Rudi Cloots

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.

Well Shaped Mn 3 O 4 Nano-octahedra with Anomalous Magnetic Behavior and Enhanced Photodecomposition Properties

Very uniform and well shaped Mn₃O₄ nano-octahedra are synthesized using a simple hydrothermal method under the help of polyethylene glycol (PEG200) as a reductant and shape-directing agent. The nano-octahedra formation mechanism is monitored. The shape and crystal orientation of the nanoparticles is reconstructed by scanning electron microscopy and electron tomography, which reveals that the nano-octahedra only selectively expose {101} facets at the external surfaces. The magnetic testing demonstrates that the Mn₃O₄ nano-octahedra exhibit anomalous magnetic properties: the Mn₃O₄ nano-octahedra around 150 nm show a similar Curie temperature and blocking temperature to Mn₃O₄ nanoparticles with 10 nm size because of the vertical axis of [001] plane and the exposed {101} facets. With these Mn₃O₄ nano-octahedra as a catalyst, the photodecomposition of rhodamine B is evaluated and it is found that the photodecomposition activity of Mn₃O₄ nano-octahedra is much superior to that of commercial Mn₃O₄ powders. The anomalous magnetic properties and high superior photodecomposition activity of well shaped Mn₃O₄ nano-octahedra should be related to the special shape of the nanoparticles and the abundantly exposed {101} facets at the external surfaces. Therefore, the shape preference can largely broaden the application of the Mn₃O₄ nano-octahedra.

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.

From RE-211 to RE-123. How to control the final microstructure of superconducting single-domains

This paper reviews the usual techniques for producing YBCO-type single-domains and the microstructure of the as-obtained samples. The problems of seed dissolution and parasite nucleations are discussed in detail. The formation of microstructural defects, such as pores and cracks, is examined. An important part of this review is devoted to the study of the influence of RE-211 particles (RE2BaCuO5 where RE denotes Y, Yb, Nd, Sm, Dy, Gd, Eu or a mixture of them. Generally Nd4Ba2Cu2O10 is preferred to Nd2BaCuO5) for the microstructure and properties of RE?Ba?Cu?O single-domains. Pushing/trapping theory is described in order to explain the spatial distribution of RE-211 particles in the RE-123 ((RE)Ba2Cu3O7??) monoliths. The formation of RE-211-free regions is discussed. Different ways to limit the RE-211 coarsening are reviewed. Microstructural defects in the RE-123 matrix caused by the RE-211 particles are presented. It is also shown that RE-211 particles play a significant role in the mechanical properties of single-domain samples. We finish this review by discussing the infiltration and growth process as a good technique to control the microstructure.

Structural templating effects in molecular heterostructures grown by organic molecular-beam deposition

Powder x-ray diffraction has been used to study the structural properties of multilayered heterostructures grown by organic molecular-beam deposition and based on the molecular materials H2Pc, perylene-3, 4, 9, 10-tetracarboxylic dianhydride (PTCDA) and Alq3. Structural templating has been observed for multilayers of PTCDA and H2Pc, with the first layer completely disrupting the structure of subsequent layers. H2Pc adopts a new structure when deposited on PTCDA, in which the molecular plane is oriented parallel to the substrate and this configuration is retained for film thicknesses >380 nm. The templating effect extends through molecular thin-film structures involving several different layers, but is attenuated by insertion of an amorphous layer such as Alq3.

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.

Synthesis and characterization of new inorganic polymeric composites based on kaolin or white clay and on ground-granulated blast furnace slag

Alkali activation of dehydroxylated kaolin or clay yielded high-strength polymeric materials, so-called geopolymers. They were synthesized by mixing the aluminosilicate with solutions of sodium metasilicate and KOH followed by adding 45 wt.% of ground-granulated blast furnace slag. The influence of the aluminosilicate source, its activation temperature, and the order of mixing raw materials were studied on the workability of the blending paste, the microstructure, and the Vickers hardness of the geopolymer samples. The polymeric material is completely amorphous according to x-ray diffraction. Solid-state 2 7 A1 and 2 9 Si magic-angle-spinning nuclear magnetic resonance showed that the geopolymer consists of AlO 4 and SiO 4 tetrahedra linked together through a polymeric network constituted by branched entities SiQ 4 (4A1) and SiQ 4 (3A1), but also by less-polymerized silicates SiQ 1 and SiQ 2 . Scanning electron microscopy showed a homogeneous polymeric gel matrix containing unreacted slag (and quartz) grains; thermogravimetric analysis and differential scanning calorimetry exhibited a high content of water and an elevated melting point (1260 °C). Vickers hardness values are in the range of 200 MPa.

Titanium release from dental implants: an in vivo study on sheep

Abstract Titanium and its alloys release passive metal dissolution products. This raises the issues of the amount and fate of these products. In this study, we document titanium levels released from dental implants. We compared commercially pure titanium, titanium alloy (Ti6Al4V) and the effect of hydroxyapatite (HA) coating on dental implants. Seventeen screw type implants were inserted into the cortical bone of sheeps tibias. Bone and soft tissues (liver, spleen, kidney, lymph nodes and connective tissues) were harvested. Samples were analyzed for Ti content by proton induced X-ray emission (PIXE). Results from bone were compared with those obtained by the energy-dispersive X-ray analysis (EDX) on scanning electron microscopy (SEM). The results suggest that bone remodeling may reduce the local accumulation of titanium.

Magnetic shielding properties of high-temperature superconducting tubes subjected to axial fields

We have experimentally studied the magnetic shielding properties of a cylindrical shell of BiPbSrCaCuO subjected to low frequency AC axial magnetic fields. The magnetic response has been investigated as a function of the dimensions of the tube, the magnitude of the applied field and the frequency. These results are explained quantitatively by employing the method of Brandt (1998 Phys. Rev. B 58 6506) with a Jc(B) law appropriate for a polycrystalline material. Specifically, we observe that the applied field can sweep into the central region either through the thickness of the shield or through the opening ends, the latter mechanism being suppressed for long tubes. For the first time, we systematically detail the spatial variation of the shielding factor (the ratio of the applied field over the internal magnetic field) along the axis of a high-temperature superconducting tube. The shielding factor is shown to be constant in a region around the centre of the tube, and to decrease as an exponential in the vicinity of the ends. This spatial dependence comes from the competition between two mechanisms of field penetration. The frequency dependence of the shielding factor is also discussed and shown to follow a power law arising from the finite creep exponent n.