Photoelectrochemical properties of copper pyrovanadate (Cu2V2O7) thin films synthesized by pulsed laser deposition.

Polymorphic phases of copper pyrovanadate (α- and ß-Cu2V2O7) were synthesized by solid state reaction and the mechanisms governing the phase transitions have been highlighted by the ThermoGravimetric Analysis (TGA) and the Differential Scanning Calorimetry (DSC). The thermal evolution of the lattice parameters was determined by high temperature X-ray Diffraction revealing negative thermal expansion coefficients. The thermogravimetric analysis coupled with differential scanning calorimetry was also used to determine the optimal conditions to obtain a dense target in order to produce thin films by the Pulsed Laser Deposition (PLD) technique. Thin films elaborated under different oxygen pressures and temperatures exhibit a ß-Cu2V2O7 polycrystalline phase and their band gap indicates absorption in the visible range. These oxides can be used as photoanodes and their photoelectrochemical properties were studied for both bulk (α-Cu2V2O7) and thin films (ß-Cu2V2O7), as a function of the wavelength and/or intensity of the luminous flux. The best photocurrent efficiency was obtained under 450 nm illumination. Moreover, in the case of thin films, we have observed a linear evolution of the current density with the luminous flux. Finally, the photostability of thin films was measured and shows a reduction in the photocurrent of 8% after 1 h of measurement. This photocorrosion phenomenon was also highlighted by the elemental mapping performed on thin films by Scanning Electron Microscopy (SEM) coupled with Energy Dispersive X-ray Spectrometry (EDS).

Self-Healing Glassy Thin Coating for High-Temperature Applications.

Glass thin films (with nanometer to micrometer thicknesses) are promising in numerous applications, both as passive coatings and as active components. Self-healing is a feature of many current technological developments as a means of increasing the lifetime of materials. In the context of these developments, we report on the elaboration of the first self-healing glassy thin-film coating developed specifically for high-temperature applications. This coating is obtained by pulsed laser deposition of alternating layers of vanadium boride (VB) and a multicomponent oxide glass. Self-healing is obtained through the oxidation of VB at the operating temperature. The investigation of the effect of elaboration parameters on the coating composition and morphology made it possible to obtain up to seven-layer coatings, with good homogeneity and perfect interfaces, and with a total thickness of less than 1 µm. The autonomic self-healing capacity of the coating has been demonstrated by an in situ experiment, which shows that a crack of nanometric dimension can be healed within a few minutes at 700 °C.

Tailoring Anisotropic Interactions between Soft Nanospheres Using Dense Arrays of Smectic Liquid Crystal Edge Dislocations.

We investigated composite films of gold nanoparticles (NPs)/liquid crystal (LC) defects as a model system to understand the key parameters, which allow for an accurate control of NP anisotropic self-assemblies using soft templates. We combined spectrophotometry, Raman spectroscopy, and grazing incidence small-angle X-ray scattering with calculations of dipole coupling models and soft sphere interactions. We demonstrate that dense arrays of elementary edge dislocations can strongly localize small NPs along the defect cores, resulting in formation of parallel chains of NPs. Furthermore, we show that within the dislocation cores the inter-NP distances can be tuned. This phenomenon appears to be driven by the competition between "soft (nano)sphere" attraction and LC-induced repulsion. We evidence two extreme regimes controlled by the solvent evaporation: (i) when the solvent evaporates abruptly, the spacing between neighboring NPs in the chains is dominated by van der Waals interactions between interdigitated capping ligands, leading to chains of close-packed NPs; (ii) when the solvent evaporates slowly, strong interdigitation between the is avoided, leading to a dominating LC-induced repulsion between NPs associated with the replacement of disordered cores by NPs. The templating of NPs by topological defects, beyond the technological inquiries, may enable creation, investigation, and manipulation of unique collective features for a wide range of nanomaterials.

Lead-Free α-La2WO6 Ferroelectric Thin Films.

(001)-Epitaxial La2WO6 (LWO) thin films are grown by pulsed laser deposition on (001)-oriented SrTiO3 (STO) substrates. The α-phase (high-temperature phase in bulk) is successfully stabilized with an orthorhombic structure (a = 16.585(1) Å, b = 5.717(2) Å, c = 8.865(5) Å). X-ray-diffraction pole-figure measurements suggest that crystallographic relationships between the film and substrate are [100]LWO ∥ [110]STO, [010]LWO ∥ [11̅0]STO and [001]LWO ∥ [001]STO. From optical properties, investigated by spectroscopic ellipsometry, we extract a refractive-index value around 2 (at 500 nm) along with the presence of two absorption bands situated, respectively at 3.07 and 6.32 eV. Ferroelectricity is evidenced as well on macroscale (standard polarization measurements) as on nanoscale, calling for experiments based on piezo-response force-microscopy, and confirmed with in situ scanning-and-tunneling measurements performed with a transmission electron microscope. This work highlights the ferroelectric behavior, at room temperature, in high-temperature LWO phase when stabilized in thin film and opens the way to new functional oxide thin films dedicated to advanced electronic devices.

Bioinspired Titanium Drug Eluting Platforms Based on a Poly-ß-cyclodextrin-Chitosan Layer-by-Layer Self-Assembly Targeting Infections.

In the field of implantable titanium-based biomaterials, infections and inflammations are the most common forms of postoperative complications. The controlled local delivery of therapeutics from implants through polyelectrolyte multilayers (PEMs) has recently emerged as a versatile technique that has shown great promise in the transformation of a classical medical implant into a drug delivery system. Herein, we report the design and the elaboration of new biodegradable multidrug-eluting titanium platforms based on a polyelectrolyte multilayer bioactive coating that target infections. These systems were built up in mild conditions according to the layer-by-layer (L-b-L) assembly and incorporate two biocompatible polysaccharides held together through electrostatic interactions. A synthetic, negatively charged ß-cyclodextrin-based polymer (PCD), well-known for forming stable and reversible complexes with hydrophobic therapeutic agents, was exploited as a multidrug reservoir, and chitosan (CHT), a naturally occurring, positively charged polyelectrolyte, was used as a barrier for controlling the drug delivery rate. These polyelectrolyte multilayer films were strongly attached to the titanium surface through a bioinspired polydopamine (PDA) film acting as an adhesive first layer and promoting the robust anchorage of PEMs onto the biomaterials. Prior to the multilayer film deposition, the interactions between both oppositely charged polyelectrolytes, as well the multilayer growth, were monitored by employing surface plasmon resonance (SPR). Several PEMs integrating 5, 10, and 15 bilayers were engineered using the dip coating strategy, and the polyelectrolyte surface densities were estimated by colorimetric titrations and gravimetric analyses. The morphologies of these multilayer systems, as well as their naturally occurring degradation in a physiological medium, were investigated by scanning electron microscopy (SEM), and their thicknesses were measured by means of profilometry and ellipsometry studies. Finally, the ability of the coated titanium multilayer devices to act as a drug-eluting system and to treat infections was validated with gentamicin, a relevant water-soluble antibiotic commonly used in medicine due to its broad bactericidal spectrum.

Combined ellipsometry and refractometry technique for characterisation of liquid crystal based nanocomposites.

Spectroscopic ellipsometry is a technique especially well suited to measure the effective optical properties of a composite material. However, as the sample is optically thick and anisotropic, this technique loses its accuracy for two reasons: anisotropy means that two parameters have to be determined (ordinary and extraordinary indices) and optically thick means a large order of interference. In that case, several dielectric functions can emerge out of the fitting procedure with a similar mean square error and no criterion to discriminate the right solution. In this paper, we develop a methodology to overcome that drawback. It combines ellipsometry with refractometry. The same sample is used in a total internal reflection (TIR) setup and in a spectroscopic ellipsometer. The number of parameters to be determined by the fitting procedure is reduced in analysing two spectra, the correct final solution is found by using the TIR results both as initial values for the parameters and as check for the final dielectric function. A prefitting routine is developed to enter the right initial values in the fitting procedure and so to approach the right solution. As an example, this methodology is used to analyse the optical properties of BaTiO(3) nanoparticles embedded in a nematic liquid crystal. Such a methodology can also be used to analyse experimentally the validity of the mixing laws, since ellipsometry gives the effective dielectric function and thus, can be compared to the dielectric function of the components of the mixture, as it is shown on the example of BaTiO(3)/nematic composite.

Formation of nanometric HT-LiCoO(2) by a precipitation and aging process in an alcoholic solution.

In this paper, we detailed the formation/evolution of precipitates in alcoholic media containing Co(II+) and Li(+) species, together with the evolution of the composition and structure/texture of the resulting solid phases during the aging process at controlled constant temperature. While the end product is found to be well-crystallized HT-LiCoO(2), its formation is shown to result from a two-step process enlisting the initial fast precipitation of ß-HCoO(2) and then its slow dissolution followed by recrystallization of the lithium-containing material. These results were obtained through combined X-ray diffraction, Raman and IR spectroscopy, elemental and oxidation-state analysis, and high-resolution transmission electron microscopy/selected-area electron diffraction observations. Depending on the cationic concentration, the size of the precipitated material can be controlled within the nanometric range. The electrochemical performances of these aged materials are slightly improved compared to those of the directly precipitated ones that we previously reported. The main limitation of these materials remains the presence of surface protons.

Noncovalent functionalization of multiwall carbon nanotubes by methylated-ß-cyclodextrins modified by a triazole group.

Multiwall carbon nanotubes have been efficiently suspended into water thanks to methylated ß-cyclodextrins (CDs) containing a triazole group, itself substituted in the 4-position by hydrophilic moieties.