Silicone rubber insulators have been replacing conventional insulators made from toughened glass and porcelain in the power system, due to the non-wetting properties of silicone rubber insulation housing. However, silicone elastomers will eventually wet-out leading to leakage current and dry-band arcing giving rise to erosion of the silicone housing material, and eventually insulation failure. Well-established formulations of insulation housing composites have been developed and validated for erosion performance using the standard inclined plane tracking and erosion test, yet no such formulations have been developed and validated for DC. With the assumption that equivalent performance will be obtained, an adjustment to the creepage distance has been the measure taken in using the AC insulators for DC, without taking into consideration the differing aspects of the DC as compared to the AC dry-band arcing. This practice questions the existing DC insulators as an unknown entity that requires further investigation to ensure the reliability of the power supply. In addition recent demands have been raised to develop housing composites specifically for DC outdoor insulation, particularly with the increased interest in DC. It follows that developing a standard DC inclined plane tracking and erosion test is necessary for the development of more suitable materials for outdoor DC insulation applications. This thesis provides a thorough study of the DC dry-band arcing mechanism as opposed to the well understood mechanism of the AC dry-band arcing and provides a mechanistic understanding to the dry-band arcing leading to erosion as a foundation for the development of a standard DC inclined plane tracking and erosion test. To this end, the influence of inorganic fillers in silicone rubber on resisting erosion due to dry-band arcing is also presented, as an essential step towards obtaining more suitable silicone composite for DC outdoor insulation applications.

Tesis por compendio / "Development of polylactic acid (PLA)-derived formulations by plasticization and additives from renewable resources" The main objective of this doctoral thesis is the study, development and characterization of biodegradable or biocompatible materials from poly(lactic acid) (PLA) with improved properties for uses in several sectors such as food packaging, medical sector, etc. In order to modify the ductility and the stiffness of PLA, with the subsequent effects on its potential uses in different sectors, different fillers and/or additives were incorporated to PLA formulations by extrusion. Several plasticizers derived from vegetable oils and fatty acids were used; particularly, an epoxidized plasticizer derived from stearic acid (octyl epoxy stearate - OES) and a maleinized linseed oil - MLO were used. Another strategy that has been used in this research has focused on the development of binary blends with other polymers with increased ductility such as polycaprolactone (PCL) and thermoplastic starch (TPS). Finally, incorporation of several biocompatible/resorbable fillers derived from calcium orthophosphate (Ca3(PO4)2) such as ß-tricalcium phosphate (ß-TCP) and hydroxyapatite (HA), was carried out to widen the potential of these PLA-based materials in medical applications. / "Desarrollo de formulaciones derivadas de ácido poliláctico (PLA), mediante plastificación e incorporación de aditivos de origen natural" El objetivo principal de esta tesis doctoral es el estudio, desarrollo y caracterización de materiales biodegradables o biocompatibles de ácido poliláctico (PLA) con propiedades mejoradas para su aplicación en diversos sectores como el envasado de alimentos, sector médico, etc. Para modificar la ductilidad o rigidez del PLA y con ello su aptitud en los distintos campos, se lleva a cabo un estudio de la incorporación de diferentes cargas o aditivos, mediante mezclado por extrusión. Se han utilizado plastificantes derivados de aceites vegetales y ácidos grasos; en particular, un plastificante epoxidado derivado del ácido esteárico (epoxi estearato de octilo - OES) y un derivado maleinizado de aceite de linaza - MLO. Otra de las estrategias que se han abordado se ha centrado en el desarrollo de mezclas binarias con otros biopolímeros con mayor ductilidad como la policaprolactona (PCL) y el almidón termoplástico (TPS). Finalmente, se ha llevado a cabo la incorporación de cargas biocompatibles tipo ortofosfato cálcico (Ca3(PO4)2) como el ß-fosfato tricálcico (ß-TCP) y la hidroxiapatita (HA) para ampliar el potencial de estos materiales basados en PLA en el sector médico. / "Desenvolupament de formulacions derivades d'àcid polilàctic (PLA), mitjançant plastificació i incorporació d'additius d'origen natural" L'objectiu principal d'aquesta tesi doctoral és l'estudi, desenvolupament i caracterització de materials biodegradables i biocompatibles d'àcid polilàctic (PLA) amb propietats millorades per a la seua aplicació en diversos sectors com ara l'envasat d'aliments, sector mèdic, etc. Per tal de modificar la ductilitat o rigidesa del PLA, i amb això, la seua aptitud en els esmentats camps, s'ha fet un estudi de la incorporació de diferents càrregues o additius, mitjançant mesclat per extrusió. S'han utilitzat plastificants derivats d'olis vegetals i àcids grassos; en particular, un plastificant epoxidat derivat de l'àcid esteàric (epoxi estearat d'octil - OES) i un derivat maleinitzat d'oli llinós - MLO. Una altra estratègia que s'ha seguit s'ha centrat en el desenvolupament de mescles binàries amb altres polímers amb major ductilitat com ara la policaprolactona (PCL) i el midó termoplàstic (TPS). Finalment, s'ha dut a terme la incorporació de càrregues biocompatibles de tipus ortofosfat càlcic (Ca3(PO4)2) com ara el ß-fosfat tricàlcic (ß-TCP) i la hidroxiapatita (HA) per tal d'ampliar el potencial d'aquests materials basats en PLA al sector mèdic. / Ferri Azor, JM. (2017). Desarrollo de formulaciones derivadas de ácido poliláctico (PLA), mediante plastificación e incorporación de aditivos de origen natural [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/86166 / Premios Extraordinarios de tesis doctorales / Compendio

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L'objectif de ce projet de recherche est la mise au point et l'utilisation de charges inorganiques barrière aux rayonnements infrarouge pour la préparation de matériaux d'enduction à base de plastisols PVC. Dans un premier temps, cette étude a été consacrée à la caractérisation rhéologique, morphologique et optique de la matrice PVC et à l'élaboration de nouvelles formulations, en incorporant dans le plastisol des charges commerciales de natures chimiques différentes (nacre, billes de verre, alumine, oxyde de Zinc, TiO2 …). Ensuite, des mesures radiatives sur des films de plastisols chargés à différents taux massiques ont été réalisées dans le but de sélectionner les charges présentant les meilleures performances optiques. Enfin, les formulations optimales ont été enduites sur un textile polyester et la stabilité des revêtements soumis à des rayonnements UV a été suivie par plusieurs techniques analytiques. Diverses caractérisations mécaniques, esthétiques et morphologiques sont venues compléter cette étude. Dans un second temps, un modèle de transfert radiatif permettant de simuler la propagation du rayonnement dans les systèmes de protection développés a été testé / This project aims to develop new filled PVC plastisol composite offering enhanced optical properties. Different types of inorganic fillers were tested and added to the PVC matrix. Rheological, morphological and optical characterization of the PVC matrix and development of new formulations by incorporation of different fillers (nacre, glass beads, alumina, zinc oxide, TiO2 ...) were the subject of the first phase of the project. Then, radiative measurements on plastisol films loaded at different mass ratios were performed in order to select the fillers having the best optical performance. The second phase was dedicated to the validation and the testing of the optimal formulations coated on polyester textile substrate. Different analytic technics were used in order to rank the UV stabilization as a function of the tested formulations. In addition, mechanical, aesthetic and morphological characterizations were used to complete this study. Finally, radiative transfer model was developed to simulate the radiative behavior of the different formulations

La thèse détermine les principaux paramètres de la formation des structures de la phase conductrice de nanocomposites polymères chargés avec des nanotubes de carbone (NTC) ou des nanocharges combinées, pour étudier l'influence de la morphologie de la structure hétérogène du composite et l'interaction des nanocharges sur les propriétés électriques, thermophysiques et mécaniques des composites. Les trois types de systèmes polymères ont été étudiés, à savoir: 1) les systèmes ségrégés avec distribution ordonnée de nanocharges, 2) les mélanges polymère conducteur; 3) les composites avec des charges binaires où les nanotubes de carbone ont été combinés avec des composés organo-argileux modifiés (MOC) dans un cas et des nanoparticules métalliques d’autre part. Les résultats sur les composites polymères ségrégés chargés avec des NTC ont montré que dans de tels systèmes, la charge conductrice crée un réseau continu conducteur au sein de la matrice polymère. Cela conduit à un seuil de percolation ultra faible avec la valeur de φc~0,045vol.%. Il a été démontré que les systèmes conducteurs à base de mélanges de polymères ont un seuil de percolation inférieur en raison d'effet de double percolation. Il a été constaté que l'introduction simultanée de composés MOC et de NTC dans la matrice thermoplastique permet une meilleure répartition des nanotubes de carbone, ce qui empêche leur agrégation. Il en résulte une diminution du seuil de percolation des composites. Il a été démontré que la formation de la phase conductrice est plus efficace avec des charges mixtes CNT/nanométal en comparaison avec les charges individuelles / The thesis research field determines the main parameters, of the conductive phase structure formation in polymer nanocomposites filled with conductive fillers such as carbon nanotubes (CNTs) or combined nanofillers. The influence of the morphology of the heterogeneous structure of the composite and interaction of nanofillers on the electrical, thermophysical and mechanical properties of the composites was studied. The three types of polymer systems filled with carbon nanotubes have been investigated, namely: 1) segregated systems with ordered distribution of the nanofiller; 2) conductive polymer blends; 3) composites with binary fillers in which carbon nanotubes have been combined with organo-modified clay (OMC) in one case and with metal nanoparticles in another case. The investigation of the segregated polymer composites filled with CNTs has shown that the conducting filler creates continuous conductive framework inside the polymer matrix. This provides the presence of ultralow percolation threshold with the value of φc~0.045vol.%. Conductive polymer blends have demonstrated a lower percolation threshold in comparison with individually filled polymers due to a double percolation effect. It has been found that the simultaneous introduction of OMC and CNTs into thermoplastic matrix provides a better distribution of carbon nanotubes, preventing their aggregation and decreasing the percolation threshold. It has been shown that the formation of the conducting phase is more effective in the polymeric matrix with combined nanofillers CNT/nanometal in comparison with individual fillers and the higher conductivity of such conductive system is due to metallic filler content