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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Evaluation of Moisture Susceptibility of Warm Mix Asphalt

Garcia Cucalon, Maria Lorena 03 October 2013 (has links)
Economic, environmental and engineering benefits promote the rapid implementation of WMA technologies. However, concerns remain based on changes in the production process that may lead to moisture susceptibility in the early life as compared to HMA. To evaluate WMA moisture susceptibility during this critical period, standard laboratory tests were used for three field projects each with an HMA control mixtures and multiple WMA mixtures. Different specimen types were also evaluated to capture differences in mix design, quality control/quality assurance, and field performance. Specimens were evaluated for moisture susceptibility by Indirect Tensile (IDT) Strength, Resilient Modulus (MR) and Hamburg Wheel-Track Testing (HWTT). Specimens for IDT and MR were tested dry and then tested wet after conditioning as described in AASHTO T283 with one freeze-thaw cycle. HWTT was used to assess both moisture susceptibility and rutting potential under repeated loads in the presence of water at elevated temperatures (i.e., 122°F [50°C]), and the output parameters used for evaluation were the calculated Stripping Inflection Point (SIP) and the rut depth at 5000 load cycles. Based on the results of the laboratory tests performed on PMFC cores acquired at construction and with time, WMA during its early life exhibited inferior moisture resistance when compared to HMA. However, with time, specifically after one summer, the dry and wet properties of WMA became equivalent to those of HMA. For WMA constructed in the fall, the results from this study suggest that the inclusion of recycled asphalt pavement (RAP) or an anti-stripping agent may alleviate possible moisture susceptibility issues in the early life during wet, winter weather conditions. While some laboratory test results demonstrated that WMA is more moisture susceptible than HMA, field performance reported to date from the three projects used in this study shows no evidence of moisture damage. Therefore the search for a laboratory test to screen mixtures for moisture susceptibility continues. An alternative approach, applying Griffith crack growth theory and utilizing IDT, MR and air voids% the adhesive bond energy of asphalt mixtures was calculated for Texas field project. This value holds promise for characterizing performance of asphalt mixtures by considering basic properties and grouping into one representative value.
2

Synthetic, Structural and Thermochemical Studies of N-Heterocyclic Carbene (NHC) and Tertiary Phosphine Ligands in the Ni(CO)2(L)x (L-PR3, NHC) Systems

Mahjoor, Parisa 17 December 2004 (has links)
Carbonyl complexes of Ni(0) incorporating two N-heterocyclic carbenes of the type Ni(CO)2(NHC)2 (NHC = ICy [N, N'-bis(cyclohexylimidazol)-2-ylidene], IMes [N, N'- bis(2, 4, 6-trimethylphenyl)-imidazol)-2-ylidene]) have been prepared. The complexes Ni(CO)2(ICy)2 (8) and Ni(CO)2(IMes)2 (9) have been synthesized and characterized by single crystal X-ray diffraction. The enthalpy of substitution reactions of Ni(CO)2(NHC) (NHC = ItBu [N, N'-bis(tert-butylimidazol)-2-ylidene], IAd [N, N'-bis(1- adamentylimidazol)-2-ylidene]) with NHC and tertiary phosphine ligands leading to the formation of Ni(CO)2(L)2 (L = NHC, PR3) complexes have been determined. The solution calorimetric investigations reiterate the greater electron donating property of the NHC ligands compared to tertiary phosphines. Thermochemical studies of the substitution reactions of Ni(CO)2(NHC) (NHC = ItBu, IAd) forming complexes (8) and (9) led to the determination of average bond dissociation energy of Ni-NHC (NHC = ICy, IMes) and Ni-P (P = PCy3, PPh3, P(p-Tol)3, P(m-Tol)3).
3

Impact of Mass and Bond Energy Difference and Interface Defects on Thermal Boundary Conductance

Choi, ChangJin 01 May 2016 (has links)
Many portions of energy generated in the U.S. are not used and take the form of wasted heat due to a poor heat transfer efficiency. This fact leads research communities to focus on thermoelectrics as a means for using waste heat through direct thermal to electrical energy conversion. One way to enhance thermoelectric efficiency is to reduce thermal conductivity through nanostructuring. In nanostructures, understanding energy transport across the interface of two materials is important because interfaces dominate the resistance to overall thermal transport of the system and can be described by thermal boundary conductance (TBC). Also of note, an understanding of thermal transport cannot be achieved without an understanding of transfer via atomic vibration, known as phonons. In this study, two different techniques of molecular dynamics (MD) simulation are introduced in order to improve the understanding of the phonon transport at the interface of dissimilar materials and the impact of different material properties on TBC. Non-equilibrium MD simulations are used to study relative and combined contributions of mass and bond energy difference on TBC and phonon wave-packet simulations are used to obtain a detailed description of phonon interactions at the interface. At the end of this study, a simple analytical model for the prediction of effective thermal conductivity, using knowledge of thermal boundary resistance, an inverse of TBC, and the interface geometry, is developed.
4

Relationship Between Surface Free Energy and Total Work of Fracture of Asphalt Binder and Asphalt Binder-Aggregate Interfaces

Howson, Jonathan Embrey 2011 August 1900 (has links)
Performance of asphalt mixtures depends on the properties of its constituent materials, mixture volumetrics, and external factors such as load and environment. An important material property that influences the performance of an asphalt mixture is the surface free energy of the asphalt binder and the aggregate. Surface free energy, which is a thermodynamic material property, is directly related to the adhesive bond energy between the asphalt binder and the aggregate as well as the cohesive bond energy of the asphalt binder. This thermodynamic material property has been successfully used to select asphalt binders and aggregates that have the necessary compatibility to form strong bonds and resist fracture. Surface free energy, being based on thermodynamics, assumes the asphalt binder is a brittle elastic material. In reality, the asphalt binder is not brittle and dissipates energy during loading and unloading. The total work of fracture is the culmination of all energy inputted into the sample to create two new surfaces of unit area and is dependent on the test geometry and testing conditions (e.g., temperature, loading rate, specimen size, etc.). The magnitude of the bond energy (either adhesive or cohesive) can be much smaller in magnitude when compared to the total work of fracture measured using mechanical tests (i.e., peel test, pull-off test, etc.). Despite the large difference in magnitude, there exists evidence in the literature supporting the use of the bond energy to characterize the resistance of composite systems to cohesive and/or adhesive failures. If the bond energy is to be recognized as a useful screening tool by the paving industry, the relationship between the bond energy and total work of fracture needs to be understood and verified. The effect of different types of modifications (addition of polymers, addition of anti-strip agents, and aging) on the surface free energy components of various asphalt binders was explored in order to understand how changes in the surface free energy components are related to the performance of the asphalt mixtures. After the asphalt binder-aggregate combination was explored, the next step was to study how the surface free energy of water was affected by contact with the asphalt binder-aggregate interface. Aggregates, which have a pH of greater than seven, will cause the pH of water that contacts them to increase. A change in the pH of the contacting water could indicate a change in its overall surface free energy, which might subsequently increase or decrease the water's moisture damage potential. With surface free energy fully explored, the total work of fracture was measured using pull-off tests for asphalt binder-aggregate combinations with known surface free energy components. In order to fully explore the relationship between bond energy and total work of fracture, temperature, loading rate, specimen geometry, and moisture content were varied in the experiments. The results of this work found that modifications made to the asphalt binder can have significant positive or negative effects on its surface free energy components and bond energy. Moreover, the results from the pull-off tests demonstrated that a relationship exists between bond energy (from surface free energy) and total work of fracture (from pull-off tests), and that surface free energy can be used to estimate the performance of asphalt binder-aggregate combinations.
5

THROUGH-BOND ENERGY TRANSFER CASSETTES FOR MULTIPLEXING & DEVELOPMENT OF METHODS FOR PROTEIN MONO-LABELING

Ueno, Yuichiro 2009 May 1900 (has links)
A set of three through-bond energy transfer cassettes based on BODIPY as a donor and cyanine dyes as acceptors has been prepared via Sonogashira couplings, and their photophysical properties were examined. These cassettes fluoresce around 600 to 800 nm and are resolved by approximately 100 nm. This property is an important factor for multiplexing study in cellular imaging. Several useful fluorescent probes such as 5- and 6-carboxyfluorescein, water-soluble BODIPY, and water-soluble Nile Blue dyes, have also been synthesized and their photophysical properties studied. We have also attempted to develop a method for protein mono-labeling via a solidphase approach. The labeling of protein with one fluorescent dye facilitates quantification and single molecule imaging in biological applications. Various solidsupports such as PEGA, CPG, and BSA-coated CPG, were tested. Photolabile and chemically cleavable linkers were prepared to connect solid-supports and fluorophores. Unfortunately, our approach to the fluorescent mono-labeling of native proteins did not give us any conclusive results.
6

Activité et stabilité de phases sulfures pour l’hydrotraitement d’huiles végétales / Activity and stability of sulfur catalytic phases for hydrotreating of vegetable oils

Ruinart de Brimont, Mathias 13 October 2011 (has links)
En combinant expérimentations et calculs ab initio, nous proposons une étude rationnelle des mécanismes de désoxygénation de molécules modèles pertinentes (heptanoate d'éthyle et heptanal) afin de fournir des guides pour définir des systèmes catalytiques optimaux pour l'hydrotraitement de matières premières renouvelables (huiles végétales, graisses animales). L'hydrotraitement d'huiles végétales, par la réaction de désoxygénation, est une voie alternative à la transestérification et peut être envisagée pour obtenir une base gazole de haute qualité. La transformation des composés oxygénés modèles a été étudiée sous une pression totale de 1.5 MPa, à une température de 523 K, dans un réacteur à lit fixe en présence de différents sulfures de métaux de transition massiques (SMT). Cette étude a mis en évidence l'influence de la nature phase sulfure sur la sélectivité des voies de désoxygénation (hydrodésoxygénation (HDO) et/ou décarbonylation/ décarboxylation (DCO)) ainsi que la réactivité particulière du sulfure de rhodium lors de la transformation de l'heptanoate d'éthyle. À l'inverse, quelle que soit la phase sulfure utilisée, la transformation de l'heptanal suit principalement la voie HDO. Dans nos conditions réactionnelles, l'heptanal a été identifié comme un intermédiaire de cette voie de désoxygénation. L'effet promoteur du cobalt et du nickel sur l'activité du sulfure de molybdène monométallique a été observé lors de la transformation de l'heptanal. La relation entre les activités en désoxygénation et en HDO et l'énergie de liaison métal-soufre (E(MS)) calculée ab initio des solides suit une courbe en volcan. Le sulfure mixte NiMoS (0.43), qui présente une E(MS) intermédiaire (127 kJ.mol-1), est le SMT le plus actif pour les deux réactions. Le catalyseur bimétallique CoMoS (0.1) présente la sélectivité HDO/DCO la plus élevée. À l'aide des résultats catalytiques et de calculs ab initio, deux mécanismes réactionnels sont proposés pour les voies de réactions HDO et DCO / By combining well defined experiments and density functional theory (DFT) calculations, we propose a rational understanding of the deoxygenation mechanisms of relevant oxygenate molecules (ethyl heptanoate and heptanal) so as to provide guides to define optimal catalytic systems for the hydrotreating of renewable feedstocks (vegetable oils, animals fats). The hydrotreatment of vegetable oils, with the deoxygenation reaction, is an alternative route to transesterification and can be used to obtain high quality diesel. The transformation of oxygenated model compounds was studied under a total pressure of 1.5 MPa, at 523 K, in a fixed bed reactor over various unsupported transition metal sulfide catalytic phases (TMS). Results have shown the influence of the sulfide phase on the selectivity for deoxygenation reaction (hydrodeoxygenation (HDO) and/or decarbonylation/ decarboxylation (DCO)) and the specific reactivity of the rhodium sulfide for the transformation of ethyl heptanoate. The study of the transformation of heptanal shows the reaction of deoxygenation is preferentially following the HDO pathway over all the catalysts. In our reaction conditions, heptanal was identified as a reaction intermediate of this deoxygenation pathway. The promoting effect of cobalt and nickel on the activity of monometallic molybdenum sulphide was observed for the transformation of heptanal. The relation between the deoxygenation and HDO rates and the ab initio calculated sulphur-metal bond energy E(MS) in the bulk TMS is following a volcano curve. Bimetallic sulfide NiMoS (0.43), with an intermediate E(MS) (127 kJ.mol-1), is found as the most active TMS for both reactions. The maximum of the HDO/DCO selectivity is obtained for the mixed catalyst CoMoS (0.1). Thanks to catalytic results and ab initio calculations, two reaction pathways are proposed for HDO and DCO reactions

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