L'objectif de cette thèse était d'étudier les propriétés thermoélectriques de couches minces d'oxyde de type delafossite déposées par pulvérisation cathodique magnétron. Pour cela, les oxydes CuCrO2:3%Mg, CuFeO2:3%Mg et CuCr0,84Fe0,16O2:3%Mg ont été déposés avec différentes épaisseurs sur des substrats de silice amorphe puis traités sous vide à différentes températures afin d'obtenir la structure delafossite. La température de traitement thermique optimale permettant d'obtenir les meilleures propriétés thermoélectriques est de 550°C pour CuCrO2:Mg et CuCr0,84Fe0,16O2:Mg et de 700°C pour CuFeO2:Mg. L'épaisseur optimale des couches minces est de 100 nm pour la delafossite au chrome et de 300 nm pour celle au fer. La conductivité électrique des couches augmente avec la température tout en conservant un coefficient Seebeck positif et constant pour les trois compositions données impliquant un mécanisme par saut de polarons. Le facteur de puissance des couches minces CuCrO2:Mg, CuFeO2:Mg et CuCr0,84Fe0,16O2:Mg dont l'épaisseur et la température de recuit ont été optimisées atteint respectivement 59 µW.m-1K-2, 84 µW.m-1K-2 et 36 µW.m-1K-2 à 200°C. Les études microstructurales et structurales ont permis de comprendre la variation du facteur de puissance avec la température de recuit et l'épaisseur. Elles ont notamment montré que la décroissance de la conductivité électrique des films traités à haute température est due à des phénomènes concomitants de fissuration de la couche et de ségrégation du magnésium. Une étude thermique utilisant la modélisation avec la méthode des éléments finis a permis de démontrer que dans le cas des couches minces, la conductivité thermique du substrat peut se substituer à celle du film dans le calcul de facteur de mérite. La validité du facteur de mérite modifié ((ZT)* = S2σ/ksubstrat) a été énoncée en fonction de l'épaisseur, l'émissivité et la conductivité thermique de la couche mince. L'utilisation de la méthode 3ω a permis de déterminer une valeur de conductivité thermique de 4,82 W.m-1k-1 à 25°C pour le film mince CuFeO2:Mg, qui se situe dans le domaine de validité établi pour l'utilisation de (ZT)*.[...] / The aim of this thesis was to study the thermoelectric properties of delafossite type oxides thin-films deposited by RF-magnetron sputtering. Several thicknesses of CuCrO2:3%Mg, CuFeO2:3%Mg and CuCr0,84Fe0,16O2:3%Mg oxides were deposited on fused silica then annealed under vacuum at different temperatures in order to obtain delafossite structure. The optimal annealing temperature which leads to an acceptable thermoelectric properties is 550°C for CuCrO2:Mg and CuCr0,84Fe0,16O2:Mg thin films and 700°C for CuFeO2:Mg thin film. The optimal thickness is 100 nm for the delafossite with chrome and 300 nm for delafossite with iron. The electrical conductivity of the studied thin films increases with the temperature, while maintaining a positive and constant Seebeck coefficient for the three given compositions that implies a hopping mechanism. The power factor of CuCrO2:Mg, CuFeO2:Mg and CuCr0,84Fe0,16O2:Mg thin films for which the annealing temperature and the thickness were optimized, reached 59 µW.m-1K-2, 84 µW.m-1K-2 and 36 µW.m-1K-2 respectively at 200°C. The microstructural and structural analysis allowed to understand the variation of the power factor with the annealing temperatures and the thicknesses. In particular, they showed that the decrease in the electrical conductivity of the thin films annealed at high temperature is due to concomitant phenomena of film cracking and magnesium segregation. A thermal analysis using modeling with the finite element method has demonstrated that in the case of thin films, the thermal conductivity of the substrate can be substituted for the thermal conductivity of the film in the calculation of figure of merit. The validity of the modified figure of merit ((ZT)* = S2σ/ksubstrate) was given as a function of the film thickness, emissivity and thermal conductivity. The thermal conductivity of CuFeO2:Mg was measured using the 3ω method and it was 4.82 W.m-1k-1 at 25°C which is within the range of validity established for the use of (ZT)*[...]

Silver containing chalcogenide glasses have been extensively studied during the last few decades; the main interest in these materials being their electrical conductivity which changes by several orders of magnitude upon silver doping. Glassy chalcogenides doped with silver have applications in optical elements, gratings, micro-lenses, waveguides, bio & chemical sensors, solid electrolytes, batteries, etc. Chalcohalide glasses have become important in the recent times, from both scientific & technological points of view, due to the interesting properties exhibited by these glasses such as the transparency in the infrared region, the stability against devitrification, solubility of rare earth elements, etc. In this thesis work, the thermal properties and electrical switching behavior of certain silver and iodine doped chalcogenide glasses have been investigated The thesis contains five chapters: Chapter 1: This chapter is an introduction to the fundamental aspects of amorphous semiconductors with a particular reference to chalcogenide glasses. The advantages and applications of chalcogenide glasses are also described. Chapter 2: The methods of preparation and characterization of the glasses investigated are described in this chapter. Also, the details of the experiments undertaken, namely temperature modulated Alternating Differential Scanning Calorimetry (ADSC), electrical switching analysis, Photo-thermal Deflection Spectroscopy (PDS), etc, are outlined. Chapter 3: In this chapter, the thermal behavior and electrical switching of silver doped Ge-Se and As-Se chalcogenide glasses are described. Bulk, melt-quenched Se-rich Ge0.15Se0.85-xAgx glasses have been found to be microscopically phase separated and composed of Ag2Se clusters and GeSe2-Se network. When the silver concentration exceeds 10 atom %, the Ag2Se clusters embedded in the GeSe2-Se network percolate. The signature of this percolation threshold is clearly observed as the sudden appearance of two exothermic crystallization peaks in ADSC runs. Density, molar volume and micro hardness studies also strongly support the view of a percolation transition. The super-ionic conduction observed earlier in these glasses at higher silver proportions, is likely to be connected with the silver phase percolation. It has been found that Ge0.15Se0.85-xAgx glasses of lower silver concentration (x = 0.07 and 0.08) do not exhibit electrical switching at voltages up to 1100 V. A negative resistance behavior and threshold type electrical switching is seen in Ge0.15Se0.85-xAgx samples with x 0.09. Also, fluctuations are observed in the I-V characteristics of these samples, which have been attributed to the difference in thermal conductivities between the Ag2Se inclusions and the Ge-Se base glass. A sharp drop has been observed in the switching voltage with Ag concentration which is due to the more metallic nature of silver and the presence of Ag+ ions. Further, the saturation in the decrease of VT around x = 0.10, is related to silver phase percolation in these glasses. Bulk As20Se80-xAgx glasses (0 x 15) have been found to exhibit two endothermic glass transitions and two exothermic crystallization reactions on heating. Based on which it is suggested that As20Se80-xAgx glasses are also microscopically phase separated, containing Ag2Se phases embedded in an As-Se backbone. The occurrence of microscopic phase separation in As20Se80-xAgx glasses is also confirmed by SEM studies. With increasing silver concentration, the Ag2Se phase percolates in the As-Se matrix, with a well-defined percolation threshold at x = 8. This silver phase percolation is exemplified by sudden jumps in the composition dependence of the second crystallization peak and non-reversible heat-flow, Hnr obtained at the second glass transition reaction of As20Se80-xAgx glasses. The super-ionic conduction observed earlier in these glasses at higher silver proportions, is likely to be associated with the observed silver phase percolation. Like Ge0.15Se0.85-xAgx glasses, As20Se80-xAgx glasses also exhibit threshold type electrical switching with fluctuations in the I-V characteristics; these fluctuations have been attributed to the difference in thermal conductivities between the Ag2Se inclusions and the As-Se base glass. A sharp drop has been observed in the switching voltage with Ag concentration which is due to the more metallic nature of silver and the presence of Ag+ ions. Further, the saturation in the decrease of VT around x = 8, is found to be related to silver phase percolation in these glasses, which has been proposed on the basis of ADSC experiments. Chapter 4: The chapter 4 deals with thermal studies, electrical switching investigations and Photo-thermal Deflection Spectroscopic (PDS) measurements on certain Ge-Te-I and As-Te-I chalcohalide glasses. It has been found that the compositional variation of the glass transition temperature of Ge22Te78-xIx glasses, obtained by Alternating Differential Scanning Calorimetry (ADSC), exhibits a broad hump around 5 atom % of iodine. Further, a sharp minimum is seen in the composition dependence of non-reversing enthalpy (Hnr) of Ge22Te78-xIx glasses at x = 5, which is suggestive of a thermally reversing window at this composition. Electrical switching studies on Ge22Te78-xIx glasses indicate that these glasses exhibit memory type electrical switching. At lower iodine concentrations, a decrease is seen in switching voltages with an increase in iodine content (in comparison with the base Ge22Te78 glass), which is due to the decrease in network connectivity. The increase seen in switching voltages of Ge22Te78-xIx glasses at higher iodine contents, suggests that the influence of the metallicity is stronger at higher iodine proportions. It is also interesting to note that the composition dependence of the threshold voltages shows a slope change at x = 5, the inverse rigidity percolation threshold of the Ge22Te78-xIx system. . Further, it is found that the thermal diffusivities ( D) of Ge22Te78-xIx glasses decrease with the increase in iodine content, which has been understood on the basis of fragmentation of the Ge-Te network with the addition of iodine. Also, a cusp is seen in the composition dependence of thermal diffusivity at the composition x = 5 (average coordination number, r = 2.39), which has been identified to be the inverse rigidity percolation threshold of the system at which the network connectivity is lost. ADSC studies on As45Te55-xIx chalcohalide glasses (3 x 10) reveal that there is not much variation in the glass transition temperature of As45Te55-xIx glasses, even though there is a wide variation in r . Based on this observation we suggest that the variation in glass transition temperature of network glasses is dictated by the variation in average bond energy rather than the average coordination number. Further, the non-reversing enthalpy Hnr of As45Te55-xIx glasses is found to exhibit a sharp minimum at the composition x = 6. A broad hump is also seen in glass transition and crystallization temperatures in the composition range 5 x 7. These results indicate a narrow thermally reversing window in As45Te55-xIx glasses around the composition x = 6. As45Te55-xIx glasses have been found to exhibit a memory to threshold type change in switching behavior with iodine content (x 6), which has been understood on the basis of the sharp increase in thermal diffusivity above x = 6. It is also observed that the switching voltages do not change appreciably with composition/average coordination number. Though no pronounced signature of a stiffness transition is seen in the variation with composition of VT, fluctuations are seen in the switching voltages around x = 6, the composition corresponding to the sharp thermally revering window. PDS studies indicate that the thermal diffusivities () of As45Te55-xIx chalcohalide exhibit a sharp minimum at the composition x = 6. This result reasserts the presence of a sharp thermally reversing window in As45Te55-xIx glasses around the composition x = 6. Chapter 5: The significant results obtained in the present thesis work have been summarized in this chapter. Further, the scope for future work is also presented.

Trapping centres in as-grown TlInS2 layered single crystals have been studied by using a thermally stimulated current (TSC) technique. TSC measurements have been performed in the temperature range of 10-300 K with various heating rates. Experimental evidence has been found for the presence of five trapping centres with activation energies 12, 14, 400, 570 and 650 meV. Their capture cross-sections and concentrations were also determined. It is concluded that in these centres retrapping is negligible as confirmed by the good agreement between the experimental results and the theoretical predictions of the model that assumes slow retrapping. An exponential distribution of traps was revealed from the analysis of the TSC data obtained at different light excitation temperatures. The transmission and reflection spectra of TlInS2 crystals were measured over the spectral region of 400-1100 nm to determine the absorption coefficient and refractive index. The analysis of the room temperature absorption data revealed the coexistence of the indirect and direct transitions. The absorption edge was observed to shift toward the lower energy values as temperature increases from 10 to 300 K. The oscillator and the dispersion energies, and the zero-frequency refractive index were also reported. Furthermore, the chemical composition of TlInS2 crystals was determined from energy dispersive spectroscopic analysis. The parameters of monoclinic unit cell were found by studying the x-ray powder diffraction.

A challenging application space exists for high-aspect-ratio, high-fidelity dielectrics in micro-electro-mechanical system (MEMS), microelectronic, and photonic applications. Photosensitive polymers are widely used in these fields because they are relatively easy to process and pattern, and have good mechanical properties. Photosensitive polynorbornene (PNB)-based dielectrics have been shown to have high sensitivity, excellent photodefinition properties, and high mechanical strength making them suitable for MEMS, microelectronic packaging, and photonic applications. PNB-based dielectrics can be functionalized with epoxide, carboxylic acid, or fluorinated alcohol groups. Epoxy or carboxylic acid groups can be used to provide cross-linkable sites, resulting in improved chemical and thermal properties while fluorinated alcohol groups can provide solubility in aqueous base. The focus of this study has been on the epoxy-based cross-linking of ultraviolet and electron beam (e-beam) sensitive negative-tone PNB-based dielectrics. The impact of multifunctional epoxy-based additives on the cross-linking, photolithographic properties, and adhesion properties of the photosensitive PNB dielectric was investigated. High aspect ratio features of 13:1 (height:width) were produced in 40 µm thick films (a single coat) with straight side-wall profiles and high fidelity. Contrast values as high as 33.4 were obtained at doses below 15 mJ/cm2. To evaluate the polymer's suitability to MEMS and microelectronics applications, epoxy cross-linking reactions were studied as a function of processing condition through Fourier transform infrared spectroscopy (FTIR), nanoindentation, swelling and dielectric measurements. The fully cross-linked films had an elastic modulus of 2.9 GPa and hardness of 0.18 GPa which can improve the mechanical compliance of the packaging device. To explore the feasibility of the PNB dielectric as a highly sensitive e-beam resist for nano scale fabrication, the e-beam initiated reaction between PNB cross-linking sites and the multifunctional epoxy cross-linkers was investigated. In this study, the interaction of an e-beam with the PNB mixture and its compounds was investigated. The contrast, photodefinability, and e-beam activation of the components in the PNB formulations were studied. The PNB polymer had very high e-beam sensitivity and contrast. It was shown that the addition of a photoacid generator (PAG) to the polymer-epoxy mixture enhanced the contrast and sensitivity. Formulations with the additional cross-linker showed improved contrast, sensitivity, and substrate adhesion. 100 nm structures with 13.5 nm line edge roughness (LER) were fabricated. The influence of the developing time, the developer concentration, PEB, and film thickness on the contrast and sensitivity were studied. Structures with contrast values as high as approximately 8 were fabricated at doses as low as 0.38 µC/cm2. The acid-catalyzed epoxy ring opening reaction of the PNB dielectric was studied using FTIR spectroscopy. The photo and thermal acid generation initiated epoxy ring opening reactions and subsequent cross-linking of polymer. Additionally, polymer properties were characterized as a function of processing conditions for this polymer system. It was shown that thermal cure conditions have a substantial impact on the mechanical and electrical properties of the polymer. The rate and ultimate conversion of the epoxy ring opening reaction increased with increasing cure temperature, resulting in a higher degree of cross-linking at cure temperatures above 140°C. Degradation reactions occurred at temperatures above 160°C, indicating loss of epoxide cross-linking groups and linkages. These hypotheses were supported by electrical and mechanical property studies. It was shown that curing the PNB polymer at 160°C for 1 h after develop resulted in full epoxy ring opening and highest cross-link density. This sample showed lower dielectric constant (3.9), residual stress (20 MPa), and solvent swelling (3.1%). Variable frequency microwave (VFM) processing of the PNB dielectric was studied to investigate the rapid curing of the polymer at lower temperatures. The FTIR results showed that the microwave reaction rates were higher at each isothermal cure temperature compared to convective heating, indicating that the rapid VFM curing of PNB at low temperatures is feasible. The PNB film was fully cross-linked after 15 min VFM cure at the low temperature of 150˚C. The shortest time to fully cure the polymer was found to be 5 min at 160°C. Also, the feasibility of rapid VFM curing of PNB in air was studied. All samples VFM-cured (140˚C-180˚C) in air showed no signs of oxidation. The electrical and mechanical properties of VFM-cured films were characterized and compared with thermally cured films to determine the effectiveness of the VFM processing. VFM-cured samples showed higher degree of cross-linking than thermally-cured samples, which was congruent with the FTIR results. Improved or equivalent properties were obtained for VFM-cured samples at shorter cure cycles and lower cure temperatures compared to thermally-cured films. The PNB dielectric was also used as an overcoat material to make micro and nano fluidic channels. In this work, incorporation of advanced micro/nano fluidics with high-sensitivity photonic sensors was demonstrated. 500 nm to 50 µm channels were fabricated by thermal decomposition of epoxy-based PNB polymers. Microdisks with quality factors of over 106 were presented in complementary metal-xide-semiconductor (CMOS) compatible SiN on oxide technology. These ultra-high quality factor SiN resonators were demonstrated in the visible range for the first time. The fluidic structures were interfaced with photonics for index and florescence sensing. This study was a collaboration with Dr. Ehsan Shahhosseini from the Photonics Group at Georgia Tech.

The field of hybrid electronics of molecules and traditional semiconductors is deemed to be a realistic route towards possible use of molecular electronics. Such hybrid electronics finds its potential technological applications in nuclear detectors, near-infrared detectors, organic thin film transistors and gas sensors. Specifically Metal / organic / n-Silicon structures in this regard are mostly reported to have two regimes of charge transport at lower and higher applied voltages in such two terminal devices. The fact is mostly attributed to the change in conduction mechanism while moving from lower to higher applied voltages. These reports describe interactions between the semiconductors and molecules in terms of both transport and electrostatics but finding the exact potential distribution between the two components still require numerical calculations. The challenge in this regard is to give the exact relations and the transport models, towards practical quantification of charge transport properties of metal / organic / inorganic semiconductor devices. Some of the most exiting questions in this regard are; whether the existing models are sufficient to describe the device performances of the hybrid devices or some new models are needed? What type of charge carriers are responsible for conduction at lower and higher applied voltages? What is the source of such charge carriers in the sandwiched organic layer between the metal and inorganic semiconductors? How the transition applied voltage for the change in conduction mechanism is determined? What is the role of dopants in the organic layer semiconductors? What are the possible explanations for observed temperature effects in such devices? In present work the charge transport properties of metal / metal-phthalocyanine / n-Si structures with low (ND = 4×1014 cm-3), medium (ND = 1×1016 cm-3) and high (ND = 2×1019 cm-3) doped n-Si as injecting electrode and the effect of air exposure of the vacuum evaporated metal-phthalocyanine film in these structures is investigated. The results obtained through temperature dependent electrical characterizations of the structures suggest that in terms of dominant conduction mechanism in these devices Schottky-type conduction mechanism dominates the charge transport in low-bias region of these devices up to 0.8 V, 0.302 V and 0.15 V in case of low, medium and high doped n-Silicon devices. For higher voltages, in each case of devices, the space-charge-limited conduction, controlled by exponential trap distribution, is found to dominate the charge transport properties of the devices. The interface density of states at the CuPc / n-Si interface of the devices are found to be lower in case of lower work function difference at the CuPc / n-Si interface of the devices. The results also suggest that the work function difference at the CuPc / n-Si interface of these devices causes charge transfer at the interface and these phenomena results in formation of interface dipole. The width of the Schottky depletion region at the CuPc / n-Si interface of these devices is found to be higher with higher work function difference at the interface. The investigation of charge transport properties of Al / ZnPc / medium n-Si and Au / ZnPc / medium n-Si devices suggest that the Schottky depletion region formed at the ZnPc / n-Si interface of these devices determines the charge transport in the low-bias region of both the devices. Therefore, the Schottky-type (injection limited) and the space-charge-limited (bulk limited) conduction are observed in the low and the high bias regions of these devices, respectively. The determined width of the Schottky depletion region at the ZnPc / n-Si interface of these devices is found to be similar for both the devices, therefore, the higher work function difference at the metal / ZnPc interface of the devices has no influence on the Schottky depletion region formed at the ZnPc / n-Si interface of the devices. The similar diode ideality factor, barrier height and the width of the Schottky depletion region, determined for both of these devices, demonstrates that these device characteristics originate from ZnPc / n-Si interface of these devices. Therefore, the work function difference at the metal / ZnPc interface of these devices has no noticeable influence on the device properties originating from ZnPc / n-Si interface in these devices. The investigation of charge transport properties of Al / CuPc / low n-Si devices with and without air exposure of the CuPc film, before depositing metal contact demonstrate that Schottky-type conduction mechanism dominates the charge transport in these devices up to bias of 0.45 V in case devices with the air exposure, and up to 0.8 V in case devices without the air exposure. This decrease in the threshold voltage, for the change in conduction mechanism in the devices, is attributed to wider Schottky depletion width determined at the CuPc / n-Si interface of the devices without the air exposure of CuPc film. For higher voltage the space-charge-limited conduction controlled by exponential trap distribution, is found to dominate the charge transport properties of the devices without the air exposure of CuPc, and in case of devices with the air exposure of CuPc film, the SCLC is controlled by single dominating trap level probably introduced by oxygen impurities.

The thesis relates to synthesis and investigation of nanostructured polymer composites based on oligomers of cyanate esters of bisphenol a (DCBA) or cyclic butylene terephthalate (CBT) and multiwalled carbon nanotubes (MWCNTS). Catalytic effect of mwcnts in process of DCBA polycyclotrimerization as well as in cbt polymerization has been observed. Significant increase in crystallization temperature of nanocomposites based on polybutylene terephthalate (cPBT) with adding of MWCNTS is observed. The effect of processing method of cpbt/mwcnts nanocomposites on its electrical properties has been found. It has been established that the additional heating of the samples (annealing) at temperatures above melting of cPBT leads to reagglomeration of MWCNTS in the system. It is established that reagglomeration of MWCNTS results in increase of conductivity values of nanocomposites due to formation of percolation pathways of MWCNTS through polymer matrix. In the case of polycyanurate matrix (PCN), it is found that addition of small mwcnts contents (0.03-0.06 weight percents) provides increasing tensile strength by 62-94 percents. It has been found that addition of even 0.01 weight percents of MWCNTS provides significant increase in storage modulus of cPBT matrix. This is explained by effective dispersing of small amount of the nanofiller during in situ synthesis of pcn or cpbt matrix that is confirmed by microscopy techniques. It has been established that the properties of the nanocomposites based on heterocyclic esters and MWCNTS can be varied from isolator to conductor and has low percolation thresholds (0.22 and 0.38 weight percents for cPBT and PCN nanocomposites respectively). The conductivity of samples is particularly stable on a very large range of temperature from 300 to 10 degrees Kelvin that make these materials perspective for practical applications in microelectronics, as parts of aircraft and space constructions.

Thesis (Ph.D.); Submitted to Iowa State Univ., Ames, IA (US); 19 Dec 2004. / Published through the Information Bridge: DOE Scientific and Technical Information. "IS-T 2692" Satoshi Matsuzaki. US Department of Energy 12/19/2004. Report is also available in paper and microfiche from NTIS.

Orientador: Darcy Hiroe Fujii Kanda / Banca: Luiz Francisco Malmonge / Banca: Dante Luis Chinaglia / Resumo: Compósitos poliméricos condutores, também chamados de polímeros condutores extrínsecos, têm sido alvo de intensa pesquisa científica devido ao seu grande potencial de aplicação nos mais diversificados setores industriais. Esses materiais combinam as características de um polímero (leveza, flexibilidade, fácil processamento) com as de cargas condutoras (alta condutividade). O poliuretano derivado de óleo de mamona (PUR) é um polímero obtido pela mistura de pré-polímero e poliol (derivado de óleo de mamona) que apresenta grande potencial para ser utilizado como matriz polimérica em compósitos. Ele possui propriedades equivalentes aos dos poliuretanos (PU) convencionais e tem como vantagem ser um polímero biodegradável e proveniente de fonte renovável. Em relação às cargas condutoras, o negro de fumo (NF) é um dos materiais mais utilizados para esse fim, enquanto que pouco se encontra na literatura sobre o carvão ativado nano em pó (CANP), mesmo possuindo estrutura semelhante e maior condutividade que o NF. Neste contexto, o presente trabalho tem como objetivo viabilizar os processos de síntese e fazer a caracterização elétrica dos compósitos poliuretano derivado de óleo de mamona/carvão ativado nano em pó (PUR/CANP) e poliuretano derivado de óleo de mamona/negro de fumo (PUR/NF) na forma de filmes pelo método "casting", mantendo fixa a razão pré-polímero/poliol e variando a fração de volume de CANP e NF. A análise térmica foi feita por Calorimetria Diferencial de Varredura (DSC), o estudo da condutividade dc e ac foram feitas pelo Método de Duas Pontas (tensão x corrente) (MDP) e pela técnica de Espectroscopia de Impedância Elétrica (EIE), respectivamente, e a análise morfológica foi feita em Microscópio Eletrônico de Varredura com canhão de elétrons por... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Conductive polymer composites, also called extrinsic conducting polymers, has been the subject of intense scientific research due to its great potential for industrial application. These materials combine the characteristics of a polymer (lightness, flexibility, easy processing) with the conductive fillers (high conductivity). The castor oil based polyurethane (PUR) is a polymer obtained from pre-polymer and polyol (based castor oil) mixing which has great potential to be used as matrix polymer in composites. It has properties equivalent to those of conventional polyurethane (PU) and has the advantage of being a biodegradable polymer and from a renewable source. In relation to conductive fillers, carbon black (CB) is one of the most widely used materials for this purpose, while in the literature there are few data about activated carbon nanopowder (ACNP), despite having similar structure and that the higher conductivity than CB. In this context, this work aims to provide the synthesis processes and electrically characterize of composite castor oil based polyurethane/activated carbon nanopowder (PUR/ACNP) and castor oil based polyurethane/carbon black (PUR/CB) in the form of films by casting, keeping the ratio pré-polímero/poliol fixed and varying the volume fraction ACNP and CB. The sample were characterized using Differential Scanning Calorimetry (DSC), Two Points Method (voltage x current) (TPM), Electrical Impedance Spectroscopy (EIS) and Scanning Electron Microscope with electron gun for field emission (FEG-SEM). DSC results showed that the glass transition temperature (Tg) of composites do not depend of type or volume fraction of conductive fillers. The results of electrical analysis showed that the samples of PUR/CB have lower percolation threshold than those of PUR/ACNP (20% vs. 40%). This result is due the distribution... (Summary complete electronic access click below) / Mestre

Orientador: Jorge Luis Akasaki / Resumo: Com a vigente expansão dos canaviais brasileiros, um estudo direcionado para os resíduos provenientes da cana-de-açúcar torna-se imprescindível no cenário atual. Neste sentido, pesquisas estão sendo desenvolvidas para a utilização de cinza do bagaço da cana-de-açúcar (CBC) em compósitos cimentícios, sendo que esta cinza é obtida a partir da queima do bagaço que é utilizado como combustível em processos de cogeração de energia. A CBC é predominantemente constituída de dióxido de silício, e esta característica tem conduzido à avaliação da potencialidade pozolânica do material, principalmente em substituição ao cimento Portland. Nos últimos anos, tem havido um crescente interesse em se determinar o que é conhecido como Fator k de Eficácia Cimentante, que corresponde a um número que caracteriza o material pozolânico e determina a equivalência entre este e o cimento, do ponto de vista das características aglomerantes, e o seu consequente resultado no desenvolvimento das resistências mecânicas. O coeficiente de eficácia não é único para cada tipo de material, isto é, depende de algumas variáveis como por exemplo a relação água/cimento, proporção entre cimento e pozolana, idade de cura, entre outros parâmetros. Sendo assim, o objetivo principal deste trabalho é determinar o fator de eficácia cimentante da cinza do bagaço de cana-de-açúcar, em termos de resistência mecânica à compressão de microconcretos e concretos. O estudo do fator k se deu a partir da substituição de cimento Port... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: A specific study related to the reusing of wastes from sugarcane industry is essential nowadays, mainly due to the increasing on the brazilian sugar cane plantations. On this way, several studies have been performed using sugarcane bagasse ash (SCBA) in cementitious composites, where the SCBA was obtained from the energy cogeneration process. Due to the chemical composition of SCBA, mainly silicon, studies related to its use as pozzolanic material in Portland cement binder have been reported. In the last years, the knowledge about factor k, that corresponds to a number characterize a pozzolanic material and determines its equivalence with Portland cement (OPC) from mechanical strength point of view, is increasing. Factor k depends on some variables used in mortars or concretes mixtures such as water/OPC ratio, proportion between OPC and pozzolanic material, curing time, among other parameters. The aim of this work is to assess the factor k of SCBA from mechanical point of view micro-concretes and concretes. The assessment of factor k was performed replacing OPC by SCBA and adding SCBA to the control mixture (without SCBA) for a fixed water/OPC ratio. Phisico-chemical characterization of SCBA and its reactivity on calcium hydroxide/SCBA and OPC/SCBA were assessed on pastes. Conductivity/resistivity and electrical impedance measurements were performed on mortar samples. Pozzolanic reactivity of SCBA could be detected by modifications on the conductivity/resistivity and electric... (Complete abstract click electronic access below) / Doutor

Les élastomères diélectriques sont de plus en plus utilisés pour la réalisation des transducteurs dans de nombreux domaines industriels : interface haptique, robotique, biomimétisme, conversion d’énergie. Pour le fonctionnement de toutes ces applications, le polymère électroactif est soumis à une haute tension (de 1 à 10kV). Toutefois, le courant de fuite diminue l’efficacité et la durée de vie des dispositifs utilisant ces matériaux.Par ailleurs, une précontrainte mécanique (étirement) est généralement appliquée au polymère pour accroître l’efficacité énergétique dans la conversion mécanique-électrique. Les courants de fuite (et donc le champ de claquage du polymère) seront ainsi conditionnés par cette précontrainte et ce point doit faire l’objet d’une étude détaillée.L’objet de ce travail de thèse est de mener des analyses de courant de fuite sur des polymères électroactifs (élastomères polyacrylates du commerce VHB4910 et silicones Sylgard 186) non contraints et contraints mécaniquement pour évaluer l’amélioration ou la dégradation des performances électriques lorsqu’ils seront plus tard intégrés en géométrie électrode-polymère-électrode dans des transducteurs.Tout d’abord, nous avons mené une étude exhaustive sur l’influence des facteurs externes (étirement, température, champ électrique, nature de l’électrode) sur les propriétés électriques du polyacrylate VHB4910. Les études ont été réalisés sur des durées de polarisation courtes (quelques minutes) et longues (jusqu’à 15 heures). Au cours de ce travail, nous sommes également intéressés à l’étude du phénomène d’autocicatrisation sur le sylgard 186. Les tests ont été conduits pour différents types d’électrodes (or, aluminium, graphène, nanoplaquettes de graphène : GnP) déposées sur la surface de silicone. Une analyse par microscopie optique de la zone évaporée a été menée.La finalité de ces travaux aura permis d’optimiser des structures de récupération d’énergie électrostatique à base de polymères électroactifs. / Electroactive polymers known as dielectric elastomers have shown considerable promise for transducers. They are attractive for a wide range of innovative applications including softs robots, adaptive optics, haptic interface or biomedical actuation thanks to their high energy density and good efficiency. For the functioning of all these application, the electroactive polymer is subjected to high electrical field. Nevertheless, the performances of these transducers are affected by the losses and especially the ones induced by the leakage current.Mechanical pre-stretch is an effective method to improve actuation when a voltage is applied to the device made up of a dielectric elastomer sandwiched between two compliant electrodes. The overall performances of the structure (electromechanical conversion, efficiency, strain induced…) depend strongly on the electric and mechanical properties of the elastomer. Regarding electric characteristics, dielectric permittivity, dissipation factor and electric breakdown field have been deeply investigated according to various parameters such as frequency, temperature, pre-stretch, or nature of the electrodes but complete analysis of the leakage current is missing in the scientific literature.Thus, this work reports an extensive investigation on the stability of the current-time characteristics in dielectric elastomer. Particularly, we focus on the influence of the nature of the electrodes and pre-stress applied to the transducer. In order to evaluate the influence of the time duration on the behavior of the leakage current, short and long-term electrical stress times was applied during short times and up to 15 hours.Leakage current in electroactive polymers were discussed for a commercial polyacrylate (VHB4910 from 3M) currently used for soft transducers applications. This current is investigated as a function of external factors (stretching, temperature, type of material for electrodes)In order to evaluate the limitations in term of voltage and in the goal to increase the lifetime of these transducers, the second part of our study is focused on the dielectric strength of silicone rubbers for various types of electrodes (gold, Aluminum, graphene nanoplatelets, graphene : GnP). The effect of self-healing is particularly studied and a selection of electrodes for soft transducers based on dielectric elastomers is proposed.