Thin films composed of gold nanoparticles dispersed in a dielectric matrix: the influence of the host matrix on the optical and mechanical responses

Gold nanoparticles were dispersed in two different dielectric matrices, TiO2 and Al2O3, using magnetron sputtering and a post-deposition annealing treatment. The main goal of the present work was to study how the two different host dielectric matrices, and the resulting microstructure evolution (including both the nanoparticles and the host matrix itself) promoted by thermal annealing, influenced the physical properties of the films. In particular, the structure and morphology of the nanocomposites were correlated with the optical response of the thin films, namely their localized surface plasmon resonance (LSPR) characteristics. Furthermore, and in order to scan the future application of the two thin film system in different types of sensors (namely biological ones), their functional behaviour (hardness and Young's modulus change) was also evaluated. Despite the similar Au concentrations in both matrices (~ 11 at.%), very different microstructural features were observed, which were found to depend strongly on the annealing temperature. The main structural differences included: (i) the early crystallization of the TiO2 host matrix, while the Al2O3 one remained amorphous up to 800 °C; (ii) different grain size evolution behaviours with the annealing temperature, namely an almost linear increase for the Au:TiO2 system (from 3 to 11 nm), and the approximately constant values observed in the Au:Al2O3 system (4–5 nm). The results from the nanoparticle size distributions were also found to be quite sensitive to the surrounding matrix, suggesting different mechanisms for the nanoparticle growth (particle migration and coalescence dominating in TiO2 and Ostwald ripening in Al2O3). These different clustering behaviours induced different transmittance-LSPR responses and a good mechanical stability, which opens the possibility for future use of these nanocomposite thin film systems in some envisaged applications (e.g. LSPR-biosensors).

Le "jeu de la constance" et le plus "apparent vice de nostre nature" : constance et inconstance dans les Essais de Michel de Montaigne

Thèse de doctorat effectuée en cotutelle au Département de philosophie Faculté des arts et des sciences de l’Université de Montréal et au département de philosophie école doctorale V de l’Université de la Sorbonne – Paris IV. Soutenue à Paris le 8 avril 2010.

Power characteristics of dielectric optical piet hein waveguides

A fairly rigorous analytical treatment of the power characteristics of dielectric optical waveguides with Piet Hein core-cross sectional geometry is presented in this paper. This kind of wareguide structure would be advantageous owing to the absence of corners, which are found in rectangular guides, resulting in undesirable loss (hit to the scattering of light. In order to simplify this theoretical approach. em approximation of vanishing refractive index difference between the guiding and the non-guiding sections is implemented. The variation eJ logarithmic power is shown for different dimensions of the core, corresponding to different azimuthal modal indices. It is found that the nutlet with higher index values carry less logaritlunic power in the lower tail of the propagation 's constant range, and this feature affects the higher tail. A better kind of uniformity of the power distribution is observed near the higher tail of the range of propagation Constants

Dielectric Dispersion of Water in the Frequency Range from 10 mHz to 30 MHz

We investigate the dielectric dispersion of water, specially in the low-frequency range, by using the impedance spectroscopy technique. The frequency dependencies of the real R and imaginary Z parts of the impedance Could not be explained by means of the Usual description of the dielectric properties of the water as all insulating liquid containing ions. This is due to the incomplete knowledge of the parameters entering in the fundamental equations describing the evolution of the system, and oil the mechanisms regulating the exchange of charge of the cell with the external circuit. We propose a simple description of our experimental data based on the model of Debye, by invoking a dc conductivity of the cell, related to the nonblocking character of the electrodes. A discussion on the electric Circuits able to simulate the cell under investigation, based oil bulk and Surface elements, is also reported. We find that the simple circuit formed by a series of two parallels of resistance and capacitance is able to reproduce the experimental data concerning the real and imaginary part of the electrical impedance of the cell for frequency larger than 1 Hz. According to this description, one of the parallels takes into account the electrical properties of interface between the electrode and water, and the other of the bulk. For frequency lower than 1 Hz, a good agreement with the experimental data is obtained by simulating the electrical properties of the interface by means of the constant phase element.

Dielectric properties of thermosetting material nanocomposites

The dieletric relaxation properties of thermosetting material nanocomposites based on spherosilicate nanoplatforms were studied from room temperature to 170 degrees C, varying the frequency from 10 to 1000 KHz. Permittivity (epsilon'), dielectric loss (epsilon ''), and activation energy (E-a) were calculated. The results of dielectric relaxation were confirmed by those of the final properties. The dielectric loss amplitude decreases with increasing ODPG content until about 70-73 wt % and slightly increases at higher ODPG content. This means that the increasing of the ODPG content in the composite samples decreases the number of pendants groups and/or increases crosslink densitv, causing decreased motion of organic tethers, and subsequently decreasing of the dipolar mobility. The results of apparent activation energy, fracture toughness and tensile modulus mechanical properties show the same profile with respect to ODPG content, in the sense that they exhibit maxima around 70 wt % ODPG. For the ODPG/MDA composites, this formulation of 70 wt % ODPG containing excess of amine is not composition where the highest crosslinked density is reached. This implies that the best mechanical properties and E-a are provided by some degree of chain flexibility. (c) 2007 Wiley Periodicals, Inc.

Dielectric spectroscopy on Bi3Zn2Sb3O14 ceramic: an approach based on the complex impedance

The dielectric properties and loss of Bi1.5ZnSb1.5O7 a poor-semiconducting ceramic were investigated by impedance spectroscopy, in the frequency range from 5 Hz to 13 MHz. Electric measurements were performed from 100 to 700 degreesC. Pyrochlore type phase was synthesized by the polymeric precursor method. Dense ceramic with 97% of the theoretical density was prepared by sintering via constant heating rate. The dielectric permittivity dependence as a function of frequency and temperature showed a strong dispersion at frequency lower than 10 kHz. The losses (tan delta) exhibit slight dependence with the frequency at low temperatures presenting a strong increase at temperatures higher than 400 degreesC. A decrease of the loss magnitude occurs with increasing frequency. Relaxation times were extracted using the dielectric functions Z(omega) and M(omega). The plots of the relaxation times tau(Z'), and tau(M) as a function of temperature follow the Arrhenius law, where a single slope is observed with activation energy values equal to 1.38 and 1.37 eV, respectively. (C) 2003 Elsevier Ltd. All rights reserved.

Effect of apparent viscosity on fluidized bed drying process parameters of guava pulp

Pressure drop and minimum fluidization velocity were experimentally studied in a vibro-fluidized bed of inert particles subjected to different vibration intensities during drying of guava pulp. Maltodextrin was added to the pulp in order to prevent stickiness between particles and the consequent bed collapse. Pulps were initially concentrated, resulting in pastes with different soluble solids content, and a constant fraction of maltodextrin was guaranteed in the final pulp samples. The pulp rheological behavior as affected by temperature and total soluble solids content, including maltodextrin, was evaluated and the effect of pulp apparent viscosity on pressure drop and minimum vibro-fluidization velocity were investigated. Two types of inert particles -3.6 mm glass beads and 3 mm Teflon cylinders were tested and, due to lower pressure drop presented by Teflon cylinders during operation of the dry vibro-fluidized bed, these particles were adopted for pulp drying process. Increasing pulp apparent viscosity caused a considerable increase in the vibro-fluidized bed pressure drop during pulp drying and, as a consequence resulted in a larger value of minimum vibro-fluidization velocity. on the other hand, the negative effect of increasing apparent viscosity could be attenuated by increasing the fluidized bed vibration intensity, which could prevent stickiness between particles. (c) 2006 Elsevier Ltd. All rights reserved.

Effect of apparent viscosity on the pressure drop during fluidized bed drying of soursop pulp

Pressure drop and minimum fluidization velocity were experimentally studied in a vibro-fluidized bed of inert particles subjected to different vibration intensities during drying of soursop pulp. Maltodextrin was added to the pulp in order to prevent stickiness between particles and the consequent bed collapse. Pulps were initially concentrated, resulting in pastes with different soluble solids content, and a constant fraction of maltodextrin was guaranteed in the final pulp samples. The pulp theological behavior as affected by temperature and total soluble solids content, including maltodextrin, was evaluated and the effect of pulp apparent viscosity on pressure drop and minimum vibro-fluidization velocity were investigated. Two types of inert particles -3.6 mm glass beads and 3 mm Teflon cylinders (length and diameter) - were tested and, due to lower pressure drop presented by Teflon cylinders during operation of the dry vibro-fluidized bed, these particles were adopted for pulp drying process. Increasing pulp apparent viscosity caused a considerable increase in the vibro-fluidized bed pressure drop during pulp drying and, as a consequence resulted in a larger value of minimum vibro-fluidization velocity. on the other hand, the negative effect of increasing apparent viscosity could be attenuated by increasing the fluidized bed vibration intensity, which could prevent stickiness between particles. (c) 2006 Elsevier B.V. All rights reserved.

Kinetics of the polarization reversal process in a non-constant applied electric field and the generalized superposition principle

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

On Designing Compliant Actuators Based On Dielectric Elastomers

Dielectric Elastomers (DE) are incompressible dielectrics which can experience deviatoric (isochoric) finite deformations in response to applied large electric fields. Thanks to the strong electro-mechanical coupling, DE intrinsically offer great potentialities for conceiving novel solid-state mechatronic devices, in particular linear actuators, which are more integrated, lightweight, economic, silent, resilient and disposable than equivalent devices based on traditional technologies. Such systems may have a huge impact in applications where the traditional technology does not allow coping with the limits of weight or encumbrance, and with problems involving interaction with humans or unknown environments. Fields such as medicine, domotic, entertainment, aerospace and transportation may profit. For actuation usage, DE are typically shaped in thin films coated with compliant electrodes on both sides and piled one on the other to form a multilayered DE. DE-based Linear Actuators (DELA) are entirely constituted by polymeric materials and their overall performance is highly influenced by several interacting factors; firstly by the electromechanical properties of the film, secondly by the mechanical properties and geometry of the polymeric frame designed to support the film, and finally by the driving circuits and activation strategies. In the last decade, much effort has been focused in the devolvement of analytical and numerical models that could explain and predict the hyperelastic behavior of different types of DE materials. Nevertheless, at present, the use of DELA is limited. The main reasons are 1) the lack of quantitative and qualitative models of the actuator as a whole system 2) the lack of a simple and reliable design methodology. In this thesis, a new point of view in the study of DELA is presented which takes into account the interaction between the DE film and the film supporting frame. Hyperelastic models of the DE film are reported which are capable of modeling the DE and the compliant electrodes. The supporting frames are analyzed and designed as compliant mechanisms using pseudo-rigid body models and subsequent finite element analysis. A new design methodology is reported which optimize the actuator performances allowing to specifically choose its inherent stiffness. As a particular case, the methodology focuses on the design of constant force actuators. This class of actuators are an example of how the force control could be highly simplified. Three new DE actuator concepts are proposed which highlight the goodness of the proposed method.

Apparent diffusion coefficient in the aging mouse brain: a magnetic resonance imaging study

Novel magnetic resonance imaging sequences have and still continue to play an increasing role in neuroimaging and neuroscience. Among these techniques, diffusion-weighted imaging (DWI) has revolutionized the diagnosis and management of diseases such as stroke, neoplastic disease and inflammation. However, the effects of aging on diffusion are yet to be determined. To establish reference values for future experimental mouse studies we tested the hypothesis that absolute apparent diffusion coefficients (ADC) of the normal brain change with age. A total of 41 healthy mice were examined by T2-weighted imaging and DWI. For each animal ADC frequency histograms (i) of the whole brain were calculated on a voxel-by-voxel basis and region-of-interest (ROI) measurements (ii) performed and related to the animals' age. The mean entire brain ADC of mice <3 months was 0.715(+/-0.016) x 10(-3) mm2/s, no significant difference to mice aged 4 to 5 months (0.736(+/-0.040) x 10(-3) mm2/s) or animals older than 9 months 0.736(+/-0.020) x 10(-3) mm2/s. Mean whole brain ADCs showed a trend towards lower values with aging but both methods (i + ii) did not reveal a significant correlation with age. ROI measurements in predefined areas: 0.723(+/-0.057) x 10(-3) mm2/s in the parietal lobe, 0.659(+/-0.037) x 10(-3) mm2/s in the striatum and 0.679(+/-0.056) x 10(-3) mm2/s in the temporal lobe. With advancing age, we observed minimal diffusion changes in the whole mouse brain as well as in three ROIs by determination of ADCs. According to our data ADCs remain nearly constant during the aging process of the brain with a small but statistically non-significant trend towards a decreased diffusion in older animals.

Mixing-cell boundary conditions and apparent mass balance errors for advective-dispersive solute transport

In many field or laboratory situations, well-mixed reservoirs like, for instance, injection or detection wells and gas distribution or sampling chambers define boundaries of transport domains. Exchange of solutes or gases across such boundaries can occur through advective or diffusive processes. First we analyzed situations, where the inlet region consists of a well-mixed reservoir, in a systematic way by interpreting them in terms of injection type. Second, we discussed the mass balance errors that seem to appear in case of resident injections. Mixing cells (MC) can be coupled mathematically in different ways to a domain where advective-dispersive transport occurs: by assuming a continuous solute flux at the interface (flux injection, MC-FI), or by assuming a continuous resident concentration (resident injection). In the latter case, the flux leaving the mixing cell can be defined in two ways: either as the value when the interface is approached from the mixing-cell side (MC-RT -), or as the value when it is approached from the column side (MC-RT +). Solutions of these injection types with constant or-in one case-distance-dependent transport parameters were compared to each other as well as to a solution of a two-layer system, where the first layer was characterized by a large dispersion coefficient. These solutions differ mainly at small Peclet numbers. For most real situations, the model for resident injection MC-RI + is considered to be relevant. This type of injection was modeled with a constant or with an exponentially varying dispersion coefficient within the porous medium. A constant dispersion coefficient will be appropriate for gases because of the Eulerian nature of the usually dominating gaseous diffusion coefficient, whereas the asymptotically growing dispersion coefficient will be more appropriate for solutes due to the Lagrangian nature of mechanical dispersion, which evolves only with the fluid flow. Assuming a continuous resident concentration at the interface between a mixing cell and a column, as in case of the MC-RI + model, entails a flux discontinuity. This flux discontinuity arises inherently from the definition of a mixing cell: the mixing process is included in the balance equation, but does not appear in the description of the flux through the mixing cell. There, only convection appears because of the homogeneous concentration within the mixing cell. Thus, the solute flux through a mixing cell in close contact with a transport domain is generally underestimated. This leads to (apparent) mass balance errors, which are often reported for similar situations and erroneously used to judge the validity of such models. Finally, the mixing cell model MC-RI + defines a universal basis regarding the type of solute injection at a boundary. Depending on the mixing cell parameters, it represents, in its limits, flux as well as resident injections. (C) 1998 Elsevier Science B.V. All rights reserved.

Part of the global DOC versus AOU (dissolved organic carbon/apparent oxygen utilization) data compilation, Ross Sea

Dissolved and particulate organic matter was measured during six cruises to the southern Ross Sea. The cruises were conducted during late austral winter to autumn from 1994 to 1997 and included coverage of various stages of the seasonal phytoplankton bloom. The data from the various years are compiled into a representative seasonal cycle in order to assess general patterns of dissolved organic matter (DOM) and particulate organic matter (POM) dynamics in the southern Ross Sea. Dissolved organic carbon (DOC) and particulate organic carbon (POC) were at background concentrations of approximately 42 and 3 µM C, respectively, during the late winter conditions in October. As the spring phytoplankton bloom progressed, organic matter increased, and by January DOC and POC reached as high as 30 and 107 µM C, respectively, in excess of initial wintertime conditions. Stocks and concentrations of DOC and POC returned to near background values by autumn (April). Approximately 90% of the accumulated organic matter was partitioned into POM, with modest net accumulation of DOM stocks despite large net organic matter production and the dominance of Phaeocystis antarctica. Changes in NO3 concentration from wintertime values were used to calculate the equivalent biological drawdown of dissolved inorganic carbon (DICequiv). The fraction of DICequiv drawdown resulting in net DOC production was relatively constant (ca. 11%), despite large temporal and spatial variability in DICequiv drawdown. The C : N (molar ratio) of the seasonally produced DOM had a geometric mean of 6.2 and was nitrogen-rich compared to background DOM. The DOM stocks that accumulate in excess of deep refractory background stocks are often referred to as "semi-labile" DOM. The "semi-labile" pool in the Ross Sea turns over on timescales of about 6 months. As a result of the modest net DOM production and its lability, the role DOM plays in export to the deep sea is small in this region.

Part of the global DOC versus AOU (dissolved organic carbon/apparent oxygen utilization) data compilation, WOCE14

Total organic carbon (TOC) samples were collected at 6 stations spaced ~800 km apart in the eastern South Atlantic, from the Equator to 45°S along 9°W. Analyses were performed by high temperature catalytic oxidation (HTCO) in the base laboratory. Despite the complex advection and mixing patterns of North Atlantic and Antarctic waters with extremely different degrees of ventilation, TOC levels below 500 m are quasi-constant at 55±3 µmol C/l, pointing to the refractory nature of deep-water TOC. On the other hand, a TOC excess from 25 to 38 g C/m**2 is observed in the upper 100 m of the permanently stratified nutrient-depleted Equatorial, Subequatorial and Subtropical upper ocean, where vertical turbulent diffusion is largely prevented. Conversely, TOC levels in the nutrient-rich upper layer of the Subantarctic Front only exceeds 9 g C/m**2 the deep-water baseline. As much as 70% of the TOC variability in the upper 500 m is due to simple mixing of reactive TOC formed in the surface layer and refractory TOC in deep ocean waters, with a minor contribution (13%) to oxygen consumption in the prominent subsurface AOU maximum at 200-400 m depth.