Rare-earth quinolinates: Infrared-emitting molecular materials with a rich structural chemistry

Near-infrared-emitting rare-earth chelates based on 8-hydroxyquinoline have appeared frequently in recent literature, because they are promising candidates for active components in near-infrared-luminescent optical devices, such as optical amplifiers, organic light-emitting diodes, .... Unfortunately, the absence of a full structural investigation of these rare-earth quinolinates is hampering the further development of rare-earth quinolinate based materials, because the luminescence output cannot be related to the structural properties. After an elaborate structural elucidation of the rare-earth quinolinate chemistry we can conclude that basically three types of structures can be formed, depending on the reaction conditions: tris complexes, corresponding to a 1:3 metal-to-ligand ratio, tetrakis complexes, corresponding to a 1:4 metal-to-ligand ratio, and trimeric complexes, with a 3:8 metal-to-ligand ratio. The intensity of the emitted near-infrared luminescence of the erbium(Ill) complexes is highest for the tetrakis complexes of the dihalogenated 8-hydroxyquinolinates.

Optical and Thermal Characterization of Dye Intercalated Montmorillonites and Rare Earth Doped Materials

Nondestructive photothermal methods as well as optical absorption and fluorescence spectroscopy are utilized to characterise three different materials, both thermally and optically. The possibility of using montmorillonite clay minerals, after textile waste-water treatment, is investigated for further applications. The laser induced luminescence studies and thermal characterisation of certain rare earth titanates prepared by self propagating high temperature synthesis method are also presented. Moreover, effort is made to characterise rare earth doped sol gel silica glasses with the help of these nondestructive techniques.

Optical and thermal characterization of dye intercalated montmorillonites and rare earth doped materials

The advent of high optical quality transparent nano—structured glasses, the so-called transparent glass ceramics or vitroceramics disclosed the possibility of producing nano-sized photonic devices based on rare-earth doped up—converters. Transparent glass ceramics have been investigated as hosts for lanthanide ions envisioning the production of materials that are easy to shape and with high performance for photonic applications. Rare earth doped glasses have been extensively studied due to their potential applications in optical devices such as solid state lasers and optical fibers. Various photothermal and optical techniques have been successfully applied for the thermal and optical characterization of these rare earth doped materials. In the present thesis, the effective thermal parameters like thermal diffusivity and thermal effusivity of complex materials for various applications have been investigated using photothermal methods along with their optical characterization utilising the common optical absorption as well as fluorescence spectroscopic techniques. These sensitive optical procedures are also essential for exploiting these materials for further photonic applications.

PbO-GeO2 rare earth doped glasses with silver nanoparticles as materials for IR laser triggers

We have shown the possibility of operation by the piezooptical response of PbO-GeO2 glasses doped with rare earth ions and silver nanoparticles by illumination of double frequency CO2 nanosecond laser. Substantial influence of thermoannealing on the output photoinduced elastooptical susceptibilities was established. The effect is very sensitive to temperature and to the corresponding tensor components. The effect of thermoannealing leads to enhanced long-range ordering with the occurrence of corresponding trapping levels within the forbidden gaps. The discovered effects may be used for creation of low-temperature IR laser triggers.

Sandwich complexes of naphthalocyanine with the rare earth metals

Over the past two decades and in particular the past five years, numerous sandwich-type rare earth complexes containing naphthalocyanine ligands have been synthesized. The more extended delocalized π-electron system of naphthalocyanine in comparison with phthalocyanine generates unique physical, spectroscopic, electrochemical and photoelectrochemical properties which have aroused significant research interest in these compounds. This review summarizes recent progress in research on this important class of molecular materials and overviews the current status of the field.

Piezoelectric PVDF materials performance and operation limits in space environments

Piezoelectric polymers based on polyvinylidene fluoride (PVDF) are of interest for large aperture space-based telescopes. Dimensional adjustments of adaptive polymer films are achieved via charge deposition and require a detailed understanding of the piezoelectric material responses which are expected to suffer due to strong vacuum UV, gamma, X-ray, energetic particles and atomic oxygen under low earth orbit exposure conditions. The degradation of PVDF and its copolymers under various stress environments has been investigated. Initial radiation aging studies using gamma- and e-beam irradiation have shown complex material changes with significant crosslinking, lowered melting and Curie points (where observable), effects on crystallinity, but little influence on overall piezoelectric properties. Surprisingly, complex aging processes have also been observed in elevated temperature environments with annealing phenomena and cyclic stresses resulting in thermal depoling of domains. Overall materials performance appears to be governed by a combination of chemical and physical degradation processes. Molecular changes are primarily induced via radiative damage, and physical damage from temperature and AO exposure is evident as depoling and surface erosion. Major differences between individual copolymers have been observed providing feedback on material selection strategies.

Power-law viscous materials for analogue experiments: New data on the rheology of highly-filled silicone polymers

The selection of appropriate analogue materials is a central consideration in the design of realistic physical models. We investigate the rheology of highly-filled silicone polymers in order to find materials with a power-law strain-rate softening rheology suitable for modelling rock deformation by dislocation creep and report the rheological properties of the materials as functions of the filler content. The mixtures exhibit strain-rate softening behaviour but with increasing amounts of filler become strain-dependent. For the strain-independent viscous materials, flow laws are presented while for strain-dependent materials the relative importance of strain and strain rate softening/hardening is reported. If the stress or strain rate is above a threshold value some highly-filled silicone polymers may be considered linear visco-elastic (strain independent) and power-law strain-rate softening. The power-law exponent can be raised from 1 to ~3 by using mixtures of high-viscosity silicone and plasticine. However, the need for high shear strain rates to obtain the power-law rheology imposes some restrictions on the usage of such materials for geodynamic modelling. Two simple shear experiments are presented that use Newtonian and power-law strain-rate softening materials. The results demonstrate how materials with power-law rheology result in better strain localization in analogue experiments.

Intercalation of kaolins by alkaline earth metal salts

A suite of new materials, based on chemical modification of kaolins, has been successfully prepared via manipulation of the kaolin structure and subsequent intercalation by CaCl2 and MgCl2. A standard kaolinite(KGa-1)and a commercially available halloysite (New Zealand china clay) were used for this study. The kaolins are given several cycles of intercalation and deintercalation using a common intercalant such as potassium acetate. The number of cycles given depends on the type of kaolin. After this treatment, both kaolinite and halloysite hydrate show considerable broadening of the (00l) reflections which indicate extensive exfoliation of the layers. In the case of kaolinite, exfoliated layers roll to form tubes similar to proper halloysite. Kaolins modified by the above treatment readily intercalate MgCl2 and CaCl2 from saturated solutions of these salts. On intercalation with CaCl2 and MgCl2, kaolinite layers expand to 10A and 9.8A, and those of halloysite to 12.8A and 15.5A, respectively. To our knowledge, this is the first report of successful intercalation of alkaline-earth halides by kaolins.

Factors affecting the stability analysis of earth dam slopes subjected to reservoir drawdown

The drawdown of reservoirs can significantly affect the stability of upstream slopes of earth dams. This is due to the removal of the balancing hydraulic forces acting on the dams and the undrained condition within the upstream slope soils. In such scenarios, the stability of the slopes can be influenced by a range of factors including drawdown rates, slope inclination and soil properties. This paper investigates the effects of drawdown rate, saturated hydraulic conductivity and unsaturated shear strength of dam materials on the stability of the upstream slope of an earth dam. In this study, the analysis of pore-water pressure changes within the upstream slope during reservoir drawdown was coupled with the slope stability analysis using the general limit equilibrium method. The results of the analysis suggested that a decrease in the reservoir water level caused the stability of the upstream slope to decrease. The dam embankment constructed with highly permeable soil was found to be more stable during drawdown scenarios, compared to others. Further, lower drawdown rates resulted in a higher safety factor for the upstream slope. Also, the safety factor of the slope calculated using saturated shear strength properties of the dam materials was slightly higher than that calculated using unsaturated shear strength properties. In general, for all the scenarios analysed, the lowest safety factor was found to be at the reservoir water level of about 2/3 of drawdown regime.

Investigation on characteristics and performance of recycled concrete aggregates as granular materials for unbound pavements

This research was a step forward in investigating the characteristics of recycled concrete aggregates to use as an unbound pavement material. The results present the guidelines for successfully application of recycled concrete aggregates in high traffic volume roads. Outcomes of the research create more economical and environmental benefits through reducing the depletion of natural resources and effectively manage the generated concrete waste before disposal as land fill.

Verification and Operation of Adaptive Materials in Space

Piezoelectric polymers based on polyvinylidene fluoride (PVDF) are of interest as smart materials for novel space-based telescope applications. Dimensional adjustments of adaptive thin polymer films are achieved via controlled charge deposition. Predicting their long-term performance requires a detailed understanding of the piezoelectric property changes that develop during space environmental exposure. The overall materials performance is governed by a combination of chemical and physical degradation processes occurring in low Earth orbit as established by our past laboratory-based materials performance experiments (see report SAND 2005-6846). Molecular changes are primarily induced via radiative damage, and physical damage from temperature and atomic oxygen exposure is evident as depoling, loss of orientation and surface erosion. The current project extension has allowed us to design and fabricate small experimental units to be exposed to low Earth orbit environments as part of the Materials International Space Station Experiments program. The space exposure of these piezoelectric polymers will verify the observed trends and their degradation pathways, and provide feedback on using piezoelectric polymer films in space. This will be the first time that PVDF-based adaptive polymer films will be operated and exposed to combined atomic oxygen, solar UV and temperature variations in an actual space environment. The experiments are designed to be fully autonomous, involving cyclic application of excitation voltages, sensitive film position sensors and remote data logging. This mission will provide critically needed feedback on the long-term performance and degradation of such materials, and ultimately the feasibility of large adaptive and low weight optical systems utilizing these polymers in space.

Giant Magnetoresistance and Related Properties of Rare Earth Manganates and Other Oxide Systems

Giant magnetoresistance (GMR), which was until recently confined to magnetic layered and granular materials, as well as doped magnetic semiconductors, occurs in manganate perovskites of the general formula Ln(1-x)A(x)MnO(3) (Ln = rare earth; A = divalent ion). These manganates are ferromagnetic at or above a certain value of x (or Mn4+ content) and become metallic at temperatures below the curie temperature, T-c. GMR is generally a maximum close to T-c or the insulator-metal (I-M) transition temperature, T-im. The T-c and %MR are markedly affected by the size of the A site cation, [r(A)], thereby affording a useful electronic phase diagram when T-c or T-im is plotted against [r(A)]. We discuss GMR and related properties of manganates in polycrystalline, thin-film, and single-crystal forms and point out certain commonalities and correlations. We also examine some unusual features in the electron-transport properties of manganates, in particular charge-ordering effects. Charge ordering is crucially dependent on [r(A)] or the e(g) band width, and the charge-ordered insulating state transforms to a metallic ferromagnetic state on the application of a magnetic field.