An aqueous route to organically functionalized silica diatom skeletons

Diatomaceous earth was functionalized by grafting organotrialkoxysilane precursors onto the surface of the porous silica cell walls of this biomineral. Vinyl- and mercapto-containing structures were prepared in aqueous media without disruption of the diatomic architecture. Successful grafting of the organic moieties was confirmed using solid state ²⁹Si MAS NMR spectroscopy, and the presence of the intact diatom framework by scanning electron microscopy. The sorption properties of mercaptopropyl-functionalized diatoms towards heavy metals was studied by measuring the accessibility and diffusion rates of mercury(II) species to the binding sites (-SH) by the means of electrochemical methods.     

Reactivity of a Ti–45.9Al–8Nb alloy in air at 700–900°C

A Ti–45.9Al–8Nb (at%) alloy with a lamellar structure (γ+α₂) was oxidised in air at 700, 800, 850 and 900°C in isothermal and thermal cycling conditions. The reaction progress was followed by thermogravimetric measurements. In isothermal conditions the oxidation kinetics followed approximately a parabolic rate law and the rate constants ranged from about 10^–12 kg² m^–4 s^–1 at 700°C to 10^–10 kg² m^–4 s^–1 at 900°C. The oxide scales were built of Al₂O₃ and TiO₂, the former being the main component of the outermost layer. The oxidation behaviour of Ti–45.9Al–8Nb was referred to a commercial titanium alloy, WT4 (Ti–6Al–1Mn), and selected oxidation-resistant alloys.     

Complex morphology of melt-spun nylon-6 fibres investigated by 1H double-quantum-filtered NMR spin-diffusion experiments.

The complex morphology of high-speed melt-spun nylon-6 fibres hydrated with D2O was investigated using 1H double-quantum-filtered spin-diffusion NMR experiments. The magnetisation exchange from selected crystalline domains along the fibrils and interfibrils was simulated with the help of a three-dimensional solution of a spin-diffusion equation approximated by a product of one-dimensional analytical NMR signals, which correspond to a lamellar morphology. This allows to measure the sizes of crystalline and less-mobile amorphous domains along the fibrils, as well as the diameter of the fibrils and interfibril distances. A series of nylon-6 fibres with extreme values of winding speed and draw ratio was investigated. The changes detected in the domain size along the fibrils and interfibrils show the same trend in the data obtained from wide-angle X-ray diffraction and small-angle X-ray scattering.     

A kinetic Monte Carlo method on super-lattices for the study of the defect formation in the growth of close packed structures

A modified Kinetic Lattice Monte Carlo model has been developed to predict growth rate regimes and defect formation in the case of the homo-epitaxial growth of close packed crystalline structures. The model is an improvement over standard Monte Carlo algorithms, which usually retain fixed atom positions and bond partners indicative of perfect crystal lattices. Indeed, we extend the concepts of Monte Carlo growth simulations on super-lattices containing additional sites (defect sites) with respect to those of the reference material. This extension implies a reconsideration of the energetic mapping, which is extensively presented, and allows to describe a complex phenomenology that is out of accessibility of standard stochastic approaches. Results obtained using the Kawasaki and the Bond-Counting rules for the transition probability of the Monte Carlo event are discussed in details. These results demonstrate how the defect types (local or extended), the formation mechanisms and the defect generation regimes can be characterized using our approach.     

Slow-light enhanced optical detection in liquid-infiltrated photonic crystals

Slow-light enhanced optical detection in liquid-infiltrated photonic crystals is theoretically studied. Using a scattering-matrix approach and the Wigner–Smith delay time concept, we show that optical absorbance benefits both from slow-light phenomena as well as a high filling factor of the energy residing in the liquid. Utilizing strongly dispersive photonic crystal structures, we numerically demonstrate how liquid-infiltrated photonic crystals facilitate enhanced light–matter interactions, by potentially up to an order of magnitude. The proposed concept provides strong opportunities for improving existing miniaturized absorbance cells for optical detection in lab-on-a-chip systems.     

Reverse micellar synthesis and properties of nanocrystalline GMR materials (LaMnO3, La0.67Sr0.33MnO3 and La0.67Ca0.33MnO3): Ramifications of size considerations

Nanoparticles of complex manganites (viz. LaMnO₃, La_0.67Sr_0.33MnO₃ and La_0.67Ca{0.33}MnO₃) have been synthesized using the reverse micellar route. These manganites are prepared at 800‡C and the monophasic nature of all the oxides has been established by powder X-ray diffraction studies. TEM studies show an average grain size of 68, 80 and 50 nm for LaMnO₃, La_0.67Sr_0.33MnO₃ and La_0.67Ca{0.33}MnO₃respectively. Ferromagnetic ordering is observed at around 250 K for LaMnO₃, 350 K for La_0.67Sr_0.33MnO₃ and 200 K for La_0.67Ca{0.33}MnO₃. These Curie temperatures correspond well with those reported for bulk materials with similar composition.     

Increase of refractive index induced by absorbing centres

An analytical expression of the complex permittivity is derived for absorbing centres featuring inhomogeneous absorption-line broadening. Such an expression gives the dispersion law of the real part of the permittivity when the imaginary part has a Gaussian lineshape. Our mathematical approach starts from an overlap integral of Lorentzian-type dielectric susceptibilities weighted by a Gaussian probability distribution of the resonance absorption energies. The analytical solution found is consistent with the Kramers–Kronig relation. We demonstrate that, like in the case of homogeneous absorption-line broadening, the refractive index increases at photon energies lower than the resonance absorption energy also for inhomogeneous absorption-line broadening; if the absorbing centres emit Stokes-shifted radiation, such an increase can be exploited for passive and active waveguiding applications. An example is reported regarding active waveguides based on colour centres in a lithium fluoride crystal.     

FexNi100−x nanometric films deposited by laser ablation on SiO2/Si substrates

Fe_xNi_100−x nanometric films were deposited on SiO₂/Si substrates at room temperature using the pulsed laser deposition technique. The targets were Fe-Ni amorphous magnetic foils with composition Fe₅₀Ni₅₀, Fe₃₅Ni₆₅ and Fe₂₂Ni₇₈. Morphological and structural properties of the deposited films were investigated using scanning electron microscopy, Rutherford backscattering spectrometry, grazing incidence X-ray diffraction, and X-ray reflectivity. Electrical and magnetic characteristics of the films were investigated by using the four-point probe and the magneto-optic Kerr effect techniques, respectively. The film properties are strictly dependent on the Fe-Ni compositional ratio.     

Thickness dependence of free‐standing thin films

Below a critical thickness, of about 60 nm, the glass transition temperature of polystyrene (PS) films decreases with film thickness, as demonstrated using free‐standing films. A geometrical model is developed here describing this phenomenon in the case of ideal (Gaussian) chains. This model, which can be considered as an application of the free volume model, assumes that the decrease of the glass transition temperature from thick to ultrathin films is due to the modification of the interpenetration between neighboring chains. The theoretical curve deduced from the model is in excellent agreement with the PS experimental results, without using any adjustable parameters. From these results, it can be concluded that new chain motions, usually buried in bulk samples, are expressed by the presence of the surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 10–17, 2007