Um Lebewesen oder Bauwerke vor Impakteinwirkungen zu schützen, können die unterschiedlichsten Herangehensweisen angewandt werden. Es kann beispielsweise Energie durch innere Reibung, plastische Verformung oder Abfederung absorbiert oder umgelenkt werden. Möglichkeiten der Umsetzung sind lose Schüttungen, die beispielsweise im Fall von Steinschlagschutzgalerien eingesetzt werden, oder geschichtete Aufbauten, wie sie zum Beispiel für Personenrüstungen zum Einsatz kommen. Letztere sind sowohl in der Natur als auch in der Technik oft zu finden und dienen als Grundlage für die nachfolgend entworfenen Schutzkonstruktionen, die sich aus mineralisch gebundenen Kompositen zusammensetzen. Sie sollen in der Lage sein, Stahlbetonkonstruktionen vor Impakteinwirkungen zu schützen. Zunächst wurden die Eigenschaften der verwendeten Materialien unter statischen und dynamischen Lasten untersucht. Anschließend wurden mehrlagige Dämpfungsschichtaufbauten auf Stahlbetonbauteile aufgebracht, um das Dämpfungsverhalten in größerem Maßstab in Fallturmversuchen zu charakterisieren.

Carbon-bonded alumina filters and their binders, lactose, tannin and CarboresP, were investigated by Raman spectroscopy. Special emphasis was placed on the pyrolysis study of the binders. In situ measurements were performed on the tannins gallic acid, ellagic acid and tannic acid to determine the pyrolysis temperatures and products. Furthermore, the binder samples fired in a reducing atmosphere in a coke bed were analyzed by Raman spectroscopy and their transition from an amorphous carbon system to nanocrystalline graphite was observed. The influence of different binders on the carbon-bound alumina filters was studied, as well as the influence of different additives. However, no significant difference was observed between samples with different binder compositions or with additives. In addition, Raman measurements on the spinel MgAlON indicate an increased disorder of the structure due to the incorporated nitrogen.

The minimum energy paths and transition states for the first two pyrolysis reactions of the tannin building blocks gallic acid and (+)-catechin were calculated by combining density functional theory with the climbing-image nudged elastic band method. For both investigated, the combined pyrolysis reaction was found to be endothermic across the full investigated temperature range and exergonic for temperatures of 1000 K and above when evaluated with the quantum chemical 'gold standard' approach CCSD(T). In the case of gallic acid, the dehydrogenation of pyrogallol was identified as the rate-determining pyrolysis step, whereas the catechol split-off was determined to be the rate-determining step of (+)-catechin pyrolysis. Additionally, simulated Raman spectra were able to explain the presence of subtle shoulder peaks in the spectrum of the binder Carbores®P. Another series of spectra assisted the identification of an ellagic acid pyrolysis product.

Quantum chemical calculations at BP86/TZVPP//BP86/SVP have been carried out for the Nheterocylic carbene and analogues complexes (tetrylene) [(CO)4W-NHE] (W4-NHE) with E = C – Pb. The tetrylene complexes W4-NHE possess end-on-bonded NHE ligands (E = C, Si), while for E = Ge and Sn, they possess slightly side-on-bonded ligands. The strongest side-on-bonded ligand when E = Pb has a bending angle of 102.9°. The trend of the bond dissociations energies (BDEs) for the W-E bond is W4-NHC > W4-NHSi > W4-NHGe > W4-NHSn > W4-NHPb. Analysis of the bonding situation suggests that the NHE ligands in W4-NHE are strong σ-donors and weak π-donors. This is because the tetrylenes have only one lone-pair orbital available for donation. The polarization of the W-E bond and the hybridization at atom E explain the trend in the bond strength of the tetrylene complexes W4-NHE. The W-E bonds of the heavier systems W4-NHE are strongly polarized toward atom E giving rise to rather weak electrostatic attraction with the tungsten atom which is the main source for the decreasing trend of the bond energies. The theoretical calculations suggest that transition-metal complexes tetrylenes [(CO)4W-{NHE}] (E = C – Pb) should be synthetically accessible compounds with tetrylenes NHE act as two-electron-donor ligands in complexes. / Phân tích cấu trúc và bản chất liên kết hóa học của hợp chất với kim loại chuyển tiếp chứa phối tử N-heterocyclic carbene và các đồng đẳng (tetrylene) [(CO)4W–NHE] (W4-NHE) với E = C – Pb sử dụng tính toán hóa lượng tử ở mức BP86/TZVPP//BP86/SVP. Cấu trúc của phức W4-NHE cho thấy các phối tử NHE với E = C, Si tạo với phân tử W(CO)4 một góc thẳng α = 180,0°, trong khi đó các phức W4-NHE thì phối tử NHE với E = Ge – Pb tạo liên kết với nhóm W(CO)4 một góc cong α < 180,0° và góc cong càng trở nên nhọn hơn khi E = Pb (α = 102.9°). Năng lượng phân ly liên kết của liên kết W-E giảm dần: W4-NHC > W4-NHSi > W4-NHGe > W4-NHSn > W4-NHPb. Tính toán hóa lượng tử trong phức [(CO)4W-{NHE}] (E = C – Pb) cho thấy phối tử tetrylene là chất cho electron. Điều này có thể do phối tử tetrylene chỉ giữ lại một cặp electron tại nguyên tử E để đóng vai trò là chất cho điện tử. Độ bền liên kết của phức W4-NHE được giải thích nhờ vào độ phân cực của liên kết W-E và sự lai hóa của nguyên tử trung tâm E. Nguyên nhân chính làm giảm dần năng lượng liên kết là do liên kết W-E của các phức nặng hơn W4-NHE bị phân cực mạnh về phía nguyên tử E dẫn đến lực hút tĩnh điện với nguyên tử W yếu dần. Hệ phức nghiên cứu được coi là hợp chất điển hình cho các nghiên cứu thực nghiệm.

No description available.

Structural adhesives are widely used with great success, and yet occasional failures can occur, often resulting from improper bonding procedures or joint design, overload or other detrimental service situations, or in response to a variety of environmental challenges. In these situations, cracks can start within the adhesive layer or debonds can initiate near an interface. The paths taken by propagating cracks can affect the resistance to failure and the subsequent service lives of the bonded structures. The behavior of propagating cracks in adhesive joints remains of interest, including when some critical environments, complicated loading modes, or uncertainties in material/interfacial properties are involved. From a mechanics perspective, areas of current interest include understanding the growth of damage and cracks, loading rate dependency of crack propagation, and the effect of mixed mode fracture loading scenarios on crack path selection. This dissertation involves analytical, numerical, and experimental evaluations of crack propagation in several adhesive joint configurations. The main objective is an investigation of crack path selection in adhesively bonded joints, focusing on in-plane fracture behavior (mode I, mode II, and their combination) of bonded joints with uniform bonding, and those with locally weakened interfaces. When removing cured components from molds, interfacial debonds can sometimes initiate and propagate along both mold surfaces, resulting in the molded product partially bridging between the two molds and potentially being damaged or torn. Debonds from both adherends can sometimes occur in weak adhesive bonds as well, potentially altering the apparent fracture behavior. To avoid or control these multiple interfacial debonding, more understanding of these processes is required. An analytical model of 2D parallel bridging was developed and the interactions of interfacial debonds were investigated using Euler-Bernoulli beam theory. The numerical solutions to the analytical results described the propagation processes with multiple debonds, and demonstrated some common phenomena in several different joints corresponding to double cantilever beam configurations. The analytical approach and results obtained could prove useful in extensions to understanding and controlling debonding in such situations and optimization of loading scenarios. Numerical capabilities for predicting crack propagation, confirmed by experimental results, were initially evaluated for crack behavior in monolithic materials, which is also of interest in engineering design. Several test cases were devised for modified forms of monolithic compact tension specimens (CT) were developed. An asymmetric variant of the CT configuration, in which the initial crack was shifted to two thirds of the total height, was tested experimentally and numerically simulated in ABAQUS®, with good agreement. Similar studies of elongated CT specimens with different specimen lengths also revealed good agreement, using the same material properties and cohesive zone model (CZM) parameters. The critical specimen length when the crack propagation pattern abruptly switches was experimentally measured and accurately predicted, building confidence in the subsequent studies where the numerical method was applied to bonded joints. In adhesively bonded joints, crack propagation and joint failure can potentially result from or involve interactions of a growing crack with a partially weakened interface, so numerical simulations were initiated to investigate such scenarios using ABAQUS®. Two different cohesive zone models (CZMs) are applied in these simulations: cohesive elements for strong and weak interfaces, and the extended finite element method (XFEM) for cracks propagating within the adhesive layer. When the main crack approaches a locally weakened interface, interfacial damage can occur, allowing for additional interfacial compliance and inducing shear stresses within the adhesive layer that direct the growing crack toward the weak interface. The maximum traction of the interfacial CZM appears to be the controlling parameter. Fracture energy of the weakened interface is shown to be of secondary importance, though can affect the results when particularly small (e.g. 1% that of the bulk adhesive). The length of the weakened interface also has some influence on the crack path. Under globally mixed mode loadings, the competition between the loading and the weakened interface affects the shear stress distribution and thus changes the crack path. Mixed mode loading in the opposite direction of the weakened interface is able to drive the crack away from the weakened interface, suggesting potential means to avoid failure within these regions or to design joints that fail in a particular manner. In addition to the analytical and numerical studies of crack path selection in adhesively bonded joints, experimental investigations are also performed. A dual actuator load frame (DALF) is used to test beam-like bonded joints in various mode mixity angles. Constant mode mixity angle tracking, as well as other versatile loading functions, are developed in LabVIEW® for use with a new controller system. The DALF is calibrated to minimize errors when calculating the compliance of beam-like bonded joints. After the corrections, the resulting fracture energies ( ) values are considered to be more accurate in representing the energy released in the crack propagation processes. Double cantilever beam (DCB) bonded joints consisting of 6061-T6 aluminum adherends bonded with commercial epoxy adhesives (J-B Weld, or LORD 320/322) are tested on the DALF. Profiles of the values for different constant mode mixity angles, as well as for continuously increasing mode mixity angle, are plotted to illustrate the behavior of the crack in these bonded joints. Finally, crack path selection in DCB specimens with one of the bonding surfaces weakened was studied experimentally, and rate-dependency of the crack path selection was found. Several contamination schemes are attempted, involving of graphite flakes, silicone tapes, or silane treatments on the aluminum oxide interfaces. In all these cases, tests involving more rapid crack propagation resulted in interfacial failures at the weakened areas, while slower tests showed cohesive failure throughout. One possible explanation of this phenomenon is presented using the rate-dependency of the yield stress (commonly considered to be corresponding to the maximum traction) of the epoxy adhesives. These experimental observations may have some potential applications tailoring adhesive joint configurations and interface variability to achieve or avoid particular failure modes. / Ph. D.

Die besonderen Eigenschaften von Graphen ermöglichen das Design von elektronischen Bauteilen im Nanometerbereich. Graphen kann auf der Oberfläche von Siliziumkarbonat (SiC) durch das Ausdampfen von Si epitaktisch gewachsen werden. Ein detailliertes Verständnis der atomaren und elektronischen Struktur der Grenzschicht zwischen Graphen und SiC ist ein wichtiger Schritt um die Wachstumsqualität zu verbessern. Wir nutzen Dichtefunktionaltheorie um das Hybridsystem Graphen-SiC auf atomarer Ebene zu beschreiben. Experimentelle Arbeiten auf der Si Seite von SiC haben gezeigt, dass die Grenzschicht (ZLG) durch eine teilweise kovalent gebundene Kohlenstofflage wächst; darüber bildet sich die erste Graphenlage (MLG). Durch das Konstruieren eines ab initio Oberflächenphasendiagrams zeigen wir, dass sowohl ZLG als auch MLG Gleichgewichtsphasen sind. Unsere Ergebnisse implizieren, dass Temperatur- und Druckbedingungen für den selbstbegrenzenden Graphenwachstum existieren. Wir zeigen, dass sich das Doping und die Riffellung von epitaktischem Graphene durch H-Interkalation reduzieren. Im Experiment unterscheidet sich das Graphenwachstum auf der C Seite qualitativ von der Si Seite. Zu Beginn des Graphenwachstums wird eine Mischung verschiedener Oberflächenphasen beobachtet. Wir diskutieren die Stabilität dieser konkurierenden Phasen. Die atomaren Strukturen von einigen dieser Phasen, inklusive der Graphen-SiC Grenzschicht, sind nicht bekannt wodurch die theoretische Beschreibung erschwert wird. Wir präsentieren ein neues Model für die bisher unbekannte (3x3) Rekonstruktion, das Si Twist Model. Die Oberflächenenergie vom Si Twist Model und von der bekannten (2x2)c Phase schneiden sich direkt an der Grenze zur Graphitbildung. Dies erklärt die experimentell beobachtete Phasenkoexistenz zu Beginn des Graphenwachstums. Wir schlussfolgern, dass auf der C Seite der kontrollierte Graphenewachstum durch Si-reiche Oberflächenphasen blockiert wird. / Graphene with its unique properties spurred the design of nanoscale electronic devices. Graphene films grown by Si sublimation on SiC surfaces are promising material combinations for graphene applications. Understanding the atomic and electronic structure of the SiC-graphene interface, is an important step to refine the growth quality. In this work, density-functional theory is used to simulate the SiC-graphene interface on an atomistic level without empirical parameters. Experimental work has shown that on the Si face of SiC, a partially covalently bonded carbon layer, the zero-layer graphene (ZLG), grows. On top of the ZLG layer forms mono-layer graphene (MLG) as large ordered areas and then few-layer graphene. By constructing an ab initio surface phase diagram, we show that ZLG and MLG are at least near equilibrium phases. Our results imply the existence of temperature and pressure conditions for self-limiting growth of MLG key to the large-scale graphene production. H intercalation significantly reduces both the corrugation and the graphene doping. Our calculations demonstrate that unsaturated Si atoms in the ZLG influence the electronic structure of graphene. The situation on the C face of SiC is very different. The experimental growth of large areas of graphene with well defined layer thickness is difficult. At the onset of graphene formation a phase mixture of different surface phases is observed. We will address the stability of the different occuring surface phases. However, the atomic structure of some of the competing surface phases, as well as of the SiC-graphene interface, is unknown. We present a new model for the (3x3) reconstruction, the Si twist model. The surface energies of this Si twist model, the known (2x2)c adatom phase, and a graphene covered (2x2)c phase cross at the chemical potential limit of graphite, which explains the observed phase mixture. We argue that well-controlled graphene formation is hindered by Si-rich surface phases.

No description available.

Cette thèse est consacrée à la caractérisation et la modélisation du transport électronique dans des matériaux et dispositifs SOI avancés pour la microélectronique. Tous les matériaux innovants étudiés(ex: SOI fortement dopé, plaques obtenues par collage etc.) et les dispositifs SOI sont des solutions possibles aux défis technologiques liés à la réduction de taille et à l'intégration. Dans ce contexte,l'extraction des paramètres électriques clés, comme la mobilité, la tension de seuil et les courants de fuite est importante. Tout d'abord, la caractérisation classique pseudo-MOSFET a été étendue aux plaques SOI fortement dopées et un modèle adapté pour l'extraction de paramètres a été proposé. Nous avons également développé une méthode électrique pour estimer la qualité de l'interface de collage pour des plaquettes métalliques. Nous avons montré l'effet bipolaire parasite dans des MOSFET SOI totalement désertés. Il est induit par l’effet tunnel bande-à-bande et peut être entièrement supprimé par une polarisation arrière. Sur cette base, une nouvelle méthode a été développée pour extraire le gain bipolaire. Enfin, nous avons étudié l'effet de couplage dans le FinFET SOI double grille, en mode d’inversion. Un modèle analytique a été proposé et a été ensuite adapté aux FinFETs sans jonction(junctionless). Nous avons mis au point un modèle compact pour le profil des porteurs et des techniques d’extraction de paramètres. / This thesis is dedicated to the electrical characterization and transport modeling in advanced SOImaterials and devices for ultimate micro-nano-electronics. SOI technology is an efficient solution tothe technical challenges facing further downscaling and integration. Our goal was to developappropriate characterization methods and determine the key parameters. Firstly, the conventionalpseudo-MOSFET characterization was extended to heavily-doped SOI wafers and an adapted modelfor parameters extraction was proposed. We developed a nondestructive electrical method to estimatethe quality of bonding interface in metal-bonded wafers for 3D integration. In ultra-thin fully-depletedSOI MOSFETs, we evidenced the parasitic bipolar effect induced by band-to-band tunneling, andproposed new methods to extract the bipolar gain. We investigated multiple-gate transistors byfocusing on the coupling effect in inversion-mode vertical double-gate SOI FinFETs. An analyticalmodel was proposed and subsequently adapted to the full depletion region of junctionless SOI FinFETs.We also proposed a compact model of carrier profile and adequate parameter extraction techniques forjunctionless nanowires.

Le dimensionnement des joints collés est une préoccupation majeure du CNES pour lesapplications spatiales des futurs lanceurs. Pour dimensionner une structure collée, il est nécessaire depouvoir apprécier les caractéristiques mécaniques du joint collé.Dans cette étude, trois adhésifs structuraux ont été sélectionnés (Hysol®EA 9321, Hysol®EA9394 et Hysol EA® 9395). Après leur caractérisation massique, une étude statistique pour mettre enévidence les effets des différents paramètres (vitesse d’essai, géométrie éprouvette, le degré depolymérisation…) a été entreprise.La deuxième étape a pour objectif de fiabiliser l’analyse des essais de fissuration etd’améliorer la compréhension des mécanismes d’endommagement et de propagation de fissure dansles liaisons collées. Trois types d’essai ont été utilisés, à savoir, l’essai Double Cantilever Beam(DCB), pour l’étude du mode I, l’essai End Notched Flexure (ENF), pour le mode II, et l’essai MixedMode Bending (MMB), pour les chargements en mode mixte I/II. Nous avons développé de nouvellesinstrumentations et méthodologies d’analyse. Pour affiner le protocole de test standard, la techniquedite de « backface strain monitoring » a été utilisée. Elle consiste à positionnées des jauges dedéformation sur les surfaces de l’éprouvette de façon à enregistrer l’évolution du signalextensométrique durant la propagation de la fissure. Cette méthode permet une meilleure estimation dela position front de fissure ainsi que l'étude de la répartition des contraintes le long du joint de colle.La corrélation d'images numériques (DIC) a également été utilisée afin de proposer un nouveauprotocole de calibrage de la longueur de fissure et pour comparer un modèle analytique (poutre deTimoshenko sur fondation élastique) avec les résultats expérimentaux. / Adhesive bonding is being strongly considered in space applications CNES as anadvantageous assembly technique for future launchers. Correct design of adhesive joints is of majorconcern. Aerospace adhesives are tough viscoelastic matrices (special epoxy resins) reinforced withnano-, or microparticles. Extended use of adhesive joints in structural applications is limited due to thedifficulties in predicting in-service performance, frequently leading to over-conservative design.Three structural adhesives (Hysol®EA 9321, Hysol®EA 9394 and Hysol®EA 9395) wereselected. After their bulk characterization, statistical studies to highlight effects of different parameterse.g. speed, test piece geometry, degree of polymerization were undertaken.In the second stage, fracture mechanics tests were effected employing: the double cantileverbeam (DCB) configuration (mode I characterisation), the three point bending end-notched flexure(ENF) (mode II) and the mixed-mode bending (MMB) (combined mode I/II loading). Crack growth inbonded joints was investigated in a novel way. To refine standard test protocol, the backface strainmonitoring technique was used. Strain gauges were used to measure the strain on the exposed skin ofthe adherends during crack onset and propagation. This method allows better estimation of the crackfront position as well as fine investigation of the stress distribution along the bondline and in the crackfront vicinity. Digital image correlation (DIC) was also used to compare analytical models, e.g.Timoshenko beam on elastic foundation model with experimental results.