The actual life of a transformer is determined by ageing of the cellulosic insulation such as transformer paper. The presence of moisture in the insulation system decreases the electrical strength of paper and accelerates the aging. It is an efficient way to monitor the moisture content in paper insulation by measuring the dielectric constant of the paper. The moisture dependent permittivity of impregnated transformer paper below 1 MHz has been widely investigated. High frequency (> 1 MHz) dielectric spectroscopy is under requirement since the loss peak information is missing. The impregnated paper is kept in desiccators with saturated salt solutions to get the samples with moisture content from 1 % to 5.5 %. Then they are placed in a coaxial line and the scattering parameters are obtained by modern Vector Network Analyzer. Full wave analysis is utilized to calculate the permittivity from the obtained S-parameters due to its high accuracy. The magnitude of the dielectric spectroscopy below 100 Hz is very dependent on the moisture content while there is a horizontal shift of curves towards higher frequencies depending on the water content over a wide frequency range. The loss peaks appear between 1 MHz and 1 GHz for the impregnated paper with moisture level less than 5.5 %. Due to the limited system accuracy, there is a blank frequency band from 1 MHz to 100 MHz.

Nous avons cherché dans cette thèse à caractériser la phase vitreuse formée par des molécules organiques. Pour cela, nous y avons dilué des molécules sur lesquelles on a greffé un fragment d’azobenzène, de façon à pouvoir les orienter sélectivement en les illuminant. On souhaite ainsi s’approcher de la procédure de clouage aléatoire, qui permet en théorie et par simulations de caractériser d’une manière nouvelle la phase vitreuse "idéale", stable thermodynamiquement, qui se formerait pendant la transition vitreuse. On caractérise en temps réel les effets de l’illumination sur ces molécules modifiées (isomérisations cis-trans, orientation) par spectroscopie d’absorption UV polarisée. On mesure l’impact de l’illumination sur la transition vitreuse de leur matrice par spectroscopie diélectrique. Nous avons observé une accélération de la dynamique pendant illumination (diminution du temps de relaxation alpha). Celle-ci n’est pas due à l’orientation de l’azobenzène mais aux autres effets de l’illumination : les isomérisations cycliques cis-trans, et la présence d’isomères cis. Au total, la viscosité du verre est divisée par presque 50 en dessous de Tg, ce qui représente une augmentation de la température effective de l’échantillon de plus de 6K, alors que le chauffage réel dû à l’illumination est inférieur à 100mK. Derrière ces deux effets majoritaires, nous avons repéré que plus l’orientation est grande, plus le temps de relaxation alpha est grand, toute chose égale par ailleurs. Cette influence de l’orientation semble être très forte car nos fractions orientées sont faibles. En suivant les prédictions de la théorie RFOT, on trouve que la transition vitreuse idéale aurait lieu pour une concentration en molécules orientées entre 0,5 et 2% à Tg. Les expériences de random pinning sur des verres moléculaires semblent donc bien réalisables avec l’azobenzène. On jette dans cette thèse les bases d’une nouvelle voie expérimentale qui nous semble prometteuse pour l’étude de la transition vitreuse. / In this thesis we have sought to characterize the glassy phase formed by organic molecules. To do this, we diluted molecules on which we grafted an azobenzene fragment, so that we could selectively orient them by illuminating them. In this way, we wish to approach the random pinning procedure, which makes it possible in theory and by simulations to characterize in a new way the "ideal" thermodynamically stable glass phase that would be formed during the glass transition. The effects of illumination on these modified molecules (cis-trans isomerizations,orientation) are characterized in real time by polarized UV absorption spectroscopy. The impact of illumination on the glass transition of the matrix is measured by dielectric spectroscopy. We observed an acceleration of the dynamics during illumination (decrease of the alpha relaxation time). This is not due to the orientation of azobenzene but to other effects of illumination : cyclic cis-trans isomerizations, and the presence of cis isomers. In total, the viscosity of the glass is divided by almost 50 below Tg, which represents an increase in the effective temperature of the sample of more than 6K, while the actual heating due to illumination is less than 100 mK. Behind these two majority effects, we have identified that the greater the orientation, the greater the alpha relaxation time, all other things being equal. This influence of orientation seems to be very strong because our oriented fractions are small. Following the predictions of the RFOT theory, we find that the ideal glass transition would occur for a concentration of oriented molecules between 0.5 and 2% at Tg. Therefore random pinning experiments on molecular glasses seem to be feasible using azobenzene. In this thesis, we are laying the foundations for a new experimental approach that seems promising to us for the study of glass transition.

No description available.

The theory of orientation polarization and dielectric relaxation was developed by P. Debye more than 100 years ago. It is based on approximating a molecule by a sphere having one or more dipole moments. By that the detailed intra- and intermolecular interactions are explicitly not taken into consideration. In this article, the principal limitations of the Debye approximation are discussed. Taking advantage of the molecular specificity of the infrared (IR) spectral range, measurements of the specific IR absorption of the stretching vibration (OH) (at 3370 cm1) and the asymmetric as(CH2) (at 2862.9 cm1) are performed in dependence on the frequency and the strength of external electric fields and at varying temperature. The observed effects are interpreted as caused by orientation polarization of the OH and the adjacent CH2 moieties.

No description available.

Broadband Dielectric Spectroscopy (BDS) in combination with a nanostructured electrode arrangement – which circumvents the conventional need to evaporate metal electrodes onto soft matter – is used to study the molecular dynamics of several glass forming materials confined in nanometric (> 5 nm) layers. Other complementary experimental tools employed in this work include spectroscopic vis-Ellipsometry (SE), AC-chip calorimetry (ACC), X-ray reflectrometry (XRR), Differential Scanning Calorimetry (DSC) and Atomic Force Microscopy (AFM). The latter is used to characterize the topography of the samples and to determine their thicknesses. Under the conditions of annealing samples (Tg + 50K) in high oil-free vacuum (10E-6 mbars) for at least 12 h and carrying out measurements in inert (dry nitrogen or argon) atmosphere, it is found for all studied thin layers that the structural relaxation, and hence the dynamic glass transition – in its mean relaxation times – remains within a margin ±3 K from the respective bulk behaviour. It is revealed, inter alia, that the one-dimensional confinement of thin films introduces restrictions on other (slower) molecular relaxation processes which manifest, depending on the specific system under investigation, as (i) an interruption of the end-to-end (normal mode) fluctuation of the chains, or (ii) a slowing down of the delta-relaxation when the system is cooled towards glass-formation. Furthermore, (iii) evidence is provided to show that the dimensionality of confinement plays a significant role in determining the resulting dynamics. A molecular understanding of these findings is given, and the discussion presented with respect to the on-going international debate about dynamics in confinement.

Biosensors are used for the detection of a range of analytes for applications in healthcare, food production, environmental monitoring and biodefence. However, many biosensing platforms are large, expensive, require skilled operators or necessitate the analyte to be labelled. Direct electrochemical detection methods present a particularly attractive platform due to the simplified instrumentation when compared to other techniques such as fluorescence-based biosensors. With modern integrated circuit capabilities electrochemical biosensors offer greater suitability for monolithic integration with any necessary signal processing circuitry. This thesis explores micro- and nanogap devices for both redox cycling and dielectric spectroscopy sensing mechanisms. By using two electrodes with interelectrode separation down to distances in the micro- and nanometre scale, several benefits can be realised. Firstly the close proximity of the two electrodes significantly reduces the interdiffusion time. This allows an electroactive species to be rapidly shuttled across the gap and switched between reduced and oxidised states. The result is feedback amplification of the amperometric response, increasing the signal. The second benefit is that the screening effect caused by electric double layers at the electrode–electrolyte interface is reduced due to the electric double layers occupying a larger fraction of the sensing volume. This significantly improves the sensor suitability for dielectric spectroscopy by increasing the potential drop across the biolayer. These two sensing mechanisms are demonstrated using a large area dual-plate microgap device for the detection of two different analytes. Utilising the first mode, detection of cysteine–cystine, an important redox couple involved in the signalling mechanism for the regulation of protein function, interaction and localisation is shown. The microgap device is then used for dielectric spectroscopy sensing of a mannose-specific uropathogenic Escherichia coli strain whilst also demonstrating the effect of ionic concentration on the capacitive response. The response of these devices is highly dependent on the interelectrode separation as well as the surface area of the electrodes. However, fabrication of large-area nanogap devices presents a significant challenge. This meant that careful optimisation and the development of novel techniques was necessary. This work reports the design, fabrication and characterisation of both a vertical and a horizontal coplanar large area nanogap device. The vertical nanogap device is fabricated using an inductively-coupled plasma reactive ion etching process to create a channel in a silicon substrate. A lower electrode is then optically patterned in the channel before anodically bonding a second identical electrode patterned on glass directly above. The horizontal nanogap device uses a different approach, utilising a state-of-the-art electron-beam lithography system to create a long serpentine nanogap with passivation to reduce fringing effects. The design allows the electron-beam lithography step to be substituted with nanoimprint lithography to reduce cost and improve throughput. Both of these devices have integrated microfluidic channels and provide a capacity for relatively high-throughput production.

This thesis concerns studies of aqueous soft matter systems, especially surfactant micelle systems. The aim has been to study the molecular arrangement and electronic structure of the constituents of, as well as transport properties in such a system. The molecular arrangement and electronic structure has been studied by means of X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray spectroscopy (RIXS). The transport properties have been investigated by low-frequency dielectric spectroscopy (LFDS) and small angle X-ray scattering (SAXS) as well as a theoretical modelling. The latter was based on Fick’s laws of the release from binary surfactant system and was validated by experiments. The RIXS and XAS measurements show the electronic structure in bulk water and the influence of the chemical surrounding of the water molecule in bulk water and of the water molecules confined in a micelle lattice. The spectra are highly dependent on the molecular arrangement in such systems. For glycine and sodium polyacrylate RIXS and XAS spectra show features which are unique for carboxyl and carboxylate groups and such measurements can thus be used for fingerprinting. The LFDS and SAXS measurements show a strong correlation between structure in a surfactant/poly-ion system and apparent mobility of surfactants. This conclusion is in line with earlier observations. By the theoretical modelling a predictive model for the surfactant release from a binary surfactant micelle system has been obtained and the importance of different factors for surfactant release has been further clarified.

The aim of doctoral dissertation „Grain Size Effect on Dielectric Properties of Ferroelectrics and Relaxors“ by Maksim Ivanov is to investigate, how grain size of ceramics and powders of a few ferroelectrics and relaxors influences macroscopic dielectric properties. The studied materials are powders of a relaxor PbMg⅓Nb⅔O3 (PMN), ceramics of a relaxor with a spontaneous phase transition PbSc½Nb½O3 (PSN), ceramics of a ferroelectric 0.36BiScO3-0.64PbTiO3, and ceramics of Ba2SnO4, which were compared to a better investigated BaSnO3. Investigations were performed in broad frequency (100 Hz – 55 GHz) and temperature (30 K – 1000 K) ranges. Experimental investigations and modelling showed, that bulk properties of relaxor materials are heavily influenced by polar nanoregions, but they do not fully determine them. Morphology of the material (i.e. grain size of ceramics) determines growth and interactions of the nanoregions, thus influencing bulk properties. Moreover, effective medium approximation can explain evolution of dielectric properties of ferroelectrics and relaxors only if dependence of bulk properties on grain size is known. The most interesting result is, that there exist polar entities in ferroelectrics, which are different from ferroelectric domains and are similar to polar nanoregions in relaxors. Their contribution to dielectric permittivity can be comparable to all other contributions. Dimensions of these entities depend on grain size in accordance with Kittel's law. / Maksimo Ivanovo daktaro disertacijos tema yra “Grūdų dydžio įtaka dielektrinėms feroelektrikų ir relaksorių savybėms”. Šio darbo tikslas yra ištirti, kaip keramikų ar miltelių grūdų dydis įtakoja makroskopiškai stebimas kelių feroelektrikų bei feroelektrinių relaksorių dielektrines savybes. Tirtos medžiagos yra klasikinio relaksoriuas PbMg⅓Nb⅔O3 (PMN) milteliai, relaksoriaus su savaiminiu feroelektriniu faziniu virsmu PbSc½Nb½O3 (PSN) keramikos, feroelektriko 0.36BiScO3-0.64PbTiO3 keramikos, bei Ba2SnO4 keramiką, kuri buvo palyginta su kiek labiau žinoma BaSnO3 keramika. Tyrimai buvo atlikti plačiame dažnių (100 Hz – 55 GHz) bei temperatūrų (30 K – 1000 K) intervaluose. Eksperimentiniai tyrimai bei modeliavimai parodė, kad polinės nanosritys labai stipriai įtakoja tūrines relaksorių savybes, tačiau jų neapsprendžia. Medžiagos morfologija (antai keramikų grūdų dydis) lemia nanosričių augimą bei tarpusavio sąveikas, tokiu būdų įtakojamos tūrinės savybės. Be to, efektyvios terpės aproksimacija gali paaiškinti feroelektrikų ir relaksorių dielektrinių savybių priklausomybę nuo grūdų dydžio tik, jei žinomas sąryšis tarp dydžio ir tūrinių savybių. Įdomiausia yra tai, kad feroelektrikuose yra objektų, kurie nėra feroelektriniai domenai ir yra panašūs į relaksorių polines nanosritis. Jų indėlis į dielektrinę skvarbą gali būti palyginamas su visų kitų procesų (pvz. domenų sienelių ir polinių modų) indėliais. Šių objektų dydis priklauso nuo grūdų dydžio pagal Kittel'io dėsnį.

Maksimo Ivanovo daktaro disertacijos tema yra “Grūdų dydžio įtaka dielektrinėms feroelektrikų ir relaksorių savybėms”. Šio darbo tikslas yra ištirti, kaip keramikų ar miltelių grūdų dydis įtakoja makroskopiškai stebimas kelių feroelektrikų bei feroelektrinių relaksorių dielektrines savybes. Tirtos medžiagos yra klasikinio relaksoriuas PbMg⅓Nb⅔O3 (PMN) milteliai, relaksoriaus su savaiminiu feroelektriniu faziniu virsmu PbSc½Nb½O3 (PSN) keramikos, feroelektriko 0.36BiScO3-0.64PbTiO3 keramikos, bei Ba2SnO4 keramiką, kuri buvo palyginta su kiek labiau žinoma BaSnO3 keramika. Tyrimai buvo atlikti plačiame dažnių (100 Hz – 55 GHz) bei temperatūrų (30 K – 1000 K) intervaluose. Eksperimentiniai tyrimai bei modeliavimai parodė, kad polinės nanosritys labai stipriai įtakoja tūrines relaksorių savybes, tačiau jų neapsprendžia. Medžiagos morfologija (antai keramikų grūdų dydis) lemia nanosričių augimą bei tarpusavio sąveikas, tokiu būdų įtakojamos tūrinės savybės. Be to, efektyvios terpės aproksimacija gali paaiškinti feroelektrikų ir relaksorių dielektrinių savybių priklausomybę nuo grūdų dydžio tik, jei žinomas sąryšis tarp dydžio ir tūrinių savybių. Įdomiausia yra tai, kad feroelektrikuose yra objektų, kurie nėra feroelektriniai domenai ir yra panašūs į relaksorių polines nanosritis. Jų indėlis į dielektrinę skvarbą gali būti palyginamas su visų kitų procesų (pvz. domenų sienelių ir polinių modų) indėliais. Šių objektų dydis priklauso nuo grūdų dydžio pagal Kittel'io dėsnį. / The aim of doctoral dissertation „Grain Size Effect on Dielectric Properties of Ferroelectrics and Relaxors“ by Maksim Ivanov is to investigate, how grain size of ceramics and powders of a few ferroelectrics and relaxors influences macroscopic dielectric properties. The studied materials are powders of a relaxor PbMg⅓Nb⅔O3 (PMN), ceramics of a relaxor with a spontaneous phase transition PbSc½Nb½O3 (PSN), ceramics of a ferroelectric 0.36BiScO3-0.64PbTiO3, and ceramics of Ba2SnO4, which were compared to a better investigated BaSnO3. Investigations were performed in broad frequency (100 Hz – 55 GHz) and temperature (30 K – 1000 K) ranges. Experimental investigations and modelling showed, that bulk properties of relaxor materials are heavily influenced by polar nanoregions, but they do not fully determine them. Morphology of the material (i.e. grain size of ceramics) determines growth and interactions of the nanoregions, thus influencing bulk properties. Moreover, effective medium approximation can explain evolution of dielectric properties of ferroelectrics and relaxors only if dependence of bulk properties on grain size is known. The most interesting result is, that there exist polar entities in ferroelectrics, which are different from ferroelectric domains and are similar to polar nanoregions in relaxors. Their contribution to dielectric permittivity can be comparable to all other contributions. Dimensions of these entities depend on grain size in accordance with Kittel's law.