Red-emitting LaOF:Eu3+ phosphors: Synthesis, structure and their Judd-Ofelt analysis for LED applications

In the present study, we have synthesized a series of La1-xEuxOF (0.01 <= x <= 0.09) phosphors by the conventional solid-state reaction route at relatively low temperature (500 degrees C) and shorter duration of 2 h. The compounds were crystallized in the rhombohedral structure with the space group R-3m (No. 166). Upon UV excitation (254 nm), the photoluminescence spectra exhibit characteristic luminescence D-5(0) -> F-7(J) (J= 1, 2, 3, and 4) intra-4f shell Eu3+ ion transitions. An intense red emission peak at 610 nm was observed due to electric dipole (D-5(0) -> F-7(2)) transition. Judd-Ofelt theory was employed to evaluate various radiative parameters such as radiative emission rates, lifetime, branching and asymmetry ratios. CIE color coordinates confirmed the red emission of the phosphors. The luminescent results reveal that LaOF:Eu3+ phosphor can be used as potential candidate for developing red component in white LED applications. (C) 2015 Elsevier Ltd. All rights reserved.

Formation, Thermal Stability and Deformation Behavior of Graphite-Flakes Reinforced Cu-based Bulk Metallic Glass Matrix Composites

Graphite-flake reinforced Cu47Ti34Zr11 Ni-8 bulk metallic glass matrix composite was fabricated by water-cooled copper mould cast. Most of the graphite flakes still keep unreacted and distribute uniformly in the amorphous matrix except that some reactive wetting occurs by the formation of TiC particles around the flakes. It reveals that the presence of graphite flakes does not affect the onset of the glass transition temperature, crystallization reaction and liquidus of the metallic glass. The resulting material shows obvious serrated flow and higher fracture strength under room temperature compressive load, comparing with the monolithic bulk metallic glass (BMG). Three types of interaction between the shear bands and graphite flakes, namely, shear band termination, shear bands branching and new shear bands formation near the graphite flakes can be observed by quasi-static uniaxial compression test and bonded interface technique through Vickers indentation.

Cell shape changes indicate a role for extrinsic tensile forces in Drosophila germ-band extension.

Drosophila germ-band extension (GBE) is an example of the convergence and extension movements that elongate and narrow embryonic tissues. To understand the collective cell behaviours underlying tissue morphogenesis, we have continuously quantified cell intercalation and cell shape change during GBE. We show that the fast, early phase of GBE depends on cell shape change in addition to cell intercalation. In antero-posterior patterning mutants such as those for the gap gene Krüppel, defective polarized cell intercalation is compensated for by an increase in antero-posterior cell elongation, such that the initial rate of extension remains the same. Spatio-temporal patterns of cell behaviours indicate that an antero-posterior tensile force deforms the germ band, causing the cells to change shape passively. The rate of antero-posterior cell elongation is reduced in twist mutant embryos, which lack mesoderm. We propose that cell shape change contributing to germ-band extension is a passive response to mechanical forces caused by the invaginating mesoderm.

Behavior of Multiple Shear Bands in Zr-Based Bulk Metallic Glass

The deformation behavior of Zr41.2Ti13.8Cu12.5Ni10Be22.5 bulk metallic glass was studied by in situ scanning electron microscopy (SEM) quasi-static uniaxial compression tests at room temperature. Multiple shear bands were observed with a large plasticity. Microscopic examination demonstrates that slipping, branching and intersecting of multiple shear bands are the main mechanisms for enhancing the plasticity of this metallic glass. Additionally, nano/micro-scale voids and cracks at the intersecting sites of shear bands and preferential etching of shear bands were observed as well. These observations demonstrated that the formation of shear bands in bulk metallic glasses is resulted mainly from local free volume coalescence.

The investigation on dynamic fracture behavour of materials under compressive-shear combined stress waves

In this paper, an improved plate impact experimental technique is presented for studying dynamic fracture mechanism of materials, under the conditions that the impacting loading is provided by a single pulse and the loading time is in the sub-microsecond range. The impacting tests are carried out on the pressure-shear gas gun. The loading rate achieved is dK/dt similar to 10(8) MPa m(1/2) s(-1). With the elimination of influence of the specimen boundary, the plane strain state of a semi-infinite crack in an infinite elastic plate is used to simulate the deformation fields of crack tip. The single pulses are obtained by using the "momentum trap" technique. Therefore, the one-time actions of the single pulse are achieved by eradicating the stress waves reflected from the specimen boundary or diffracted from the crack surfaces. In the current study, some important phenomena have been observed. The special loading of the single pulse can bring about material damage around crack tip, and affect the material behavior, such as kinking and branching of the crack propagation. Failure mode transitions from mode I to mode II crack are observed under asymmetrical impact conditions. The mechanisms of the dynamic crack propagation are consistent with the damage failure model.

Electromechanical influence of crack velocity at bifurcation for poled ferroelectric materials

The piezoelastodynamic field equations are solved to determine the crack velocity at bifurcation for poled ferroelectric materials where the applied electrical field and mechanical stress can be varied. The underlying physical mechanism, however, may not correspond to that assumed in the analytical model. Bifurcation has been related to the occurrence of a pair of maximum circumferential stress oriented symmetrically about the moving crack path. The velocity at which this behavior prevails has been referred to as the limiting crack speed. Unlike the classical approach, bifurcation will be identified with finite distances ahead of a moving crack. Nucleation of microcracks can thus be modelled in a single formulation. This can be accomplished by using the energy density function where fracture initiation is identified with dominance of dilatation in relation to distortion. Poled ferroelectric materials are selected for this study because the microstructure effects for this class of materials can be readily reflected by the elastic, piezoelectic and dielectric permittivity constants at the macroscopic scale. Existing test data could also shed light on the trend of the analytical predictions. Numerical results are thus computed for PZT-4 and compared with those for PZT-6B in an effort to show whether the branching behavior would be affected by the difference in the material microstructures. A range of crack bifurcation speed upsilon(b) is found for different r/a and E/sigma ratios. Here, r and a stand for the radial distance and half crack length, respectively, while E and a for the electric field and mechanical stress. For PZT-6B with upsilon(b) in the range 100-1700 m/s, the bifurcation angles varied from +/-6degrees to +/-39degrees. This corresponds to E/sigma of -0.072 to 0.024 V m/N. At the same distance r/a = 0.1, PZT-4 gives upsilon(b) values of 1100-2100 m/s; bifurcation angles of +/-15degrees to +/-49degrees; and E/sigma of -0.056 to 0.059 V m/N. In general, the bifurcation angles +/-theta(0) are found to decrease with decreasing crack velocity as the distance r/a is increased. Relatively speaking, the speed upsilon(b) and angles +/-theta(0) for PZT-4 are much greater than those for PZT-6B. This may be attributed to the high electromechanical coupling effect of PZT-4. Using upsilon(b)(0) as a base reference, an equality relation upsilon(b)(-) < upsilon(b)(0) < upsilon(b)(+) can be established. The superscripts -, 0 and + refer, respectively, to negative, zero and positive electric field. This is reminiscent of the enhancement and retardation of crack growth behavior due to change in poling direction. Bifurcation characteristics are found to be somewhat erratic when r/a approaches the range 10(-2)-10(-1) where the kinetic energy densities would fluctuate and then rise as the distance from the moving crack is increased. This is an artifact introduced by the far away condition of non-vanishing particle velocity. A finite kinetic energy density prevails at infinity unless it is made to vanish in the boundary value problem. Future works are recommended to further clarify the physical mechanism(s) associated with bifurcation by means of analysis and experiment. Damage at the microscopic level needs to be addressed since it has been known to affect the macrocrack speeds and bifurcation characteristics. (C) 2002 Published by Elsevier Science Ltd.

Some theorems in asymptotic analysis

Basing ourselves on the analysis of magnitude of order, we strictly prove fundamental lemmas for asymptotic integral, including the cases of infinite region. Then a general formula for asymptotic expansion of integrals is given. Finally, we derive a sufficient condition for an ordinary differential equation to possess a solution of the Frobenius series type at finite irregular singularities or branching points.

CHARACTERIZATION OF SHEAR BANDS IN TWO BULK METALLIC GLASSES WITH DIFFERENT INHERENT PLASTICITY

Shear banding characterization of Zr64.13Cu15.75Ni10.12Al10 and Zr65Cu15Ni10Al10 bulk metallic glasses (BMGs) with significant difference in inherent plasticity and quite similar chemical composition was studied by depth sensitive macroindentaion tests with conical indenter. Well-developed shear band pattern can be found for both BMGs after indentation. Distinct difference in the shear band spacing, scale of plastic deformation region and the shear band branching in the two BMGs account for the different plasticity.

Alkene selenenylation: A comprehensive analysis of relative reactivities, stereochemistry and asymmetric induction, and their comparisons with sulfenylation

A broad perspective of various factors influencing alkene selenenylation has been developed by concurrent detailed analysis of key experimental and theoretical data, such as asymmetric induction, stereochemistry, relative reactivities, and comparison with that of alkene sulfenylation. Alkyl group branching a to the double bond was shown to have the greatest effect on alkene reactivity and the stereochemical outcome of corresponding addition reactions. This is in sharp contrast with other additions to alkenes, which depend more on the degree of substitution on C=C or upon substituent electronic effects. Electronic and steric effects influencing asymmetric induction, stereochemistry, regiochemistry, and relative reactivities in the addition of PhSeOTf to alkenes are compared and contrasted with those of PhSCl.

Characterization Of Shear Bands In Two Bulk Metallic Glasses With Different Inherent Plasticity

Shear banding characterization of Zr64.13Cu15.75Ni10.12Al10 and Zr65Cu15Ni10Al10 bulk metallic glasses (BMGs) with significant difference in inherent plasticity and quite similar chemical composition was studied by depth sensitive macroindentaion tests with conical indenter. Well-developed shear band pattern can be found for both BMGs after indentation. Distinct difference in the shear band spacing, scale of plastic deformation region and the shear band branching in the two BMGs account for the different plasticity.

Vortex dislocations in wake-type flow induced by spanwise disturbances

Vortex dislocations in wake-type flow induced by three types of spanwise disturbances superimposed on an upstream velocity profile are investigated by direct numerical simulations. Three distinct modes of vortex dislocations and flow transitions have been found. A local spanwise exponential decay disturbance leads to the appearance of a twisted chainlike mode of vortex dislocation. A stepped spanwise disturbance causes a streamwise periodic spotlike mode of vortex dislocation. A spanwise sinusoidal wavy disturbance with a moderate waviness causes a strong unsteadiness of wake behavior. This unsteadiness starts with a systematic periodic mode of vortex dislocation in the spanwise direction followed by the spanwise vortex shedding suppressed completely with increased time and the near wake becoming a steady shear flow. Characteristics of these modes of vortex dislocation and complex vortex linkages over the dislocation, as well as the corresponding dynamic processes related to the appearance of dislocations, are described by examining the variations of vortex lines and vorticity distribution. The nature of the vortex dislocation is demonstrated by the substantial vorticity modification of the spanwise vortex from the original spanwise direction to streamwise and vertical directions, accompanied by the appearance of noticeable vortex branching and complex vortex linking, all of which are produced at the locations with the biggest phase difference or with a frequency discontinuity between shedding cells. The effect of vortex dislocation on flow transition, either to an unsteady irregular vortex flow or suppression of the Kaacutermaacuten vortex shedding making the wake flow steady state, is analyzed. Distinct similarities are found in the mechanism and main flow phenomena between the present numerical results obtained in wake-type flows and the experimental-numerical results of cylinder wakes reported in previous studies.

Some modified bifurcation problems with application to imperfection sensitivity in buckling

The branching theory of solutions of certain nonlinear elliptic partial differential equations is developed, when the nonlinear term is perturbed from unforced to forced. We find families of branching points and the associated nonisolated solutions which emanate from a bifurcation point of the unforced problem. Nontrivial solution branches are constructed which contain the nonisolated solutions, and the branching is exhibited. An iteration procedure is used to establish the existence of these solutions, and a formal perturbation theory is shown to give asymptotically valid results. The stability of the solutions is examined and certain solution branches are shown to consist of minimal positive solutions. Other solution branches which do not contain branching points are also found in a neighborhood of the bifurcation point.

The qualitative features of branching points and their associated nonisolated solutions are used to obtain useful information about buckling of columns and arches. Global stability characteristics for the buckled equilibrium states of imperfect columns and arches are discussed. Asymptotic expansions for the imperfection sensitive buckling load of a column on a nonlinearly elastic foundation are found and rigorously justified.

Photodissociation and reaction dynamics of chlorine-containing species important in stratospheric ozone chemistry

Chlorine oxide species have received considerable attention in recent years due to their central role in the balance of stratospheric ozone. Many questions pertaining to the behavior of such species still remain unanswered and plague the ability of researchers to develop accurate chemical models of the stratosphere. Presented in this thesis are three experiments that study various properties of some specific chlorine oxide species.

In the first chapter, the reaction between ClONO_2 and protonated water clusters is investigated to elucidate a possible reaction mechanism for the heterogeneous reaction of chlorine nitrate on ice. The ionic products were various forms of protonated nitric acid, NO_2 +(H_20)_m, m = 0, 1, 2. These products are analogous to products previously reported in the literature for the neutral reaction occurring on ice surfaces. Our results support the hypothesis that the heterogeneous reaction is acid-catalyzed.

In the second chapter, the photochemistry of ClONO_2 was investigated at two wavelengths, 193 and 248 nm, using the technique of photofragmentation translational spectroscopy. At both wavelengths, the predominant dissociation pathways were Cl + NO_3 and ClO + NO_2. Channel assignments were confirmed by momentum matching the counterfragments from each channel. A one-dimensional stratospheric model using the new 248 nm branching ratio determined how our results would affect the predicted Cl_x and NO_x partitioning in the stratosphere.

Chapter three explores the photodissociation dynamics of Cl_2O at 193, 248 and 308 nm. At 193 nm, we found evidence for the concerted reaction channel, Cl_2 + O. The ClO + Cl channel was also accessed, however, the majority of the ClO fragments were formed with sufficient internal energies for spontaneous secondary dissociation to occur. At 248 and 308 nm, we only observed only the ClO + Cl channel. . Some of the ClO formed at 248 nm was formed internally hot and spontaneously dissociated. Bimodal translational energy distributions of the ClO and Cl products indicate two pathways leading to the same product exist.

Appendix A, B and C discuss the details of data analysis techniques used in Chapters 1 and 2. The development of a molecular beam source of ClO dimer is presented in Appendix D.

Search for heavy neutral resonances in the dielectron channel with the CMS detector at the LHC

A search for dielectron decays of heavy neutral resonances has been performed using proton-proton collision data collected at √s = 7 TeV by the Compact Muon Solenoid (CMS) experiment at the Large Hadron Collider (LHC) in 2011. The data sample corresponds to an integrated luminosity of 5 fb⁻¹. The dielectron mass distribution is consistent with Standard Model (SM) predictions. An upper limit on the ratio of the cross section times branching fraction of new bosons, normalized to the cross section times branching fraction of the Z boson, is set at the 95 % confidence level. This result is translated into limits on the mass of new neutral particles at the level of 2120 GeV for the Z′ in the Sequential Standard Model, 1810 GeV for the superstring-inspired Z′_ψ resonance, and 1940 (1640) GeV for Kaluza-Klein gravitons with the coupling parameter k/M_Pl of 0.10 (0.05).

Developing peptide based capture agents for diagnostics and therapeutics

Iterative in situ click chemistry (IISCC) is a robust general technology for development of high throughput, inexpensive protein detection agents. In IISCC, the target protein acts as a template and catalyst, and assembles its own ligand from modular blocks of peptides. This process of ligand discovery is iterated to add peptide arms to develop a multivalent ligand with increased affinity and selectivity. The peptide based protein capture agents (PCC) should ideally have the same degree of selectivity and specificity as a monoclonal antibody, along with improved chemical stability. We had previously reported developing a PCC agent against bovine carbonic anhydrase II (bCAII) that could replace a polyclonal antibody. To further enhance the affinity or specificity of the PCC agent, I explore branching the peptide arms to develop branched PCC agents against bCAII. The developed branched capture agents have two to three fold higher affinities for the target protein. In the second part of my thesis, I describe the epitope targeting strategy, a strategy for directing the development of a peptide ligand against specific region or fragment of the protein. The strategy is successfully demonstrated by developing PCC agents with low nanomolar binding affinities that target the C-terminal hydrophobic motif of Akt2 kinase. One of the developed triligands inhibits the kinase activity of Akt. This suggests that, if targeted against the right epitope, the PCC agents can also influence the functional properties of the protein. The exquisite control of the epitope targeting strategy is further demonstrated by developing a cyclic ligand against Akt2. The cyclic ligand acts as an inhibitor by itself, without any iteration of the ligand discovery process. The epitope targeting strategy is a cornerstone of the IISCC technology and opens up new opportunities, leading to the development of protein detection agents and of modulators of protein functions.