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Genetic progress and inbreeding rate in complex breeding programmes – Applications to sport horses and laying hensSitzenstock, Florian 21 May 2012 (has links)
Die vorliegende Arbeit befasst sich mit der Optimierung von Zuchtprogrammen. Zum einen wurde eine neue Methode zur Berücksichtigung der mittleren Inzucht in Zuchtplanungsrechnungen entwickelt. Zum anderen werden zwei gänzlich unterschiedliche Zuchtprogramme modelliert und aktuelle Optimierungsansätze validiert. Dabei werden sowohl der naturale als auch der monetäre Zuchtfortschritt und der diskontierte Züchtungsgewinn berücksichtigt. Im Projekt FUGATO+brain wurde die Zuchtplanungssoftware ZPLAN neu programmiert und mit weiteren zuchtplanerischen Werkzeugen versehen. Als Ergebnis des Projektes entstand die Software ZPLAN+. Diese ermöglicht die Modellierung von komplexen Zuchtprogrammen und kann zur Optimierung von Zuchtprogrammen genutzt werden. Die Software ist anwenderfreundlich und umfasst alle Bereiche der Zuchtplanung.
Zur Berechnung der mittleren Inzucht wurde eine neue Methode für die Implementierung in der Zuchtplanung entwickelt. Die Methode basiert auf der mittleren Kinship in einer Zuchtpopulation. Die Kinship ist definiert als die Wahr-scheinlichkeit, dass innerhalb einer Gruppe am gleichen Locus zwei zufällig gewählte Allele herkunftsgleich sind. Die Berechnung der Kinship erfolgt auf Grundlage der Genflussmethode. Zur Validierung der Methode wurde eine früher beschriebene Schafpopulation verwandt, die in unterschiedlichen Weisen modifiziert wurde. Insgesamt wurden drei verschiedene Szenarien modelliert, wovon das erste von einem Populationswachstum ausging. Im zweiten Szenario wurde angenommen, dass die Populationsgröße durch einen Flaschenhals verringert wird und sich dann wieder erhöht. Für die dritte Modellierung wurde die Population über einen Zeitraum getrennt und dann wieder zusammengeführt. Es konnte gezeigt werden, dass sich mit der vorgeschlagenen Methode in sämtlichen komplexen Populationsstrukturen die mittlere Inzucht und die effektive Populationsgröße berechnet lässt.
In einer Zuchtplanungsrechnung für Reitpferde sollte der gezielte Einsatz von Embryotransfer in einem Pferdezuchtprogramm validiert werden. Hierfür wurde ein Zuchtprogramm in ZPLAN+ modelliert, welches das aktuelle Zuchtprogramm des Hannoveraner Verbandes e.V. näherungsweise abbildet. In verschiedenen Szenarien wurde eine schärfere Selektion auf der Stutenseite modelliert, wobei die besten Stuten des Zuchtprogramms als Spenderstuten für den Embryotransfer eingesetzt wurden. Es wurde davon ausgegangen, dass die zur Selektion zur Verfügung stehenden Stuten sowohl Ergebnisse in der Eintragung, als auch Ergebnisse einer Leistungsprüfung haben. Die Anzahl der zur Selektion verfügbaren Stuten wurde ebenso variiert wie die Anzahl der selektierten Stuten und die Anzahl der geborenen Fohlen je Spenderstute. Deutlich wurde, dass der Embryotransfer die Möglichkeit bietet den Zuchtfortschritt in einem Pferdezuchtprogramm stark zu steigern, wobei dies mit einer Steigerung der Kosten für die Züchter einhergeht. Mit dem vorgeschlagenen Ansatz zur Inzuchtberechnung konnte gezeigt werden, dass die scharfe Selektion und der starke Einsatz der Spenderstuten eine Erhöhung der mittleren Inzucht und daraus folgend eine geringere effektive Populationsgröße nach sich zieht.
Im dritten Abschnitt der Arbeit sollten die Auswirkungen der Einbeziehung von genomischen Informationen in ein Legehennenzuchtprogramm gezeigt werden. Dafür wurde in enger Kooperation mit der Lohmann Tierzucht GmbH ein Zuchtprogramm zur Produktion von 500 Mio. Legehennen in ZPLAN+ nachgebildet. Die Produktion der Elterntiere basiert auf einer Kreuzung von vier Nukleuslinien, die konventionelle Selektion stützt sich vor allem auf die Leistungsprüfung von Hennen in den einzelnen Linien. Zur Nutzung der genomischen Informationen wurde von unterschiedlich großen Kalibrierungsstichproben ausgegangen. In einem ersten Schritt wurden die genomischen Informationen der Hähne zusätzlich zu allen konventionellen Selektionskriterien genutzt. Dabei wurde die Anzahl der getesteten Hähne variiert und in einem weiteren Schritt wurde davon ausgegangen, dass die Hennen ebenfalls genotypisiert sind. In einem weiteren Szenario basierte die Selektion nur auf Pedigreedaten und genomischen Informationen. Deutlich wurde, dass in der zweiten Variante das Generationsintervall massiv gesenkt werden konnte. Der Zuchtfortschritt konnte in allen modellierten Varianten erhöht werden, wobei es Unterschiede in den Einzelmerkmalen gab. Die Einführung der genomischen Informationen in die Legehennenzucht ist verbunden mit einem massiven Kostenanstieg. Inwieweit der gesteigerte Zuchtfortschritt den Kostenanstieg rechtfertigt bedarf einer Marktanalyse seitens der Zuchtunternehmen.
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Fe-C-Cr-B lydinių atsparumo abrazyviniam dilimui tyrimas / Investigation of Abrasive Wear Resistance of Fe-C-Cr-B AlloysRaimondas, Kreivaitis 16 August 2007 (has links)
Darbe analizuojamas abrazyvinio dilimo mechanizmas. Nustatomi šiems procesams didžiausią įtaką turintys veiksniai. Analizuojama abrazyvinių dalelių formos ir jų abrazyvumo vertinimo metodika. Apžvelgiami abrazyvinio dilimo modeliai. Abrazyvinių dalelių veikiami darbinių dalių paviršiai intensyviai dyla, todėl atsižvelgiant į jų darbo sąlygas būtina tinkamai parinkti jų savybes – kietumą, stiprumą bei sudėtį (legiravimą). Šių paviršių atnaujinimui ir sustiprinimui dažnai racionalu naudoti įvairios sudėties apvirinamus sluoksnius. Šio darbo tikslas – ištirti apvirintų kietųjų sluoksnių abrazyvinio dilimo ypatybes. Taip pat, ištirti lydinių abrazyvinio dilimo įtaką dylančio paviršiaus mikrogeometriniams parametrams. Atliktais tyrimais nustatyta legiruojančių elementų įtaka apvirintų sluoksnių abrazyviniam dilimui. Nustatyta optimali apvirinto sluoksnio sudėtis abrazyvinio dilimo sumažinimui. Tai pat nustatyta, kad termiškai apdirbtų plienų ir apvirintų sluoksnių dilimo atvejais nudilimas turi ryšį su paviršiaus parametru SPQP. Tuo remiantis, matuojant paviršiaus profilį, galima prognozuoti nudilimo dydį. / There is analysis of abrasive wear mechanism in this work. The most important factors in these processes were established. There are analysed technique of abrasive particles properties and abrasive wear models. Surfaces witch are under the abrasive sway wear very fast. Considering to working conditions of these surfaces it is necessarily to choose there properties – hardness, strength and composition. For renovation and fortify of these surfaces it is often rational hard facing. The aim of this work was to estimate the influence of alloying elements content to abrasive wear. And estimate the abrasive wear influence to micro geometry of wearing surface. The influence of alloying elements to abrasive wear was estimated. To decrease abrasive wear the optimal chromium content in the arc welded alloy was investigated. Clear influence of heat treated steels and arc welded alloys abrasive wear on surface profile quality parameter SPQP is estimated. Considering with that we can measure surface profile and predict the wear rates.
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NEAR WALL SHEAR STRESS MODIFICATION USING AN ACTIVE PIEZOELECTRIC NANOWIRE SURFACEGuskey, Christopher R. 01 January 2013 (has links)
An experimental study was conducted to explore the possible application of dynamically actuated nanowires to effectively disturb the wall layer in fully developed, turbulent channel flow. Actuated nanowires have the potential to be used for the mixing and filtering of chemicals, enhancing convective heat transfer and reducing drag. The first experimental evidence is presented suggesting it is possible to manipulate and subsequently control turbulent flow structures with active nanowires. An array of rigid, ultra-long (40 μm) TiO2 nanowires was fabricated and installed in the bounding wall of turbulent channel flow then oscillated using an attached piezoelectric actuator. Flow velocity and variance measurements were taken using a single sensor hot-wire with results indicating the nanowire array significantly influenced the flow by increasing the turbulent kinetic energy through the entire wall layer.
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Rotation and non-Oberbeck-Boussinesq effects in turbulent Rayleigh-Bénard convectionHorn, Susanne 30 September 2014 (has links)
No description available.
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Application of a Network Model for Complex Fenestration SystemsRogalsky, Christine Jane January 2011 (has links)
In the fight to reduce carbon emissions, it is easy to see the necessity of reducing energy consumption. Buildings consume a large amount of energy, and have significant potential for energy savings. One tool for realising these potential savings is building simulation. To be able to use building simulation, accurate models for windows are needed. The models include individual layer models, to determine the solar and longwave radiative behaviours,
as well as whole-system models to determine heat flows through the various layers of
fenestration systems.
This thesis looks at both kinds of models for incorporating windows into building
simulations. A new network whole-system model is implemented, and integrated into the
California Simulation Engine building simulation software. This model is also used as the calculation engine for a stand-alone rating tool. Additionally, a measurement technique used to measure off-normal solar properties of drapery materials, as part of developing shading layer models, is investigated using a Monte Carlo simulation.
The network model uses a very general resistance network, allowing heat transfer between any two layers in a complex fenestration system (CFS), whether they are adjacent or not, between any layer and the indoor or outdoor side, or between the indoor and outdoor sides, although this last case is unlikely. Convective and radiative heat transfer are treated using the same format, resulting in increased stability. This general resistance network is
used to calculate indices of merit for the CFS using numerical experiments. This approach requires fewer iterations to solve than previous solution methods, and is more
flexible.
The off-normal measurement technique which was investigated used a sample holder
inserted into an integrating sphere. This is a non-standard way of using an integrating
sphere, and early analyses did not provide conclusive information as to the effect of the sample holder. A Monte Carlo analysis confirmed the amount of beam attenuation as being 20% for the sample holder used in the experiments. Also con firmed was the effectiveness of dual-beam integrating spheres in correcting for the presence of a sample holder.
The stand-alone rating tool which uses the general network framework, incorporates
an easy-to-use visual interface. This tool models multiple types of shading layers with
no restrictions on how they are combined. Users can easily change any one layer to see
the effects of different arrangements. Users may specify any combination of indoor and
outdoor ambient and mean radiant temperatures, insolation, and beam/diffuse split.
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Establishing very low speed, disturbance-free flow for anemometry in turbulent boundary layersLanspeary, Peter V. January 1998 (has links)
This document addresses problems encountered when establishing the very low air-flow speeds required for experimental investigations of the mechanisms of low-Reynolds-number boundary-layer turbulence. Small-scale motions in the near-wall region are important features of turbulent boundary-layer dynamics, and, if these features are to be resolved by measurements in air with conventionally-sized hot-wire probes, a well-behaved canonical turbulent boundary layer must be developed at free stream flow speeds no higher than 4 m/s. However, at such low speeds, the turbulent boundary layers developed on the walls of a wind tunnel are very susceptible to perturbation by non-turbulent time-dependent flow structures which originate upstream from the test section in the laminar flow at the inlet and in the contraction. Four different non-turbulent flow structures have been identified. The first is a result of quasi-two-dimensional separation of the laminar boundary-layer from the surfaces of the wind-tunnel contraction. Potential flow simulations show that susceptibility to this form of separation is reduced by increasing the degree of axisymmetry in the cross-section geometry and by decreasing the streamwise curvature of the concave surfaces. The second source of time-dependence in the laminar boundary-layer flow is an array of weak streamwise vortices produced by Goertler instability. The Goertler vortices can be removed by boundary-layer suction at the contraction exit. The third form of flow perturbation, revealed by visualisation experiments with streamers, is a weak large-scale forced-vortex swirl produced by random spatial fluctuations of temperature at the wind-tunnel inlet. This can be prevented by thorough mixing of the inlet flow; for example, a centrifugal blower installed at the inlet reduces the amplitude of temperature nonuniformity by a factor of about forty and so prevents buoyancy-driven swirl. When subjected to weak pressure gradients near the start of a wind-tunnel contraction, Goertler vortices in laminar wall layers can develop into three-dimensional separations with strong counter-rotating trailing vortices. These trailing vortices are the fourth source of unsteady flow in the test-section. They can be suppressed by a series of appropriately located screens which remove the low-speed-streak precursors of the three-dimensional separations. Elimination of the above four contaminating secondary flows permits the development of a steady uniform downstream flow and well-behaved turbulent wall layers. Measurements of velocity in the turbulent boundary layer of the test-section have been obtained by hot-wire anemometry. When a hot-wire probe is located within the viscous sublayer, heat transfer from the hot-wire filament to the wall produces significant errors in the measurements of both the mean and the fluctuating velocity components. This error is known as wall-proximity effect and two successful methods are developed for removing it from the hot-wire signal. The first method is based on the observation that, if all experimental parameters except flow speed and distance from the wall are fixed, the velocity error may be expressed nondimensionally as a function of only one parameter, in the form DeltaU^+=f(y^+). The second method, which also accommodates the effect of changing the hot-wire overheat ratio, is based on a dimensional analyis of heat transfer to the wall. Velocity measurements in the turbulent boundary layer at the mid-plane of a nearly square test-section duct have established that, when the boundary-layer thickness is less than one quarter of the duct height, mean-velocity characteristics are indistinguishable from those of a two-dimensional flat-plate boundary layer. In thicker mid-plane boundary layers, the mean-velocity characteristics are affected by stress-induced secondary flow and by lateral constriction of the boundary-layer wake region. A significant difference between flat-plate and duct boundary layers is also observed in momentum-balance calculations. The momentum-integral equation for a duct requires definitions of momentumd and displacement thickness which are different from those given for flat-plate boundary layers. Momentum-thickness growth rates predicted by the momentum-integral equation for a duct agree closely with measurements of the newly defined duct momentum thickness. Such agreement cannot be obtained in terms of standard flat-plate momentum thickness. In duct boundary layers with Reynolds numbers Re_theta between 400 and 2600, similarity in the wake-region distributions of streamwise turbulence statistics has been obtained by normalising distance from the wall with the flat-plate momentum thickness, theta_2. This result indicates that, in contrast with the mean velocity characteristics, the structure of mid-plane turbulence does not depend on the proportion of duct cross-section occupied by boundary layers and is essentially the same as in a flat-plate boundary layer. For Reynolds numbers less than 400, both wall-region and wake-region similarity fail because near-wall turbulence events interact strongly with the free stream flow and because large scale turbulence motions are directly influenced by the wall. In these conditions, which exist in both duct and flat-plate turbulent boundary layers, there is no distinct near-wall or wake region, and the behaviour of turbulence throughout the boundary layer depends on both wall variables and on outer region variables simultaneously. / Thesis (Ph.D.)--School of Mechanical Engineering, 1998.
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Proteomics of wheat bran (Triticum aestivum var. Babbler)Jerkovic, Ante January 2006 (has links)
Thesis (MSc (Hons))--Macquarie University, Division of Environmental & Life Sciences, Dept. of Chemistry & Biomolecular Sciences, 2006. / Bibliography: leaves 153-158. / Wheat is a major crop in Australia with around 25 million tonnes of grain harvested in an average year. Improved wheat grain cultivars and wheat grain milling can result in higher biological yields and flour quality. The introduction covers the general aspects of the wheat grain from bran development and structure through to millings and the importance of flour quality in flour-based products. It also highlights the problem with bran contamination in flour during milling and other factors that may have an effect on flour quality. Proteomics was used to identify proteins in three separate bran tissue fractions: the inner fraction (aleurone), intermediate fraction (nucellar tissue, testa, tube cells and cross cells) and the outer faction (hypodermis and epidermis). The aim of the project was to identify proteins in bran tissue fractions which may potentially be useful in improvements in wheat quality for farmers and consumers and flour yield for millers. The results show that more than 80% of the identified proteins in the outer and intermediate tissue factions are defence-and stress-related proteins (chitinase, xylanase, thaumatin-like protein, wheatwin 1, lipid-transfer protein, oxalatae oxidase (OXO), polyphenol oxidase (PPO), peroxidase (POX)). Almost 60% of the proteins identified in the inner tissue fraction are 7S Globulin storage proteins and around 15% are protein synthesis-and energy-related. Water-soluble proteins were also identified and it was found that endochitinase, OXO, PPO and POX all leach out from the grain durings imbibition. This study has added to the knowledge of bran tissue-specific proteins and has broad implications for improving crop yield and flour quality. / Mode of access: World Wide Web. / xiii, 158 leaves ill
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Etude expérimentale de la microstructure et des propriétés électriques et optiques de couches minces et de nanofils d'oxydes métalliques (delta-Bi2O3 et ZnO) synthétisés par voie électrochimiqueLaurent, Kevin 08 July 2008 (has links) (PDF)
L'intérêt porté sur la miniaturisation des systèmes par la communauté scientifique est grand, que ce soit pour des raisons de mobilité, d'économie d'énergie ou d'innovation technologique. L'objectif de cette thèse est de déterminer les caractéristiques physiques et structurales des couches minces et des nanofils d'oxydes métalliques synthétisés par la méthode électrochimique.<br />La première partie de cette thèse est consacrée à l'oxyde de bismuth en phase delta. Les couches minces élaborés par électrochimie sont de très bonne qualité cristalline, et seul la phase delta-Bi2O3 est présente. Le caractère nano structuré des couches minces est mis en évidence par les expériences de microscopie électronique en transmission (MET) et participe à la stabilisation de cette phase à température ambiante. Les mesures de conductivité réalisées par spectroscopie d'impédance complexe montrent un comportement différent selon la nature du substrat utilisé. Nous observons une excellente conductivité électrique des dépôts réalisés sur les substrats en argent doré (4•10-3 S•cm-1), alors que les dépôts obtenus sur l'inox montre un comportement très résistif (10-7 S•cm-1).<br />La seconde partie de cette étude concerne l'oxyde de zinc. Les conditions d'élaboration par électrochimie influence les propriétés structurales et physiques des couches minces obtenues. Les différents traitements thermiques réalisés sur les couches minces de ZnO ont permis d'améliorer la qualité optique des couches et de modifier la structure du ZnO par incorporation d'azote lors de recuit dans l'ammoniaque.<br />La dernière partie est consacrée à la synthèse et à la caractérisation de nanofils de ZnO élaborés par la méthode « template ». Cette méthode nous a permis de confiner la croissance par électrochimie dans des pores de différents diamètres. Les observations réalisés par MET et MET en Haute Résolution montrent que les nanofils obtenus sont monocristallins et de bonne qualité. Les propriétés d'émission observées en PL sont très proches des propriétés d'émission des couches minces.
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Πειραματική μελέτη και αναλυτική εκτίμηση της συμπεριφοράς δοκών οπλισμένου σκυροδέματος ενισχυμένων με νέες στρώσεις σκυροδέματοςΤσιούλου, Ουρανία 22 November 2011 (has links)
Η παρούσα διατριβή ασχολείται με την καμπτική ενίσχυση δοκών οπλισμένου σκυροδέματος με στρώσεις σκυροδέματος στο εφελκυόμενο ή στο θλιβόμενο πέλμα τους. Ιδιαίτερα ασχολείται με τον προσδιορισμό της ολίσθησης στη διεπιφάνεια τους.
Συγκεκριμένα στο 1ο Κεφάλαιο γίνεται βιβλιογραφική ανασκόπηση για τις διεπιφάνειες σκυροδέματος. Παρουσιάζονται όλα τα προσομοιώματα που προτείνονται είτε σε Κανονισμούς, είτε από διάφορους ερευνητές, για τον προσδιορισμό της διατμητικής αντοχής της διεπιφάνειας, καθώς και για τον προσδιορισμό της σχέσης διατμητικής τάσης – ολίσθησης στη διεπιφάνεια σκυροδέματος.
Στο 2ο Κεφάλαιο, παρουσιάζεται βιβλιογραφική ανασκόπηση για τις διεπιφάνειες σκυροδέματος με χάλυβα ή σύνθετα υλικά, σε σύμμικτες κατασκευές και σε μέλη ενισχυμένα με ελάσματα χάλυβα ή από ινοπλισμένα πολυμερή (ΙΟΠ), καθώς και πειραματικά αποτελέσματα κατανομής ολίσθησης σε διεπιφάνεια δοκών οπλισμένου σκυροδέματος ενισχυμένες με στρώση σκυροδέματος.
Στο 3ο Κεφάλαιο παρουσιάζεται η πειραματική διερεύνηση δοκών οπλισμένου σκυροδέματος (Ο.Σ.) ενισχυμένων με στρώσεις σκυροδέματος. Εξετάστηκαν δύο ομάδες δοκιμίων. Στην πρώτη ομάδα εξετάστηκαν τέσσερα πρισματικά δοκίμια σκυροδέματος που ενισχύθηκαν με στρώση σκυροδέματος και στη συνέχεια δοκιμάστηκαν με φόρτιση τριών σημείων. Η δεύτερη ομάδα αναφέρεται σε πέντε δοκούς Ο.Σ. ενισχυμένες επίσης με στρώση σκυροδέματος, καθώς και σε αντίστοιχες μονολιθικές δοκούς που όλες δοκιμάστηκαν με φόρτιση τεσσάρων σημείων. Σε όλα τα δοκίμια και των δύο ομάδων μετρήθηκε η αντοχή τους καθώς και η ολίσθηση στη διεπιφάνεια τους.
Στο 4ο Κεφάλαιο προτείνεται αναλυτική διαδικασία για τον υπολογισμό της ολίσθησης στη διεπιφάνεια σκυροδέματος και η εφαρμογή της στα πειραματικά δοκίμια που παρουσιάστηκαν στο Κεφάλαιο 3 καθώς και σε κάποια άλλα δοκίμια της βιβλιογραφίας που παρουσιάστηκαν στο 1ο Κεφάλαιο.
Το 5ο Κεφάλαιο της παρούσας διατριβής, εξετάζει την επιρροή της συστολής ξήρανσης στο μέγεθος της ολίσθησης. Στο κεφάλαιο αυτό, παρουσιάζονται πειραματικές μετρήσεις της παραμόρφωσης και ολίσθησης λόγω συστολής ξήρανσης στα δοκίμια και των δύο ομάδων πειραματικών δοκιμίων που παρουσιάζονται στο Κεφάλαιο 3 και προτείνεται αναλυτικός τρόπος υπολογισμού της ολίσθησης και της διατμητικής τάσης στη διεπιφάνεια, συνυπολογίζοντας την επιρροή της συστολής ξήρανσης.
Τέλος, παρουσιάζονται τα συνολικά συμπεράσματα που προέκυψαν στα πλαίσια της παρούσας διατριβής, καθώς και προτάσεις για μελλοντική έρευνα. / The present thesis concerns the flexural strengthening of reinforced concrete (RC) beams by placing a new concrete layer on their compressive or tensile side. The main objective of the thesis is to evaluate interface slip.
The first chapter is a literature review on concrete interfaces. Theoretical models, suggested by design codes or other researchers, for the calculation of the shear resistance and the relationship between the shear stress and the slip at the interface are presented. Moreover, experimental results for the shear stress against slip relationship at the concrete interface are given.
The second chapter presents a literature review on the shear stress and slip distribution at concrete to steel or concrete to fibre reinforced polymer (FRP) interfaces. Theoretical and experimental results for the value of shear stress at the interface of concrete beams strengthened with steel or FRP plates and shear stress and slip distribution at the interface of composite steel and concrete beams are presented.
The third chapter concerns an experimental investigation of RC beams strengthened with concrete layers. Two types of specimens are examined. The first group are prismatic RC specimens strengthened with a concrete layer and tested by three point bending. The second group contains 10 RC beams. Five are strengthened with a concrete layer on their compressive or tensile side, four are respective monolithic specimens and the final one is a control beam without any strengthening. These beams are tested under four point bending. In all tests, for both groups of specimens, load against deflection curves are determined and the slip along the interface is measured.
An analytical evaluation of the slip at the interface of RC beams strengthened with concrete layers and the verification of the method comparing the analytical results with respective experimental results presented in Chapters one and three is presented in Chapter four.
The shrinkage effect on interface slip and shear stress is examined in Chapter five. Experimental measurements of shrinkage strains and slip on specimens of both experimental groups presented in Chapter three are presented. An analytical evaluation of the extra slip and shear stress at the interface caused by shrinkage effect is also suggested.
Finally, all results of the thesis and suggestions for future work are given.
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Des phases MAX au MXenes : synthèse,caractérisation et propriétés électroniques / From MAX to MXenes : synthesis, characterization and electronic propertiesShi, Lu 12 December 2017 (has links)
Les phases MAX sont des carbures ou des nitrures ternaires nano-lamellaires comportant un métal de transition (M), un élément des colonnes 13-16 (A), X=C ou N.Ces phases combinent certaines des meilleures propriétés des céramiques à celles des métaux. Leurs propriétés physiques (rigidité, résistance aux chocs mécaniques et thermiques, bonnes conductivités thermique et électrique), associées à la possibilité d’usinage, les rend très attractives en termes d’applications technologiques potentielles.En 2011, il a été établi qu’un traitement à l’acide fluorhydrique (HF) des phases MAX comprenant de l’aluminium permet une élimination sélective des plans d’atomes Al, avec pour résultat la formation de matériaux bi-dimensionnels (2D) appelés MXènes pour souligner la perte des atomes de Al. Ces nouveaux membres de la famille des matériaux 2D sont plus résistants, chimiquement plus polyvalents et possèdent une conductivité supérieure à nombre d’autres matériaux. Ils se révèlent par conséquent très intéressants pour de nouvelles applications, par exemple pour des systèmes de délivrance de médicaments in vivo, le stockage d’hydrogène, ou pour remplacer d’autres matériaux dans des batteries, le traitement des eaux usées ou divers capteurs.Dans cette thèse, nous présentons notre travail sur la synthèse, la caractérisation structurale et le transport électronique dans les phases MAX et leurs dérivés 2D, les MXènes. En ce qui concerne les phases MAX, et motivés par les propriétés fortement anisotropes attendues de tels matériaux nano-lamellaires, produire des monocristaux massifs est le moyen le plus naturel d’obtenir des échantillons où l’anisotropie des propriétés physiques peut être sondée expérimentalement. En utilisant avec succès la méthode de croissance en solution à haute température associée à un refroidissement lent, nous avons obtenu des monocristaux de divereses phases MAX, incluant Cr2AlC, V2AlC, Ti3SiC2, etc.La caractérisation structurale confirme le caractère mono-cristallin des échantillons. Expérimentalement, nous avons acquis un jeu exhaustif de mesures de magnéto-transport de monocristaux en fonction de la température et du champ magnétique. De plus, nous obtenons un rapport d’anisotropie très important entre la résistivité dans le plan ab et celle parallèle à l’axe c, allant de plusieurs centaines à plusieurs milliers. A partir des courbes de magnétorésistance et d’effet Hall, nous avons étudié en détail le comportement du transport dans le plan basal. D’un point de vue théorique, nous avons proposé un modèle général mais simple pour décrire les propriétés de magnéto-transport d’électrons presque libres dans des métaux 2D hexagonaux. Ce modèle a été modifié pour être appliqué aux propriétés de transport des phases MAX nano-lamellaires.En ce qui concerne les MXènes, nous avons synthétisé avec succès des écailles de MXènes V2CTx de grande surface à partir du traitement HF conventionnel de monocristaux de V2AlC. La délamination mécanique de ces écailles multi-couches de V2CTx en échantillons comportant peu de monocouches a aussi été réalisée. Nous avons établi la morphologie typique de ces couches à partir d’images de microscopies MEB ou TEM. A partir d’analyse EDX, nous concluons que les terminaisons -OH dominent et sont les plus stables énergétiquement. Nous détaillons ensuite le procédé de fabrication des dispositifs électriques utilisés pour obtenir les résultats de mesures de transport électrique jusqu’à basse température. Nous avons obtenu avec succès des résultats originaux sur les MXènes V2CTx, avec une valeur moyenne de résistivité de l’ordre de 2 × 10-5 ohmm. La mesure d’effet de champ indique une mobilité de 22.7 cm2/Vs. Du fait de l’intensité des recherches portées actuellement sur les MXènes, nous espérons que ces résultats contribueront de manière significative à une meilleure compréhension de cette classe de matériaux et de la façon dont leurs propriétés peuvent être contrôlées. / MAX phases are layered early transition metal ternary carbides and nitrides so called because they are composed of M, an early transition metal, A, a group A element and X is C and/or N. MAX phase structure is composed of near close-packed planes of M atoms with the X atoms occupying all the octahedral sites between them. Their physical properties (stiffness, damage and thermal shock resistance, high thermal and electrical conductivity) along with the fact they are readily machinable, make them extremely attractive in terms of the potential technological applications.In 2011, it was discovered that by immersing Al-containing MAX phases in HF acid, it was possible to selectively etch the Al, resulting in two-dimensional (2D) materials, that were labeled MXene to denote the removal of the A-group element and make the connection to another conducting 2D material, graphene. This new member of 2D materials family owns stronger, more chemically versatile, and have higher conductivity than other materials. As such they are highly interesting on new applications, e.g. specialized in vivo drug delivery systems, hydrogen storage, or as replacements of common materials in e.g. batteries, sewage treatment, and sensors.In this thesis, as its self-telling title indicated, we present our work on the synthesis, structural characterization and the electron transport in the MAX phases and their 2D derivatives, MXenes.For MAX phase: motivated by the theoretically expected anisotropic properties of these layered materials, producing bulk single crystals is a natural way to obtain samples where the anisotropy of the physical properties can be experimentally probed. Also, knowledge of low-temperature behavior of single crystal is vital because it can provide insight into MAX intrinsic physical properties. Using high temperature solution growth and slow cooling technique, several MAX phases single crystals have been successfully grown, including Cr2AlC, V2AlC, Ti3SiC2, etc. Structural characterization confirms the single crystalline character of the samples. Experimentally, a set of experimental data was obtained from single crystals of V2AlC and Cr2AlC as a function of temperature and magnetic field. In particular, we obtain a very high ratio between the in-plane and parallel to the c-axis resistivity, which is very substantial, in the range of a few hundreds to thousands. From MR and Hall effect measurement, in-plane transport behaviors of MAX phases have been studied. The extracted mobility is in the range from 50 to 120 cm2/V·s, which is the same order of magnitude of polycrystalline sample. Theoretically, a general, yet simple model was proposed for describing the weak field magneto-transport properties of nearly free electrons in two-dimensional hexagonal metals. It was then modified to be applicable for the transport properties of layered MAX phases.For MXene: Large scale V2CTx MXene flakes was successfully synthesized by conventional HF-etching of V2AlC single crystals. Mechanical delamination of multilayered V2CTx flakes into few layer flakes and transfer on Si/SiO2 substrate was also achieved. Structural characterization demonstrated an enlarged interplane distance, while prior DMSO intercalation seems to have no effect on this type of MXenes. From EDS results, we concluded that -OH terminations on V2CTx is the dominated, and the most energetically favorable, compared to -F and -O functional groups. We then detail the electrical device fabrication process and proceed with electrical measurements results, performed down to low temperature, with the aim to extract useful information on charge carrier behavior. We successfully obtained some first hand transport data on V2CTx MXenes, the average value for the resistivity of V2CTx MXenes is 2 × 10-5 Ω ∙m, which is in consistent with reported other MXene samples. The mobility, 22.7 cm2/V·s , which stays in the same order of magnitude as its parent MAX phase.
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