Effect of pH on the synthesis and properties of luminescent SiO2/calcium phosphate:Eu3+ core-shell nanoparticles

A novel method for the synthesis of luminescent SiO(2)/calcium phosphate (CaP):Eu(3+) core-shell nanoparticles (NPs) was developed via a sol-gel route followed by annealing at a temperature of 800 °C. The object of this study was the investigation of the effect of pH on the formation of a CaP shell around the silica core. The resulting annealed NPs exhibited an amorphous SiO(2) core and a crystalline luminescent shell. The formation of a CaP layer was possible at pH below 4.5 and above 6.5 during the coating step. The crystal structure of the shell was studied by X-ray diffraction analysis. Hydroxyapatite (HAp) and α-tricalcium phosphate were detected as crystal phases of the surrounding layer. However, NPs produced under basic conditions exhibited a higher crystallinity of the CaP layer than did samples coated at pH below 4.5. In the pH interval between 4.5 and 6.5, no shell growth but the formation of secondary NPs containing CaO and Ca(OH)(2) was observed. Furthermore, SiO(2)/CP:Eu(3+) core-shell NPs were investigated by transmission electron microscopy, dynamic light scattering, Fourier transform infrared spectroscopy, inductively coupled plasma optical emission spectrometry, and photoluminescence spectroscopy. The resulting HAp-coated NPs were successfully tested by a cell-culture-based viability assay with respect to a later application as a luminescent marker for biomedical applications.     

Theory of nanoparticle diffusion in unentangled and entangled polymer melts

We propose a statistical dynamical theory for the violation of the hydrodynamic Stokes-Einstein (SE) diffusion law for a spherical nanoparticle in entangled and unentangled polymer melts based on a combination of mode coupling, Brownian motion, and polymer physics ideas. The non-hydrodynamic friction coefficient is related to microscopic equilibrium structure and the length-scale-dependent polymer melt collective density fluctuation relaxation time. When local packing correlations are neglected, analytic scaling laws (with numerical prefactors) in various regimes are derived for the non-hydrodynamic diffusivity as a function of particle size, polymer radius-of-gyration, tube diameter, degree of entanglement, melt density, and temperature. Entanglement effects are the origin of large SE violations (orders of magnitude mobility enhancement) which smoothly increase as the ratio of particle radius to tube diameter decreases. Various crossover conditions for the recovery of the SE law are derived, which are qualitatively distinct for unentangled and entangled melts. The dynamical influence of packing correlations due to both repulsive and interfacial attractive forces is investigated. A central finding is that melt packing fraction, temperature, and interfacial attraction strength all influence the SE violation in qualitatively different directions depending on whether the polymers are entangled or not. Entangled systems exhibit seemingly anomalous trends as a function of these variables as a consequence of the non-diffusive nature of collective density fluctuation relaxation and the different response of polymer-particle structural correlations to adsorption on the mesoscopic entanglement length scale. The theory is in surprisingly good agreement with recent melt experiments, and new parametric studies are suggested.     

Glassy dynamics and mechanical response in dense fluids of soft repulsive spheres. I. Activated relaxation, kinetic vitrification, and fragility

The microscopic nonlinear Langevin equation theory of activated glassy dynamics is applied to dense fluids of spherical particles that interact via a finite range Hertzian contact soft repulsion. The activation barrier and mean alpha relaxation time are predicted to be rich functions of volume fraction and particle stiffness, exhibiting a non-monotonic variation with concentration at high volume fractions. The latter is due to a structural "soft jamming" crossover where the real space local cage order weakens when soft particles significantly overlap. The highly variable dependences of the relaxation time on temperature and volume fraction are reasonably well collapsed onto two distinct master curves that are qualitatively consistent with a recent scaling ansatz and computer simulation study. A kinetic vitrification diagram is constructed and compared to its dynamic crossover analog. Intersection of the dynamic crossover and soft jamming threshold boundaries occurs for particles that are sufficiently soft, implying the nonexistence of a clear activated dynamics regime or kinetic arrest transition for such particles. The isothermal dynamic fragility is predicted to vary over a wide range as a function of particle stiffness, and soft particles behave as strong glasses. Qualitative comparisons with simulations and microgel experiments reveal good agreement.     

Shear banding during nonlinear creep with a solution of monodisperse polystyrene

Creep experiments with a solution of polystyrene (M _w = 2.6 MDa, 16 vol.%, 25 °C) in diethyl phthalate are reported for stresses between 100 and 2,500 Pa (≈ 3G _N ⁰/4). The aim was to look for a flow transition as reported for strongly entangled poly(isobutylene) solutions. The experiments with the polystyrene solution were repeated for cone angles of 2, 4, and 6° (radius 15 mm) and showed no dependence on cone angle. The Cox–Merz rule was not fulfilled for stresses beyond about 800 Pa. The tangential observation with a CCD camera showed that the edge took a concave shape because of the second normal stress difference. Beyond 1,000 Pa, the concave edge develops into a crevice, thus substantially reducing the effective cross-section. This leads to runaway in a constant torque experiment. At p ₂₁ = 800 Pa, head-on particle tracking confirms that the originally linear velocity profile takes a gooseneck shape, thus revealing shear banding. When the creep stress is stepped down to 100 Pa, this velocity profile evolves back to a linear one. The conclusion from this work is that even if nonlinear creep experiments are reproducible and a steady state is reached, this does not mean that the flow field is homogeneous. This paper was presented at Annual European Rheology Conference (AERC) held in Hersonisos, Crete, Greece, April 27–29, 2006.     

Selective growth of GaInN quantum dot structures

In this work, we present an approach to fabricate GaInN quantum dots. The idea is to have a complete control of the position of the quantum dot during the growth and to use this positioned dot for future functioning. For this purpose we have prepared templates with selectively grown GaN pyramids by MOVPE. After proper adjustment of the GaN growth we have overgrown these templates with InGaN to form the quantum dots on top of the pyramids. Finally the structures were capped with GaN and photoluminescence measurements were performed.     

Über Oxocuprate. XV Zur Kristallstruktur von Seltenerdmetalloxocupraten: La2CuO4, Gd2CuO4

About Oxocuprates. XV. The Crystal Structure of Rare Earth Oxocuprates: La₂CuO₄, Gd₂CuO₄ Gd₂CuO₄ and La₂CuO₄ are examined by single crystal X-ray methods. Gd₂CuO₄ is isotypic with Nd₂CuO₄, La₂CuO₄ however shows a slightly distorted K₂NiF₄ structure. Cu²⁺ has square (Gd₂CuO₄) or octahedral (La₂CuO₄) coordination. La₂CuO₄ is the only compound in the system of Rare Earth cuprates with K₂NiF₄-type structure.