Dissertationen zum Thema „Interfacial degradation“

The aim of the research was to develop predictive models for the interfacial degradation of adhesively bonded joints when exposed to aggressive environmental conditions. Four different joint configurations using the same adhesive system were exposed to a variety of conditions including immersion at 50°C, 96%RH at 50°C and 80%RH at 70°C. In addition data from joints for other adhesive systems were also incorporated into the investigation. Moisture has a degrading effect on the strength of adhesively bonded joints. Therefore the diffusion into the bulk material was determined by gravimetric experiments. However, the mobility of the water molecules at the interface between the adhesive and the substrate may be higher than in the bulk material. In order to assess this, the spatial moisture distribution in bonded epoxy laminates was detennined by a nuclear reaction analysis (NRA) technique. The moisture profile found experimentally and the modelling undertaken of the interfacial diffusion indicated that the ingress in the interfacial region was a few times faster than in the bulk material for the adhesive system investigated. Both hygroscopic (swelling) and thermal residual strains may affect joint durability. The thermal expansion was determined by means of a bi-material beam and the hygroscopic expansion was determined by measuring the expansion of bulk samples at various moisture levels. Creep properties for the adhesives studied were determined to investigate the relaxation of residual stresses during the aging process. The coefficients of thermal expansion and hygroscopic expansion were of the same order of magnitude for the adhesives investigated. Creep was seen to be enhanced in the presence of moisture. The AVl19 adhesive was seen to creep much more than FM73 and also absorbed more moisture. As a consequence, the residual stresses in the joints bonded with A Vl19 were seen to relax nearly totally whilst the residual stresses in the joints bonded with FM73 relaxed to about half of their original magnitude. Different interfacial fracture tests were carried out in order to assess which was most appropriate. Notched coating adhesion tests (NCA) were carried out initially. However, it was very difficult to produce a repeatable notch and the adhesive often cracked before the coating debonded. Good results were obtained then these samples were immersed in water. Another test investigated was a split beam specimen. However this test was of limited use as the secondary bond was weaker than the aged interface of interest. Finally, a mixed mode flexure specimen (MMF) was selected to determine the fracture energy of the adhesive systems in the 80%RH and 96%RH environments. The fracture energy degraded rapidly initially with moisture content and then at a slower rate as more moisture reached the interface. The fracture energy was found to be a function of the amount of moisture at the interface. No further degradation was found when the joints were held at equilibrium. The degradation and the progressive damage were simulated with a cohesive zone model (CZM). The model was extended from 2D to 3D. This was ~eful when predicting where 2 the crack initiated in the width direction and how the initiation site changed after aging for a L-joint configuration. When using a CZM the interfacial strength was defmed by a traction-separation law. The parameters governing the traction-separation law were determined using the interfacial fracture tests (NCA and MMF). The parameters were the tripping traction and the fracture energy. It was shown to be essential to incorporate elasto-plastic adhesive continuum behaviour in order to simulate the complete joint response correctly. The tripping traction was determined by correlating the deviation of the load-displacement curve with the simulated result. The fracture energy was then determined by correlating the experimental load-crack length response with the simulation. This gave a unique set of moisture dependent CZM parameters for various moisture concentrations. These parameters were then used to predict the response of other joint configurations. For most of the joints, the residual strength was predicted closely using the moisture dependent CZM parameters. However, in some cases other degradation mechanisms were active. These included stress enhanced degradation and cathodic delamination. When these mechanisms were included in the modelling, the prediction of the durability of all joint configurations was good.

High-voltage (HV) outdoor composite insulators used in transmission lines are made of two polymers, comprising the core and housing, bonded together with metallic end-connections. The interface between these polymers is parallel to the electric field, which makes the insulators more prone to interfacial problems at these common points [1]. If interfacial ageing occurs, degradation and catastrophic breakdown can result [2]. Therefore, the design reliability of outdoor composite insulators depends on the high-strength bond between the core and the housing [3],[4]. Research findings by Kutil and Froshlic [5] indicate that delaminated areas, cavities and/or micro cracks in the medium are enough to initiate streamer discharges along the interface that are capable of degrading both insulating materials. The heat, UV radiation, and high-energy electrons produced from such discharge activity resulted in the growth of carbon paths along the interface, known as ‘tracking’, ultimately causing failure [6]. This investigation focuses on the development of tracking between silicone rubber and epoxy resin, with a view to replicating the tracking phenomena seen within composite insulators in service. A fine wire is placed between the dielectrics materials to enhance the local electric field magnitude and initiate discharge processes. The resulting partial discharge (PD) activity has been monitored. This Information has been used to understand the inception and propagation of the interfacial tracking. A strong relationship was found between maximum PD magnitude and track length. PD patterns and unique detailed images of the interfacial tracking development, allowed identification of the growth characteristics of interfacial channels and phases of tracking growth. Furthermore, a correlation in the mechanisms of interfacial degradation was found between the lab-fabricated samples and commercial composite rods. Finally, a growth model of interfacial ageing has been developed with the information from FEA models, PD patterns and the detailed images of tracking growth. The physical structure and chemical analysis of interfacial tracking is also disclosed to provide an insight into interfacial ageing mechanisms that occur in the composite insulators under electrical stress.

Les durées de vie des cellules solaires photovoltaïques organiques (OPV) doivent être améliorées afin que cette technologie puisse être commercialisée sur une grande échelle. Ce travail étudie l’influence de la sélection des matériaux pour l’interface supérieure sur la dégradation des OPV inversées. La première partie de cette étude s’occupe des effets de la dégradation thermale. Il a été constaté que la tension de circuit-ouvert (VOC) et le facteur de forme (FF) diminuent lors du vieillissement des OPVs ayant une HTL de MoO3 et une électrode d’argent. Des expériences de caractérisation physique ont mis en évidence que les électrodes d’argent démouillent lors du vieillissement thermique ce qui peut conduire à la mort rapide des cellules avec des électrodes minces. Des analyses de rupture ont également faites. Il a été constaté que l’adhésion d’interface supérieure augmente fortement dans les échantillons avec électrode en argent due à la diffusion de matière, et il est possible qu’il y ait une relation entre cette diffusion et la perte de VOC et FF. Dans la deuxième partie, les effets de la lumière sur la dégradation et l’influence de la présence d’oxygène ou d’humidité ont été étudiés. Quelques effets des matériaux ont été notés, en particulier sur la durée de vie. L’oxygène a eu l’effet d’accélérer notablement la dégradation, et aucune différence n’a été notée selon les matériaux utilisés. En revanche, l’humidité a eu un effet prononcé sur les échantillons avec certains HTLs. Ce travail souligne l’importance de penser à la durée de vie quand on désigne les dispositifs OPV, en particulier pour sélectionner des matériaux appropriés afin d’optimiser la durée de vie
Organic photovoltaic (OPV) solar cells show great promise but suffer from short operating lifetimes. This study examines the role that the selection of materials for the hole extraction interface in inverted OPV devices plays in determining the lifetime of a device. In the first part of the study, the effects of thermal degradation were examined. It was found that devices containing MoO3 HTLs and silver top electrodes exhibit an open-circuit voltage (VOC)/fill factor (FF)-driven mechanism. Physical characterisation experiments showed that, with heating, the silver electrode undergoes de-wetting. With thin electrodes this can result in the catastrophic failure of the device. A fracture analysis study found that silver-containing devices experience an increase in adhesion of their top layers to the active layer due to interdiffusion between the layers. This interdiffusion may be related to the loss of VOC and FF in Ag/MoO3 devices through diffused species forming charge traps in the active layer. In the second part of the study, the effects of photodegradation in different atmospheres were studied. Some material-dependent effects were observed when the devices were aged in an inert atmosphere, including variations in projected lifetime. The effect of oxygen was to greatly accelerate degradation, and remove any of the material-dependence observed in the inert experiment, while humidity led to a substantial increase in the degradation rate of devices containing PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate). This study underlines the importance of considering device lifetime in device design, and choosing materials to minimise degradation

The operating efficiency and reliability of modern jet engines have undergone significant improvement largely owing to the advances of the materials science over the past 60 years. The use of both superalloys and TBCs in engine components such as turbine blades has made it possible for jet engines to operate at higher temperatures, allowing an optimal balance of fuel economy and thrust power. Despite the vast improvement in high temperature capability of superalloys, the utilization of TBCs has brought the concern of coating adhesion during their usage. TBCs are prone to spallation failure due to interfacial rumpling, which is driven primarily by thermal coefficient mismatch of the multi-layered structure. Although interfacial degradation of TBCs has been widely studied by detailed numerical and analytical models, the predicted results (i.e. stress state and rumpling amplitude) often deviate from that obtained by experiments. This is largely due to the lack of consideration of the influence of bond coat and substrate chemistry on the interfacial evolution of TBC systems. It is only in recent year that more and more study has been focused on studying the role of chemistry on the interfacial degradation of TBCs. The purpose of this PhD project is to clarify how the bond coat and substrate chemical compositions dictate the mechanisms of interfacial degradation, leading to the final spallation. A cross-sectional indentation technique was utilized to quantitatively characterize the adhesion of oxide-bond coat interface among 5 systematically prepared TBC systems. The adhesion of isothermally exposed oxide-bond coat interface was then correlated with different microstructure parameters, in an attempt to identify the key parameters controlling the TBC spallation lifetime. EBSD and EPMA analyses were conducted on the bond coat near the oxide-bond coat interface, in order to understand the relationship between the key parameters and specific alloying elements. The results clearly demonstrated that the phase transformation of bond coat near the oxide-bond coat interface plays the dominant role in the degradation of interfacial adhesion. Particularly, the co-existence of gamma prime and martensitic phases, each having very different thermomechanical response under thermal exposure, can generate a misfit stress in the TGO layer, and ultimately causes early TBC spallation. In addition, the phase transformation behavior has been closely associated with the inherent chemistry of the bond coat and substrate.

Organic Solar Cells (OSCs) represent a photovoltaic technology with multiple interesting application properties. However, the establishment of this technology into the market is subject to the achievement of operational lifetimes appropriate to their application purposes. Thus, comprehensive understanding of the degradation mechanisms occurring in OSCs is mandatory in both selecting more intrinsically stable components and/or device architectures and implementing strategies that mitigate the encountered stability issues. Inverted devices can suffer from mechanical stress and delamination at the interface between the active layer, e.g. poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM), and the hole transport layer, e.g. poly(3,4-ethylenedioxythiophene):poly(p-styrene sulfonate) (PEDOT:PSS). This work proposes the incorporation of a thin adhesive interlayer, consisting of a diblock copolymer composed of a P3HT block and a thermally-triggerable, alkyl-protected PSS block. In this context, the synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) with controlled molar mass and low dispersity (Ð ≤ 1.50) via Reversible Addition-Fragmentation chain Transfer (RAFT) polymerisation has been extensively studied. Subsequently, Atomic Force Microscopy (AFM) was explored to characterise the thermal deprotection of P3HT-b-PNSS thin layers to yield amphiphilic P3HT-b-PSS, indicating that surface deprotection prior to thermal treatment could occur. Finally, structural variation of the alkyl protecting group in PSS allowed reducing the thermal treatment duration from 3 hours (P3HT-b-PNSS) to 45 minutes for the poly(isobutyl p-styrene sulfonate) (PiBSS) analogous copolymer. Another critical issue regarding the stability of OSCs is the sunlight-driven chemical degradation of the active layer. In the study herein, the combination of experimental techniques and theoretical calculations has allowed identification of the structural weaknesses of poly[(4,4’- bis(2-ethylhexyl) dithieno [3,2-b:2’,3’-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5’-diyl], Si-PCPDTBT, upon photochemical treatment in air. Additionally, the study of the relative photodegradation rates in air of a series of polymers with systematically modified backbones and/or alkyl side chains has shown no direct correlation between chemical structure and stability. It is proposed instead that photostability is highly dependent on the crystalline character of the deposited films. Furthermore, it was verified that photostability of blends based on these polymers is dictated by the (de)stabilising effect that [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) has over each polymer. Finally, a multiscale analysis on the degradation of solar cells based on poly[4,4' bis(2- ethylhexyl) dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-[2,5 bis(3 tetradecylthiophen 2-yl)thiazole[5,4-d]thiazole)-1,8-diyl] and PCBM, indicated that by judicious selection of device layers, architectures, and encapsulation materials, operational lifetimes up to 3.3 years with no efficiency losses can be successfully achieved.

La faible durée de vie des cellules solaires organiques constitue un frein à leur développement commercial. Dans ce contexte, ce travail de thèse a été consacré à l’amélioration de la résistance mécanique des cellules d’une part, et d’autre part à l’étude de leur stabilité chimique sous l’impact de la lumière. Concernant le premier axe de recherche, nous avons proposé la synthèse de nouveaux copolymères à blocs (P3HT-b-P(R)SS) susceptibles d’améliorer l’adhésion entre la couche active (P3HT:PCBM) et la couche qui transporte les trous (PEDOT:PSS) dans des dispositifs inverses. Puis, concernant le second axe de recherche, à savoir l’amélioration de la résistance à la lumière de la couche active des cellules, nous avons élucidé les mécanismes de dégradation des polymères et identifié celles de leurs propriétés physico-chimiques impactant leur stabilité. En combinant techniques analytiques et modélisation, il a tout d’abord été possible d’identifier les points faibles d’un polymère modèle, le Si-PCPDTBT. Puis, dans l’objectif d’établir une relation structure-stabilité, l’effet de la variation systématique du squelette conjugué et de la chaîne latérale du polymère a été étudié. Finalement, une analyse multi-échelle a été mise en oeuvre, allant de la stabilité de la couche active jusqu’à celle de la cellule solaire correspondante. Il a alors été montré qu’en choisissant judicieusement les matériaux de la couche active, les couches interfaciales, l’architecture et l’encapsulation des cellules, il était tout à fait possible d’atteindre des durées de vie supérieures à trois ans sans perte significative de performance électrique des dispositifs
The commercial application of Organic Solar Cells is limited by their short operational lifetimes. In this context, this work has been devoted to the improvement of both the mechanical resistance of these devices and their chemical stability when exposed to light. Concerning the former, the synthesis of P3HT-b-P(R)SS block copolymers as adhesive materials has been proposed to improve adhesion between the active layer (P3HT:PCBM) and the hole transport layer (PEDOT:PSS) in inverted devices. In order to improve the photochemical resistance of the active layer, the second main objective of this project was to identify both polymer degradation pathways and the properties determining polymer stability. Firstly, analytical techniques and modelling have been employed to identify the weak structural points in model low bandgap polymer, Si-PCPDTBT. Then, a series of polymers with systematically modified backbones and/or alkyl side chains has been studied with the aim of establishing a relationship between chemical structure and stability. Finally, multiscale analysis was undertaken on the degradation of solar cells, going from the stability of separate active layers to that of complete devices. It was shown that judicious selection of device layers, architectures, and encapsulation materials, can lead to operational lifetimes over three years with no efficiency losses

Lithium-ion batteries with higher capacity and longer cycle life than that available today are required as secondary energy sources for a wide range of emerging applications. In particular, the cycling performance of several candidate materials for lithium-ion battery electrodes is insufficient because of the fast capacity fading and short cycle life, which is mainly a result of mechanical degradation. This dissertation mainly focuses on the issue of mechanical degradation in advanced lithium-ion battery electrodes. Thin films of tin electrodes were studied where we observed whisker growth as a result of electrochemical cycling. These whiskers bring safety concerns because they may penetrate through the separator, and cause short-circuit of the electrochemical cells. Cracking patterns generated in amorphous silicon thin film electrodes because of electrochemical cycling were observed and analyzed. A two-dimensional spring-block model was proposed to successfully simulate the observed cracking patterns. With semi-quantitative study of the cracking pattern features, two strategies to void cracking in thin-film electrodes were proposed, namely reducing the film thickness and patterning the thin-film electrodes. We also investigated electrodes consisting of low melting point elements and showed that cracks can be self-healed by the solid-to-liquid phase transformation upon cycling. Using gallium as an example, mechanical degradation as a failure mechanism for lithium-ion battery electrodes can be eliminated. In order to quantitatively understand the effect of surface modification on electrodes, we analyzed diffusion equations with boundary conditions of finite interfacial reactions, and proposed a modified potentialstatic intermittent titration technique (PITT) as an electro-analytical technique to study diffusion and interfacial kinetics. The modified PITT has been extended to thin-film geometry and spherical geometry, and thus can be used to study thin-film and composite electrodes consisting of particles as active materials.

Plants and some unicellular algae store carbon in the form of transitory starch on a diurnal basis. The turnover of this glucose polymer is tightly regulated and timely synthesis as well as mobilization is essential to provide energy for heterotrophic growth. Especially for starch degradation, novel enzymes and mechanisms have been proposed recently. However, the catalytic properties of these enzymes and their coordination with metabolic regulation are still to be discovered. This thesis develops theoretical methods in order to interpret and analyze enzymes and their role in starch degradation. In the first part, a novel description of interfacial enzyme catalysis is proposed. Since the initial steps of starch degradation involve reactions at the starch-stroma interface it is necessary to have a framework which allows the derivation of interfacial enzyme rate laws. A cornerstone of the method is the introduction of the available area function - a concept from surface physics - to describe the adsorption step in the catalytic cycle. The method is applied to derive rate laws for two hydrolases, the Beta-amylase (BAM3) and the Isoamylase (DBE/ISA3), as well as to the Glucan, water dikinase (GWD) and a Phosphoglucan phosphatase (DSP/SEX4). The second part uses the interfacial rate laws to formulate a kinetic model of starch degradation. It aims at reproducing the stimulatory effect of reversible phosphorylation by GWD and DSP on the breakdown of the granule. The model can describe the dynamics of interfacial properties during degradation and suggests that interfacial amylopectin side-chains undergo spontaneous helix-coil transitions. Reversible phosphorylation has a synergistic effect on glucan release especially in the early phase dropping off during degradation. Based on the model, the hypothesis is formulated that interfacial phosphorylation is important for the rapid switch from starch synthesis to starch degradation. The third part takes a broader perspective on carbohydrate-active enzymes (CAZymes) but is motivated by the organization of the downstream pathway of starch breakdown. This comprises Alpha-1,4-glucanotransferases (DPE1 and DPE2) and Alpha-glucan-phosphorylases (Pho or PHS) both in the stroma and in the cytosol. CAZymes accept many different substrates and catalyze numerous reactions and therefore cannot be characterized in classical enzymological terms. A concise characterization is provided by conceptually linking statistical thermodynamics and polymer biochemistry. Each reactant is interpreted as an energy level, transitions between which are constrained by the enzymatic mechanisms. Combinations of in vitro assays of polymer-active CAZymes essential for carbon metabolism in plants confirmed the dominance of entropic gradients. The principle of entropy maximization provides a generalization of the equilibrium constant. Stochastic simulations confirm the results and suggest that randomization of metabolites in the cytosolic pool of soluble heteroglycans (SHG) may contribute to a robust integration of fluctuating carbon fluxes coming from chloroplasts.
Stärke hat eine herausragende Bedeutung für die menschliche Ernährung. Sie ist ein komplexes, wasserunlösliches Glucosepolymer und dient - als eine der wichtigsten Speicherformen von Kohlenhydraten in Pflanzen - der Aufrechterhaltung des Energiestoffwechsels. Unterschiedliche Organe enthalten Stärke. In Knollen und Samen wird die sogenannte Speicherstärke über lange Zeiträume auf- und abgebaut. Die im Allgemeinen weniger bekannte transitorische Stärke in Blättern und einigen einzelligen Algen wird in einem täglichen Rhythmus umgesetzt: Sie wird während der Photosynthese aufgebaut und in der Nacht abgebaut. Experimentelle Studien haben nachgewiesen, dass die Fähigkeit der Pflanze, den Abbau transitorischer Stärke zu regeln, essentiell ist, um während der Nacht das Wachstum der Pflanze zu gewährleisten. Da die Geschwindigkeit von biochemischen Reaktionen über Enzyme reguliert wird, ist die Aufklärung ihrer Funktion im Stoffwechsel eine notwendige Voraussetzung, um den komplexen Prozess des Wachstums zu erklären. Die vorliegende Arbeit stellt einen Versuch dar, die Funktion von Enzymen beim Stärkeabbau anhand von mathematischen Modellen und Computersimulationen besser zu verstehen. Dieser Ansatz erlaubt es, Eigenschaften des Systems durch Abstraktion anhand eines idealisierten Abbildes herzuleiten. Die mathematisch notwendigen Folgerungen dienen der Aufstellung von Hypothesen, die wiederum mit experimentellen Resultaten konfrontiert werden können. Stoffwechselsysteme sind komplexe Untersuchungsobjekte, bei denen eine rein qualitative Argumentation schnell an Grenzen gerät, wo mathematische Methoden die Möglichkeit von Aussagen noch zulassen. Der erste Teil der Arbeit entwickelt einen theoretischen Rahmen, um Gleichungen für die Geschwindigkeit oberflächenaktiver Enzyme herzuleiten. Dies ist notwendig, da die ersten Reaktionen, die dem Stärkeabbau zugeordnet werden, an ihrer Oberfläche stattfinden. Die Methode wird auf vier essentielle Enzyme angewandt: zwei abbauende Enzyme (Beta-Amylase und Isoamylase) und zwei den Abbau unterstützende Enzyme (Alpha-Glucan,Wasser-Dikinase und Phosphoglucan Phosphatase). Der zweite Teil entwickelt ein kinetisches Modell des Stärkeabbaus unter Verwendung der hergeleiteten Ratengleichungen. Das Modell bildet die Dynamik des Systems realistisch ab und legt nahe, dass ein spontaner Phasenübergang an der Oberfläche von geordneten zu weniger geordneten Zuständen stattfindet. Ferner wird die Hypothese aufgestellt, dass die reversible Modifikation der Oberfläche durch Enzyme besonders in der Anfangsphase des Abbaus einen synergetischen Effekt hat, d.h. den Abbau enorm beschleunigt. Dies könnte beim schnellen Umschalten von Stärkeaufbau zu Stärkeabbau regulatorisch relevant sein. Im letzten Teil werden kohlenhydrataktive Enzyme betrachtet, die in der löslichen Phase die Produkte des Stärkeabbaus weiterverarbeiten. Da diese sogenannten Transferasen auch in vielen anderen Organismen und Stoffwechselwegen vorkommen, wird ein allgemeiner Standpunkt eingenommen. Anhand von Methoden aus der statistischen Physik wird theoretisch wie experimentell nachgewiesen, dass diese Enzyme spontan die Entropie innerhalb des Stoffwechselsystems erhöhen. Diese Neigung, "Unordnung" zu schaffen, wird vom Organismus aber paradoxerweise ausgenutzt, um die Weiterverarbeitung von Kohlenhydraten im Stärkestoffwechsel zu stabilisieren. Dieser Mechanismus eröffnet einen neuen Blick auf energie- und entropiegetriebene Prozesse in Zellen.

This Ph.D. Thesis focuses on the investigation of organic photovoltaic (OPV) technology, especially in aspects of experimental device processing, and optoelectronic and electrical characterization on OPV devices to be readily marketable. More specifically, the topics addressed are the following: origin of recombination current,open-circuit voltage and crystallinity, transport driving force, contact selectivity and interface states, alternative hole transporting layers and oxygen and degradation routes.

We studied PLA-microcrystalline cellulose composites, focusing on the effects of processing, particle size and surface modification. The thermal and mechanical properties of these PLA based composites were studied and the effect of cellulose addition on PLA degradation was analyzed. For our system, the degradation rate was found to depend on initial sample crystallinity, pH of the degradation media and cellulose content of the composite. Composites were prepared using solution processing and melt mixing methods. The processing methods influenced the polymer's ability to crystallize affecting the mechanical properties. Isothermal crystallization studies carried out to study the kinetics of crystallization showed melt processed samples to have lower half time for crystallization and higher value for the Avrami exponent. The crystallization rate of PLA was also found to depend on surface chemical composition of cellulose particles and the particle size. Influence of filler surface modification on the composite properties was studied via grafting of lactic acid and polylactic acid to cellulose particles and the effect of filler size was studied using hydrolyzed microcrystalline cellulose particles. A simple esterification reaction that required no external catalyst was used for surface modification of cellulose particles. Surface modification of cellulose particles enhanced the static and dynamic mechanical properties of the composite samples due to improvement in the PLA-cellulose compatibility that resulted in better interfacial interactions. The utility of cellulose, available from a renewable resource, as an effective reinforcement for PLA is demonstrated.

Les batteries à l'état solide (ASSB) qui reposent sur l'utilisation d'électrolytes solides (SE) à conductivité ionique élevée sont le Saint-Graal de la future technologie des batteries, car elles pourraient théoriquement permettre une augmentation de près de 70 et 40 % des densités d'énergie volumétrique (Wh/l) et gravimétrique (Wh/kg), respectivement, ainsi qu'une sécurité accrue par rapport à la technologie des batteries au lithium-ion. À cette fin, la dernière décennie a vu le développement des ASSB, principalement grâce à des SE à base de sulfure, en raison de leurs propriétés intrinsèques favorables. Toutefois, ces progrès n'ont pas permis de mettre au point des ASSB pratiques et performants en raison des réactions complexes de décomposition interfaciale qui se produisent aux électrodes négative et positive et qui entraînent une détérioration de la durée de vie des cycles. En se concentrant sur l'électrode positive, cela nécessite une meilleure compréhension de la compatibilité électrochimique/chimique des SE qui est cruellement nécessaire pour les applications du monde réel.Ce travail vise à fournir des réponses concernant la meilleure paire d'oxyde en couche SE dans la cathode composite pour les ASSB. En menant une étude systématique sur l'effet de la nature des SE sur les performances des batteries, nous montrons que les performances de Li6PS5Cl rivalisent avec celles de Li3InCl6, surpassant toutes deux celles de β-Li3PS4 et ce, indépendamment de la voie de synthèse. Ces performances sont préservées lors de l'assemblage de piles à l'état solide, puisque l'appariement de Li6PS5Cl avec une cathode en oxyde stratifié présente la meilleure rétention en cas de cyclage. Cette étude révèle également que les halogénures réagissent avec les sulfures dans les cellules hétérostructurées, ce qui entraîne une diminution rapide de la capacité en cas de cyclage en raison de réactions de décomposition interfaciales. Pour éliminer ce processus de dégradation interfaciale, nous proposons une stratégie d'ingénierie de surface qui permet d'atténuer la détérioration de la surface et de débloquer des ASSB très performants. Enfin, l'analyse électrochimique, structurelle et spectroscopique combinée démontre que Li3InCl6 ne peut pas résister à des potentiels d'oxydation plus élevés, ce qui entraîne des produits de décomposition contrairement à ce que les calculs théoriques prévoyaient
All-solid-state batteries (ASSBs) that rely on the use of solid electrolytes (SEs) with high ionic conductivity are the holy grail for future battery technology, since it could theoretically enable achieving nearly 70 and 40 % increase in volumetric (Wh/l) and gravimetric (Wh/kg) energy densities, respectively, as well as enhanced safety compared to lithium-ion battery technology. To this end, the last decade has witnessed the development of ASSBs mainly through sulfide-based SEs pertaining to their favorable intrinsic properties. However, such advancements were not straightforward to unlock high-performing practical ASSBs because of complex interfacial decomposition reactions taking place at both negative and positive electrodes, leading to a worsening cycling life. Focusing on the positive electrode, this calls for a better understanding of electrochemical/chemical compatibility of SEs that is sorely needed for real-world applications.This work aims to provide answers regarding the best SE-layered oxide pair in composite cathode for ASSBs. By conducting a systematic study on the effect of nature of SEs in battery performances, we show that Li6PS5Cl performances rival that of Li3InCl6, both outperforming β-Li3PS4 and this, independently of the synthesis route. This is preserved when assembling solid-state cells since Li6PS5Cl pairing with layered oxide cathode shows the best retention upon cycling. This study also unravels that halides react with sulfides in hetero-structured cell design, hence resulting in a rapid capacity decay upon cycling stemming from interfacial decomposition reactions. To eliminate such interfacial degradation process, we suggest a surface engineering strategy that helps to alleviate the surface deterioration, unlocking highly performing ASSBs. Eventually, combined electrochemical, structural and spectroscopic analysis demonstrate that Li3InCl6 cannot withstand at higher oxidation potentials, resulting in decomposition products in contrast to what the theoretical calculations predicted

Dans le cadre de l’évolution du plus grand accélérateur circulaire de particules « LHC », un important programme de mise à niveau sur l’ensemble des détecteurs qui le constitue a été lancé. Parmi eux, on retrouve la mise à niveau du détecteur LHCb qui comprend le remplacement complet de plusieurs sous-détecteurs. La fréquence de lecture élevée de 40MHz, sans précédent dans une expérience de physique des particules, et l’environnement de rayonnement sévère lié à l’augmentation de l’intensité du LHC, sont les principaux défis à relever par les nouveaux sous-détecteurs. Le travail présenté dans ce manuscrit, décrit une petite partie de l’évolution du détecteur LHCb. Le développement et la construction d’un nouveau trajectographe à grande échelle, basé sur une nouvelle technologie à fibres scintillantes «SciFi», lues avec des photomultiplicateurs au silicium «SiPM», est l’un des projets clés du programme de mise à niveau de LHCb. La première partie, consiste à étudier les échanges thermiques et à concevoir un système de refroidissement pour chaque Read-Out Box « ROB » qui contient deux cartes électroniques frontales « FE », et qui permettent de lire les données du détecteur. Ces dernières possèdent une dissipation thermique d’environ 110W.Pour assurer le bon fonctionnement des composants électroniques, il est obligatoire de mettre en place un refroidisseur. Des contraintes importantes sont prisent en compte dans cette étude, la première représente l’espace limité en regard du besoin du système de refroidissement, des interfaces électroniques et mécanique, la seconde concerne les SiPM. Reliés à l’électronique par des câbles flexibles, elles sont situées à proximité de l’électronique « FE » et leur température de fonctionnement doit être parfaitement réglée autour des -40°C. Des travaux de simulations numériques sur les logiciels FloTHERM et ANSYS ont été menés sur le banc expérimental réalisé au sein du laboratoire, et qui nous ont permis de déterminer la solution de refroidissement la mieux adaptée. Cette étude nous a aussi montré qu’il est plus que nécessaire d’intégrer des interfaces thermiques « IT» telles que des pâtes thermiques afin d’assurer un meilleur transfert de chaleur entre les composants électroniques et le refroidisseur. La deuxième partie, représente une étude approfondie sur les interfaces thermiques qui sont un point délicat de transfert de chaleur, car elles peuvent avoir plusieurs dizaines de pour cent de la résistance thermique globale. Pour garantir une utilisation adéquate et durable de ces matériaux, plusieurs paramètres ont été vérifiés, en particulier la dureté, la consistance (pas de production de graisse ou d’huile) et la conductivité thermique, grâce à un banc de mesures adapté d’après la méthode normalisé ASTM D5470, grâce auquel on a pu mesurer le flux de chaleur qui traverse l’échantillon d’interface thermique testé et qui est généré par une source chaude et un source froide qui sont montées aux extrémités de notre banc.Grâce à l’installation CHARME (CERN) et à la plate-forme PAVIRMA (Campus des Cézeaux), une série de mesure d’irradiations aux neutrons et aux rayons X sont également effectuées, correspondant à l’environnement dans lequel elles seront exposées dans l’expérience, d’un côté pour identifier les dégradations et changements possibles sur les résistances thermiques par l’analyse de l’impédance thermique, de l’autre pour identifier l’interface thermique qui convient le mieux à notre application et qui permet d’assurer un excellent échange thermique et donc un bon refroidissement de l’électronique frontale au sein du trajectographe du détecteur LHCb
In the context of the evolution of the biggest circular accelerator of particles «LHC», an important program of upgrade on all the detectors which establishes itself was thrown. Among them, we find the upgrade of the detector LHCb which includes the complete replacement of several sub-detectors. The frequency of high reading of 40MHz, an unprecedented in an experiment of physical appearance of particles, and the environment of severe radiation bound to the increase of the intensity of the LHC, are the main challenges by the new sub-detectors. The work presented in this manuscript, described as a small part of the evolution of the LHCb detector. The development and the construction of a new wide-scale tracker, based on a new technology with scintillating fiber «SciFi», read with photomultipliers to the silicon «SiPM», is one of the key projects of the LHCb upgrade program. The first part, consists in studying the thermal exchanges and designing a cooling system for every Read-Out Box «ROB» which contains two electronic front-end « FE », and which allow to read the data of the detector. The latter has a thermal dissipation about 110W. To ensure the smooth running of electronic components, it is compulsory to set up a cooler. Important constraints are taken into account in this study, the first one represents the space limited compared to the need for the cooling system, the electronic interfaces and mechanical, the second concerns the SiPM. Connected with the electronics by flexible cables, they are located near the electronics «FE» and their temperature of operation is perfectly settled around -40 ° C. Works of digital simulations on the software FloTHERM and ANSYS were led on the experimental bench realized within the laboratory, and which allowed us to determine the best adapted solution of cooling. This study also showed to us that he is more than necessity to integrate thermal interfaces «IT» such as thermal pastas to assure a better transfer of heat between electronic components and cooler. The second part, represents an in-depth study on the thermal interfaces which are a delicate point of transfer of heat, because they can have dozens percent of the global thermal resistance. To guarantee an adequate and sustainable use of these materials, several parameters were verified, in particular hardness, consistency (no production of fat or oil) and the thermal conductivity, thanks to a bench of measures adapted according to the method normalized ASTM D5470, with this bench we could measure the flow of heat through the tested thermal interface sample and which is generated by a hot source and a cold source that are mounted at the ends of our bench.With the installation CHARME (CERN) and PAVIRMA (Cézeaux), a series of measure of irradiations at the neutrons and the X-rays are also made, correspond-ing to the environment in which they will be exposed in the experience, on one side to identify the damages and the possible changes on the thermal resistances by the analysis of the thermal impedance, the other one to identify the thermal interface which suits best our application and which allows to assure an excellent thermal exchange and thus a good cooling of the frontal electronics within the trajectographe of the detector LHCb

碩士
國立臺北科技大學
土木工程系土木與防災碩士班
106
Reinforced concrete structure is exposed to open air. High temperature or chemical environment causes the concrete cover to crack. Then, moisture or chloride intrudes into the cracks, directly contacting the reinforcement steel and causing reinforcement steel to corrode. As the crack widens, corrosion accelerates and affects the interfacial bonding between concrete and reinforcement steel. The conventional non-destructive testing (NDT) focuses on the concrete damage without discussing the internal damage occurring to the interfacial bonding between reinforced steel and concrete. Therefore, this study intended to construct a damage assessment technique in order to measure the interfacial bonding between reinforcement steel and concrete (ductile-brittle interface), using guided wave to measure the damages occurring to reinforced concrete in order to detect and explain the bond damages, and at the same time introducing the conceptual model of material-interface-defect as the core index of bond damage assessment technique to examine the wave-propagating behaviors on the surface of reinforced concrete. Rectangular specimen was produced using reinforced concrete with design strength 420 kgf/cm2 as the primary material for the experiment. The details of the specimen – reinforcement steel cover’s thickness 1.5, 4 cm, type of reinforcement steel, normalized thickness diameter ratio (c/db, cover’s thickness divided by reinforcement steel’s diameter), damage’s length (30 cm) and thickness (0.3 cm) – were used as experimental variables. Reinforcement steel was packed with plastic bubble wrap to simulate the opening of interfacial bonding for the guided wave to detect the damage preliminarily. Multi-channel seismic surface wave was measured. Broadband receiver and steel balls were used together in the experiment. According to the preliminary detection, seismics serves as the comparison group when it is not under the influence of reinforcement steel. If reinforcement steel is found in seismics, reinforcement steel can be detected. If the bond is totally damaged, seismic signals indicate the specimen in the shallow level of concrete, having a noticeable amplitude of dispersion that is concentrated with an amplified effect, which will be investigated in a later stage. Based on the preliminary detection and explanation of the multi-channel seismic for the surface wave measured by guided wave, this study presented the difference between the guided wave signals with damage and the guided wave signals without damage based on the assessment of the damages occurring to the interfacial bonding in order to demonstrate the guided wave measurement method presented by this study has the potential to detect reinforcement steel and the damages occurring to the structures. In the subsequent researches, the bond damages resulted from actual damage (e.g. real fire) will be investigated.

by Xu Mingsheng.
"October 2002."
Thesis (Ph.D.)--Chinese University of Hong Kong, 2002.
Includes bibliographical references.
Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Electronic reproduction. Ann Arbor, MI : ProQuest Information and Learning Company, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Mode of access: World Wide Web.

Crosslinking soft tissue has become more common in tissue engineering applications, and recent studies have demonstrated that soft tissue mechanical behavior can be directly altered through crosslinking, but increased understanding of how crosslinking affects intervertebral disc mechanical behavior is needed. In vitro testing of bovine disc and motion segments was used to characterize several important aspects of disc behavior in response to crosslinking after both soaking and injection treatment. The first study was a comparison of different crosslinkers to determine the effect on tensile properties of disc tissue. Circumferential specimens were taken from bovine annulus and then soak treated with an optimized crosslinking formulation or sham solution. A non-contacting laser micrometer was used to measure cross sectional area, after which tension testing until failure was performed to determine yield strain, yield stress, ultimate stress, peak modulus, and resilience. The crosslinkers were observed to produce different changes in the properties, with the measured properties generally increasing. The second study used bilateral annular injections to simulate a clinically relevant delivery method. The dose response of the motion segment’s neutral zone stability metrics against injection concentration was mapped. Concentrations of 20 mM and less had no significant effects on the stability metrics. 40mM demonstrated a change in neutral zone stiffness, while at least 80mM was required to significantly affect neutral zone length. Thus, meaningful changes in joint neutral zone stability were demonstrated using clinically relevant injection and chemical formulations. The third study used combinations of biochemical and accelerated mechanical cyclic loading to degrade gelatin and annulus fibrosus specimens with and without genipin treatment. Genipin crosslinking attenuated changes during cyclic loading to specimen geometry and compliance relative to control samples. Full recovery of genipin treated samples appeared to be hampered, at least partially from continued crosslinking during the accelerated testing. The fourth study tested the effect of genipin crosslinking to resist interlamellar shearing of the annulus lamella. Using a recently reported test method that shears adjacent lamella, crosslinked specimens were noted to have significantly higher yield force, peak force, and resilience compared to sham treated controls, supporting the hypothesis that crosslinking would increase the load bearing ability of the interface.

other
no
The effect of sulphuric acid on the chemical and physical behaviour of the piston ring lubricant in a marine engine cylinder was investigated. To reveal the basic influence of H2SO4 on the lubricant film, the saturated hydrocarbon Squalane (C30H62) was chosen as a simple model oil. The interfacial tension between aqueous H2SO4 (0-98% w/w) and C30H62 was measured between -3 and 165 degrees C to understand droplet formation in the lubricant. Interfacial tension decreases with increasing acid concentration and is temperature dependent.
The wettability of engine parts with corrosive sulphuric acid was characterised by the contact angle. The contact angle of H2SO4 (0-98% w/w) on a grey cast iron cylinder liner material (Wartsila, RT84) and a piston ring chrome-ceramic coating (Federal Mogul Goetze, CKS, empty set960 mm) immersed in C30H62 was measured over a temperature range from 20 to 165 degrees C. In general, larger contact angles were measured under higher temperature conditions and on chrome surfaces.
In addition to the physical measurements, chemical reaction between H2SO4 and C30H62 was observed which influenced the interfacial tension, visual appearance, phase separation and formation of solid matter. The reaction time was found to be faster than the neutralisation times of commercially formulated lubricants. The reaction products were analysed using FTIR spectroscopy and EDX to find oxidation and sulphonation.