Linking origin of the electric field-assisted beta-PbF2 crystallization in lead oxyfluoroborate glasses below T (g) to simultaneous cathode/anode-compensated electrochemical reactions

Full validation of the electrochemical mechanisms so far postulated as driving force of electric field-assisted non-spontaneous crystallization development in given glasses has suffered experimental restrictions. In this work, we looked into origin of this phenomenon in lead oxyfluoroborate glasses, resulting in beta-PbF2 growth even below the corresponding glass transition temperatures, through achieving a systematic study of not only Pt,Ag/Glass/Ag,Pt- but also Pt,Ag/Glass/YSZ:PbF2/Ag,Pt-type cells, where YSZ:PbF2 represents a two-phase system (formed by Y2O3-doped ZrO2 and PbF2). It is demonstrated that crystallization induction in these glasses involves Pb2+ ions reduction at the cathode, the phenomenon being, however, confirmed only when the F- ions were simultaneously also able to reach the anode for oxidation, after assuring either a direct glass-anode contact or percolation pathways for free fluoride migration across the YSZ:PbF2 mixtures. A further support of this account is that the electrochemically induced beta-PbF2 phase crystallizes showing ramified-like microstructure morphology that arises, accordingly, from development of electroconvective diffusion processes under electric field action.

Lineare und nichtlineare dielektrische Spektroskopie am Relaxor-Ferroelektrikum Bleimagnesiumniobat

Relaxor-Ferroelektrika sind wegen ihrer möglichen technischen Anwendungen und vom Standpunkt der Grundlagenforschung als Beispiel für ungeordnete Systeme von wissenschaftlichem Interesse. Trotz zahlreicher experimenteller Untersuchungen sind die mikroskopischen Ursachen ihrer Eigenschaften aber nach wie vor ungeklärt. Im Rahmen dieser Arbeit wurde das Relaxor-Ferroelektrikum Bleimagnesiumniobat-Bleititanat (PMN-10PT) mittels linearer und nichtlinearer dielektrischer Spektroskopie untersucht. Durch Anregung mit starken elektrischen Wechselfeldern konnten mit der Methode des nichtresonanten dielektrischen Lochbrennens frequenzselektiv einzelne spektrale Bereiche aus dem verbreiterten Relaxationsspektrum herausgegriffen und deren Rückrelaxation separat verfolgt werden. Die experimentellen Ergebnisse zeigten, daß eine langlebige dynamische Heterogenität der dipolaren Reorientierung existiert. Durch ihr ausgeprägt nichtergodisches Verhalten zeigen Relaxor-Ferroelektrika starke Alterungseffekte. Die Untersuchung des Alterungsverhaltens der dielektrischen Suszeptibilität zeigte, daß ein Gedächtnis für die bei einer Alterungstemperatur eingenommene Konfiguration bestehen bleibt, sofern die Temperatur nach einer unvollständigen isothermen Alterung nur um einige Grad abgesenkt oder erhöht wurde.Außerdem wurde die induzierte Polarisation bei stochastischen dielektrischen Anregungen mit elektrischen Feldern, die in sehr guter Näherung ein weißes Rauschen darstellten, untersucht. Über die Bildung der Kreuzkorrelationsfunktion zwischen Feld und Polarisation konnte die Impulsantwortfunktion des Systems berechnet werden.Die experimentellen Ergebnisse am Relaxor-Ferroelektrikum PMN-10PT können sehr gut mit einem Modell eines ungeordneten Ferroelektrikums erklärt werden, dessen Domänenwände unordnungsbedingt an sogenannten Pinning-Zentren festhaften.

Charge generation and recombination in hybrid organic,inorganic solar cells

This thesis deals with the investigation of exciton and charge dynamics in hybrid solar cells by time-resolved optical spectroscopy. Quasi-steady-state and transient absorption spectroscopy, as well as time-resolved photoluminescence spectroscopy, were employed to study charge generation and recombination in solid-state organic dye-sensitized solar cells, where the commonly used liquid electrolyte is replaced by an organic solid hole transporter, namely 2,2′7,7′-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9′-spirobifluorene (spiro-MeOTAD), and polymer-metal oxide bulk heterojunction solar cells, where the commonly used fullerene acceptor [6,6]-phenyl C61 butyric acid methyl ester (PCBM) is replaced by zinc oxide (ZnO) nanoparticles. By correlating the spectroscopic results with the photovoltaic performance, efficiency-limiting processes and processes leading to photocurrent generation in the investigated systems are revealed. rnIt is shown that the charge generation from several all-organic donor-π-bridge-acceptor dyes, specifically perylene monoimide derivatives, employed in solid-state dye-sensitized solar cells, is strongly dependent on the presence of a commonly used additive lithium bis(trifluoromethanesulphonyl)imide salt (Li-TFSI) at the interface. rnMoreover, it is shown that charges can not only be generated by electron injection from the excited dye into the TiO2 acceptor and subsequent regeneration of the dye cation by the hole transporter, but also by an alternative mechanism, called preceding hole transfer (or reductive quenching). Here, the excited dye is first reduced by the hole transporter and the thereby formed anion subsequently injects an electron into the titania. This additional charge generation process, which is only possible for solid hole transporters, helps to overcome injection problems. rnHowever, a severe disadvantage of solid-state dye-sensitized solar cells is re-vealed by monitoring the transient Stark effect on dye molecules at the inter-face induced by the electric field between electrons and holes. The attraction between the negative image charge present in TiO2, which is induced by the positive charge carrier in the hole transporter due to the dielectric contrast between the organic spiro-MeOTAD and inorganic titania, is sufficient to at-tract the hole back to the interface, thereby increasing recombination and suppressing the extraction of free charges.rnBy investigating the effect of different dye structures and physical properties on charge generation and recombination, design rules and guidelines for the further advancement of solid-state dye-sensitized solar cells are proposed.rnFinally, a spectroscopic study on polymer:ZnO bulk heterojunction hybrid solar cells, employing different surfactants attached to the metal oxide nanoparticles, was performed to understand the effect of surfactants upon photovoltaic behavior. By applying a parallel pool analysis on the transient absorption data, it is shown that suppressing fast recombination while simultaneously maintaining the exciton splitting efficiency by the right choice of surfactants leads to better photovoltaic performances. Suppressing the fast recombination completely, whilst maintaining the exciton splitting, could lead to a doubling of the power conversion efficiency of this type of solar cell.

Intracavity Generation of Radially Polarized CO2 Laser Beams Based on a Simple Binary Dielectric Diffraction Grating

We present experimental results on the intracavity generation of radially polarized light by incorporation of a polarization-selective mirror in a CO2 -laser resonator. The selectivity is achieved with a simple binary dielectric diffraction grating etched in the backsurface of the mirror substrate. Very high polarization selectivity was achieved, and good agreement of simulation and experimental results is shown. The overall radial polarization purity of the generated laser beam was found to be higher than 90% .

The Effect of Cobalt Upon Current Efficiency in the Electrolysis of Zinc Sulphate Solutions

The detrimental effect of the presence of cobalt upon the current efficiency, in the commercial production of zinc by electrolysis, has been recognized for some time. Most authorities differ upon the maximum amount of cobalt allowable. This is due to the fact that the presence of other impurities either increases or diminishes the detrimental effects of the cobalt. The following tests were made with the object in view of ascertaining the relation, if any, between the amount of cobalt present and the current efficiency during the electrolysis of an otherwise pure zinc sulfate solution. The results obtained from these observations indicate that there is little apparent relation between the cobalt concentration of a given solution of zinc sulfate and the current efficiency that may be obtained on the electrolysis of that solution. For certain cobalt concentrations, however, it was noted that the time factor played an important part.

Electrolytic Recovery of Copper and Zinc from Brass.

The reclamation of metals from scrap is becoming increasingly important in the metallurgical industry. Copper, because it does not corrode readily and is electronegative to most common metals, is peculiarly adapted to reclamation.

Refining of Low Grade Zinc-Gold Precipitates

The purpose of this investigation was to ascertain if advantage could be taken of the copper in the precipitates as a collecting agent of the precious metals in the direct smelting furnace.The products produced to be low grade anode bullion and a slag low in precious metals, high in zinc and lead.

Thermodynamics of zinc insertion in CuGaS2:Ti, used as a modulator agent in an intermediate-band photovoltaic material

An intermediate-bandphotovoltaicmaterial, which has an isolated metallic band located between the top of the valence band and bottom of the conduction band of some semiconductors, has been proposed as third generation solar cell to be used in photovoltaic applications. Density functional theory calculations of Zn in CuGaS2:Ti have previously shown that, the intermediate-band position can be modulated in proportion of Zn insertion in such a way that increasing Zn concentration can lead to aband-gap reduction, and an adjustment of the intermediate-band position. This could be interesting in the formation of an intermediate-bandmaterial, that has the maximum efficiency theoretically predicted for the intermediate-band solar cell. In this work, the energetics of several reaction schemes that could lead to the decomposition of the modulated intermediate-bandphotovoltaicmaterial, CuGaS2:Ti:Zn, is studied in order to assess the thermodynamic stability of this material. Calculations of the total free energy and disorder entropy have been taken into account, to get the reaction energy and free energy of the compound decomposition, which is found to be thermodynamically favorable

Towards materials with enhanced electro-mechanical response: CaCu3Ti4O12-polydimethylsiloxane composites

We describe a straightforward production pathway of polymer matrix composites with increased dielectric constant for dielectric elastomer actuators (DEAs). Up to date, the approach of using composites made of high dielectric constant ceramics and insulating polymers has not evidenced any improvement in the performance of DEA devices, mainly as a consequence of the ferroelectric nature of the employed ceramics. We propose here an unexplored alternative to these traditional fillers, introducing calcium copper titanate (CCTO) CaCu3Ti4O12, which has a giant dielectric constant making it very suitable for capacitive applications. All CCTO-polydimethylsiloxane (PDMS) composites developed display an improved electro-mechanical performance. The largest actuation improvement was achieved for the composite with 5.1 vol% of CCTO, having an increment in the actuation strain of about 100% together with a reduction of 25% in the electric field compared to the raw PDMS matrix.

An Asymptotic Solution for Surface Fields on a Dielectric-Coated Circular Cylinder with an Effective Impedance Boundary Condition.

Reverberation chambers are well known for providing a random-like electric field distribution. Detection of directivity or gain thereof requires an adequate procedure and smart post-processing. In this paper, a new method is proposed for estimating the directivity of radiating devices in a reverberation chamber (RC). The method is based on the Rician K-factor whose estimation in an RC benefits from recent improvements. Directivity estimation relies on the accurate determination of the K-factor with respect to a reference antenna. Good agreement is reported with measurements carried out in near-field anechoic chamber (AC) and using a near-field to far-field transformation.

Surface Impedance Characterization for UTD Based Solution with IBC for Surface Fields on a Dielectric-Coated PEC Circular Cylinder

A novel formulation for the surface impedance characterization is introduced for the canonical problem of surface fields on a perfect electric conductor (PEC) circular cylinder with a dielectric coating due to a electric current source using the Uniform Theory of Diffraction (UTD) with an Impedance Boundary Condition (IBC). The approach is based on a TE/TM assumption of the surface fields from the original problem. Where this surface impedance fails, an optimization is performed to minimize the error in the SD Green?s function between the original problem and the equivalent one with the IBC. This new approach requires small changes in the available UTD based solution with IBC to include the geodesic ray angle and length dependence in the surface impedance formulas. This asymptotic method, accurate for large separations between source and observer points, in combination with spectral domain (SD) Green?s functions for multidielectric coatings leads to a new hybrid SD-UTD with IBC to calculate mutual coupling among microstrip patches on a multilayer dielectric-coated PEC circular cylinder. Results are compared with the eigenfunction solution in SD, where a very good agreement is met.

Surface Impedance Characterization for Mutual Coupling Calculation of Patches on a Dielectric-Coated PEC Circular Cylinder

A novel formulation for the surface impedance characterization is introduced for the canonical problem of surface fields on a perfect electric conductor (PEC) circular cylinder with a dielectric coating due to a electric current source using the Uniform Theory of Diffraction (UTD) with an Impedance Boundary Condition (IBC). The approach is based on a TE/TM assumption of the surface fields from the original problem. Where this surface impedance fails, an optimization is performed to minimize the error in the SD Green?s function between the original problem and the equivalent one with the IBC. This asymptotic method, accurate for large separations between source and observer points, in combination with spectral domain (SD) Green?s functions for multidielectric coatings leads to a new hybrid SD-UTD with IBC to calculate mutual coupling among microstrip patches on a multilayer dielectric-coated PEC circular cylinder. Results are compared with the eigenfunction solution in SD, where a very good agreement is met.

Surface impedance for scattered field on a dielectric-coated circular cylinder

In the scattering analysis of a circular cylindrical structure, the impedance boundary condition (IBC) can approximate and simplify the perfect electric conductor (PEC) boundary condition. The circular cylinder problem can be solved with modal methods but they require a large number of terms when the cylinder radius is large in terms of the wave length. The uniform theory of diffraction (UTD) [1] is commonly used to overcome this issue. The two-dimensional problem of scattering on a circular cylinder covered by a dielectric layer has been analyzed by [2]–[5], but their solutions either do not consider oblique incidence, fail on the transition region or use a constant surface impedance.

Surface impedance for electromagnetic fields over a dielectric-coated circular cylinder

For small or medium size conformal array antennas in terms of the wave length, modal solutions in spectral domain for mutual coupling analysis are convenient for canonical shapes such as circular cylinder [1] or sphere [2], but as the antenna dimensions increase a large number of terms are necessary. For large structures the uniform theory of diffraction (UTD) is commonly used to solve this problem for canonical and arbitrarily convex shaped perfect electric conductor (PEC) surfaces [3]. A UTD solution for mutual coupling on an impedance cylinder has been introduced in [4], [5] but using a constant surface impedance.