Influence of volatile chlorides on the molten salt synthesis of ternary oxide nanorods and nanoparticles

A molten salt synthesis route, previously reported to yield BaTiO3, PbTiO3, and Na2Ti6O13 nanorods, has been re-examined to elucidate the role of volatile chlorides. A precursor mixture containing barium (or lead) and titanium was annealed in the presence of NaCl at 760 or 820 degrees C. The main products were respectively isometric nanocrystalline BaTiO3 and PbTiO3. Nanorods were also detected, but electron diffraction revealed that the composition of the nanorods was respectively BaTi2O5/BaTi5O11 and Na2Ti6O13 for the two different systems, in contradiction to the previous studies. It was shown that NaCl reacted with BaO (PbO) resulting in loss of volatile BaCl2 (PbCl2) and formation and preferential growth of titanium oxide-rich nanorods instead of the target phase BaTiO3 (or PbTiO3). The molten salt synthesis route may therefore not necessarily yield nanorods of the target ternary oxide as reported previously. In addition, the importance of NaCl(g) for the growth of nanorods below the melting point of NaCl was demonstrated in a special experimental setup, where NaCl and the precursors were physically separated.     

Cholesky decomposition of the two-electron integral matrix in electronic structure calculations

A standard Cholesky decomposition of the two-electron integral matrix leads to integral tables which have a huge number of very small elements. By neglecting these small elements, it is demonstrated that the recursive part of the Cholesky algorithm is no longer a bottleneck in the procedure. It is shown that a very efficient algorithm can be constructed when family type basis sets are adopted. For subsequent calculations, it is argued that two-electron integrals represented by Cholesky integral tables have the same potential for simplifications as density fitting. Compared to density fitting, a Cholesky decomposition of the two-electron matrix is not subjected to the problem of defining an auxiliary basis for obtaining a fixed accuracy in a calculation since the accuracy simply derives from the choice of a threshold for the decomposition procedure. A particularly robust algorithm for solving the restricted Hartree-Fock (RHF) equations can be speeded up if one has access to an ordered set of integral tables. In a test calculation on a linear chain of beryllium atoms, the advocated RHF algorithm nicely converged, but where the standard direct inversion in iterative space method converged very slowly to an excited state.     

Three-dimensional chemical concentration maps in a microfluidic device using two-photon absorption fluorescence imaging

Two-photon absorption fluorescence is employed within a microfluidic device to create a three-dimensional chemical concentration map for mixing uniformity characterization. This multiphoton technique images fluorescence intensity directly and provides a simple, rapid, and readily employed route to composition characterization within microfluidic systems.     

To D or not to D? On estimating the microenvironment polarity of biomolecular cavities

Knowledge of the local polarity of specific cavities in biopolymers can facilitate the design of selective low MW ligands that impact the structure and function of macromolecules. The most common tools for interrogating local polarity are fluorescent probes that are sensitive to their microenvironment. Researchers often evaluate and express this local polarity using dielectric constants, a parameter that reflects an inherent bulk property. A more appropriate expression should take into account solvent-solute interactions at the molecular level. Reevaluation of commonly used fluorophores illustrates the improved correlation between observed Stokes shift changes and E(T)(30) values as compared to the corresponding dielectric constants.     

Investigation of final-stage sintering of various microsize structures prepared by micro powder injection molding

Micro powder injection molding (μPIM) has been developed as a potential technique for mass production of microcomponents in microsystems due to its shaping complexity at low cost, in which sintering is a crucial step to dictate the final properties of the microcomponents. In this paper, final-stage sintering behavior of 316L stainless steel microsize structures prepared by μPIM, φ100 μm and φ60 μm, respectively, was studied. The effect of size reduction in the regime of micrometers on the density of various microsize structures was investigated. Sintering kinetics of the microsize structures of φ100 μm and φ60 μm were studied based on particle level sintering models. It is found that the microsize structures of φ60 μm had higher density than the microsize structures of φ100 μm given the same sintering condition. The results indicate that size reduction in the regime of micrometers facilitated densification of microsize structures. The grain growth mechanism of microsize structures varied with size. Whereas the grain growth of the microsize structures of φ100 μm is governed by surface-diffusion-controlled pore drag, the grain growth of the microsize structures of φ60 μm is controlled by boundary diffusion. During densification, the microsize structures, φ100 μm and φ60 μm, are both controlled by lattice diffusion. The corresponding activation energies are reported in the paper.     

Micro-hot-embossing of 316L stainless steel micro-structures

In this paper, the fabrication of an array of 316L stainless steel cylindrical micro-structures by hot-embossing is studied. The effects of various embossing parameters on the filling of the micro-cavities of silicon mold insert and the demolding of micro-structures are investigated. They include different silicon mold insert configurations, embossing pressure, embossing temperature, embossing time and the thickness of embossing substrate on which the micro-structures stand. Two types of silicon mold insert configurations are investigated. Hot-embossing study with the silicon mold insert attached on the upper mold plate shows that it is not feasible to achieve complete filling. Incomplete filling occurs and increasing the embossing pressure causes excessive thinning of the embossing substrate, so that micro-structures are torn off during demolding. Experiments show that the configuration that the silicon mold insert is positioned flush with lower mold surface improves complete filling. Using suitable embossing pressure and temperature, the larger substrate thickness and longer embossing time ensure the fabrication of defect-free fully filled micro-structures.