The predictive values of standard and non-standard germination temperatures, standard accelerated ageing (AA) and saturated salt accelerated ageing (SSAA) tests were investigated. Germination tests were performed at standard and non-standard temperatures of 10°, 20°, 20°/30° and 30°C for cabbage and tomato, and 10°, 15°, 20° and 30°C for onion. The AA and SSAA tests were conducted using four relative humidities: standard AA (RH100), NaCl (RH75), Ca(NO3)2 (RH43) and MgCl2 (RH32). Emergence trials were also conducted at a range of temperatures (winter, 15°/25° and 30°C) and media (Hygromix and soil) using seedling trays. Correlations were calculated to evaluate the relationship between laboratory and emergence test results. Three onion seed lots that have different vigour levels were primed with PEG or NaCl and were germinated and planted under varying temperatures and levels of salinity. There were vigour differences among different seed lots of cabbage, onion and tomato seeds used in this study. Using the different laboratory tests, seed lots were distinguished as high, medium and low vigour seed lots. The low temperature germination test (10°C) for cabbage and onion; and 20°C for tomato were found to be effective for separation of seed lots according to their vigour levels. All SSAA vigour tests were also useful in differentiating seed lots based on their physiological stage of deterioration. Using the standard AA (RH100) the seed moisture content was high (29 to 45%), resulting in fungal growth. However, in the SSAA test the moisture content was below 14% and no fungal growth was observed. Ageing of seed lots using NaCl and MgCl2 resulted in a low narrow range of moisture contents, but using Ca (NO3)2 the range of the moisture content between seed lots was higher. For all crop seeds, there was no significant difference in the percentage emergence between the two growth media but larger seedlings were observed from the commercial growth medium (Hygromix). For cabbage, highly significant correlations were obtained between germination percentage at 10°C and RH32 and all emergence trials. In onion, the correlations were not consistent; highly significant correlations were observed from germination capacity (GC), 15°C, 20°C, 30°C, RH75 and RH32; and emergence parameters at specific conditions. However, the germination percentage from 30°C correlated significantly with the final emergence percentage and seedling vigour index. Germination of tomato seeds at 20°C and all SSAA had highly significant correlation with all emergence parameters. The germination rate parameters: MGT (mean germination time) and GI (germination index) were valuable in categorising seed lots with moderate vigour levels, however, except GE in cabbage and onion, all other germination rate characters failed to correlate with any emergence parameters. The radicle percentage germination (viability or GC) and final emergence percentage (FEP) were not enhanced by priming in all seed lots in the germination and emergence trials at all temperatures. The percentage of normal seedling was increased due to priming when seeds were subjected to low temperature and higher salinity levels. Priming was effective in improving the rate, uniformity of germination/emergence; and increased the seedling dry mass of onion seeds when grown under relatively cold environmental conditions. Priming was more beneficial for low vigour seed lots (seed lot A) than for high vigour seed lots (B, C). Priming also improved germination rate and uniformity at all salinity levels, but faster rate of emergence, more uniform and higher seedling dry mass were only observed when seeds were watered with low salinity levels (25 mM of NaCl). No significant difference was observed using NaCl or PEG as priming agent. Onion seeds are tolerant to salinity during germination and the effect of priming was more beneficial at emergence. / Dissertation (MSc (Agric) Horticulture)--University of Pretoria, 2007. / Plant Production and Soil Science / unrestricted

Un composite époxy/fibre de verre élaboré à partir de matériaux simplifiés a été soumis en parallèle à du vieillissement artificiel (UV et thermohydrique) et à du vieillissement naturel (climat tropical humide). Une étude des matériaux (résine seule et composite) à travers un large panel de techniques de caractérisation physico-chimiques, mécaniques et de moyens d’observation (MEB, AFM) a permis d’identifier clairement la structure, la morphologie et les principales propriétés du réseau époxy-amine de l’état initial. Une caractérisation systématique des échantillons par couches de 20 microns d’épaisseur a permis, en particulier, d’identifier un gradient de structure et de propriétés dans les 200 premiers microns à la surface des plaques de résine et de composite. Ce gradient est attribué à l’évaporation du durcisseur amine lors de l’élaboration des matériaux. Dans les plaques de composites, le DMA ainsi que l’AFM ont permis de mettre en évidence une zone d’interphase autour des fibres pour laquelle le réseau époxy-amine présente des caractéristiques différentes de celles de la résine en masse.La même méthodologie a été adoptée pour suivre l’évolution de ces matériaux lors des vieillissements artificiels et naturels.Les études séparées des vieillissements UV et thermohydrique ont permis de mettre en évidence les altérations chimiques et physico-chimiques de la matrice seule d’une part, et des interphases fibres/matrice d’autre part. Le vieillissement photochimique se montre le plus dégradant pour la surface des plaques, alors que les effets du vieillissement thermohydrique sont principalement observés au niveau des interfaces fibres/matrice dans les composites. Dans les deux cas également, nous pouvons proposer des mécanismes simplifiés de dégradation de la résine époxy-amine.Enfin, les résultats de caractérisation après le vieillissement naturel nous permettent de faire des corrélations avec les vieillissements artificiels et de pointer les effets prépondérants des deux paramètres de vieillissement, ainsi que d’avancer un facteur d’accélération. / A simplified glass fiber/epoxy composite was exposed to artificial ageing conditions (UV and Hygrothermal) and natural ageing (humid tropical climate). A wide range of physicochemical, mechanical and observation techniques (SEM, AFM) were used to clearly identify the structure, morphology and the main properties of the epoxy-amine network of the resin alone and composite in the initial state. A gradient in structure and properties was shown up in the first 200 microns of resin and composite plates surfaces thanks to the systematic characterization of sample layers of 20 microns thickness. It is attributed to an amine deficit during the sample elaboration process. In composite plates, DMA and AFM measurements have highlighted the existence of an interphase area around the fibers with a higher molecular mobility and a lower stiffness than the epoxy-amine network in the bulk resinThe same methodology was used to follow the materials evolution during artificial and natural ageing.The effects of UV and hygrothermal ageing were analyzed independently on the resin and on the composite in order to identify the chemical and physicochemical alterations of the matrix on one hand and of fiber/matrix interphases on the other hand. Photochemical ageing effects are mainly localized on materials surfaces, while the hygrothermal ageing affects mainly fiber/matrix interfaces in composite. In both cases simplified degradation mechanisms of epoxy-amine network are proposed.Finally, the characterization results after natural exposure allow us to establish correlations with artificial ageing. Predominant effects are identified and an acceleration factor is proposed.

Introduction: Through large neuroimaging consortia, researchers have identified a series of neuroanatomical alterations in mood and psychotics disorders, such as major depressive disorder (MDD), bipolar disorder (BD), and schizophrenia (SCZ). However, the mechanism behind these alterations is not well understood. One of the existing hypotheses suggests that the observed brain changes are related to a process of accelerated brain ageing. Studies investigating this hypothesis use a measure called the brain age gap (i.e., the difference between machine learning model predictions of brain age and chronological age). Thus far, there is limited understanding on how mood and psychotic disorders affect model predictions, how can predictions be clinically useful, and what is the biological meaning behind the brain age gap. In this thesis, we investigated accelerated brain ageing in mood and psychotic disorders. We sought to estimate the effect of the brain age gap and propose new ways of modeling brain age. We also explored the clinical utility and meaning of the brain age gap. Results: We confirmed the presence of a brain age gap in MDD, BD, and SCZ through a systematic review and meta-analysis. SCZ presented the highest levels of brain age gap, followed by BD and MDD. We analyzed the clinical utility of brain age for antidepressant treatment response and concluded that the brain age gap is not a predictor of antidepressant treatment response in weeks 8 and 16. We proposed a new method for brain age prediction that is more interpretable than previous approaches while preserving good predictive performance. We have also used model explanation strategies and identified that the brain age gap is largely associated with total gray matter volume reduction and ventricle enlargement in SCZ. Conclusion: The results of this thesis suggest that the brain age gap is present across mood and psychotic disorders. The results have also helped to clarify the meaning behind the brain age gap, a largely used but still poorly understood measure in neuroimaging research. So far, there is no indication that the brain age gap can be a useful tool for treatment response prediction in MDD. / Thesis / Doctor of Philosophy (PhD)

O entendimento dos mecanismos de degradação que agem sob os nanocompósitos poliméricos frente ao intemperismo (luz UV, calor, oxigênio, chuva ácida, entre outros), é o ponto chave para o desenvolvimento de novos aditivos e novas aplicações. Para este trabalho a síntese do nanocompósito foi realizada no estado fundido, utilizando-se uma extrusora de dupla rosca. A matriz polimérica utilizada foi o HMS-PP (polipropileno com alta resistência do fundido) sintetizado por irradiação gama e a argila Montmorilonita. Para melhor compatibilização entre a matriz e a nanocarga, foi utilizada o agente compatibilizante andrido maléico. Para os ensaios de envelhecimento ambiental e acelerado em estufa, os corpos de prova foram confeccionados por meio de termoprensagem. A caracterização dos efeitos da adição de argila e do envelhecimento nos nanocompósitos, presupôs o emprego das técnicas de ensaios mecânicos, Calorimetria Diferencial Exploratória (DSC), Termogravimetria (TGA), Espectroscopia no Infravermelho por Transformada de Fourier (FT-IR), Espectrometria de Fluorescêcia de Raios X por Dispersão de Comprimento de Onda (WDXRF), Microscopia Eletrônica de Varredura (MEV), Índice de Fluidez (IF), Difração de Raios-X (DRX) e Espectroscopia de Energia Dispersiva (EDS). Foram ensaiadas amostras com 0,1; 1; 3; 5 e 10% de argila. A amostra com porcentagem de 5% de argila demonstrou uma melhor estabilidade frente ao ensaio de envelhecimento ambiental e no envelhecimento acelerado em estufa. Por outro lado na amostra com maior porcentagem de argila (10%) ocorreu o inverso, sob ensaio ambiental houve maior degradação e sob envelhecimento acelerado em estufa, manteve-se resistente até 56 dias de envelhecimento. Nas porcentagens estudas (menor que ≤ 3%) de argila, pode-se constatar um equilíbrio entre o efeito barreira da argila e a ação dos íons metálicos que aceleram o processo degradativo. / The understanding of degradation mechanism action on the polymer nanocomposites in face of weathering (UV light, heat, acid rain, among others), is the key for development of new additives and new applications. In this work the nanocomposite synthesis was carried in molten state, using twin-screw extruder. The polymer matrix was the HMS-PP (high melt polypropylene) synthesized by gamma irradiation and the nanometric inorganic component was the montmorillonite clay. For better compatibilization between the matrix and clay, it were used maleic anhydride as coupling agent. For environment and in oven accelerated aging assays, the dumbbell samples were prepared under hot pressing. The characterization of clay addition effects and aging effects on the nanocomposites, required the use of techiniques of Differential Scanning Calorimetry (DSC), Thermogravimetry (TGA), Fourier Transformed Infrared Spectroscopy (FT-IR), Xray Fluorescence (WDXRF), Scanning Eletron Microscopy (SEM), Energy Dispersive Spetroscopy (EDS) and mechanical properties. Samples with 0.1; 1; 3; 5; 10 % of clay were tested. The sample with 5% of clay showed better stability on the environmental assay and accelerated aging in oven assay. On the other hand, the sample with higher percent of clay (10%), was more degraded under on environmental aging than under accelerated aging in stove. In this case, became more resistant until 56 days of assay. On the studied concentrations (less than ≤ 3%) of clay, it can be seen an equilibrium between barrier effect and metallic ions action accelerating the degradative process.

O entendimento dos mecanismos de degradação que agem sob os nanocompósitos poliméricos frente ao intemperismo (luz UV, calor, oxigênio, chuva ácida, entre outros), é o ponto chave para o desenvolvimento de novos aditivos e novas aplicações. Para este trabalho a síntese do nanocompósito foi realizada no estado fundido, utilizando-se uma extrusora de dupla rosca. A matriz polimérica utilizada foi o HMS-PP (polipropileno com alta resistência do fundido) sintetizado por irradiação gama e a argila Montmorilonita. Para melhor compatibilização entre a matriz e a nanocarga, foi utilizada o agente compatibilizante andrido maléico. Para os ensaios de envelhecimento ambiental e acelerado em estufa, os corpos de prova foram confeccionados por meio de termoprensagem. A caracterização dos efeitos da adição de argila e do envelhecimento nos nanocompósitos, presupôs o emprego das técnicas de ensaios mecânicos, Calorimetria Diferencial Exploratória (DSC), Termogravimetria (TGA), Espectroscopia no Infravermelho por Transformada de Fourier (FT-IR), Espectrometria de Fluorescêcia de Raios X por Dispersão de Comprimento de Onda (WDXRF), Microscopia Eletrônica de Varredura (MEV), Índice de Fluidez (IF), Difração de Raios-X (DRX) e Espectroscopia de Energia Dispersiva (EDS). Foram ensaiadas amostras com 0,1; 1; 3; 5 e 10% de argila. A amostra com porcentagem de 5% de argila demonstrou uma melhor estabilidade frente ao ensaio de envelhecimento ambiental e no envelhecimento acelerado em estufa. Por outro lado na amostra com maior porcentagem de argila (10%) ocorreu o inverso, sob ensaio ambiental houve maior degradação e sob envelhecimento acelerado em estufa, manteve-se resistente até 56 dias de envelhecimento. Nas porcentagens estudas (menor que ≤ 3%) de argila, pode-se constatar um equilíbrio entre o efeito barreira da argila e a ação dos íons metálicos que aceleram o processo degradativo. / The understanding of degradation mechanism action on the polymer nanocomposites in face of weathering (UV light, heat, acid rain, among others), is the key for development of new additives and new applications. In this work the nanocomposite synthesis was carried in molten state, using twin-screw extruder. The polymer matrix was the HMS-PP (high melt polypropylene) synthesized by gamma irradiation and the nanometric inorganic component was the montmorillonite clay. For better compatibilization between the matrix and clay, it were used maleic anhydride as coupling agent. For environment and in oven accelerated aging assays, the dumbbell samples were prepared under hot pressing. The characterization of clay addition effects and aging effects on the nanocomposites, required the use of techiniques of Differential Scanning Calorimetry (DSC), Thermogravimetry (TGA), Fourier Transformed Infrared Spectroscopy (FT-IR), Xray Fluorescence (WDXRF), Scanning Eletron Microscopy (SEM), Energy Dispersive Spetroscopy (EDS) and mechanical properties. Samples with 0.1; 1; 3; 5; 10 % of clay were tested. The sample with 5% of clay showed better stability on the environmental assay and accelerated aging in oven assay. On the other hand, the sample with higher percent of clay (10%), was more degraded under on environmental aging than under accelerated aging in stove. In this case, became more resistant until 56 days of assay. On the studied concentrations (less than ≤ 3%) of clay, it can be seen an equilibrium between barrier effect and metallic ions action accelerating the degradative process.

Les matériaux polymères ont de nombreux avantages comme la légèreté, le coût, la formabilité… mais sont aussi à l’origine de certains problèmes environnementaux actuels. La substitution des polymères conventionnels d’origine pétrochimique et non biodégradables par des polymères biosourcés et biodégradables tels que le polylactide (PLA) ou les polyhydroxyalcanoates (PHA) peut apparaître comme une alternative crédible. Cependant, un des freins à leur développement demeure la faible connaissance de la durée de vie de ces biopolymères lorsqu’ils sont exposés à différents types d’environnements, en particulier en milieu marin si l’on considère une application marine. Dans le cadre de cette étude, il a donc été entrepris de suivre le vieillissement naturel et le vieillissement accéléré du PLA et des PHA en milieu marin dans l’objectif d’appréhender les mécanismes et les cinétiques de dégradation. Dans le but de découpler les effets liés à l’eau, aux sels minéraux et aux microorganismes, les échantillons ont été immergés dans différentes conditions, i.e. en eau distillée, en eau de mer naturelle et en eau de mer filtrée et renouvelée à différentes températures. L’influence du milieu sur la dégradation de ces biopolymères est analysée et discutée, de même que l’influence de la géométrie des pièces (films de différentes épaisseurs, éprouvettes ou fibres). Enfin, la prédiction de la durée de vie de ces polymères a été envisagée par l’intermédiaire de deux approches, conduisant à une estimation de leur durabilité dans un milieu bien défini et au regard d’une propriété donnée. / Pollution of nature by plastics is a major environmental problem and better management of the lifetime of polymers is a major challenge for the future. In recent years, bio-based and biodegradable polymers, such as polylactide (PLA), or polyhydroxyalkanoates (PHA) have appeared as an alternative solution in order to solve these problems. One of the limits remains the relative lack of knowledge of their lifetime and degradation behaviour in aqueous environments, and more specifically in the marine environment. In this study natural and accelerated ageing tests were performed under several conditions, distilled water, filtered and renewed seawater and natural seawater, at different temperatures, in order to decouple enzymatic and hydrolytic mechanisms. The aim of this study is to establish a baseline on degradation mechanisms and kinetics, in order to make lifetime predictions of biopolymer behaviour in seawater.Degradation phenomena have been identified. Biodegradation tests were also performed in a marine environment by following the release of CO2. Then, lifetime predictions of the properties of these biopolymers at seawater temperature were made using two different approaches.

This project aimed to address the lack of research into the mechanical properties and degradation mechanisms for historical tapestries at the fabric level and understand how effective conservation support strategies can be in the preservation of these artifacts. The research incorporated a large range of techniques from diverse disciplines including weaving, ageing, computer modeling, biochemistry and conservation science. The successful manufacture and ageing of relevant samples provided an excellent opportunity to include testing of historical samples for comparison. Tensile testing of all samples provided a valuable insight into the characteristics of degraded historical samples compared to artificially aged samples. Although individual ageing processes – including UV ageing, Relative Humidity (RH) – thermal cycling and mechanical strain ageing produced a reduction in strength, the historical samples showed a far greater loss of strength due to the combination of all types of ageing in addition to handling and pollution damage. A proteomic analysis of the wool fibres resulted in a greater understanding of the degradative “dark” wool ageing process which suggests that wool yellowing and tendering can be produced not just through photo-chemical reaction. Additionally, the chemical analysis laid an important foundation for future research into linking chemical mechanisms of damage with mechanical loss of strength. Analysis using electron paramagnetic resonance spectroscopy (EPR) provided an insight into the free radical chemistry of a range of wool/wool samples. It was observed that the light aged samples produced thiyl radicals whereas thioperoxy radicals were seen in the heat-humidity aged samples. This implies separate chemical reactions occur to produce degradation in the different ageing regimes. EPR analysis of some historical samples produced a carbon-based radical peak linked to a soot calibration signal. Further research on historical samples found phenolic radicals, possibly linked to the complex dye chemistry. Further research needs to be undertaken to fully clarify these findings. A world-wide questionnaire to textile conservators has provided a useful resource in terms of a survey of methods and materials used across the world – including technical data as well as more “ethical” motivations for conservation. The results of this survey were used along with the physical data collated in the mechanical testing as information inputted into a finite element model (FEA) to undertake the digital modeling of a tapestry hanging under its own weight. Although more research is needed to fully develop this model, a preliminary investigation has been established which can be used in future research as a tool for textile conservators across the world.

In this diploma thesis the current methods of color fastness evaluation of color digital prints were solved. The theoretical part provides basic information needed to understand the experiment. Samples of inkjet prints were subjected to accelerated and long-term lightfastness test. The long-term test took place in the spaces of the Faculty of Chemistry, Brno University of Technology, which fulfilled the condition of direct light in a closed room. For one year, samples were exposed and their reflection spectra were measured at monthly intervals. An accelerated lightfastness test was performed in a solar chamber with a xenon lamp. Only some samples were selected for this test because of the small space in the chambre and thw failure of the instrument. At regular intervals were measured again their reflection spectra from which the colorimetric values were calculated. After completion of the testing, the rate parameter was determined from the dependence of the loss of the normalized gamut volume on different doses of irradiation. In the case of long-term testing, it was based on data from the Hydrometeorological Institute, which gave values of direct outdoor solar radiation. In the accelerated test, the irradiation dose of the sample up to 800 nm was determined. Finally, the lightfastness of each sample was examined and compared with each other and the relevance of the accelerated test was assessed.

This diploma thesis follows the degradation of inkjet print by ultraviolet radiation and ozone effect for different types of papers. Colour test charts for the evaluation of accelerated ageing effect of ultraviolet light and gas fading were designed. These test charts were printed by dye-based inks on selected receiving media and exposed to ozone-enriched environment, UV radiation and their combination. The colorimetric values L* a* b* were calculated from spectral data of all patches of the test charts. The ozone effect on the prints was evaluated in the terms of total colour difference and dye concentration. The degradation of dye caused by ozone was observed also in a long-term period, after the contact of sample with ozone was terminated. Results of printed samples accelerated ageing by UV radiation and those that were influenced by the ozone effect were evaluated in the same way. It was found out that UV radiation and ozone treatment have a different effect on the degradation of dyes. The degradation rate is also strongly influenced by the receiving layer composition of papers used for inkjet printing. Also the catalytic effect of dyes was evaluated.

This diploma thesis deals with recent methods of lightfastness evaluation of both classic and digitally printed photographs. It summarizes the experimental methods used for colour change measurements. Primarily, it studies an influence of additional protection on lightfastness enhancement. Lightfastness testing of colour prints was carried out by accelerated ageing. Samples were prepared by 3 types of inkjet printers and 3 different print media. The surface of photographs was left untreated or modified by varnishing or lamination. A set of samples, thus achieved, was used to monitor a print behaviour during the light exposure. In conclusion effects of used receiving layer, ink or additional surface treatment were discussed. Colour changes were evaluated on the basis of measured reflectance spectra from which colorimetric quantities were calculated. Results were processed using VolGa application. An actual print-life was calculated from the plot of the normalized gamut volume loss and the exposure.