: effect of fluorinated block copolymers

This paper demonstrates that the addition of fluorinated block copolymers to PET solutions can be used to prepare PET films with controlled surface morphology, porosity and chemical composition, by exploiting the phenomenon known as breath figures (BF) formation during a spin-coating procedure. Surface features, such as number, depth and diameter of pores and chemical composition, can be tuned by varying the experimental conditions: relative humidity, solution composition and amount of the fluorinated block copolymer added to the PET solutions (in the range of 0.5-10 wt% with respect to PET). BF patterns are more evident at relatively high concentrations of PET (3 wt%) and content of fluorinated block copolymer (10 wt% with respect to PET) in the solution. According to the obtained results, the fluorinated block copolymer seems to play a role in different steps of the mechanism of BF formation. XPS measurements showed a surface composition much richer in fluorinated segments than expected from bulk composition. The combined surface roughness and surface segregation of fluorinated segments have only a limited effect on the macroscopic wettability of the surfaces.     

Oxygen permeability of novel organic-inorganic coatings: II. Modification of the organic component with a hydrogen-bond forming polymer

The oxygen permeability of composite materials, consisting of a LDPE substrate coated with a thin layer (0.7-1 μm) of new hybrid organic/inorganic materials based on SiO₂ and PE-PEG block copolymers, has been characterized at 35 and 50 °C. The effect of adding a second organic component capable to form hydrogen bonds, namely either poly(4-hydroxystyrene) (PHS) or malic acid, has been studied. While the addition of PHS leads to a further significant decrease (50-70%) of the oxygen permeability both at 35 and 50 °C, on the contrary, the addition of malic acid leads to poorer barrier properties. A slight decrease of the permeability was obtained after plasma treatment of the LDPE surface.