Organic particulate matter represents a significant fraction of sub-micrometer atmospheric aerosol mass. However, organic aerosol (OA) consists of thousands of different organic compounds making the simulation of its concentration, chemical evolution, physical and chemical properties extremely challenging. The identity of the great majority of these compounds remains unknown. The volatility of atmospheric OA is one of its most important physical properties since it determines the partitioning of these organic compounds between the gas and particulate phases. The use of lumped compounds with averaged properties is a promising solution for the representation of OA in atmospheric chemical transport models. The two-dimensional volatility basis set (2D-VBS) is a proposed method used to describe OA distribution as a function of the volatility and oxygen content of the corresponding compounds. In the first part of the work we evaluate our ability to measure the OA volatility distribution using a thermodenuder (TD). We use a new method combining forward modeling, introduction of ‘experimental’ error and inverse modeling with error minimization for the interpretation of TD measurements. The OA volatility distribution, its effective vaporization enthalpy, the mass accommodation coefficient and the corresponding uncertainty ranges are calculated. Our results indicate that existing TD-based approaches quite often cannot estimate reliably the OA volatility distribution, leading to large uncertainties, since there are many different combinations of the three properties that can lead to similar thermograms. We propose an improved experimental approach combining TD and isothermal dilution measurements. We evaluate this experimental approach using the same model and show that it is suitable for studies of OA volatility in the lab and the field. Measurements combining a thermodenuder (TD) and a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) took place during summer and winter in Paris, France as part of the collaborative project MEGAPOLI and during the winter of 2013 in the city of Athens. The above volatility estimation method with the uncertainty estimation algorithm is applied to these datasets in order to estimate the volatility distribution for the organic aerosol (OA) and its components during the two campaigns. The concentrations of the OA components as a function of temperature were measured combining data from the thermodenuder and the aerosol mass spectrometer (AMS) with Positive Matrix Factorization (PMF) analysis. Combining the bulk average O:C ratios and volatility distributions of the various factors, our results are placed into the two-dimensional volatility basis set (2D-VBS) framework. The OA factors cover a broad spectrum of volatilities with no direct link between the average volatility and average O:C of the OA components. An intercomparison among the OA components of both campaigns and their physical properties is also presented. The approach combining thermodenuder and isothermal dilution measurements is tested in smog chamber experiments using OA produced during meat charbroiling. The OA mass fraction remaining is measured as a function of temperature in the TD and as a function of time in the isothermal dilution chamber. These two sets of measurements are used together to estimate the volatility distribution of the OA and its effective vaporization enthalpy and accommodation coefficient. In the isothermal dilution experiments approximately 20% of the OA evaporate within 15 min. In the TD almost all the OA evaporated at approximately 200oC. The resulting volatility distributions suggest that around 60-75% of the cooking OA (COA) at concentrations around 500 μg m-3 consists of low volatility organic compounds (LVOCs), 20-30% of semi-volatile organic compounds (SVOCs) and around 10% of intermediate volatility organic compounds (IVOCs). The estimated effective vaporization enthalpy of COA is 100 ± 20 kJ mol-1 and the effective accommodation coefficient is around 0.05. The characteristics of the COA factor from the Athens campaign are compared to those of the OA produced from meat charbroiling in these experiments. In the next step, different parameterizations of the organic aerosol (OA) formation and evolution in the two-dimensional Volatility Basis Set (2D-VBS) framework are evaluated using ground and airborne measurements collected in the 2012 Pan-European Gas AeroSOls-climate-interaction Study (PEGASOS) field campaign in the Po Valley, Italy. A number of chemical schemes are examined, taking into account various functionalization and fragmentation pathways for biogenic and anthropogenic OA components. Model predictions and measurements, both at the ground and aloft, indicate a relatively oxidized OA with little average diurnal variation. Total OA concentration and O:C ratios were reproduced within experimental error by a number of chemical aging schemes. Anthropogenic SOA is predicted to contribute 15-25% of the total OA, while SOA from intermediate volatility compounds oxidation another 20-35%. Biogenic SOA contributions varied from 15 to 45% depending on the modeling scheme. The average OA and O:C diurnal variation and their vertical profiles showed a surprisingly modest sensitivity to the assumed vaporization enthalpy for all aging schemes. This can be explained by the intricate interplay between the changes in partitioning of the semivolatile compounds and their gas-phase chemical aging reactions. The same set of different parameterizations of the organic aerosol (OA) formation and evolution in the two-dimensional Volatility Basis Set (2D-VBS) framework are evaluated using ground measurements collected in the 2013 PEGASOS field campaign in the boreal forest station of Hyytiälä in Southern Finland. The most successful is the simple functionalization scheme of Murphy et al. (2012) while all seven aging schemes have satisfactory results, consistent with the ground measurements. Despite their differences, these schemes predict similar contributions of the various OA sources and formation pathways. Anthropogenic SOA is predicted to contribute 11- 18% of the total OA, while SOA from intermediate volatility compounds oxidation another 18- 27%. The highest contribution comes from biogenic SOA, as expected contributing 40 to 63% depending on the modeling scheme. The primary OA contributes 4% while the SOA resulting from the oxidation of the evaporated POA varies between 4 to 6%. Finally, 5-6% is according to the model the results of long range transport from outside the modeling domain.

This thesis documents and discusses the analysis of material properties and pavement performance for Highway 17 and Highway 655 pavement trial sections located in northern Ontario. The object of this work was to compare laboratory-aged material with recovered asphalt cement and to develop an improved chemical aging method that provides asphalt cement that more closely reflects properties after 8-10 years of service. Physical testing of the asphalt cements was done using a bending beam rheometer (BBR) and double-edge-notched tension (DENT) test for laboratory aged material as well as recovered material from the road. The comparison of the regular BBR, extended BBR and elastic recovery test in BBR is also done for the laboratory-aged and recovered material. Two simple modifications to the regular pressure aging vessel (PAV) aging protocol were investigated as possible ways to improve the correlation between field and laboratory material properties. The length of the PAV aging was doubled to 40 hours and the weight for each pan was halved to 25 grams. It was observed that the presently used RTFO/PAV aging protocol does not produce sufficient aging. Hence, the conditions chosen were more severe and therefore are likely to bring the laboratory aging closer to the field aged condition. It was found that both the increase in time and the reduction in weight were able to accomplish the stated objective for most but not all asphalt cements. A separate investigation involved the infrared (IR) analysis of asphalt cements recovered from a large number of contracts in eastern and northeastern Ontario. This study indicated that those asphalts with a largely paraffinic structure (low aromatics index) showed excessive and premature cracking even at lower levels of oxidation (carbonyl index). In contrast, those pavements that were largely spared of thermal distress were constructed with asphalt cements that contained more aromatics (high IR aromatics indices). Aromatics allow the largely aromatic asphaltenes that are formed upon oxidation to remain well peptized rather than flocculated. Peptized asphaltenes allow for good stress relaxation during winter and spring thaw and thus such materials show a reduced tendency for cracking. / Thesis (Master, Chemistry) -- Queen's University, 2010-12-13 11:25:17.522

Thermal and fatigue cracking are pavement distresses that deteriorate asphalt pavements in Canada. However, the current AASHTO M320 standard specification protocol does not give satisfactory correlation between the properties measured in the laboratory to thermal and fatigue cracking performance of the asphalt in service. This thesis is aimed at validating the newly developed MTO LS-299 and LS-308 specification test methods for predicting pavement distress. A secondary objective is to determine how well laboratory-aged and field-aged binders correlate with each other in terms of their chemical and physical properties. Chemical testing using infrared (IR) spectroscopy and X-ray fluorescence (XRF), as well as physical and mechanical testing using the regular bending beam rheometer (BBR), extended BBR (eBBR), dynamic shear rheometer (DSR), and double edge notched tension (DENT) tests were performed on laboratory-aged and recovered binders from Highway 417. Asphalt cements with significant amounts of waste engine oil residues as determined by XRF data were found to have cracked severely due to their high tendency for chemical aging. Western Canadian binders modified with styrene-butadiene-styrene polymer showed low affinity for both chemical and physical aging as determined from their carbonyl indices. Asphalt binders with smaller paraffinic structures exhibited insignificant pavement deterioration while the opposite occurred to those with low aromatic indices according to their IR data. The DSR data show that chemical aging occurs much faster in the laboratory-aged binders than the field-aged binders. The DENT test is able to separate superior performing binders from inferior ones with 86% accuracy according to their CTOD data. The regular BBR gave poor correlation between the laboratory test methods and the performance of the pavements. Good correlation exists between the laboratory test methods and the performance of the pavements in service according to the eBBR data. Pavements without any cracks showed lower grade losses, while pavements with severe thermal cracking recorded higher grade losses after three days of conditioning prior to testing. The study has shown that the eBBR and DENT tests are better tools for predicting pavement performance and provide good specification tests for the control of thermal and fatigue cracking in modern pavements. / Thesis (Master, Chemistry) -- Queen's University, 2012-02-28 13:16:02.222

The objective of this study was to evaluate and develop an understanding of durability of an adhesive bonded system, for application in a future high speed civil transport (HSCT) aircraft structure. The system under study was comprised of Ti-6Al-4V metal adherends and a thermosetting polyimide adhesive, designated as FM-5, supplied by Cytec Engineered Materials, Inc. An approach based on fracture mechanics was employed to assess Ti-6Al-4V/FM-5 bond durability. Initially, wedge tests were utilized to find a durable surface pretreatment for the titanium adherends. Based on an extensive screening study, chromic acid anodization (CAA) was chosen as the standard pretreament for this research project. Double cantilever beam specimens (DCB) were then made and aged at 150° C, 177° C, and 204° C in three different environments; ambient atmospheric air (14.7 psia), and reduced air pressures of 2 psi air (13.8 KPa) and 0.2 psi air (1.38 KPa). Joints were aged for up to 18 months (including several intermediate aging times) in the above environments. The strain energy release rate (G) of the adhesive joints was monitored as a function of exposure time in the different environments. A 40% drop in fracture toughness was noted over the 18 month period, with the greatest degradation observed in samples aged at 204° C in ambient atmospheric air pressure. The loss in adhesive bond performance with time was attibutable to a combination of physical and chemical aging phenomena in the FM-5 resin, and possible degradation of the metal-adhesive interface(s). Several mechanical and material tests, performed on the bonded joints and neat FM-5 resin specimens, confirmed the above statement. It was also noted that physical aging could be "erased" by thermal rejuvenation, partially restoring the toughness of the FM-5 adhesive material. The FM-5 adhesive material displayed good chemical resistance towards organic solvents and other aircraft fluids such as jet fuel and hydraulic fluid. The results from the FM-5 adhesive and its bonded joints were compared and contrasted with VT Ultem and REGULUS polyimide adhesives. The FM-5 adhesive showed the best performance among the three adhesive systems. The effect of mode-mixity on the fracture toughness of the Ti-6Al-4V/FM-5 adhesive bonded system was also evaluated. DCB tests in conjunction with end-notched flexure (ENF) and mixed-mode flexure (MMF) tests, were used to fracture the bonded joints under pure mode I, pure mode II, and a combination of mode I and II loadings. The results showed that the mode I fracture toughness was twice as large as the mode II toughness. This was a rather surprising find, in sharp contrast to what several researchers have observed in the past. Our current understanding is that the crack path selection during the failure process plays a significant role in explaining this anomalous behavior. Finally, failure envelopes were generated for the titanium/FM-5 bonded system, both prior to and following thermal aging. These envelopes could serve as useful tools for engineers designing with Ti-6Al-4V/FM-5 bonds. / Ph. D.

Cette thèse s'inscrit dans la thématique technologique des décharges électrostatiques sur les panneaux solaires des satellites de télécommunication en orbite géostationnaire. Son objectif est de déterminer les évolutions des propriétés électriques d'un adhésif silicone commercial en environnement spatial et de les corréler aux évolutions de sa structure chimique. Les principaux constituants du matériau ont été identifiés et des échantillons dépourvus de particules de renfort - assimilés à la matrice polymère isolée - ont été élaborés. Afin d'évaluer l'influence des particules, ils ont été systématiquement comparés aux échantillons nominaux dans l'ensemble de ces travaux. La structure physico-chimique du matériau à l'état initial a été caractérisée en étudiant ses relaxations enthalpiques, mécaniques et en pratiquant des analyses chimiques. Son comportement électrique (relaxations dipolaires et conductivité) a été sondé grâce à une approche expérimentale inédite croisant la technique de relaxation de potentiel électrostatique de surface, la spectroscopie diélectrique dynamique et l'analyse des courants thermo-stimulés. Le vieillissement du matériau en environnement spatial a été simulé expérimentalement par l'exposition des échantillons à des flux élevés d'électrons de haute énergie. Les analyses chimiques, notamment en RMN du solide, ont montré la prédominance d'un processus de réticulation du matériau sous irradiation, et des mécanismes de dégradation à l'échelle microscopique ont été proposés. Le comportement électrique du matériau est fortement impacté par l'évolution de sa structure chimique : sa résistivité augmente considérablement avec la dose ionisante. Il est suggéré que la résistivité de ce matériau soit directement liée à son degré de réticulation, influant sur la mobilité des porteurs dans le cadre du hopping et de la percolation électrique. Cette augmentation est beaucoup plus marquée en présence de particules, ce qui a été attribué à la formation de nœuds de réticulation matrice-particules qui constituent des pièges plus profonds pour les porteurs de charges. Ces travaux apportent une meilleure compréhension des phénomènes de vieillissement des élastomères silicones en environnement spatial. Ils permettront d'anticiper des évolutions structurales qui pourraient mettre en péril leur fonction d'adhésion, ainsi que des évolutions de résistivité électrique intrinsèque, facteur décisif dans le déclenchement de décharges électrostatiques. / This PhD thesis falls within the technical field of electrostatic discharges occurring on the solar arrays of communications satellites in the geostationary orbit. Its main objective consists in assessing the evolutions of a space-used commercial silicone adhesive's electrical properties, and to correlate them with the evolutions of its chemical structure. The main components of this material have been identified, and neat samples (deprived of fillers) were elaborated so as to study the isolated polymer matrix. In order to assess the influence of filler incorporation, neat samples were systematically compared with the commercial ones in this study. The material's physicochemical structure in the initial state was characterized by studying its enthalpy relaxations, mechanical response, and by performing chemical analysis. Its electrical behavior (dipole relaxations and conductivity) was investigated thanks to an original experimental approach combining surface potential decay measurements, broadband dielectric spectroscopy, and thermally stimulated depolarization currents. Aging in the space environment was experimentally simulated by exposing the samples to high fluxes of high energy electrons. Chemical analysis (solid state NMR in particular) revealed the predominant crosslinking tendency of this material under ionizing radiations, and allowed to suggest degradation mechanisms at the microscopic scale. These structural evolutions also strongly impact its electrical behavior: a great increase in electrical resistivity has been observed with increasing ionizing dose. It is believed that electrical resistivity directly depends on the degree of crosslinking, which affects charge carrier mobility, in the theoretical frame of hopping and percolation models. The increase in resistivity is considerably more pronounced in the filled material, which could be associated with crosslinking occurring at the matrix-particles interface. Such crosslinks are thought to represent deeper traps for charge carriers. This work brought better understanding of aging phenomena in silicone elastomers exposed to the ionizing space environment. This knowledge will help predicting structural evolutions that may compromise vital properties such as adhesion, and the evolutions of intrinsic conductivity, a critical factor involved in the triggering of electrostatic discharges.