Synthesis and Structural Elucidation of Triazolylmolybdenum(VI) Oxide Hybrids and Their Behavior as Oxidation Catalysts

A large family of bifunctional 1,2,4-triazole molecular tectons (tr) has been explored for engineering molybdenum(VI) oxide hybrid solids. Specifically, tr ligands bearing auxiliary basic or acidic groups were of the type amine, pyrazole, 1H-tetrazole, and 1,2,4-triazole. The organically templated molybdenum(VI) oxide solids with the general compositions [MoO3(tr)], [Mo2O6(tr)], and [Mo2O6(tr)(H2O)2] were prepared under mild hydrothermal conditions or by refluxing in water. Their crystal structures consist of zigzag chains, ribbons, or helixes of alternating cis-{MoO4N2} or {MoO5N} polyhedra stapled by short [N–N]-tr bridges that for bitriazole ligands convert the motifs into 2D or 3D frameworks. The high thermal (235–350 °C) and chemical stability observed for the materials makes them promising for catalytic applications. The molybdenum(VI) oxide hybrids were successfully explored as versatile oxidation catalysts with tert-butyl hydroperoxide (TBHP) or aqueous H2O2 as an oxygen source, at 70 °C. Catalytic performances were influenced by the different acidic–basic properties and steric hindrances of coordinating organic ligands as well as the structural dimensionality of the hybrid.

Transient behavior of a system composed of conductive thin wire structures excited by harmonic and lightning type signals

The transient response of a system of independent electrodes buried in a semi-infinite conducting medium is studied. Using a simple and versatile numerical scheme written by the authors and based on the Electric Field Integral Equation (EFIE), the effect caused by harmonic signals ranging on frequency from Hz to hundred of MHz, and also by lightning type driving signal striking at a remote point far from the conductors, is extensively studied. The value of the scalar potential appearing on the electrodes as a function of the frequency of the applied signal is one of the variables investigated. Other features such as the input impedance at the injection point of the signal and the Ground Potential Rise (GPR) over the electrode system are also discussed

Effects of Shallow Bi-Angle, Thin-Ply Laminates on the Structural Performance of Composite Wings

Thesis (Master's)--University of Washington, 2016-06

The structural properties of glassfibre reinforced plastics

The research work described in this thesis is concerned with the development of glassfibre reinforced plastics for structural uses in Civil Engineering construction. The first stage was primarily concerned with the design of GRP lamintes with structura1 properties and method of manufacture suitable for use with relatively large structural components. A cold setting, pressure moulding technique was developed which proved to be efficient in reducing the void content in the composite and minimising the exothermic effect due to curing. The effect of fibre content and fibre arrangement on strength and stiffness of the cornposite was studied and the maximum amount of' fibre content that could be reached by the adopted type of moulding technique was determined. The second stage of the project was concerned with the introduction of steel-wire "sheets" into the GRP cornposites, to take advantage of the high modulus of steel wire to improve the GRP stiffness and to reduce deformation. The experimental observations agreed reasonably well with theoretical predictions in both first and second stages of the work. The third stage was concerned with studying the stability of GRP flat rectangular plates subjected to uniaxial compression or pure shear, to simulate compression flanges or shear webs respectively. The investigation was concentrated on the effect of fibre arrangement in the plate on buckling load. The effect of the introduction of steel-wire sheets on the plate stability in compression was also investigated. The boundary conditions were chosen to be close to those usually assumed in built-up box-sections for both compression flanges and webs. The orthotropic plate and the mid-plane symmetric were used successfully in predicting the buckling load theoretically. In determining the buckling load experimentally, two methods were used. The Southwell plot method and electrical strain gauge method. The latter proved to be more reliable in predicting the buckling load than the former, especially for plates under uniaxial compression. Sample design charts for GRP plates that yield and buckle simultaneously under compression are also presented in the thesis. The final stage of the work dealt with the design and test of GRP beams. The investigation began by finding the optimum cross-section for a GRP beam. The cross-section which was developed was a thin walled corrugated section which showed higher stiffness than other cross-sections for the same cross-sectional area (i.e. box, I, and rectangular sections). A cold setting, hand layings technique was used in manufacturing these beams wbich were of nine types depending on the type of glass reinforcement employed and the arrangement of layers in the beam. The simple bending theory was used in the beam design and proved to be satisfactory in predicting the stresses and deflections. A factor of safety of 4 was chosen for design purposes and considered to be suitable for long term use under static load. Because of its relatively low modulus, GRP beams allowable deflection was limited to 1/120th of the span which was found to be adequate for design purposes. A general discussion of the behaviour of GRP composites and their place relative to the more conventional structural material was also presented in the thesis.

Structural properties of buried conducting layers formed by very low energy ion implantation of gold into polymer

We have investigated the fundamental structural properties of conducting thin films formed by implanting gold ions into polymethylmethacrylate (PMMA) polymer at 49 eV using a repetitively pulsed cathodic arc plasma gun. Transmission electron microscopy images of these composites show that the implanted ions form gold clusters of diameter similar to 2-12 nm distributed throughout a shallow, buried layer of average thickness 7 nm, and small angle x-ray scattering (SAXS) reveals the structural properties of the PMMA-gold buried layer. The SAXS data have been interpreted using a theoretical model that accounts for peculiarities of disordered systems.

Behavior of Socket Base Connections Emphasizing Pedestal Walls

To evaluate the main design models for socket base connections of precast concrete structures, an experimental investigation was carried out on specimens of this connection with smooth and rough interfaces in contact with cast-in-place concrete. The specimens consisted of pedestal walls and were submitted to loads with large eccentricities. Based on the experimental results, two rational design models are proposed for this connection. One of these models accounts for the friction and is applied to socket bases with smooth interfaces. The main behavior model was verified for sockets with this type of interface and the design of the longitudinal walls as corbels is also suggested in this case. Because the behavior of the rough interface specimens was very close to a monolithic connection, the other proposed model is an adaptation of the bending theory to calculate the vertical reinforcement of socket bases with rough interfaces.

Energy dissipation in depth-sensing indentation as a characteristic of the nanoscratch behavior of coatings

Wear behavior of coatings has usually been described in terms of mechanical properties such as hardness (H) and effective elastic modulus (E*). Alternatively, an energy approach appears as a promising analysis taking into account the influence of those properties. In a nanoindentation test, the dissipated energy depends not only on the hardness and elastic modulus, but also on the elastic recovery (W(e)). This work aims to establish a relation between plastic deformation energy (E(p)) during depth-sensing indentation method and the grooving resistance of coatings in nanoscratch tests. An energy dissipation coefficient (K(d)) was defined, calculated as the ratio of the plastic to the total deformation energy (E(p)/E(t)), which represents the energy dissipation of materials. Reactive depositions using titanium as the target and nitrogen and methane as reactive gases were obtained by triode magnetron sputtering, in order to assess wear and nanoindentation data. A topographical, chemical and microstructural characterization has been conducted using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), wave dispersion spectroscopy (WDS), scanning electron (SEM) and atomic force microscopy (AFM) techniques. Nanoscratch results showed that the groove depth was well correlated to the energy dissipation coefficient of the coatings. On the other hand, a reduction in the coefficient was found when the elastic recovery was increased. (C) 2009 Elsevier B.V. All rights reserved.

Annealing behavior of ferritic-martensitic 9%Cr-ODS-Eurofer steel

Oxide dispersion strengthened ferritic-martensitic steels are potential candidates for applications in future fusion power plants. High creep resistance, good oxidation resistance, reduced neutron activation and microstructural long-term stability at temperatures of about 650-700 degrees C are required in this context. In order to evaluate its thermal stability in the ferritic phase field, samples of the reduced activation ferritic-martensitic 9%Cr-ODS-Eurofer steel were cold rolled to 50% and 80% reductions and further annealed in vacuum from 300 to 800 degrees C for 1 h. The characterization in the annealed state was performed by scanning electron microscopy in the backscattered electron mode, high-resolution electron backscatter diffraction and transmission electron microscopy. Results show that the fine dispersion of Y-based particles (about 10 nm in size) is effective to prevent recrystallization. The low recrystallized volume fraction (<0.1) is associated to the nuclei found at prior grain boundaries and around large M(23)C(6) particles. Static recovery was found to be the predominant softening mechanism of this steel in the investigated temperature range. (c) 2010 Elsevier B.V. All rights reserved.

Influence of Water Content, Time, and Temperature on the Rheological Behavior of Polyethylene Terephtalate

In this work, the main factors affecting the rheological behavior of polyethylene terephtalate (PET) in the linear viscoelastic regime (water content, time delay before test, duration of experiment, and temperature) were accessed. Small amplitude oscillatory shear tests were performed after different time delays ranging from 300 to 5000 s for samples with water contents ranging from 0.02 to 0.45 wt %. Time sweep tests were carried out for different durations to explain the changes undergone by PET before and during small amplitude oscillatory shear measurements. Immediately after the time sweep tests, the PET samples were removed from the rheometer, analyzed by differential scanning calorimetry and their molar mass was obtained by viscometry analysis. It was shown that for all the samples, the delay before test and residence time within the rheometer (i.e. duration of experiment) result in structural changes of the PET samples, such as increase or decrease of molar mass, broadening of molar mass distribution, and branching phenomena. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 116: 3525-3533, 2010

Structural development of silicated films self-assembled at the air-water interface

The development of structure perpendicular to and in the plane of the interface has been studied for mesoporous silicate films self-assembled at the air/water interface. The use of constrained X-ray and neutron specular reflectometry has enabled a detailed study of the structural development perpendicular to the interface during the pre-growth phase. Off-specular neutron reflectometry and grazing incidence X-ray diffraction has enabled the in-plane structure to be probed with excellent time resolution. The growth mechanism under the surfactant to silicate source ratios used in this work is clearly due to the self-assembly of micellar and molecular species at the air/liquid interface, resulting in the formation of a planar mesoporous film that is tens of microns thick. (C) 2003 Elsevier Science B.V. All rights reserved.

A comparison of the self-association behavior of the plant cyclotides kalata B1 and kalata B2 via analytical ultracentrifugation

The recently discovered cyclotides kalata B1 and kalata B2 are miniproteins containing a head-to-tail cyclized backbone and a cystine knot motif, in which disulfide bonds and the connecting backbone segments form a ring that is penetrated by the third disulfide bond. This arrangement renders the cyclotides extremely stable against thermal and enzymatic decay, making them a possible template onto which functionalities can be grafted.We have compared the hydrodynamic properties of two prototypic cyclotides, kalata B1 and kalata B2, using analytical ultracentrifugation techniques. Direct evidence for oligomerization of kalata B2 was shown by sedimentation velocity experiments in which a method for determining size distribution of polydisperse molecules in solution was employed. The shape of the oligomers appears to be spherical. Both sedimentation velocity and equilibrium experiments indicate that in phosphate buffer kalata B1 exists mainly as a monomer, even at millimolar concentrations. In contrast, at 1.6 mM, kalata B2 exists as an equilibrium mixture of monomer (30%), tetramer (42%), octamer (25%), and possibly a small proportion of higher oligomers. The results from the sedimentation equilibrium experiments show that this self-association is concentration dependent and reversible. We link our findings to the three-dimensional structures of both cyclotides, and propose two putative interaction interfaces on opposite sides of the kalata B2 molecule, one involving a hydrophobic interaction with the Phe(6), and the second involving a charge-charge interaction with the Asp(25) residue. An understanding of the factors affecting solution aggregation is of vital importance for future pharmaceutical application of these molecules.

The use of electrospray ionization tandem mass spectrometry on the structural characterization of novel asymmetric metallo-organic supermolecules, based on pentafluorophenylporphyrins and ruthenium complexes

The novel asymmetric metallo-organic triads cis- and trans-[B(4-py)BPFPH(2){Ru(3)O(Ac)(6)(py)(2)}(Ru(bpy)(2)Cl}](PF(6))(2) (5a,b) for which cis- and trans-B(4-py)BPFPH(2)=5,10-bis(pentafluorophenyl)-15,20-bis(4-pyridyl)porphyrin and 5,15-bis(pentafluorophenyl)-10,20-bis(4-pyridyl)porphyrin, respectively; Ac = acetate; py = pyridine and bpy = 2,2`-bipyridine, as well as their corresponding monosubstituted dyads cis- and trans-[B(4-py)BPFPH(2){Ru(3)O(Ac)(6)(py)(2)}]PF(6) (4a,b) have been structurally characterized via electrospray ionization mass spectrometry (ESI-MS and ESI-MS/MS). The ESI-MS of dyads 4a,b display two characteristic Ru-multicomponent clusters of isotopologue ions corresponding to singly charged ions 4a,b(+) of m/z 1629 and doubly charged ions [4a,b+H](2+) of m/z 815 and the triads 5a,b are detected by ESI-MS as the intact doubly charged cluster of isotopologue ions of m/z 1039 [5a,b](2+). The ESI-MS/MS of 4a,b(+), [4a,b+H](2+) and [5a,b](2+) reveal characteristic dissociation pathways, which confirm the structural assignments providing additional information on the intrinsic binding strengths of the gaseous ions. Although the gas-phase behavior of each pair of isomers was rather similar, the less symmetric dyads 4a,b are distinguished via the (1)H NMR spectral profile of the pyrrolic signals. Exploratory photophysical assays have shown that both modifying motifs alter the porphyrinic core emission profile, opening the possibility to use these asymmetric systems as photophysical devices. (C) 2008 Elsevier Ltd. All rights reserved.

Synthesis, characterization and electrochemical behavior of the vanadium pentoxide/cetyl pyridinium chloride hybrid material

In situ and ex situ studies concerning the new hybrid material vanadium pentoxide xerogel in the presence of the cationic surfactant cetyl pyridinium chloride (V(2)O(5)/CPC) are presented. The in situ characterization studies revealed the presence of a lamellar structure for the V(2)O(5)/CPC hybrid material. The intercalation reaction was evidenced on the basis of the increase in the d-spacing as well as the displacement of the infrared bands toward lower energy levels. Electrochemical studies comprising the cyclic voltammetry and the electrochemical impedance spectroscopy techniques showed that the behavior of the hybrid material is considerably influenced by the electrolyte composition. The ion insertion/de-insertion into the V(2)O(5) xerogel structure accompanying the charge transfer process is influenced by the solid-state diffusion process modeled by using the finite-space Warburg element.