Quantum Mechanics Insight into the Microwave Nucleation of SrTiO3 Nanospheres

An extensive investigation of strontium titanate, SrTiO3 (STO), nanospheres synthesized via a microwave-assisted hydrothermal (MAH) method has been conducted to gain a better insight into thermodynamic, kinetic, and reaction phenomena involved in STO nucleation and crystal growth processes. To this end, quantum chemical modeling based on the density functional theory and periodic super cell models were done. Several experimental techniques were employed to get a deep characterization of structural and optical features of STO nanospheres. A possible formation mechanism was proposed, based on dehydration of titanium and strontium clusters followed by mesoscale transformation and a self-assembly process along an oriented attachment mechanism resulting in spherical like shape. Raman and XANES analysis renders a noncentrosymmetric environment for the octahedral titanium, while infrared and first order Raman modes reveal OH groups which are unsystematically incorporated into uncoordinated superficial sites. These results seem to indicate that the key component is the presence of distorted TiO6 clusters to engender a luminescence property. Analysis of band structure, density Of states, and charge map shows that there is a close relationship among local broken symmetry, polarization, and energy split of the 3d orbitals of titanium. The interplay among these electronic and structural features provides necessary conditions to evaluate its luminescent properties under two energy excitation.

A comparison of deterministic, reliability-based and risk-based structural optimization under uncertainty

In this paper, the effects of uncertainty and expected costs of failure on optimum structural design are investigated, by comparing three distinct formulations of structural optimization problems. Deterministic Design Optimization (DDO) allows one the find the shape or configuration of a structure that is optimum in terms of mechanics, but the formulation grossly neglects parameter uncertainty and its effects on structural safety. Reliability-based Design Optimization (RBDO) has emerged as an alternative to properly model the safety-under-uncertainty part of the problem. With RBDO, one can ensure that a minimum (and measurable) level of safety is achieved by the optimum structure. However, results are dependent on the failure probabilities used as constraints in the analysis. Risk optimization (RO) increases the scope of the problem by addressing the compromising goals of economy and safety. This is accomplished by quantifying the monetary consequences of failure, as well as the costs associated with construction, operation and maintenance. RO yields the optimum topology and the optimum point of balance between economy and safety. Results are compared for some example problems. The broader RO solution is found first, and optimum results are used as constraints in DDO and RBDO. Results show that even when optimum safety coefficients are used as constraints in DDO, the formulation leads to configurations which respect these design constraints, reduce manufacturing costs but increase total expected costs (including expected costs of failure). When (optimum) system failure probability is used as a constraint in RBDO, this solution also reduces manufacturing costs but by increasing total expected costs. This happens when the costs associated with different failure modes are distinct. Hence, a general equivalence between the formulations cannot be established. Optimum structural design considering expected costs of failure cannot be controlled solely by safety factors nor by failure probability constraints, but will depend on actual structural configuration. (c) 2011 Elsevier Ltd. All rights reserved.