L'objectiu d'aquest tesi és avaluar els diferents passos en el camí que va des de l'exposició a contaminants atmosfèrics/PAHs fins a la malaltia, el càncer de bufeta urinària. Es van mesurar partícules ultrafines a Barcelona. S'ha avaluat l'exposició a contaminació atmosfèrica en un estudi cas-control, recollint informació sobre la història residencial incloent diversos indicadors de l'exposició a contaminació atmosfèrica i altres factors de risc potencials. Es va dur a terme una revisió sistemàtica de la literatura per avaluar si els nivells de metabòlits del pirè i els aductes d'ADN i de proteïnes es correlacionaven amb nivells baixos d'exposició a PAHs. Vam mesurar els nivells d'aductes d'ADN en un subgrup d'individus de l'estudi cas-control amb la tècnica del radioetiquetatge amb fòsfor-32, tractament de la nucleasa P1. Vam analitzar 22 SNPs en set gens de la via de reparació de l'ADN per excisió de nucleòtids. / The aim of this thesis is to evaluate the different steps in the pathway from exposure (air-contaminants/PAHs) to disease (bladder cancer). We measured ultrafine particles in Barcelona. We evaluated the exposure to air pollutants in a case-control study, collecting information on the residential history with proxies for exposure to air pollution and other potential risk factors. We did a systematic review of the literature to evaluate if pyrene metabolites and DNA and protein adducts are correlated with low level exposure to PAHs. We measured bulky DNA adducts in a subgroup of subjects of the case-control study using 32P-Postlabeling, nuclease P1 treatment. We analyzed 22 SNPs in 7 genes of the nucleotide excision repair pathway.

Population exposure to traffic pollution is a rapidly developing, multi-disciplinary scientific field. While the link between long-term exposure and respiratory issues is well-established, there are probable links to a number of more serious health effects, which are still not fully understood. In the interests of protecting human health, it is prudent that we take a cautionary approach and actively seek to reduce exposure levels, especially in the home environment where people spend a significant portion of their time. In many large cities, a substantial number of homes are situated on land immediately adjacent to busy freeways and other heavily-trafficked roads. Characterising exposures of local residents is incredibly challenging but necessary for advancing epidemiological understandings. While existing studies are plentiful, the results are mixed and generally not transferable to other urban areas due to the localised nature of the built environment and meteorological influences. This thesis aimed to employ a variety of methods to develop a holistic understanding of the influence of traffic emissions on near-highway residents' exposure in two communities of South Auckland, New Zealand, where Annual Average Daily Traffic (AADT) is as high as 122,000 vehicles. First, ultrafine particles (UFPs), nitrogen oxides (NOx), carbon monoxide (CO) and particulate matter ≤ 10 μm (PM₁₀) were continuously monitored using a series of fixed stations at different distances from the highways, over several months during the winters of 2010 and 2011. Emissions modelling output (based on traffic composition), was used within a dispersion model to compare modelled concentrations with monitored levels. In addition, community census meshblock units were mapped by level of social deprivation in order to assess potential inequities in highway emissions exposure. The second layer of local air quality investigation involved using a bicycle platform to systematically measure concentrations of UFPs, CO and PM₁₀ using the entire street-grid network throughout each community. This was done forty times - five times at four times of day (07:00, 12:00, 17:00 and 22:00), for each study area, with the aim of mapping the diurnal fluctuation of microspatial variation in concentrations. Using global positioning system (GPS) data and geographical information system (GIS) software, spatially-resolved pollutant levels were pooled by time of day and the median values mapped, providing a visualisation of the spatial extent of the influence of emissions from the highways compared to minor roads. The third layer involved using data from multiple ambient monitors, both within the local areas and around the city, to simulate fifty-four residents' personal exposure for the month of June, 2010. This required collecting timeactivity information which was carried out by door-to-door surveying. The time-activity data were transformed into microenvironment and activity codes reflecting residents movements across a typical week, which were then run through the US-EPA's Air Pollution Exposure Model (APEX). APEX is a probabilistic population exposure model for which the user sets numerous microenvironmental parameters such as Air Exchange Rates (AERs) and infiltration factors, which are used in combination with air pollutant concentrations, meteorological, and geospatial data, to calculate individuals' exposures. Simulated exposure outputs were grouped by residents' occupations and their home addresses were artificially placed at varying distances from the highways. The effects of residential proximity to the highway, occupation, work destination and commute distance were explored using a Generalised Linear Model (GLM). Surveyed residents were also asked a series of Likert-type, ordered response questions relating to their perceptions and understandings of the potential impacts of living near a significant emissions source. Their response scores were explored as a function of proximity to the highway using multivariate linear regression. This formed the final layer of this investigation into air quality throughout these South Auckland communities of Otahuhu and Mangere Bridge. Results show that concentrations of primary traffic pollutants (UFPs, NOx, CO) are elevated by 41 - 64% within the roadside corridor compared to setback distances approximately 150 m away and that the spatial extent of UFPs can reach up to 650 m downwind early in the morning and late in the evening. Further, social deprivation mapping revealed that 100% of all census meshblocks within 150 m either side of both highways are at the extreme end of the deprivation index (NZDep levels 8 - 10). Simulations for residents dispersed across the community of Otahuhu estimated daily NOx and CO exposure would increase by 32 and 37% (p<0.001) if they lived immediately downwind of the highway. If they were to shift 100 m further downwind, daily exposure would decline by 56 - 70% (p<0.001). The difference in individuals' exposure levels by occupation varied across the same distance by a factor of eight (p<0.05), with unemployed or retired persons the most exposed due to having more free time to spend outdoors at home (recreation, gardening, etc.). Those working in ventilated offices were the least exposed, even though ambient concentrations - likely due to a strong urban street canyon effect - were higher than the nearest highway monitor (5 m downwind) by 25 - 30% for NOx and CO, respectively. Inverse linear relationships were identified for distance from highway and measures of concern for health impacts, as well as for noise (p<0.05). Positive linear relationships were identified for distance from highway and ratings of both outdoor and indoor air quality (p<0.05). Measures of level of income had no conclusive statistically significant effect on perceptions (p>0.05). The main findings within this thesis demonstrate that those living within the highway corridor are disproportionately exposed to elevated long-term average concentrations of toxic air pollutants which may impact on physical health. While the socioeconomic characteristics could also heighten susceptibility to potential health impacts in these areas, certain activity patterns can help mitigate exposure. This thesis has also shown that there may be quantifiable psychological benefits of a separation buffer of at least 100 m alongside major highways. These results enhance a very limited knowledge base on the impacts of near-roadway pollution in New Zealand. Furthermore, the results lend additional support to the international literature which is working to reduce residential exposures and population exposure disparities through better policies and improved environmental planning. Where possible, the placement of sensitive population groups within highway corridors, e.g. retirement homes, social housing complexes, schools and childcare centres, should be avoided.

The number concentration and size distribution of particles in Brisbane have been studied extensively by the researchers at The International Laboratory for Air Quality and Health, Queensland University of Technology (Morawska et al., 1998, 1999a, 1999b). However, the comprehensive studies of chemical compositions of atmospheric particles, especially with regard to the two main classes of pollutants (polycyclic aromatic hydrocarbons and trace elements), that are usually of environmental and health interest, have not been fully undertaken. Therefore, this thesis presents detailed information on polycyclic aromatic hydrocarbons (PAHs) and elemental compositions of vehicle exhausts and of urban air in Brisbane. The levels of polycyclic aromatic hydrocarbons (PAHs) and elements in three of Brisbane's urban sites (Queensland University of Technology, Woolloongabba and ANZ stadium sites) were measured. The most common PAHs found in all sites were naphthalene, phenanthrene, anthracene, fluoranthene, pyrene and chrysene while Al, Cd, Co, Cr, Cu, Fe, Mn, Mo, Si, Sn, Sr and Zn were the most common elements detected in the total suspended particles and fine particle (PM2.5). With the aid of multivariate analysis techniques, several outcomes were obtained. For example: -- Major human activities such as vehicular and industrial sources were the most contributing pollution sources in Brisbane. However, these two sources have different influential strength on the compositions of the polycyclic aromatic hydrocarbons and trace inorganic elements found in the urban air. -- Woolloongabba bus platform was the most polluted site on the basis of the elemental and PAH compositions in its air samples while QUT site was the worst polluted site in terms of PM2.5 elemental contents. These results demonstrated that the impact of traffic related pollutants on Brisbane's urban air is significant. This led to the investigations of the direct emissions of pollutants from exhaust vehicular source in the second part of this research work. The exhaust studies included the investigations of PAHs, trace inorganic elements and particles. At the time of the study, the majority of vehicles in Brisbane used low sulfur diesel (LSD) fuel or unleaded petrol (ULP). However, the importance of vehicles using ultra low sulfur diesel (ULSD) and liquefied petroleum gas (LPG) is constantly growing. Therefore, the exhaust emission studies on chassis dynamometer from heavy duty non-catalyst-equipped buses powered by LSD and ULSD with 500 ppm and 50 ppm sulfur contents respectively as well as passenger cars powered by ULP and LPG were explored. The outcomes of such studies are summarized as follows: -- Naphthalene, acenaphthene, acenaphthylene, anthracene, phenanthrene, fluorene, fluoranthene and pyrene were frequently emitted by the buses powered by LSD and ULSD. However, buses powered by ULSD emitted 91% less PAHs than those powered by LSD. On the other hand, Mg, Ca, Cr, Fe, Cu, Zn, Ti, Ni, Pb, Be, P, Se, Ti and Ge were found in measurable quantities in the exhaust of the buses. The emissions of the elements were found to be strongly influenced by the engine driving conditions of the buses and fuel parameters such as sulfur content, fuel density and cetane index. -- Naphthalene, fluorene, phenanthrene, anthracene, pyrene, chrysene, benzo(a)anthracene and benzo(b)fluoranthene were predominantly emitted by ULP and LPG cars. On the average, the total emission factors of PAHs from LPG cars were generally lower than those of ULP cars, but given the large variations in the emission factors of cars powered by the same type of fuel, differences in the emission factors from both car types were statistically insignificant. In general, platinum group elements and many other elements were found in the exhausts of cars powered by both fuels. Emissions of inorganic elements from the cars were dependent on the type and the mileage of the cars. For example, ULP cars generally emitted higher levels of Cu, Mg, Al and Zn while LPG cars emitted higher level of V. In addition, cars with higher mileages were associated with higher emissions of the major elements (Zn, Al, Fe, V and Cu). -- Buses powered by ULSD usually emitted fewer particles, which were generally 31% to 59% lower than those emitted by LSD powered buses. Similarly, cars powered by LPG emitted less particles from those powered by ULP fuel. However, more nanoparticles (those with aerodynamic diameters of less than 50 nm) were emitted by LPG powered cars than their ULP counterparts. Health effect assessment of the exhaust PAHs was evaluated in terms of benzo(a)pyrene toxicity equivalent (BAPeq). The potential toxicities of PAHs emitted by ULSD powered buses were generally lower than those emitted by their LSD counterparts. A similar trend with lower emissions of PAHs from LPG cars than from ULP cars was observed when otherwise identical passenger cars were powered by LPG and ULP fuels. In summary, this thesis has shown that the majority of airborne particles found around Brisbane have anthropogenic origins, particularly vehicle emissions, and that fuel or lubricant formulations and engine operating conditions play important roles in the physical and chemical characteristics of pollutants emitted by vehicles. The implications of these results on worldwide strategies to reduce the environmental and health effects of particles emitted by motor vehicles were discussed. In this regard, direct emission measurements from vehicles powered by LSD, ULSD, ULP and LPG unveiled the relative environmental benefits associated with the use of ULSD in place of LSD to power diesel engines, and of LPG in place of ULP to power passenger cars.

Biomass burning started to attract attention since the last decade because of its impacts on the atmosphere and the environmental air quality, as well as significant potential effects on human health and global climate change. Knowledge of particle emission characteristics from biomass burning is crucially important for the quantitative assessment of the potential impacts. This thesis presents the results of study aimed towards comprehensive characterization of particle emissions from biomass burning. The study was conducted both under controlled laboratory conditions, to quantify the particle size distribution and emission factors by taking into account various factors which may affect the particle characteristics, and in the field, to investigate biomass burning processes in the real life situations and to examine vertical profile of particles in the atmosphere. To simulate different environmental conditions, a new technique has been developed for investigating particle emissions from biomass burning in the laboratory. As biomass burning may occur in a field at various wind speeds and burning rates, the technique was designed to allow adjustment of the flow rates of the air introduced into the chamber, in order to control burning under different conditions. In addition, the technique design has enabled alteration of the high particle concentrations, allowing conducting measurements with the instrumentations that had the upper concentration limits exciding the concentrations characteristic to the biomass burning. The technique was applied to characterize particle emissions from burning of several tree species common to Australian forests. The aerosol particles were characterized in terms of size distribution and emission factors, such as PM2.5 particle mass emission factor and particle number emission factor, under various burning conditions. The characteristics of particles over a range of burning phases (e.g., ignition, flaming, and smoldering) were also investigated. The results showed that particle characteristics depend on the type of tree, part of tree, and the burning rate. In particular, fast burning of the wood samples produced particles with the CMD of 60 nm during the ignition phase and 30 nm for the rest of the burning process. Slow burning of the wood samples produced large particles with the CMD of 120 nm, 60 nm and 40 nm for the ignition, flaming and smoldering phases, respectively. The CMD of particles emitted by burning the leaves and branches was found to be 50 nm for the flaming phase and 30 nm for the smoldering phase, under fast burning conditions. Under slow burning conditions, the CMD of particles was found to be between 100 to 200 nm for the ignition and flaming phase, and 50 nm for the smoldering phase. For fast burning, the average particle number emission factors were between 3.3 to 5.7 x 1015 particles/kg for wood and 0.5 to 6.9 x 1015 particles/kg for leaves and branches. The PM2.5 emission factors were between 140 to 210 mg/kg for wood and 450 to 4700 mg/kg for leaves and branches. For slow burning conditions, the average particle number emission factors were between 2.8 to 44.8 x 1013 particles/kg for wood and 0.5 to 9.3 x 1013 particles/kg for leaves and branches, and the PM2.5 emissions factors were between 120 to 480 mg/kg for wood and 3300 to 4900 mg/kg for leaves and branches. The field measurements were conducted to investigate particle emissions from biomass burning in the Northern Territory of Australia over dry seasons. The results of field studies revealed that diameters of particles in ambient air emissions were within the size range observed during laboratory investigations. The laboratory measurements found that the particles released during the controlled burning were of a diameter between 30 and 210 nm, depending on the burning conditions. Under fast burning conditions, smaller particles were produced with a diameter in the range of 30 to 60 nm, whilst larger particles, with a diameter between 60 nm and 210 nm, were produced during slow burning. The airborne field measurements of biomass particles found that most of the particles measured under the boundary layer had a CMD of (83 ± 13) nm during the early dry season (EDS), and (127 ± 6) nm during the late dry season (LDS). The characteristics of ambient particles were found to be significantly different at the EDS and the LDS due to several factors including moisture content of vegetation, location of fires related to the flight paths, intensity of fires, and burned areas. Specifically, the investigations of the vertical profiles of particles in the atmosphere have revealed significant differences in the particle properties during early dry season and late dry season. The characteristics of particle size distribution played a significant role in these differences.

Motor vehicles are a major source of gaseous and particulate matter pollution in urban areas, particularly of ultrafine sized particles (diameters < 0.1 µm). Exposure to particulate matter has been found to be associated with serious health effects, including respiratory and cardiovascular disease, and mortality. Particle emissions generated by motor vehicles span a very broad size range (from around 0.003-10 µm) and are measured as different subsets of particle mass concentrations or particle number count. However, there exist scientific challenges in analysing and interpreting the large data sets on motor vehicle emission factors, and no understanding is available of the application of different particle metrics as a basis for air quality regulation. To date a comprehensive inventory covering the broad size range of particles emitted by motor vehicles, and which includes particle number, does not exist anywhere in the world. This thesis covers research related to four important and interrelated aspects pertaining to particulate matter generated by motor vehicle fleets. These include the derivation of suitable particle emission factors for use in transport modelling and health impact assessments; quantification of motor vehicle particle emission inventories; investigation of the particle characteristic modality within particle size distributions as a potential for developing air quality regulation; and review and synthesis of current knowledge on ultrafine particles as it relates to motor vehicles; and the application of these aspects to the quantification, control and management of motor vehicle particle emissions. In order to quantify emissions in terms of a comprehensive inventory, which covers the full size range of particles emitted by motor vehicle fleets, it was necessary to derive a suitable set of particle emission factors for different vehicle and road type combinations for particle number, particle volume, PM1, PM2.5 and PM1 (mass concentration of particles with aerodynamic diameters < 1 µm, < 2.5 µm and < 10 µm respectively). The very large data set of emission factors analysed in this study were sourced from measurement studies conducted in developed countries, and hence the derived set of emission factors are suitable for preparing inventories in other urban regions of the developed world. These emission factors are particularly useful for regions with a lack of measurement data to derive emission factors, or where experimental data are available but are of insufficient scope. The comprehensive particle emissions inventory presented in this thesis is the first published inventory of tailpipe particle emissions prepared for a motor vehicle fleet, and included the quantification of particle emissions covering the full size range of particles emitted by vehicles, based on measurement data. The inventory quantified particle emissions measured in terms of particle number and different particle mass size fractions. It was developed for the urban South-East Queensland fleet in Australia, and included testing the particle emission implications of future scenarios for different passenger and freight travel demand. The thesis also presents evidence of the usefulness of examining modality within particle size distributions as a basis for developing air quality regulations; and finds evidence to support the relevance of introducing a new PM1 mass ambient air quality standard for the majority of environments worldwide. The study found that a combination of PM1 and PM10 standards are likely to be a more discerning and suitable set of ambient air quality standards for controlling particles emitted from combustion and mechanically-generated sources, such as motor vehicles, than the current mass standards of PM2.5 and PM10. The study also reviewed and synthesized existing knowledge on ultrafine particles, with a specific focus on those originating from motor vehicles. It found that motor vehicles are significant contributors to both air pollution and ultrafine particles in urban areas, and that a standardized measurement procedure is not currently available for ultrafine particles. The review found discrepancies exist between outcomes of instrumentation used to measure ultrafine particles; that few data is available on ultrafine particle chemistry and composition, long term monitoring; characterization of their spatial and temporal distribution in urban areas; and that no inventories for particle number are available for motor vehicle fleets. This knowledge is critical for epidemiological studies and exposure-response assessment. Conclusions from this review included the recommendation that ultrafine particles in populated urban areas be considered a likely target for future air quality regulation based on particle number, due to their potential impacts on the environment. The research in this PhD thesis successfully integrated the elements needed to quantify and manage motor vehicle fleet emissions, and its novelty relates to the combining of expertise from two distinctly separate disciplines - from aerosol science and transport modelling. The new knowledge and concepts developed in this PhD research provide never before available data and methods which can be used to develop comprehensive, size-resolved inventories of motor vehicle particle emissions, and air quality regulations to control particle emissions to protect the health and well-being of current and future generations.

Outdoor air pollution is a major contributor to adverse health effects of citizens, in particular those living in urban environments. Air quality monitoring networks are set up to measure air quality in different environments in compliance with national and European legislation. Generally, only a few fixed monitoring sites are located within a city and thus cannot represent air pollutant concentrations in urban areas accurately enough to allow for a detailed human exposure assessment. Other approaches to derive detailed urban air pollutant concentration estimates exist, such as dispersion models and land-use regression (LUR) models. Low-cost portable air quality monitors are also emerging, which have the potential to add value to existing monitoring networks by providing measurements at greater spatial resolution and also to provide individual-level exposure assessment. The aim of this thesis is to demonstrate how measurements and modelling in combination allow detailed investigations of the variability of air pollutants in space and time in urban area, and in turn improve on the current exposure assessment methods. Three types of low-cost portable monitors measuring NO2, O3 (Aeroqual monitors) and PM2.5 (microPEM monitor) were evaluated against their respective reference instruments. The Aeroqual O3 monitor showed very good correlation (r2 > 0.9) with the respective reference instruments, but biases in the slope and intercept coefficients indicated that calibration of Aeroqual O3 monitor was needed. The Aeroqual NO2 monitor was subject to cross-sensitivity from O3, which, as demonstrated, can be effectively corrected by making O3 and NO2 measurements in tandem. Correlation between the microPEM monitor and its reference instrument was poor (r2 < 0.1) when PM2.5 concentrations were low (< 10 μg m-3), but significantly improved (r2 > 0.69) during periods with elevated PM2.5 concentrations. Relative humidity was not found to affect the raw results of PM2.5 measurements in a consistent manner. All three types of monitors cannot be used as equivalent or indicative methods instead of reference methods in studies that require quantification of absolute pollutant concentrations. However, the generally good correlations with reference instruments reassure their application in studies of relative trends of air pollution. Concentrations of PM2.5, ultrafine particles (UFP) and black carbon (BC) were quantified using portable monitors through a combination of mobile and static measurements in the city of Edinburgh, UK. The spatial variability of UFP and BC was large, of similar magnitude and about 3 times higher than the spatial variability of PM2.5. Elevated concentrations of UFP and BC were observed along streets with high traffic volumes whereas PM2.5 showed less variation between streets and a footpath without road traffic. Both BC and UFP significantly correlated with traffic counts, while no significant correlation between PM2.5 and traffic counts was observed. The relationships between UFP, NO2 and inorganic components of PM2.5 were further investigated through long-term measurements at roadside, urban background and rural sites. UFP moderately correlated with NOx (NO2 + NO) and showed varying relationships with NOx depending on the particle size distribution. Principal component analysis and air-mass back trajectory analysis revealed that PM2.5 concentrations were dominated by long-range transport of secondary inorganic aerosols, whereas UFP were mainly related to varying local emissions and meteorological conditions. These findings imply the need for different policies for managing human exposure to these different particle components: control of much BC and UFP appears to be manageable at local scale by restricting traffic emissions; however, abatement of PM2.5 requires a more strategic approach, in cooperation with other regions and countries on emissions control to curb long-range transport of PM2.5 precursors. A dispersion model (ADMS-Urban) was used to simulate high resolution NO2 and O3 concentrations in Edinburgh. The effects of different emission and meteorological input datasets on the resulting modelled NO2 concentrations were investigated. The modelled NO2 and O3 concentrations using the optimal model setup were validated against reference instrument and diffusion tube measurements. Temporal variability of NO2 was predicted well at locations that were not heavily influenced by local effects, such as road junctions and bus stops. Temporal variability of O3 was predicted better than for NO2. Long-term spatial variability of NO2 was found to correlate well with diffusion tube measurements, while modelled spatial variability of O3 in ADMS-Urban compared poorly with diffusion tube measurements. However, it was found that the O3 diffusion tube measurements may be subject to some unidentified biases affecting their accuracy. Land-use regression (LUR) models are widely used to estimate exposure to air pollution in urban areas. An appropriately sized and designed monitoring network is an important component for the development of a robust LUR model. Concentrations of NO2 were simulated by ADMS-Urban at ‘virtual’ monitoring sites in 54 different network designs of varying numbers and types of site, using a 25 km2 area including much of the Edinburgh city area. Separate LUR models were developed for each network. These LUR models were then used to estimate ambient NO2 concentrations at all residential addresses, which were evaluated against the ADMS-Urban modelled concentration at these addresses. The improvement in predictive capability of the LUR models was insignificant above ~30 monitoring sites, although more sites tended to yield more precise LUR models. Monitoring networks containing sites located within highly populated areas better estimated NO2 concentrations across all residential locations. LUR models constructed from networks containing more roadside sites better characterised the high end of residential NO2 concentrations but had increased errors when considering the whole range of concentrations. No particular composition of monitoring network resulted in good estimation simultaneously across all residential NO2 concentration and of the highest NO2 levels implying a lack of spatial contrast in LUR-modelled pollution surface compared with the dispersion model. Finally, the results from the measurement and modelling studies presented in thesis are synthesised in the context of current exposure assessment studies. Low-cost air-quality monitors currently do not possess and are unlikely in the near future to provide the robustness and accuracy to replace the existing routine monitoring network. Development of the low-cost air-quality should be aiming at upgrading them as the indicative method as defined in the data quality objective in the EU directive. The monitoring sites used to build LUR models should capture well the population distribution in the study area as opposed to capturing the greatest pollution contrast. The traditional methods of evaluating LUR models are also ineffective in characterising the models’ capability at estimating pollutant concentration at residential address. Given that the dispersion models are also subject to the availability and uncertainties in the input data, future air quality model development should endeavour to incorporate both dispersion and land-use regression models, where the uncertainty in the input data can be reduced by using LUR models built on actual measurements, and the limitation in the statistical modelling can be replaced by adopting the deterministic approach used in the dispersion model.

Title: Physical properties of ultrafine-grained magnesium based alloys prepared by various severe plastic deformation techniques Author: Jitka Stráská Department / Institute: Department of Physics of Materials Supervisor of the doctoral thesis: Doc. RNDr. Miloš Janeček, CSc. Abstract: The objective of the doctoral thesis is the complex investigation of ultrafine-grained magnesium alloy AZ31 prepared by two different severe plastic deformation techniques, in particular the hot extrusion followed by equal-channel angular pressing (EX-ECAP) and high pressure torsion (HPT). These severe plastic deformation methods, and as well as many others, are described in detail in the introductory theoretical section. Experimental results are summarized in the following experimental part of the thesis. Mechanical properties, lattice defect structure and especially microstructure were investigated using various experimental techniques. Thermal stability of ultrafine-grained microstructure of AZ31 after EX-ECAP was investigated and the activation energies for grain growth in different temperature ranges were calculated using kinetic equation for grain growth and Arrhenius equation. Results from the dislocation density measurements proved temperature ranges of the recovery and the following grain growth. Results from the...

Ce travail porte sur l'élaboration et l'analyse du comportement mécanique d'alliages à distribution bimodale de taille de grains. Les applications concernent les aciers inoxydables austénitiques 304L et 316L. Une approche couplée expérience-modélisation est menée pour comprendre les réponses mécaniques macroscopiques et locales de ces nouveaux alliages en se basant notamment sur l'étude des mécanismes de déformation associés. L'utilisation de deux voies d'élaboration et l'optimisation de leurs paramètres a conduit à l'obtention d'un large choix d'échantillons avec différentes distributions bimodales et différentes proportions de chaque famille de taille de grains. L'influence de ces caractéristiques microstructurales sur le comportement a été analysée sur la base d'essais en traction simple sous chargement monotone ou en charges-décharges alternées. Une base de données étendue de propriétés a ainsi été constituée et des éléments de réponse concernant les mécanismes de déformation propres aux alliages bimodaux ont pu être apportés. La présence de grains de taille conventionnelle (Coarse Grain -CG) au sein d'une matrice à grains ultrafins (UltraFine Grain - UFG) semble favoriser la relaxation d'une partie des contraintes internes de la matrice et tend ainsi à retarder l'endommagement des alliages bimodaux en comparaison aux alliages unimodaux à grains ultrafins. Une modélisation à champs complets selon deux lois de plasticité cristalline tenant compte explicitement d'une longueur interne a été proposée. Sa première motivation est de fournir un outil de prédiction du comportement effectif des alliages bimodaux en fonction de leurs caractéristiques microstructurales. Elle donne par ailleurs accès aux champs locaux et permet d'appuyer les analyses expérimentales en partition des contraintes en montrant à la fois une relaxation partielle des contraintes dans la matrice UFG mais aussi des concentrations de contrainte aux interfaces CG/UFG. / This work is focused on the elaboration and the mechanical behaviour of 304L and 316L austenitic stainless steel alloys with bimodal grain size distribution. The complementary approach between experiments and modelling enables a better understanding of both macroscopic and local mechanical responses and also of the associated deformation mechanisms.The use of two elaboration routes and optimized process parameters results in a wide range of samples with different bimodal grain size distributions. Grain sizes and fractions of each population are modified in order to study the influence of these microstructural characteristics on mechanical behavior. Uniaxial tensile tests are used to realize a database of mechanical properties of bimodal alloys and loading-unloading tests provides valuable informations about deformation mechanisms in these materials. With coarse grains (CG) embedded in an ultrafine grained (UFG) matrix, a relaxation of a part of the internal stresses seems to take place and leads to a delayed embrittlement of bimodal alloys as compared to their unimodal counterparts. Full-field modelling, based on two crystal plasticity laws with an explicit account of an internal length, is proposed. It constitutes a valuable prediction tool of effective properties of bimodal alloys in order, in particular, to study the effect of several microstructural characteristics. An access to local fields is also possible and tend, so far, to show similar results compared to experimental ones : stress relaxation is observed in the UFG matrix as well as stress concentrations at the CG/UFG interfaces.

Les alliages de cuivre sont utilisés dans de nombreuses applications électriques car ils offrent un bon compromis de résistance mécanique, de résistance à la corrosion et de conductivité électrique. Cependant pour certaines applications comme les contacteurs électriques, des matériaux plus performants sont recherchés. L’affinement de la taille de grains et l’implantation ionique sont deux voies que nous avons explorées dans ce but. Afin d’obtenir un bon compromis entre la dureté, la résistance à la corrosion et la conductivité électrique du cuivre pur (99,90%) et un bronze commercial monophasé contenant 8 % massique d’étain ont été nanostructurés par déformation plastique intense, et ensuite implantés à l’azote. Dans un premier temps, nous avons étudié l’évolution de la dureté des matériaux que nous avons corrélée aux changements microstructuraux induits par déformation plastique intense. Grâce à la microscopie électronique en transmission (MET) et la diffraction des rayons X (DRX), nous avons pu mettre en évidence la formation de grains ultrafins. Et nous avons prouvé que la solution solide CuSn métastable n’était pas décomposée au cours de la déformation. Par ailleurs, il a été montré que l’étain en solution solide favorise l’affinement des grains et que la déformation du CuSn8 à des vitesses plus rapides limite la restauration dynamique des défauts en engendrant une plus grande dureté. Un modèle qualitatif prenant en compte la production et l’annihilation de dislocations a été développé permettant de prédire l’influence des paramètres procès sur l’évolution de la microstructure et de la dureté. La stabilité thermique des nanostructures formées par déformation intense a également été étudiée, notamment par calorimétrie différentielle à balayage. Il a été montré que l’ajout d’étain en solution solide retarde la recristallisation alors que la densité de défauts et donc la force motrice est plus importante. Le Cu et le CuSn8 recristallisés et à grains ultrafins ont été implantés à l’azote. Il a été montré par nanoindentation que les duretés superficielles du Cu recristallisé et du Cu nanostructuré augmentent significativement après implantation. Nous avons mis en évidence par MET (SAED, STEM HAADF et EELS) la formation de nitrures de cuivre qui sont à l’origine du durcissement superficiel. Des nitrures de cuivre ont été également été formés dans le CuSn8 alors qu’aucun nitrure d’étain n’a été détecté. Par ailleurs, il est intéressant de noter que les défauts et notamment les mâcles formées après déformation intense semblent favoriser la diffusion de l’azote et être des sites de germination préférentielle des nitrures de cuivre. / Copper is the most used material in electrical field applications. For electrical contacts, its oxidation behavior, thermal stability and hardness is essential. In this work, we attempted to find the key to make strong, but also conductive metal with a high corrosion resistance by finding an appropriate copper microstructure and surface treatment. It is well known that material properties are determined by their microstructure. Also, it was seen that nitride films enhance the oxidation resistance and the surface hardness. Therefore, to achieve our goal, pure copper and a bronze alloy Cu-8wt. %Sn have been subjected to high pressure torsion to make ultra-fine-grains and the surface was then implanted with nitrogen ions. We have investigated the effect of deformation on the hardness and the thermal stability by Vickers microhardness and DSC measurements. It is shown that tin in solid solution delay the recrystallization of the UFG produced by HPT. Tin also promotes the grain refinement and limit the dynamic annihilation during HPT deformation. Furthermore, a correlation between the properties and the microstructure was done by SEM and TEM analyses. A qualitative model taking into account the production and annihilation of dislocations has been developed to predict the influence of process parameters on the evolution of microstructure and hardness. Recrystallized and UFG Cu and CuSn8 were implanted with nitrogen. It has been shown by nanoindentation that their surface hardness increase significantly after implantation. TEM analyses (SAED, STEM HAADF and EELS) demonstrated the formation of copper nitrides which cause superficial hardening. Copper nitrides were also formed in CuSn8 whereas no tin nitride was detected. Moreover, it is interesting to note that the defects (in particular deformation twins) seem to be preferential nucleation sites for copper nitrides.

Betong är vårt vanligaste byggmaterial men cement står globalt sett för 5 % av CO2-emissionerna. Med detta som bakgrund så har CBI Betonginstitutet anordnat en tävling, där målet är att nå den högsta tryckhållfasthet i en resurssnål betong, med enbart 200 kg cement per m3. Syftet med denna rapport är att utvärdera tävlingen, vilket har utförts genom en omfattande litteraturstudie.  En första analys av de olika betongrecepten medförde att olika grupperingar kunde urskiljas. Ur dessa fanns det tre stycken vars resultat var väldigt bra.   Concrete Innovation Centre, som med ett lågt vct, stora mängder granulerad masugnsslagg (81 %) och lite silikastoft (5 %), uppnådde en tryckhållfasthet på 80 MPa vid 28 dygn och 95 MPa vid 56 dygn.   CBI Stockholm, som genom användandet av ulltrafint filler och silikastoft (4,8 %), uppnådde en tryckhållfasthet på 84 MPa vid 28 dygn och 98 MPa vid 56 dygn.   Thomas Concrete Group som genom att ersätta cementet med en medelmåttig mängd granulerad masugnsslagg (54 %), liten mängd flygaska (9 %), kalkfiller och silikastoft (5 %), uppnådde en tryckhållfasthet på 94 MPa vid 28 dygn och 98 MPa vid 56 dygn.  Det finns således tre recept som vidare studier kan vara rättfärdigade på, de tre ovan nämnda. Det bör tilläggas att en imponerande tryckhållfasthet på nästan 100 MPa, kan uppnås i en betong med enbart 200 kg cement per m3. / Concrete is the most frequently used construction material, but cement globally stands for 5 % of the world’s CO2 emissions. With this as a background CBI Betonginstitutet has arranged a competition, where the goal is to reach the highest compressive strength in a resource economic concrete, with only 200 kg cement per m3. The purpose of this report is to evaluate the competition, which has been done via a substantial literature study.  A first analysis of the different concrete recipes resulted in that different groups could be identified. From these there were three recipes whose result was very good.   Concrete Innovation Centre, which with a low w/c, a high amount of ground granulated blast furnace slag (81 %) and little silica fume (5 %), reached a compressive strength of 80 MPa at 28 days and 95 MPa at 56 days.   CBI Stockholm, which by the usage of ultrafine filler and silica fume (4,8 %), reached a compressive strength of 84 MPa at 28 days and 98 MPa at 56 days.   Thomas Concrete Group, which by replacing the cement with a moderate amount of ground granulated blast furnace slag (54 %), a small amount of fly ash (9 %), lime filler and silica fume (5 %), reached a compressive strength of 94 MPa at 28 days and 98 MPa at 56 days.  The conclusion is that there are three recipes that further studies are justified to continue with, the three mentioned above. It should be added that an impressive concrete compressive strength of almost 100 MPa, can be reach with the use of only 200 kg cement per m3.