Theoretical and experimental study of the relation between photoluminescence and structural disorder in barium and strontium titanate thin films

Thin films of barium and strontium titanate (BST), synthesized by the polymeric precursor solution and spin coated on [Pt (140nm)/Ti (10 nM)/SiO2(1000 nm)/Si] substrates were found to be photoluminescent at room temperature when heat treated below 973 K, i.e. before their crystallization. First principles quantum mechanical techniques, based on density functional theory (DFT) were employed to study the electronic structure of two periodic models: one is standing for the crystalline BST thin film and the other one for the structurally disordered thin film. The aim is to compare the photoluminescence (PL) spectra of the crystalline and disordered thin films with their UV-vis spectra and with their computed electronic structures. The calculations show that new localized states are created inside the band gap of the crystalline model, as predicted by the UV-vis spectra. The study of the charge repartition in the structure before and after deformation of the periodic model shows that a charge gradient appears among the titanate clusters. This charge gradient, together with the new localized levels, gives favorable conditions for the trapping of holes and electrons in the structure, and thus to a radiative recombination process. Our models are not only consistent with the experimental data, they also allow to explain the relations between structural disorder and photoluminescence at room temperature. (c) 2005 Elsevier Ltd. All rights reserved.

BaZrO3 Photoluminescence Property: An Ab Initio Analysis of Structural Deformation and Symmetry Changes

This article reports a theoretical study based on experimental results for barium zirconate, BaZrO3 (BZ) thin films, using periodic mechanic quantum calculations to analyze the symmetry change in a structural order-disorder simulation. Four periodic models were simulated using CRYSTAL98 code to represent the ordered and disordered BZ structures. The results were analyzed in terms of the energy level diagrams and atomic orbital distributions to explain and understand the BZ photoluminescence properties (PL) at room temperature for the disordered structure based on structural deformation and symmetry changes. (C) 2009 Wiley Periodicals, Inc. Int J Quantum Chem 111: 694-701, 2011

Density functional theory study on the structural and electronic properties of low index rutile surfaces for TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 composite systems

The present study is concerned with the structural and electronic properties of the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 composite systems. Periodic quantum mechanical method with density functional theory at the B3LYP level has been carried out. Relaxed surface energies, structural characteristics and electronic properties of the (I 10), (0 10), (10 1) and (00) low-index rutile surfaces for TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 models are studied. For, comparison purposes, the bare rutile TiO2 and SnO2 structures are also analyzed and compared with previous theoretical and experimental data. The calculated surface energy for both rutile TiO2 and SnO2 surfaces follows the sequence (110) < (010) < (101) < (001) and the energy increases as (010) < (101) < (110) < (001) and (010) approximate to (110) < (101) < (001) for SnO2/TiO2/SnO2 and TiO2/SnO2/TiO2 composite systems, respectively. SnO2/TiO2/SnO2 presents larger values of surface energy than the individual SnO2 and TiO2 metal oxides and the TiO2/SnO2/TiO2 system renders surface energy values of the same order that the TiO2 and lower than the SnO2. An analysis of the electronic structure of the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 systems shows that the main characteristics of the upper part of the valence bands for all the studied surfaces are dominated by the external layers, i.e., by the TiO2 and the SnO2, respectively, and the topology of the lower part of the conduction bands looks like the core layers. There is an energy stabilization of both valence band top and conduction band bottom for (110) and (010) surfaces of the SnO2/TiO2/SnO2 composite system in relation to their core TiO2, whereas an opposite trend is found for the same surfaces of the TiO2/SnO2/TiO2 composite system in relation to the bare SnO2. The present theoretical results may explain the growth of TiO2@SnO2 bimorph composite nanotape.

Investigation on the structural properties in Er-doped PbTiO3 compounds: A correlation between experimental and theoretical results

The aim of this work is to investigate the structural properties of the (Pb1-xErx)TiO3 (PET) powders, with x varying from 0.01 to 0.08, prepared by the polymeric precursor method. Combined X-ray diffraction, Raman spectroscopy and ab initio calculation reveal a diffuse phase-transition of a tetragonal to a cubic phase. The crystalline models built allowed to calculate electronic properties and to analyze the behavior of the doping element in the structure of the material, which are consistent with the experimental results that indicate the beginning of phase-transition from tetragonal to cubic. (C) 2007 Elsevier B.V. All rights reserved.

Structural conditions that leads to photoluminescence emission in SrTiO3: An experimental and theoretical approach

Complex cluster [TiO5 center dot V-O(z)] and [SrO11 center dot V-O(z)] (where V-O(z)=V-O(X), V-O(center dot), V-O(center dot center dot)) vacancies were identified in disordered SrTiO3 powders prepared by the polymeric precursor method, based on experimental measurements by x-ray absorption near edge structure spectroscopy. The paramagnetic complex states of [TiO5 center dot V-O(center dot)] and [SrO11 center dot V-O(center dot)] with unpaired electrons were confirmed by electron paramagnetic resonance spectroscopy. The disordered powders showed strong photoluminescence at room temperature. Structural defects of disordered powders, in terms of band diagram, density of states, and electronic charges, were interpreted using high-level quantum mechanical calculations in the density functional framework. The four periodic models used here were consistent with the experimental data and explained the presence of photoluminescence. (C) 2008 American Institute of Physics.

Evaluation and identification of lightning models by artificial neural networks

This paper describes a novel approach for mapping lightning models using artificial neural networks. The networks acts as identifier of structural features of the lightning models so that output parameters can be estimated and generalized from an input parameter set. Simulation examples are presented to validate the proposed approach. More specifically, the neural networks are used to compute electrical field intensity and critical disruptive voltage taking into account several atmospheric and structural factors, such as pressure, temperature, humidity, distance between phases, height of bus bars, and wave forms. A comparative analysis with other approaches is also provided to illustrate this new methodology.

Marginal fit of nickel-chromium copings before and after internal adjustments with duplicated stone dies and disclosing agent.

STATEMENT OF PROBLEM: Despite careful procedures, master stone dies may be damaged during laboratory procedures. The dentist routinely adjusts castings because the marginal fit of casting is not as accurate as on the dies. PURPOSE: This study evaluated the technique of internal adjustment of castings with use of duplicated stone dies and a disclosing agent to improve marginal fit discrepancy. MATERIAL AND METHODS: Thirty-two nickel-chromium copings were fabricated and simulated standard clinical and laboratory procedures with 2 variables: tooth preparation convergence angles of 6 and 18 degrees, with or without internal relief. Master stone dies and their duplicates were selected for coping construction and internal adjustment, respectively. A specimen positioning device was coupled with a Toolmakers microscope to allow reproducibility of measurements. Each coping was evaluated at 8 locations of its marginal perimeter, before and after internal adjustment. RESULTS: Marginal fit discrepancy of copings were significantly reduced with an internal adjustment technique (mean > 52%) for all experimental groups. Tooth preparations with greater convergence and internally relieved castings recorded a better marginal fit. CONCLUSION: The casting internal adjustment technique with use of duplicated stone dies and a disclosing agent substantially reduced marginal fit discrepancy.

Structural basis for inhibition of cyclin-dependent kinase 9 by flavopiridol

Flavopiridol has been shown to potently inhibit CDK1 and 2 (cyclin-dependent kinases 1 and 2) and most recently it has been found that it also inhibits CDK9. The complex CDK9-cyclin T1 controls the elongation phase of transcription by RNA polymerase II. The present work describes a molecular model for the binary complex CDK9-flavopiridol. This structural model indicates that the inhibitor strongly binds to the ATP-binding pocket of CDK9 and the structural comparison of the complex CDK2-flavopiridol correlates the structural differences with differences in inhibition of these CDKs by flavopiridol. This structure opens the possibility of testing new inhibitor families, in addition to new substituents for the already known leading structures such as flavones and adenine derivatives. © 2002 Elsevier Science (USA). All rights reserved.

Density functional theory calculation of the electronic structure of Ba0.5Sr0.5TiO3: Photoluminescent properties and structural disorder

First-principles quantum-mechanical techniques, based on density functional theory (B3LYP level) were employed to study the electronic structure of ordered and deformed asymmetric models for Ba0.5Sr 0.5TiO3. Electronic properties are analyzed and the relevance of the present theoretical and experimental results on the photoluminescence behavior is discussed. The presence of localized electronic levels in the band gap, due to the symmetry break, would be responsible for the visible photoluminescence of the amorphous state at room temperature. Thin films were synthesized following a soft chemical processing. Their structure was confirmed by x-ray data and the corresponding photoluminescence properties measured.

Identification of structural damage in flexible structures using system norm and neural networks

Nowadays there is great interest in damage identification using non destructive tests. Predictive maintenance is one of the most important techniques that are based on analysis of vibrations and it consists basically of monitoring the condition of structures or machines. A complete procedure should be able to detect the damage, to foresee the probable time of occurrence and to diagnosis the type of fault in order to plan the maintenance operation in a convenient form and occasion. In practical problems, it is frequent the necessity of getting the solution of non linear equations. These processes have been studied for a long time due to its great utility. Among the methods, there are different approaches, as for instance numerical methods (classic), intelligent methods (artificial neural networks), evolutions methods (genetic algorithms), and others. The characterization of damages, for better agreement, can be classified by levels. A new one uses seven levels of classification: detect the existence of the damage; detect and locate the damage; detect, locate and quantify the damages; predict the equipment's working life; auto-diagnoses; control for auto structural repair; and system of simultaneous control and monitoring. The neural networks are computational models or systems for information processing that, in a general way, can be thought as a device black box that accepts an input and produces an output. Artificial neural nets (ANN) are based on the biological neural nets and possess habilities for identification of functions and classification of standards. In this paper a methodology for structural damages location is presented. This procedure can be divided on two phases. The first one uses norms of systems to localize the damage positions. The second one uses ANN to quantify the severity of the damage. The paper concludes with a numerical application in a beam like structure with five cases of structural damages with different levels of severities. The results show the applicability of the presented methodology. A great advantage is the possibility of to apply this approach for identification of simultaneous damages.

Identification of structural parameters for active vibration control

The study of algorithms for active vibration control in flexible structures became an area of enormous interest for some researchers due to the innumerable requirements for better performance in mechanical systems, as for instance, aircrafts and aerospace structures. Intelligent systems, constituted for a base structure with sensors and actuators connected, are capable to guarantee the demanded conditions, through the application of diverse types of controllers. For the project of active controllers it is necessary, in general, to know a mathematical model that enable the representation in the space of states, preferential in modal coordinates to permit the truncation of the system and reduction in the order of the controllers. For practical applications of engineering, some mathematical models based in discrete-time systems cannot represent the physical problem, therefore, techniques of identification of system parameters must be used. The techniques of identification of parameters determine the unknown values through the manipulation of the input (disturbance) and output (response) signals of the system. Recently, some methods have been proposed to solve identification problems although, none of them can be considered as being universally appropriate to all the situations. This paper is addressed to an application of linear quadratic regulator controller in a structure where the damping, stiffness and mass matrices were identified through Chebyshev's polynomial functions.

Damage detection in a benchmark structure using AR-ARX models and statistical pattern recognition

Structural health monitoring (SHM) is related to the ability of monitoring the state and deciding the level of damage or deterioration within aerospace, civil and mechanical systems. In this sense, this paper deals with the application of a two-step auto-regressive and auto-regressive with exogenous inputs (AR-ARX) model for linear prediction of damage diagnosis in structural systems. This damage detection algorithm is based on the. monitoring of residual error as damage-sensitive indexes, obtained through vibration response measurements. In complex structures there are. many positions under observation and a large amount of data to be handed, making difficult the visualization of the signals. This paper also investigates data compression by using principal component analysis. In order to establish a threshold value, a fuzzy c-means clustering is taken to quantify the damage-sensitive index in an unsupervised learning mode. Tests are made in a benchmark problem, as proposed by IASC-ASCE with different damage patterns. The diagnosis that was obtained showed high correlation with the actual integrity state of the structure. Copyright © 2007 by ABCM.

Generating VHDL-AMS models of digital-to-analogue converters from MATLAB®/SIMULINK®

Today, the trend within the electronics industry is for the use of rapid and advanced simulation methodologies in association with synthesis toolsets. This paper presents an approach developed to support mixed-signal circuit design and analysis. The methodology proposed shows a novel approach to the problem of developing behvioural model descriptions of mixed-signal circuit topologies, by construction of a set of subsystems, that supports the automated mapping of MATLAB®/SIMULINK® models to structural VHDL-AMS descriptions. The tool developed, named MS 2SV, reads a SIMULINK® model file and translates it to a structural VHDL-AMS code. It also creates the file structure required to simulate the translated model in the System Vision™. To validate the methodology and the developed program, the DAC08, AD7524 and AD5450 data converters were studied and initially modelled in MATLAB®/ SIMULINK®. The VHDL-AMS code generated automatically by MS 2SV, (MATLAB®/SIMULINK® to System Vision™), was then simulated in the System Vision™. The simulation results show that the proposed approach, which is based on VHDL-AMS descriptions of the original model library elements, allows for the behavioural level simulation of complex mixed-signal circuits.

The structural origin and biological function of pH-sensitivity in firefly luciferases

Firefly luciferases are called pH-sensitive because their bioluminescence spectra display a typical red-shift at acidic pH, higher temperatures, and in the presence of heavy metal cations, whereas other beetle luciferases (click beetles and railroadworms) do not, and for this reason they are called pH-insensitive. Despite many studies on firefly luciferases, the origin of pH-sensitivity is far from being understood. This subject is revised in view of recent results. Some substitutions of amino-acid residues influencing pH-sensitivity in firefly luciferases have been identified. Sequence comparison, site-directed mutagenesis and modeling studies have shown a set of residues differing between pH-sensitive and pH-insensitive luciferases which affect bioluminescence colors. Some substitutions dramatically affecting bioluminescence colors in both groups of luciferases are clustered in the loop between residues 223-235 (Photinus pyralis sequence). A network of hydrogen bonds and salt bridges involving the residues N229-S284-E311-R337 was found to be important for affecting bioluminescence colors. It is suggested that these structural elements may affect the benzothiazolyl side of the luciferin-binding site affecting bioluminescence colors. Experimental evidence suggest that the residual red light emission in pH-sensitive luciferases could be a vestige that may have biological importance in some firefly species. Furthermore, the potential utility of pH-sensitivity for intracellular biosensing applications is considered. © The Royal Society of Chemistry and Owner Societies.

Geotechnical and structural behavior of the railroad track in large-scale apparatus

This paper analyses the static and dynamic behavior of the railroad track model in laboratory. Measurements of stresses and strains on a large-scale railroad track apparatus were studied. The model includes: compacted soil, representing the final layers of platform, ballast layer, and ties (steel, wooden, and pre-stressed concrete). The soil and soil ballast interface were instrumented with pneumatic stress gauge. Settlement measurement device were positioned at the same levels as the load cells. Loads were applied by hydraulic actuators, statically and dynamically. After the prescribed number of load cycles, in pre-determined intervals, stresses and strains were measured. Observations indicate that stress and strain distributions, transmitted by wooden or steel ties, behave similarly. A more favorable behavior was observed with pre-stressed concrete mono block ties. Non-linear response was observed after a threshold numbers of cycles were surpassed, showing that the strain modulus increases with the numbers of cycles. © 2009 IOS Press.