Mathieu Allix

Direct Coprecipitation Route to Monodisperse Dual- Functionalized Magnetic Iron Oxide Nanocrystals Without Size Selection

Water-soluble monodisperse superparamagnetic Fe3O4 nanocrystals decorated with two distinct functional groups are prepared in a single-step procedure by injecting iron precursors into a refluxing aqueous solution of a polymer ligand, trithiol-terminated poly(methacrylic acid) (PMAA-PTTM), bearing both carboxylate and thiol functionalities. The ratio of carboxylic acid groups in the polymer-protecting ligand to the iron precursors plays a key role in determining the particle size and particle size distribution. The surface functionalities of the ligands allow post-synthesis modification of the materials to produce water-soluble fluorescent magnetic nanocrystals.

High pressure bulk synthesis and characterization of the predicted multiferroic Bi(Fe1∕2Cr1∕2)O3

Bi(Fe1∕2Cr1∕2)O3, a recently proposed candidate multiferroic perovskite, is prepared in a bulk form by high pressure solid-state synthesis. The material is isostructural with polar BiFeO3 but is paramagnetic at room temperature due to disorder of the Fe3+ and Cr3+ cations on the B site. Mossbauer and magnetization measurements show a transition to a cooperative magnetic state below 130K.

Structural Investigations of Glass Ceramics in the Ga2S3―GeS2―CsCl System

Transparent glass ceramics have been prepared in the Ga(2)S(3)-GeS(2)-CsCl pseudoternary system using appropriate heat treatment time and temperature. In situ X-ray diffraction at the heat treatment temperature and (133)Cs and (71)Ga solid-state nuclear magnetic resonance have been performed in function of annealing time to understand the crystallization process. Both techniques have evidenced the nucleating agent role played by gallium with the formation of Ga(2)S(3) nanocrystals. On the other hand, cesium is incorporated very much later into the crystallites during the ceramization. Moreover, the addition of CsCl, which is readily integrated into the glassy network, permits us to shift the optical band gap toward shorter wavelength. Thus, new glass ceramics transmitting in the whole visible range up to 11.5 mum have been successfully synthesized from the (Ga(2)S(3))(35)-(GeS(2))(25)-CsCl(40) base glass composition.

Diffraction techniques and Vibrational spectroscopy opportunities to characterise bones

From a histological point of view, bones that allow body mobility and protection of internal organs consist not only of different organic and inorganic tissues but include vascular and nervous elements as well. Moreover, due to its ability to host different ions and cations, its mineral part represents an important reservoir, playing a key role in the metabolic activity of the organism. From a structural point of view, bones can be considered as a composite material displaying a hierarchical structure at different scales. At the nanometre scale, an organic part, i.e. collagen fibrils and an inorganic part, i.e. calcium phosphate nanocrystals are intimately mixed to assure particular mechanical properties.

Highly Transparent BaAl4O7 Polycrystalline Ceramic Obtained by Full Crystallization from Glass

Transparent polycrystalline ceramics are an emerging class of photonic quality materials competing with single crystal technology for a diverse range of applications including high-energy lasers, scintillating devices, optical lenses, and transparent armour. Polycrystalline ceramics offer several advantages, particularly in the fabrication of complex shapes and large-scale industrial production, and enable greater and more homogenous doping of optically active ions than is possible in single crystals. A limited number of either cubic or nanocrystalline transparent polycrystalline ceramics are known, but require complex and time-consuming synthetic approaches. Here, we show for the fi rst time that fully dense transparent polycrystalline ceramics can be simply obtained by direct and complete crystallization from glass. This is demonstrated for the previously unreported composition, BaAl 4 O 7 , which exhibits two orthorhombic polymorphs with micrometer grain size, both optically transparent in the visible range. This innovative synthetic route to transparent polycrystalline ceramics should facilitate the discovery of new, cost-effective chemical methods for transparent ceramic applications. Conventional optically transparent single crystal materials are widely used in numerous photonic applications. However, these materials face several technological and economical challenges, including a restricted list of appropriate single crystal compounds, limitations on the type and level of chemical doping, and mechanical and manufacturing requirements for large and complex physical shapes. Many of these obstacles can be avoided through the use of ceramic materials, which afford a wider range

Topological, Geometric, and Chemical Order in Materials: Insights from Solid-State NMR

Unlike the long-range order of ideal crystalline structures, local order is an intrinsic characteristic of real materials and often serves as the key to the tuning of their properties and their final applications. Although researchers can easily assess local ordering using two-dimensional imaging techniques with resolution that approaches the atomic level, the diagnosis, description, and qualification of local order in three dimensions is much more challenging. Solid-state nuclear magnetic resonance (NMR) and its panel of continually developing instruments and methods enable the local, atom-selective characterization of structures and assemblies ranging from the atomic to the nanometer length scales. By making use of the indirect J-coupling that distinguishes chemical bonds, researchers can use solid-state NMR to characterize a variety of materials, ranging from crystalline compounds to amorphous or glassy materials. In crystalline compounds showing some disorder, we describe and distinguish the contributions of topology, geometry, and local chemistry in ways that are consistent with X-ray diffraction and computational approaches. We give examples of materials featuring either chemical disorder in a topological order or topological disorder with local chemical order. For glasses, we show that we can separate geometric and chemical contributions to the local order by identifying structural motifs with a viewpoint that extends from the atomic scale up to the nanoscale. As identified by solid state NMR, the local structure of amorphous materials or glasses consists of well-identified structural entities up to at least the nanometer scale. Instead of speaking of disorder, we propose a new description for these structures as a continuous assembly of locally defined structures, an idea that draws on the concept of locally favored structures (LFS) introduced by Tanaka and coworkers. This idea provides a comprehensive picture of amorphous structures based on fluctuations of chemical composition and structure over different length scales. We hope that these local or molecular insights will allow researchers to consider key questions related to nucleation and crystallization, as well as chemically (spinodal decomposition) or density-driven (polyamorphism) phase separation, which could lead to future applications in a variety of materials.

New nanocrystalline Cu/MnOx catalysts prepared from supercritical antisolvent precipitation

Supercritical CO2 is used as an antisolvent to precipitate out nanostructured homogeneous mixtures of Cu2+ and Mn3+ with crystallites of 10–20 nm in diameter. Following calcination, this material forms a crystalline tetragonal spinel, CuMn2O4, with a branched chainlike structure with a length of 160–200 nm and diameters of approximately 40 nm. This new material is more than twice as active per unit surface area as the conventionally prepared hopcalite catalysts for the oxidation of carbon monoxide. This is the first time that homogeneous mixed oxides have been formed using this method.

Structure Resolution of Ba5Al3F19 and Investigation of Fluorine Ion Dynamics by Synchrotron Powder Diffraction, Variable-Temperature Solid-State NMR, and Quantum Computations

The room temperature structure of Ba(5)Al(3)F(19) has been solved using electron microscopy and synchrotron powder diffraction data. One-dimensional (1D) (27)Al and ultrafast magic-angle-spinning (MAS) (19)F NMR spectra have been recorded and are in agreement with the proposed structural model for Ba(5)Al(3)F(19). The (19)F isotropic chemical shift and (27)Al quadrupolar parameters have been calculated using the CASTEP code from the experimental and density functional theory geometry-optimized structures. After optimization, the calculated NMR parameters of both the (19)F and (27)Al nuclei show improved consistency with the experimental values, demonstrating that the geometry optimization step is necessary to obtain more accurate and reliable structural data. This also enables a complete and unambiguous assignment of the (19)F MAS NMR spectrum of Ba(5)Al(3)F(19). Variable-temperature 1D MAS (19)F NMR experiments have been carried out, showing the occurrence of fluorine ion mobility. Complementary insights were obtained from both two-dimensional (2D) exchange and 2D double-quantum dipolar recoupling NMR experiments, and a detailed analysis of the anionic motion in Ba(5)Al(3)F(19) is proposed, including the distinction between reorientational processes and chemical exchange involving bond breaking and re-formation.

Characterization and properties of novel gallium-doped calcium phosphate ceramics.

Addition of a gallium (Ga) precursor in the typical reaction protocols used for the preparation of β-tricalcium phosphate (β-TCP) led to novel Ga-doped β-TCP ceramics with rhombohedral structures (R3c space group). From the refinement of their X-ray diffraction patterns, it was found that the incorporation of Ga in the β-TCP network occurs by substitution of one of the five calcium (Ca) sites, while occupation of another Ca site decreases in inverse proportion to the Ga content in the structure. The Ga local environment and the modification of the phosphorus environments due to the Ga/Ca substitution in Ga-doped β-TCP compounds are probed using (31)P and (71)Ga magic-angle spinning NMR. A decrease of the unit cell volume is observed with increasing Ga content, together with improved mechanical properties. Indeed, the compressive strength of these new bioceramics is enhanced in direct proportion of the Ga content, up to a 2.6-fold increase as compared to pure β-TCP.

Long-lasting luminescent ZnGa2O4:Cr3+ transparent glass-ceramics

Highly transparent ZnGa2O4 glass-ceramic materials are elaborated via a simple heat treatment of a 55SiO2–5Na2O–17ZnO–23Ga2O3 parent glass composition, which presents nanoscale spinodal phase separation. This optimized glass-ceramic exhibits 50 wt% of ZnGa2O4 nanocrystals showing a homogeneous and tuneable size. To describe the crystallization process, the glass and glass-ceramic nanostructures are studied by high resolution scanning transmission electron microscopy analysis coupled with in situ high temperature X-ray diffraction and optical measurements. From these results, an original mechanism is proposed to explain the crystallization process occurring in a spinodal phase separated glass. Remarkably, red long-lasting luminescence arising from the entire sample volume is observed in the Cr3+ doped transparent glass-ceramics, opening the route to a wider range of performing applications for this famous zinc gallate persistent phosphor.