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The effect of nanosize and structural disorder on the MgCl2 support of Ziegler–Natta catalysts has been investigated in terms of induced changes to their vibrational spectroscopic fingerprint. In p...

International audience; Nanocelluloses occur under various crystalline forms that are currently being selectively used for a wide variety of high performance materials. In the present study, two cellulose nanofibers (CF-I) were mercerized by alkaline treatment (CF-II) without degradation, the same molar mass of 560,000 g/mol was measured. Both samples were acid hydrolyzed, leading to cellulose nanocrystals in native (CNC-I) and mercerized (CNC-II) forms. This study focuses on the detailed characterization of these two nanoparticle morphologies (light and neutron scattering, TEM, AFM), surface chemistry (zetametry and surface charge), crystallinity (XRD, C-13 NMR), and average molar mass coupled to chromatographic techniques (SEC-MALLS-RI, A4F-MALLS-RI), revealing variations in the packing of the crystalline domains. The crystal size of CNC-II is reduced by half compared to CNC-I, with molar masses of individual chains of 41,000 g/mol and 22,000 g/mol for CNC-I and CNC-II, respectively, whereas the same surface charge density is measured. This study gives an example of complementary characterization techniques as well as results to help decipher the mechanism involved in mercerization.

International audience; Nanostructuration is one of the most promising strategies to develop performant electrode materials for energy storage devices, such as hybrid supercapacitors. In this work, we studied the influence of precipitation medium and the use of a series of 1-alkyl-3-methylimidazolium bromide ionic liquids for the nanostructuration of β(III) cobalt oxyhydroxides. Then, the effect of the nanostructuration and the impact of the different ionic liquids used during synthesis were investigated in terms of energy storage performances. First, we demonstrated that forward precipitation, in a cobalt-rich medium, leads to smaller particles with higher specific surface areas (SSA) and an enhanced mesoporosity. Introduction of ionic liquids (ILs) in the precipitation medium further strongly increased the specific surface area and the mesoporosity to achieve well-nanostructured materials with a very high SSA of 265 m2/g and porosity of 0.43 cm3/g. Additionally, we showed that ILs used as surfactant and template also functionalize the nanomaterial surface, leading to a beneficial synergy between the highly ionic conductive IL and the cobalt oxyhydroxide, which lowers the resistance charge transfer and improves the specific capacity. The nature of the ionic liquid had an important influence on the final electrochemical properties and the best performances were reached with the ionic liquid containing the longest alkyl chain.

In this work, we model thin films of β-Ca(BH4)2 to understand how nanostructuration of the material can be an effective way to decrease the dehydrogenation enthalpy. Two different crystallographic faces of Ca(BH4)2 have been investigated (i.e., (001) and (101)), and two reaction pathways have been considered that release hydrogen through the formation of CaH2 and CaB6, respectively. Quantum mechanical calculations predict that size reduction from bulk to nanoscale leads to a sizeable decrease of the decomposition enthalpy of the borohydride of about 5 kJ/molH2. Therefore, the present results corroborate the evidence that nanostructured metal borohydrides show advantages for energy storage applications compared to their bulk counterparts.

We report a detailed experimental investigation of the influence of the formation of nanocrystallites on the vibrational, electronic, and optical properties of CrSi2 thin films. Both amorphous and ...

Organic polymers can be made porous via continuous or discontinuous expansion processes in scCO2. The resulting foams properties are controlled by the interplay of three groups of parameters: (i) Chemical, (ii) physico-chemical, and (iii) technological/process that are explained in this paper. The advantages and drawbacks of continuous (extrusion, injection foaming) or discontinuous (batch foaming) foaming processes in scCO2, will be discussed in this article, especially for micro or nano cellular polymers. Indeed, a challenge is to reduce both specific mass (e.g., &rho, &lt, 100 kg&middot, m&minus, 3) and cell size (e.g., average pore diameter ϕaveragepores &lt, 100 nm). Then a particular system where small &ldquo, objects&rdquo, (coreshells CS, block copolymer MAM) are perfectly dispersed at a micrometric to nanometric scale in poly(methyl methacrylate) (PMMA) will be presented. Such &ldquo, additives&rdquo, considered as foaming aids, are aimed at &ldquo, regulating&rdquo, the foaming and lowering the pore size and/or density of PMMA based foams. Differences between these additives will be shown. Finally, in a PMMA/20 wt% MAM blend, via a quasi one-step batch foaming, a &ldquo, porous to nonporous&rdquo, transition is observed in thick samples. A lower limit of pore size (around 50 nm) seems to arise.

International audience; Coherent 3D parts of cermets, made of spinel ferrite and metallic copper, are prepared in a nitrogen atmosphere by powder bed additive manufacturing of a mixture of oxide and metallic powders. The cermets obtained are constituted by the association of blocks of about 500 μm, which create between them, a relatively large porosity (# 35%). Each block is subdivided into intimately nested zones that are either predominantly metallic or predominantly oxide type. In the metal parts, a dispersion of oxide crystals is observed, whose size varies from ten nanometers to a few micrometers. A similar distribution of metal particles in the oxide zones is also demonstrated. The chemical compositions of metallic and oxide phases are slightly different from those in the initial powders. Due to the high energy density of the laser, the melting temperature of the metal and oxides could be reached and therefore this could explain the chemical composition variations in the phases and the shape of oxide and metallic nanometric grains. The process used can therefore be described as powder bed fusion. These nanostructured cermets have been used as "inert" anodes for the electrolysis of aluminum in molten cryolite. Although penalized by a high porosity, 5 mm in diameter anodes allowed to carry out an electrolysis for 4 h. Since Spark Plasma Sintering can greatly reduce their porosity, while retaining their specific microstructure, the implementation of additive manufacturing for producing "inert" anodes is therefore of real interest.

International audience; We report here the successful design of 0–3 type nanocomposites where 30 nm ferromagnetic metallically conducting cores of manganite La0.66Sr0.34MnO3 (LSMO) are discretely distributed in an insulating silica matrix. Starting from LSMO@SiO2 core@shell nanoparticles, hydrothermal sintering process was used as a low temperature densification route (300 °C, 350 MPa, 90 min) in presence of 0.2 M aqueous sodium hydroxide solution. This process based on a pressure solution creep in the contact zones between nanoparticles allows the design of complex microstructures preventing the grain growth of the cores and the formation of interphases between the cores and the matrix.

The monolithic integration of sub-micron quartz structures on silicon substrates is a key issue for the future development of piezoelectric devices as prospective sensors with applications based on the operation in the high-frequency range. However, to date, it has not been possible to make existing quartz manufacturing methods compatible with integration on silicon and structuration by top-down lithographic techniques. Here, we report an unprecedented large-scale fabrication of ordered arrays of piezoelectric epitaxial quartz nanostructures on silicon substrates by the combination of soft-chemistry and three lithographic techniques: (i) laser interference lithography, (ii) soft nanoimprint lithography on Sr-doped SiO2 sol–gel thin films, and (iii) self-assembled SrCO3 nanoparticle reactive nanomasks. Epitaxial α-quartz nanopillars with different diameters (from 1 μm down to 50 nm) and heights (up to 2 μm) were obtained. This work demonstrates the complementarity of soft-chemistry and top-down lithographic techniques for the patterning of epitaxial quartz thin films on silicon while preserving its epitaxial crystallinity and piezoelectric properties. These results open up the opportunity to develop a cost-effective on-chip integration of nanostructured piezoelectric α-quartz MEMS with enhanced sensing properties of relevance in different fields of application., This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program, project SENSiSOFT (no. 803004); the French Agence Nationale pour la Recherche (ANR), project Q-NOSS ANR ANR-16-CE09-0006-01; the Spanish Ministry of Science Innovation and Universities in cofunding with European social funds through the Severo Ochoa Program for Centers of Excellence in R&D (SEV-2015-0496) and the Ramón y Cajal program (RyC-2012-11709 to J.G.); and the Generalitat de Catalunya (2017SGR00765). Q.Z. was financially supported by the China Scholarship Council (CSC) with no. 201506060170. Q.Z.’s work was done as a part of the PhD program in Materials Science at Universitat Autònoma de Barcelona. The authors thank the “Laboratorio de Microscopías Avanzadas-Instituto de Nanociencia de Aragón” for offering their expertise in the preparation of TEM cross sections. A. Crespi from XRD diffraction service is acknowledged for pole figure measurements. FEG-SEM instrumentation was facilitated by the Institut des Matériaux de Paris Centre (IMPC FR2482) and was funded by Sorbonne Université, CNRS and by the C’Nano projects of the Région Ile-de-France. We thank David Montero for performing the FEG-SEM images.

PbTe-based alloys have the best thermoelectric properties for intermediate temperature applications (500&ndash, 900 K). We report on the preparation of pristine PbTe and two doped derivatives (Pb0.99Sb0.01Te and Ag0.05Sb0.05Pb0.9Te, so-called LAST18) by a fast arc-melting technique, yielding nanostructured polycrystalline pellets. XRD and neutron powder diffraction (NPD) data assessed the a slight Te deficiency for PbTe, also yielding trends on the displacement factors of the 4a and 4b sites of the cubic Fm-3m space group. Interestingly, SEM analysis shows the conspicuous formation of layers assembled as stackings of nano-sheets, with 20&ndash, 30 nm thickness. TEM analysis shows intra-sheet nanostructuration on the 50 nm scale in the form of polycrystalline grains. Large numbers of grain boundaries are created by this nanostructuration and this may contribute to reduce the thermal conductivity to a record-low value of 1.6 Wm&minus, 1K&minus, 1 at room temperature. In LAST18, a positive Seebeck coefficient up to 600 &mu, V K&minus, 1 at 450 K was observed, contributing further towards improving potential thermoelectric efficiency.

More people, more cities; the energy demand increases in consequence and much of that will rely on next-generation smart materials. Zn-ferrites (ZnFe2O4) are nonconventional ceramic materials on account of their unique properties, such as chemical and thermal stability and the reduced toxicity of Zn over other metals. Furthermore, the remarkable cation inversion behavior in nanostructured ZnFe2O4 extensively cast-off in the high-density magnetic data storage, 5G mobile communication, energy storage devices like Li-ion batteries, supercapacitors, and water splitting for hydrogen production, among others. Here, we review how aforesaid properties can be easily tuned in various ZnFe2O4 nanostructures depending on the choice, amount, and oxidation state of metal ions, the specific features of cation arrangement in the crystal lattice and the processing route used for the fabrication.

International audience; Pure tysonite La0.95Ba0.05F2.95 is nanostructured by using the ball-milling technique. Size and pollution rate are minimized using the statistical method of Design of Experiment. The nanocrystalline powders are studied by X-ray and TEM analyses and by 19F solid state NMR and impedance spectroscopies. Specific surface area and F/OH substitution rate are estimated by BET measurements and thermal analysis (TGA-MS), respectively. Fluorine environments and mobilities are discussed on the basis of 19F solid state NMR data, both prior and after thermal treatment. The ionic conductivity, evaluated from sintered pellets, is compared at different thermal treatment temperatures. Thermal treatment tends to reduce microstrains up to 500 °C and to increase the grain size above this temperature. Optimal conductivity is obtained for a thermal treatment from 700 °C and no significant improvement of the conductivity by nanostructuration is observed.

International audience; Macroporous layers are grown onto n-type silicon by successive photoelectrochemical etching in HF containing solution and chemical etching in KOH. This specific latter treatment gives highly antireflective properties of the Si surface. The duration of the chemical etching is optimized to render the surface as absorbent as possible and the morphology of the as-grown layer is characterized by scanning electron microscopy. Further functionalization of such structured Si surface is carried out by atomic layer deposition of a thin conformal and homogenous TiO 2 layer that is crystallized by an annealing at 450°C. This process allows using such surfaces as photoanodes for water oxidation. The 40 nm-thick TiO 2 film acts 2 indeed as an efficient protective layer against the photocorrosion of the porous Si in KOH, enhances its wettability and enlarge the light absorption of the photoelectrode. The macroporous Si has a beneficial effect on water oxidation in 1 M KOH and leads to a considerable negative shift of onset potential of ~400 mV as well as a 50 % increase in photocurrent at 1 V vs SCE.

International audience; Iron layers with variable thicknesses, deposited onto copper thin films, are oxidized by a plasma afterglow at atmospheric pressure. Such a bilayer arrangement enables the growth of caterpillar-like patterns covered by CuO and Fe2O3 nanostructures. Two main mechanisms are at stake: either copper comes up to the surface through cracks or boundaries between the columns of the coating, or it diffuses through parts of the Fe2O3 layer made permeable by tensile stress. Structures grown by the former mechanisms are characterized by a central channel, whereas those grown by the latter exhibit a plane interface above which stands an equiaxed grain heap. This result was used to localize the growth of nanowires in cracks formed priory to the afterglow-assisted treatment. By resorting to XPS microscopy experiments carried out with the scanning photoelectron microscope at the ESCAMicroscopy beamline of the Elettra synchrotron facility in Trieste, we could gain access to the surface composition of a single isolated pattern.

The development of advanced piezoelectric α‐quartz microelectromechanical system (MEMS) for sensing and precise frequency control applications requires the nanostructuration and on‐chip integration of this material on silicon material. However, the current quartz manufacturing methods are based on bonding bulk micromachined crystals on silicon, which limits the size, the performance, the integration cost, and the scalability of quartz microdevices. Here, chemical solution deposition, soft‐nanoimprint lithography, and top‐down microfabrication processes are combined to develop the first nanostructured epitaxial (100)α‐quartz/(100)Si piezoelectric cantilevers. The coherent Si/quartz interface and film thinness combined with a controlled nanostructuration on silicon–insulator–silicon technology substrates provide high force and mass sensitivity while preserving the mechanical quality factor of the microelectromechanical systems. This work proves that biocompatible nanostructured epitaxial piezoelectric α‐quartz‐based MEMS on silicon can be engineered at low cost by combining soft‐chemistry and top‐down lithographic techniques., This project had received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (project SENSiSOFT No.803004). L.P. acknowledges the ATIP–Avenir program for financial support. The authors thank C. André for providing the transfected HT1080 cell line and C. Cazevielle (MRI‐COMET, Montpellier) for assistance with biological SEM images. The authors thank D. Montero for performing the FEG–SEM images and chemical analysis. The FEG–SEM instrumentation was facilitated by the Institut des Matériaux de Paris Centre (Grant No. IMPC FR2482) and was funded by Sorbonne Université, CNRS and by the C'Nano projects of the Région Ile‐de‐France. The authors thank Frederic Pichot, David Bourrier, and Guilhem Larrieu for the expertise and advice during the cantilever lithographic processes. The authors also thank Wioletta Trzpil, Frank Augereau, and Eric Rosenkrantz for the advice during vibrometry measurements. A.G and M.G acknowledge funding from the Spanish Ministerio de Ciencia e Innovacion through the severo Ochoa program (CEX2019‐000917‐S).

The terbium(III) ion is a particularly suitable candidate for the creation of surface-based magnetic and luminescent devices. In the present work, we report the epitaxial growth of needle-like objects composed of [Tb(hfac)3·2H2O]n (where hfac = hexafluoroacetylacetonate) polymeric units on muscovite mica, which is observed by atomic force microscopy. The needle-like shape mimics the structure observed in the crystalline bulk material. The growth of this molecular organization is assisted by water adsorption on the freshly air-cleaved muscovite mica. This deposition technique allows for the observation of a significant amount of nanochains grown along three preferential directions 60° apart from another. The magnetic properties and the luminescence of the nanochains can be detected without the need of surface-dedicated instrumentation. The intermediate value of the observed luminescence lifetime of the deposits (132 µs) compared to that of the bulk (375 µs) and the CHCl3 solution (13 µs) further reinforces the idea of water-induced growth.

Metal nanostructures are, nowadays, extensively used in applications such as catalysis, electronics, sensing, optoelectronics and others. These applications require the possibility to design and fabricate metal nanostructures directly on functional substrates, with specifically controlled shapes, sizes, structures and reduced costs. A promising route towards the controlled fabrication of surface-supported metal nanostructures is the processing of substrate-deposited thin metal films by fast and ultrafast pulsed lasers. In fact, the processes occurring for laser-irradiated metal films (melting, ablation, deformation) can be exploited and controlled on the nanoscale to produce metal nanostructures with the desired shape, size, and surface order. The present paper aims to overview the results concerning the use of fast and ultrafast laser-based fabrication methodologies to obtain metal nanostructures on surfaces from the processing of deposited metal films. The paper aims to focus on the correlation between the process parameter, physical parameters and the morphological/structural properties of the obtained nanostructures. We begin with a review of the basic concepts on the laser-metal films interaction to clarify the main laser, metal film, and substrate parameters governing the metal film evolution under the laser irradiation. The review then aims to provide a comprehensive schematization of some notable classes of metal nanostructures which can be fabricated and establishes general frameworks connecting the processes parameters to the characteristics of the nanostructures. To simplify the discussion, the laser types under considerations are classified into three classes on the basis of the range of the pulse duration: nanosecond-, picosecond-, femtosecond-pulsed lasers. These lasers induce different structuring mechanisms for an irradiated metal film. By discussing these mechanisms, the basic formation processes of micro- and nano-structures is illustrated and justified. A short discussion on the notable applications for the produced metal nanostructures is carried out so as to outline the strengths of the laser-based fabrication processes. Finally, the review shows the innovative contributions that can be proposed in this research field by illustrating the challenges and perspectives.

International audience; The development of new high performance materials faces the challenge of implementing low temperature densification processes to overcome current technological limitations. In this context, the hydrothermal sintering, inspired by the natural processes of geological and biological mineralization, has recently emerged as a major opportunity to develop new and/or optimized materials that respond to today's scientific, technological and related socio-economic issues. The purpose of this viewpoint paper is to present opinions and propose future outlook for hydrothermal sintering based on the most recent achievements.

Nanostructured metal surfaces have been known to exhibit properties that deviate from that of the bulk material. By simply modifying the texture of a metal surface, various unique optical properties can be observed. In this paper, we present a simple two step electrochemical process combining electrodeposition and anodization to generate black gold surfaces. This process is simple, versatile and up-scalable for the production of large surfaces. The black gold films have remarkable optical behavior as they absorb more than 93% of incident light over the entire visible spectrum and also exhibit no specular reflectance. A careful analysis by scanning electron microscopy reveals that these unique optical properties are due to their randomly rough surface, as they consist in a forest of dendritic microstructures with a nanoscale roughness. This new type of black films can be fabricated to a large variety of substrates, turning them to super absorbers with potential applications in photovoltaic solar cells or highly sensitive detectors and so on.

International audience; In this work, we produce bulk nanostructured Mg2Si0.4Sn0.6 thermoelectric materials made of nanograins with sizes below 200 nm and containing a fine distribution of Sn-rich nanoparticles. These materials are obtained by the mechanical alloying followed by spark plasma sintering. The microstructure and transport properties, and their evolutions upon aging, are investigated. A model is developed to capture the different contributions to the phonon scattering processes arising from the nano/microstructural parameters. The calculations show quantitative agreement with the temperature and the temporal dependence of the lattice thermal conductivity of the nanostructured Mg2Si0.4Sn0.6 alloy. This work provides a general analytic approach for identifying the individual contributions of the microstructural parameters on the thermal conductivity which is a very important property controlling the performance of thermoelectric materials.

International audience; Poly(vinylidene fluoride) (PVDF) composites have recently emerged as excellent candidates to fabricate flexible and small piezoelectric generators for portable devices. Among various techniques used to nanostructure polarized PVDF, the track-etching represents a new route for manufacturing nanostructured composite thin films. The moderate influence of irradiation on the piezoelectric response of polarized PVDF makes possible the use of this technique. In this way, a nanostructured composite based on polarized thin PVDF films comprising embedded nickel nanowires (Ni NWs) was fabricated. The nanostructured PVDF/Ni NWs composites were tested under bending conditions using a homemade pressure cell. Due to the presence of NWs, an increase of five-fold the initial dielectric permittivity, in the low-frequency range, was observed. It suggested the presence of an interfacial polarization at the PVDF/Ni interface. With respect to the etched PVDF, the nanostructured PVDF/Ni NWs composites exhibited a non-negligible enhancement by 2.5 times the piezoelectric efficiency. This result was attributed to the increased Au/Ni NWs electrode surface.

We investigated the fabrication of large-area (cm2) nanostructured glasses for solar cell modules with hydrophobic and hydrophilic properties using soft lithography and colloidal lithography. Both of these techniques entail low-cost and ease of nanofabrication. We explored the use of simple 1D and 2D nanopatterns (nanowires and nanocones) and the effect of introducing disorder in the nanostructures. We observed an increase in the transmitted light for ordered nanostructures with a maximum value of 99% for wavelengths >600 nm when ordered nanocones are fabricated on the two sides of the solar glass. They produced an increment in the efficiency of the packaged solar cell with respect to the glass without nanostructures. On the one hand, the wettability properties showed that the ordering of the nanostructures improved the hydrophobicity of the solar glasses and increased their self-cleaning capacity. On the other hand, the disordered nanostructures improved the hydrophilic properties of solar glasses, increasing their anti-fogging capacity. The results show that by selecting the appropriate nanopattern, the wettability properties (hydrophobic or hydrophilic) can be easily improved without decreasing the efficiency of the solar cell underneath., The authors acknowledge the service from the X-SEM Laboratory at IMM, and funding from MINECO under project CSIC13-4E-1794 with support from EU (FEDER, FSE), TEC2014-54449-C3-3-R and PCIN-2013-179, We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI).

International audience; In this work, the properties of cellulose (CE)/xyloglucan (XG) biopolymer blends are investigated, taking inspiration from the outstanding mechanical properties of plant cell walls. CE and XG were first co-solubilized in an ionic liquid, 1-ethy1-3-methylimidazolium acetate, in order to blend these biopolymers with a varying CE:XG ratio. The biopolymers were then regenerated together using water to produce solid blends in the form of films. Water-soluble XG persisted in the films following regeneration in water, indicating an attractive interaction between the CE and XG. The final CE:XG ratio of the blends was close to the initial value in solutions, further suggesting that intimate mixing takes place between CE and XG. The resulting CE/XG films were found to be free of ionic liquid, transparent and with no evidence of phase separation at the micron scale. The mechanical properties of the blend with a CE:XG ratio close to one revealed a synergistic effect for which a maximum in the elongation and stress at break was observed in combination with a high elastic modulus. Atomic force microscopy indicates a co-continuous nanostructure for this composition. It is proposed that the non-monotonous variation of the mechanical performance of the films with XG content is due to this observed nanostructuration. (C) 2017 Elsevier Ltd. All rights reserved.

International audience; The synthesis of ultrathin, single-crystalline zinc oxide nanowires was achieved by treating in a flowing microwave plasma oxidation process, zinc films coated beforehand by a sputtered thin buffer layer of copper. The aspect ratio of the nanowires can be controlled by the following experimental parameters: treatment duration, furnace temperature, oxygen concentration. An average diameter of 6 nm correlated with a mean length of 750 nm can be reached with a fairly high surface number density for very short treatments, typically less than 1 min. The oxidized samples are characterized by means of SEM, XRD, SIMS, HRTEM and EDX techniques. Structural characterization reveals that these nanowires are single-crystalline, with the wurtzite phase of ZnO. Nanowires are only composed of ZnO without copper particles inside or at the end of the nanowires. Temperature-dependent photoluminescence measurements confirm that ZnO nanowires are of high crystalline quality and thin enough to produce quantum confinement.

The low vapor pressure of explosives makes the gaseous detection challenging and drives even the particle detection. There is a need to provide easy portable systems, highly spreadable. A bio-inspired concept was developed to detect explosive vapors with unprecedent sensitivities. Vertically aligned TiO2 nanotubes were grown on a cantilever. The sensors successfully detected trinitrotoluene (TNT) and pentaerythritol tetranitrate (PETN) with a minimum threshold concentration down to 0.8 ppt. This work describes also the investigations undertaken to develop the characterization of explosives by nanocalorimetry, which is able to identify explosives in form of single particles.

Thanks to excellent mechanical and biochemical properties, the nickel-titanium shape memory alloy (Nitinol) constitutes an increasingly praised platform material in dental, cardiovascular and orthopedic biomedical devices. In order to strengthen their protective abilities toward corrosion, to reinforce their biocompatibility and to confer them specific osseointegrative capacities, Nitinol plates are covered with a thin tantalum layer by electrodeposition in the 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquid. XPS and SEM/EDX analyses highlight the chemical and morphological characteristics of the deposits: notably, these present an intrinsic dimpled nanometric structuration which is particularly remarkable considering the "soft" experimental conditions and very interesting for fundamental and applied bioactive perspectives. The present study investigates the specific and synergic effects of the Ni occurrence on the surface of the Nitinol substrates, the presence of fluorine species in the working bath, and the electrodeposition duration on the resulting formation process, morphology and chemical composition of the tantalum coating. Finally, samples are submitted to electrochemical characterizations and in vitro hydroxyapatite growth tests for a primary assessment of their corrosion resistance and osseoinductive features. © 2012 Elsevier Ltd. All Rights Reserved.

Made available in DSpace on 2018-12-11T17:16:39Z (GMT). No. of bitstreams: 0 Previous issue date: 2017-01-01 The recent advances in the supramolecular control in nanostructured films have improved the performance of organic-based devices. However, the effect of different supramolecular arrangement on the sensor or biosensor performance is poorly studied yet. In this paper, we show the role of the composition and nanostructuration of the films on the impedance and voltammetric-based sensor performance to catechol detection. The films here studied were composed by a perylene derivative (PTCD-NH2) and a metallic phthalocyanine (FePc), using Langmuir-Blodgett (LB) and physical vapor deposition (PVD) techniques. The deposition technique and intrinsic properties of compounds showed influence on electrical and electrocatalytic responses. The PVD PTCD-NH2 shows the best sensor performance to the detection of catechol. Quantification of catechol contents in mate tea samples was also evaluated, and the results showed good agreement compared with Folin- Ciocalteu standard method for polyphenol detection. Departamento de Física Faculdade de Ciências e Tecnologia UNESP Univ. Estadual Paulista Departamento de Física Faculdade de Ciências e Tecnologia UNESP Univ. Estadual Paulista

Ultra-hydrophobic bilayer coatings on a glass surface were fabricated by sol–gel process using hexadecyltrimethoxysilane (C16TMS) and tetramethoxysilane (TMOS) (1:4 molar ratio) as precursors. After coating, silica nanoparticles (SiO2 NPs) functionalized with different mono-alkoxy derivatives (methoxytrimethylsilane, TMeMS; ethoxydimethylvinylsilane, DMeVES; ethoxydimethylphenylsilane, DMePhES; and methoxydimethyloctylsilane, DMeC8MS) were added, assuring the microscale roughness on the glass surface. Influences of the functionalized SiO2 NPs and surface morphology on the hydrophobicity of the hybrid films were discussed. The successful functionalization of SiO2 NPs with hydrophobic alkyl groups were confirmed by Fourier transform infrared spectroscopy (FTIR). The thermal stability of hydrophobic SiO2 NPs showed that the degradation of the alkyl groups takes place in the 200–400 °C range. Bilayer coating with C16TMS/TMOS and SiO2 NPs modified with alkoxysilane substituted with C8 alkyl chain (SiO2 NP-C8) has micro/nano structure. Hydrophobicity of functionalized SiO2 NPs-C8 and its higher degree of nanometer-scale roughness gave rise to ultra-hydrophobicity performance for bilayer coating C16TMS/TMOS + SiO2 NPs-C8 (145°), compared to other similar hybrid structures. Our synthesis method for the functionalization of SiO2 NPs is useful for the modification of surface polarity and roughness.

Thermoelectric materials constitute an alternative source of sustainable energy, harvested from waste heat. BiTe is the most utilized thermoelectric alloy. We show that it can be readily prepared in nanostructured form by arc-melting synthesis, yielding mechanically robust pellets of highly oriented polycrystals. This material has been characterized by neutron powder diffraction (NPD), scanning electron microscopy (SEM), and electronic and thermal transport measurements. A microscopic analysis from NPD data demonstrates a near-perfect stoichiometry of BiTe and a fair amount of anharmonicity of the chemical bonds. The as-grown material presents a metallic behavior, showing a record-low resistivity at 320 K of 2 μΩ m, which is advantageous for its performance as a thermoelectric material. SEM analysis shows a stacking of nanosized sheets, each of them presumably single-crystalline, with large surfaces perpendicular to the c crystallographic axis. This nanostructuration notably affects the thermoelectric properties, involving many surface boundaries that are responsible for large phonon scattering factors, yielding a thermal conductivity as low as 1.2 W m K around room temperature., We are grateful to the Spanish Ministry of Economy and Competitiveness for granting the project MAT2013-41099-R, and to PSI for making all facilities available for the neutron diffraction experiments.

International audience; Poly[Styrene-b-Butadiene-b-(Methyl Methacrylate)], SBM triblock copolymers have been incorporated in different polyurethane, PU formulations in order to prepare nanostructured materials. Macrodiols used for PU synthesis were based on a central bis-phenol A, BPA unit with two hydroxyl-terminated oligo(oxypropylene), BPA-POx or oligo(oxyethylene), BPA-EO chains with varying lengths. The initial solubility of the three blocks and the rheological behavior of the solutions in macrodiols and also in two diisocyanates, isophorone diisocyanate, IPDI, and 1,3-xylylene diisocyanate, XDI have been first characterized. The PMMA block is the most soluble and its role during the reaction is to stabilize the initial nanostructure or to control the reaction-induced microphase separation. Block copolymers can be dissolved first in the macrodiol, or preferably in the diisocyanate. With BPA-POx and low SBM content (50 wt%), a twin screw extruder had to be used for the blending. Under well-defined conditions, transparent linear PUs and linear segmented polyurethane-ureas have been prepared. This study confirms that for designing a nanostructured material from a reactive mixture with a triblock additive, one block, called “the nanostructuring block” has to remain soluble up to the end of the reaction.

SnSe has been recently reported as a promising and highly efficient thermoelectric intermetallic alloy. The present material has been prepared by arc melting, as mechanically robust pellets, consisting of highly oriented polycrystals. The evolution of its orthorhombic GeS-type structure (space group Pnma) and phase transition to TlI-type structure (space group Cmcm) at high temperature has been studied in situ by neutron powder diffraction (NPD) in the temperature range 295-873 K. This transition has been identified by differential scanning calorimetry measurements, yielding sharp peaks at 795 K. In addition, thermal transport properties were measured in a similar temperature range, and large Seebeck coefficients, as high as 1050 μV K at 625 K, were found. The analysis from NPD data demonstrates an almost perfect stoichiometry, SnSe, that does not evolve with temperature, and a progressive decrease of the anharmonicity of the chemical bonds upon entering the domain of the Cmcm structure. SnSe undergoes a phase transition immediately below the maximum thermoelectric performance temperature. The present in situ neutron powder diffraction study establishes correlations between the structural evolution and the thermoelectric properties., We acknowledge the financial support of the Spanish ‘Ministerio de Economia y Competitividad’ (MINECO) to the project MAT2013-41099-R.

International audience; In this paper, we report on an improved enhancement of the surface-enhanced Raman scattering (SERS) effect. Such improvement is obtained by using a continuous gold film (underlayer), which is added below an array of gold nanostructures. Two types of nanostructures were studied to validate our results: regular disk arrays with two diameters (110 and 210 nm) and lines with a width of 110 nm, all on a gold film of 30 nm thick. A supplementary gain of one order of magnitude on the SERS enhancement factor (EF) was experimentally demonstrated for several excitation wavelengths: 633, 660, and 785 nm. With such SERS substrates, EFs of 10 7 are observed for thiophenol detection. This opens the way towards routine and reliable detection of molecules at low concentration.

Superhydrophobic nanocomposite coatings on injection-molded polypropylene (PP) samples were prepared by dipping in xylene solvent containing titanium dioxide nanoparticles (NPs) functionalized with trimethoxypropyl silane. Alternatively, PP samples were dipped in a mixture of functionalized NPs and dissolved PP pellets. As a general result, dip-coated PP samples reached a permanent superhydrophobic state with a contact angle hysteresis (CAH) depending on NPs concentration and surface chemistry. SEM and profilometer measurements show a general trend in the decrease of CAH with the increase of aggregates and roughness. However some results showed that surfaces with the same roughness presented different CAHs. XPS measurements showed that low CAHs and self-cleaning properties were obtained only when the Ti?OH relative concentration on the surface was about 20%. At higher Ti?OH relative concentrations, the surface kept a superhydrophobic static state but lost its self-cleaning properties. This work highlights the fact that both control of the roughness together with chemical surface composition of polar groups have to be taken into account for a precise tuning on the superhydrophobic dynamic component of the surface. Fil: Contreras, Cintia Belén. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto Multidisciplinario de Biología Vegetal. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Instituto Multidisciplinario de Biología Vegetal; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; Argentina Fil: Chagas, Gabriela. Universidade Federal do Rio Grande do Sul; Brasil Fil: Strumia, Miriam Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto Multidisciplinario de Biología Vegetal. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Instituto Multidisciplinario de Biología Vegetal; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; Argentina Fil: Weibel, Daniel E.. Universidade Federal do Rio Grande do Sul; Brasil

Hollow sea urchin shaped nanostructured polypyrrole powder was successfully synthesized chemically in an acidic medium through a core-shell redox mechanism by using a nanostructured MnO2 powder as oxidizing agent and sacrificial template simultaneously. The morphology and the structure of MnO2 powder based reactant and produced polypyrrole powder were characterized respectively by using FEG-SEM, TEM, EDX and XRD techniques, which led us to demonstrate clearly the formation of hollow and open microparticles of polypyrrole with the presence of nanotubes on their surface. Nanostructured polypyrrole powder was found to be rather amorphous even though the shape of the polypyrrole particles was induced by the crystalline and nanostructured sea urchin shaped MnO2 powder on which they grew. In addition, neither MnO2 nor any manganese based species were found within the produced polypyrrole powder, which ruled out the production of composite materials. Moreover, Raman technique showed that the synthesized PPy powder was produced in the oxidized and thus conducting state. It actually possesses a 0.31 doping level and a 0.05 S cm(-1) conductivity, as shown by XPS and impedance spectroscopy measurements respectively. Cyclic voltammetry and UV-vis spectroscopy studies allowed us to identify the oxidation mechanism of pyrrole by our MnO2 powder through the detection of soluble Mn2+ cations as reaction products isolated after filtration of the reaction medium. (c) 2013 Elsevier B.V. All rights reserved.

Compressibility of high-purity nanostructured cBN has been studied under quasi-hydrostatic conditions at 300 K up to 35 GPa using diamond anvil cell and angle-dispersive synchrotron powder X-ray diffraction. It has been found that the data fit to the Vinet equation of state yields the values of the bulk modulus B₀ of 375(4) GPa with its first pressure derivative B₀´ of 2.3(3), thus, the nanometer grain size (≈ 20 nm) results in a decrease of the bulk modulus by ≈ 9‰. Сжимаемость высокочистого наноструктурированного cBN была изучена в квазигидростатических условиях при 300 K до 35 GPa в алмазных наковальнях с помощью угловой дисперсионной рентгеновской дифракции синхротронного излучения. Описание полученных данных уравнением состояния Винэ дает значение модуля сжимаемости B₀ = 375(4) ГПа и его первой производной по давлению B₀' = 2.3(3). Наноразмер зерна (~ 20 нм) приводит к уменьшению модуля сжимаемости на ~ 9 %. Стисливість високочистого наноструктурованого cBN була вивчена в квазігідростатичних умовах при 300 K до 35 ГПa в алмазних наковальнях за допомогою кутової дисперсійної рентгенівської дифракції синхротронного випромінювання. Опис одержаних даних рівнянням стану Віне дає значення модуля стисливості B₀ = 375(4) ГПа і його першої похідної по тиску B₀' = 2.3(3). Нанорозмір зерна (~ 20 нм) приводить до зменшення модуля стисливості на ~ 9 %.

International audience; High pressure torsion (HPT) tests can be used to transform the structure of materials. Several studies in the literature highlight that such tests are a means of investigating certain formation mechanisms of Tribological Transformed Structures (TTS) outside contacts, as they reproduce conditions that are close to those found inside them (quasi-hydrostatic pressures and shearing) under conditions that are easier to control than in a real contact. As there is no unique path leading to deformation with TTS in real contacts, it has been decided to simplify the history of deformation as the first step in investigating the occurrence of TTS. In this study, a Bridgman anvil apparatus, which allows shearing samples in torsion under pressure, is used to test ultra high purity iron (99.99999%) with an initial grain size of 100 μm, under a mean pressure of 0.5 GPa. The microstructural investigations led to establishing a map identifying the refined zones within the volume of the sample and linked to contact conditions. This work considers these zones with the finest microstructure (size grains of about 220 nm) as "TTS". The experimental study is coupled with finite element analysis to investigate the specificity of the stress and strain cycles of the microstructure produced. Although further work is needed to validate the suggested comparison to friction induced transformed layers, the results showed that "TTS" are produced in a specific sample volume linked to sliding/adhesion contact conditions. The coupling between experiments and modeling shows that "TTS" formation can be associated with high hydrostatic stress components, high local plastic strains and high strain gradients.

International audience; In this work, a new method to prepare fluorinated coatings with mechanical properties enhanced has been developed. Pyridinium, imidazolium, and phosphonium ionic liquids have been synthesized and used as new synthetic building blocks in a polytetrafluoroethylene matrix. The strategy demonstrated using long alkyl chain cations provides an opportunity to prepare nanomaterials with a nanoscale structuration. The design of these new ionic and nanostructured materials is very dependent on the cation anion combination of ILs. The morphology analyzed by transmission electronic microscopy (TEM) shows that it is clearly tuned by the chemical nature of ILs. The finest structuration leads to a dramatic compromise between stiffness and deformation of material. The small-angle X-Ray scattering (SAXS) shows the evolution of the ionic networks during the mechanical sollicitation.

The effects of nanostructuration on the magneto-optic properties of ultrathin monocrystalline iron films grown on MgO (001) are investigated through the magneto-optic coefficients, which have a linear and quadratic dependence on the magnetization. The photon energy dependence of such magneto-optic coefficients is determined by measuring the relative variations of the reflectivity (ΔRpp/Rpp) for p-polarized incident and reflected light (p-p polarized) when the magnetization rotates in the plane of the sample. Thick Fe films present a magneto-optical anisotropy, which has a quadratic dependence on the magnetization. Such anisotropy is strongly reduced in nanostructured iron thin films formed by nanometric iron islands. The modifications induced by the nanostructuration are stronger for the magneto-optical coefficients, which have a quadratic dependence on the magnetization in contrast to the linear terms. A self-consistent effective-medium formalism is presented that explains the modifications induced in the magneto-optical coefficients by nanostructuration.

In competitive thermoelectric devices for energy conversion and generation, high-efficiency materials of both n-type and p-type are required. For this, Bi2Te3-based alloys have the best thermoelectric properties in room temperature applications. Partial replacement of tellurium by selenium is expected to introduce new donor states in the band gap, which would alter electrical conductivity and thermopower. We report on the preparation of n-type Bi2(Te1-xSex)3 solid solutions by a straightforward arc-melting technique, yielding nanostructured polycrystalline pellets. X-ray and neutron powder diffraction was used to assess Se inclusion, also indicating that the interactions between quintuple layers constituting this material are weakened upon Se doping, while the covalency of intralayer bonds is augmented. Moreover, scanning electron microscopy shows large surfaces perpendicular to the c crystallographic axis assembled as stacked sheets. Grain boundaries related to this 2D nanostructuration affect the thermal conductivity reducing it below 0.8 Wm−1K−1 at room temperature. Furthermore, Se doping increases the absolute Seebeck coefficient up to −140 μV K−1 at 400 K, which is also beneficial for improved thermoelectric efficiency., This research was funded by the Spanish Ministry of Economy and Competitivity for granting the project MAT2013-41099-R.