Catherine Henrist

MORPHOLOGICAL STUDY OF MAGNESIUM HYDROXIDE NANOPARTICLES PRECIPITATED IN DILUTE AQUEOUS SOLUTION

Abstract Among other applications, magnesium hydroxide is commonly used as a flame-retardant filler in composite materials, as well as a precursor for magnesium oxide refractory ceramic. The microstructure of the powder is of prime importance in both technical applications. The influence of synthesis parameters on the morphological characteristics of magnesium hydroxide nanoparticles precipitated in dilute aqueous medium was studied. Several parameters were envisaged such as chemical nature of the base precipitant, type of counter-ion, temperature and hydrothermal treatment. Special attention was given to the obtaining of platelet-shaped, nanometric and de-agglomerated powders. The powders were characterized in terms of particle size distribution, crystal habits, morphology and ability to be re-dispersed in water. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption and laser diffusion analyses were used for this purpose.

Polymer/layered silicate nanocomposites by combined intercalative polymerization and melt intercalation: a masterbatch process

Abstract Poly(e-caprolactone) (PCL) and poly(vinyl chloride) (PVC) layered silicate nanocomposites were prepared by combination of intercalative polymerization and melt intercalation. In a first step, high clay content PCL nanocomposites were prepared by in situ polymerization of e-caprolactone intercalated between selected organo-modified silicate layers. The polymerization was catalyzed with dibutyltin dimethoxide in the presence of montmorillonites, the surface of which were previously exchanged with (functionalized) long alkyl chains ammonium cations. Then, these highly filled PCL nanocomposites were added as masterbatches in commercial PCL and PVC by melt blending. The intercalation of PCL chains within the silicate layers by in situ polymerization proved to be very efficient, leading to the formation of intercalated and/or exfoliated structures depending on the organo-clay. These masterbatches were readily dispersed into the molten PCL and PVC matrices yielding intercalated/exfoliated layered silicate nanocomposites which could not be obtained by melt blending the matrix directly with the same organo-modified clays. The formation of nanocomposites was assessed both by X-ray diffraction and transmission electronic microscopy. Interestingly, this so-called ‘masterbatch’ two-step process allowed for preparing PCL nanocomposites even with non-modified natural clay, i.e. sodium montmorillonite, which showed a material stiffness much higher than the corresponding microcomposites recovered by direct melt intercalation. The thermal stability of PCL nanocomposites as a function of clay content was investigated by thermogravimetry (TGA).

Nanosphere lithography: a powerful method for the controlled manufacturing of nanomaterials

The never-ending race towards miniaturization of devices induced an intense research in the manufacturing processes of the components of those devices. However, the complexity of the process combined with high equipment costs makes the conventional lithographic techniques unfavorable formany researchers. Through years, nanosphere lithography (NSL) attracted growing interest due to its compatibility with wafer-scale processes as well as its potential to manufacture a wide variety of homogeneous one-, two-, or three-dimensional nanostructures. This method combines the advantages of both top-down and bottom-up approaches and is based on a two-step process: (1) the preparation of a colloidal crystal mask (CCM) made of nanospheres and (2) the deposition of the desired material through the mask. The mask is then removed and the layer keeps the ordered patterning of the mask interstices. Many groups have been working to improve the quality of the CCMs. Throughout this review, we compare the major deposition techniques to manufacture the CCMs (focusing on 2D polystyrene nanospheres lattices), with respect to their advantages and drawbacks. In traditional NSL, the pattern is usually limited to triangular structures. However, new strategies have been developed to build up more complex architectures and will also be discussed.

Experimental Design applied to spin coating of 2D colloidal crystal masks : a relevant method?

Monolayers of colloidal spheres are used as masks in nanosphere lithography (NSL) for the selective deposition of nanostructured layers. Several methods exist for the formation of self-organized particle monolayers, among which spin coating appears to be very promising. However, a spin coating process is defined by several parameters like several ramps, rotation speeds, and durations. All parameters influence the spreading and drying of the droplet containing the particles. Moreover, scientists are confronted with the formation of numerous defects in spin coated layers, limiting well-ordered areas to a few micrometers squared. So far, empiricism has mainly ruled the world of nanoparticle self-organization by spin coating, and much of the literature is experimentally based. Therefore, the development of experimental protocols to control the ordering of particles is a major goal for further progress in NSL. We applied experimental design to spin coating, to evaluate the efficiency of this method to extract and model the relationships between the experimental parameters and the degree of ordering in the particles monolayers. A set of experiments was generated by the MODDE software and applied to the spin coating of latex suspension (diameter 490 nm). We calculated the ordering by a homemade image analysis tool. The results of partial least squares (PLS) modeling show that the proposed mathematical model only fits data from strictly monolayers but is not predictive for new sets of parameters. We submitted the data to principal component analysis (PCA) that was able to explain 91% of the results when based on strictly monolayered samples. PCA shows that the ordering was positively correlated to the ramp time and negatively correlated to the first rotation speed. We obtain large defect-free domains with the best set of parameters tested in this study. This protocol leads to areas of 200 μm(2), which has never been reported so far.

Study of the morphology of copper hydroxynitrate nanoplatelets obtained by controlled double jet precipitation and urea hydrolysis

A copper hydroxynitrate of stoichiometry Cu2(OH)3NO3, analogous to the layered double hydroxide family, was synthesized by the so-called controlled double jet precipitation technique, and by hydrolysis of urea in the presence of copper nitrate. Special attention has been focused on the size, morphology and agglomeration tendency of the particles. The aim of this work is to define the optimum precipitation conditions in terms of quality and dispersability of the recovered product. Such platelet-like particles can be used as anisotropic fillers in nanocomposite materials. Several reaction parameters such as flow and concentration of the reactant solutions, design of the reactor and addition of a growth modifier were studied. r 2003 Published by Elsevier Science B.V.

Poly(e-caprolactone) layered silicate nanocomposites: effect of clay surface modifiers on the melt intercalation process

Abstract Nanocomposites based on biodegradable poly(e-caprolactone) (PCL) and layered silicates (montmorillonite) modified by various alkylammonium cations were prepared by melt intercalation. Depending on whether the ammonium cations contain non-functional alkyl chains or chains terminated by carboxylic acid or hydroxyl functions, microcomposites or nanocomposites were recovered as shown by X-ray diffraction and transmission electron microscopy. Mechanical and thermal properties were examined by tensile testing and thermogravimetric analysis. The layered silicate PCL nanocomposites exhibited some improvement of the mechanical properties (higher Young’s modulus) and increased thermal stability as well as enhanced flame retardant characteristics as result of a charring effect. This communication aims at reporting that the formation of PCL-based nanocomposites strictly depends on the nature of the ammonium cation and its functionality, but also on the selected synthetic route, i.e. melt intercalation vs. in situ intercalative polymerization. Typically, protonated w-aminododecanoic acid exchanged montmorillonite allowed to intercalate ε -caprolactone monomer and yielded nanocomposites upon in situ polymerization, whereas they exclusively formed microcomposites when blended with preformed PCL chains. In other words, it is shown that the formation of polymer layered silicate nanocomposites is not straightforward and cannot be predicted since it strongly depends on parameters such as ammonium cation type and functionality together with the production procedure, i.e., melt intercalation, solvent evaporation or in situ polymerization.

Varying TiO2 Macroscopic Fiber Morphologies toward Tuning Their Photocatalytic Properties

In a context of volatile organic compound photodecomposition, we have addressed TiO2-based macroscoscpic fiber generation. We have extruded hybrid sols of amorphous titania nanoparticles, latex nanoparticles, and nonionic surfactant (Tergitol) as structure-directing agents into a poly(vinyl alcohol) (PVA) solution bearing salts acting as a flocculating medium. The resulting nanocomposite TiO2/latex/PVA macroscopic fibers were thermally treated in air to open porosity by organic removal while generating the photocatalytically active anatase phase of TiO2 along with residual brookite. Considering the synthetic paths, we have varied both the diameter of the latex particles as well as their concentration within the starting sol. These parameters allow tuning both the voids created through the applied thermal treatment and the fiber final diameters. For gas-phase photocatalysis, we have shown that the fiber diameters, mesoscopic roughness, and macroscopic topological defects represent indeed important morphological parameters acting cooperatively toward both acetone degradation and its mineralization processes. Particularly, triggering the fiber morphological characteristics, we have increased their efficiency toward acetone degradation of around 550% when compared with previous work.

EBSD study on YBCO textured bulk samples: correlation between crystal growth and 'microtexture'

This work describes an electron backscattered diffraction (EBSD) study of the perovskite-derived structures YBa2Cu3O7−δ .A fter having pointed out the difficulties of EBSD analyses in resolving the orientations of these pseudo-cubic structures, various YBaCuO bulk samples are analysed and the correlation between the microstructure, crystal growth and global texture, determined by neutron diffraction, is carried out. Homogeneous ‘microtexture’ with small subdomain misorientation of 12 ◦ are measured for YBCO top seeding melt textured growth (TSMTG) samples. YBCO perforated samples also exhibit misoriented subdomains, giving rise to a heterogeneous ‘microtexture’ correlated to the YBCO growth front and to the pattern used for the perforating. (Some figures in this article are in colour only in the electronic version)

Texture of Alumina by neutron diffraction and SEM-EBSD

The orientation distributions of α-Al2O3 textured ceramics are determined from neutron diffraction and SEM-EBSD. A curved position-sensitive detector coupled to a tilt angle (χ) scan allowed the whole neutron diffraction pattern treatment in the combined Rietveld-WIMV-Popa algorithm. Analyses from neutron and electron diffraction data gave similar results if EBSD data are smoothed to account for grain statistics. Four textured alumina ceramics were prepared by slipcasting under a high magnetic field and sintered at 800°C, 1300°C, 1400°C and 1600°C. The inverse pole figures and EBSD-mapping highlights the influence of the magnetic field and sintering temperature on the texture development. The inverse pole figures calculated for the fiber direction show a major (001) component for all the samples. With the increasing sintering temperature, the texture strength is enhanced and the c-axis distribution is sharper. The effectiveness of the combined approach for determining the crystallite size is also evident. As a global trend, the calculated crystallite size and observed grain size are similar and increase with the increasing sintering temperature. The mechanism of the texture development in the sintered specimens is certainly initiated from the preferred orientation of the green body after slip-casting under a high magnetic field. The basal texture is enhanced during sintering by selective anisotropic grain growth. We evidenced here the powerfulness of the Rietveld texture analysis correlated to SEM-EBSD calculation to provide a basis for the correlation of texture, microstructural parameters and anisotropic properties.

The rocker bone: a new kind of mineralised tissue?

In some Ophidiiform fishes, the anterior part of the swimbladder is thickened into a hard structure called the “rocker bone”, which is thought to play a role in sound production. Although this structure has been described as cartilage or bone, its nature is still unknown. We have made a thorough analysis of the rocker bone in Ophidion barbatum and compared it with both classical bone and cartilage. The rocker bone appears to be a new example of mineralisation. It consists of (1) a ground substance mainly composed of proteoglycans (mucopolysaccharide acid) and fibres and (2) a matrix containing small mineralised spherules composed of a bioapatite and fibrils. These spherules are embedded in mineralised cement of a similar composition to the spherules themselves. The rocker bone grows via the apposition of new apatite spherules at its periphery. These spherules are first secreted by the innermost fibroblast layer of the capsule contained in the rocker bone and then grow extracellularly. Blood vessels, which represent the only means of transport for matrix and mineral material, are numerous. They enter the rocker bone via the hyle and ramify towards the capsule. We propose to call this new kind of mineralised tissue constituting the rocker bone “frigolite” (the Belgian name for styrofoam) in reference to the presence of spherules of different sizes and the peculiarity of the rocker bone in presenting a smooth surface when fractured.