AR-Glas wird in Form von Multifilamentgarn zur Verstärkung in textilbewehrtem Beton eingesetzt. Während des Herstellungsprozesses wird auf die AR-Glasfilamente die Schlichte aufgebracht, deren chemische Zusammensetzung maßgeblich die Qualität der Filament-Matrix-Grenzschicht bestimmt, sowie die chemische Beständigkeit im alkalischen Milieu gewährleistet. Zur Beurteilung der chemischen Beständigkeit in alkalischer Umgebung werden beschleunigte Alterungsversuche in wässrigen, alkalischen Lösungen durchgeführt. Die Reaktion von Hydroxid-Ionen mit dem Si-O-Si-Gruppen des Glasnetzwerkes führt zur Ausbildung hydratisierter Oberflächen und gelösten Silikaten. Das Ausmaß der Glaskorrosion ist von der chemischen Zusammensetzung der Glasfaser, der Schlichte bzw. Beschichtung und der alkalischen Lösung sowie von Zeit und Temperatur abhängig. Die beschleunigte Alterung von verschiedenen AR-Glasfasern in NaOH-Lösung sowie Zementlösung zeigt, dass sich der Korrosionsmechanismus aufgrund der vorhandenen Calcium-Ionen unterscheidet. Die Filamentbruchspannung wird anhand der Weibull-Verteilungsfunktion analysiert. Das mechanische Verhalten hängt deutlich von der chemischen Zusammensetzung der Alterungslösung ab, was zu unterschiedlichen Parametern der Weibull-Verteilungsfunktion sowie vermengten Verteilungen führen kann. Die Alterung in NaOH-Lösung führt zur Ausbildung einer korrodierten Schicht an der Filamentoberfläche. In Ca-haltigen Zementlösungen kommt es dagegen zu einer lokal begrenzten Korrosion. Für die Beurteilung verschiedener Polymerbeschichtungen werden Betonverbunde bei unterschiedlichen Temperaturen und Umgebungsfeuchten gelagert, wodurch geeignete Alterungsbedingungen evaluiert werden und den Vergleich der chemischen Beständigkeit unterschiedlicher Beschichtungen ermöglichen. / Rovings made of AR-glass are used in textile reinforced concrete. During the manufacturing process the sizing is applied on the AR-glass filaments. The chemical constitution of the sizing determines the quality of the filament-matrix-interface but also the chemical durability of the glass filaments in alkaline environment. The durability is evaluated by accelerated ageing tests in aqueous, alkaline solutions. In alkaline solutions, the reaction of hydroxyl ions with Si-O-Si-groups of the glass network leads to the formation of hydrated surfaces and dissolved silicate. The rate of this corrosion depends on the chemical constitution of the fibre and the alkaline solution as well as on time and temperature. The investigation of the ageing of glass fibres with different chemical constitutions in NaOH and cement solutions shows that the corrosion mechanism changes due to the inhibiting effect of calcium ions. The strength distributions have been evaluated using a Weibull distribution function. The mechanical behaviour strongly depends on the chemistry of the solution and determines the parameters of the Weibull distribution function in terms of either single or mixed distributions. The corrosion in NaOH solution leads to a strong dissolution of the outer layer of the glass fibres, whereas during aging in cement solution at the same pH-value a limited, local attack was revealed. The evaluation of polymer coatings is realised by the ageing of concrete composites at different temperatures and humidities to deduce adequate ageing conditions for the comparison of different coatings.

Variables for the accelerated ageing (AA) test, methods for reducing fungal contamination during the AA test, using the conductivity test as a vigour test, the effect of seed size on seed vigour and the relationship between laboratory test results and field perfonnance in selected Brassica spp were investigated. In the first experiment, three seed lots of turnip rape hybrid (B. rapa x campestris), turnip (B. campestris) and forage rape (B. napus); and seven seed lots of Asian rape (B. napus), six seed lots of Asian kale (B. oleraceae var. alboglabra L.) and five seed lots of choisum (B. rapa var. pekinensis) with germinations above 90% were aged at two different temperatures (41 and 42°C ± 0.3°C) and three ageing times (24, 48 and 72 ± 15 minutes). The second experiment was divided into three sections. In the first, the same seed lots and species were aged at one temperature (41°C) and time (72 h), but either 40 ml of saturated salts; KCl (83%RH), NaCl (76%RH), NaBr (55%RH); or distilled water (96%RH) were used as the ageing solutions. In the second, one turnip rape hyprid seed lot was aged at three temperatures (41, 42 and 45°C) and two times (72 and 96h), again using the three saturated salts and distilled water as ageing solutions. In the third, three turnip rape hybrid seed lots and three Asian kale seed lots were surface sterilised (1 % sodium hypochlorite) prior to ageing at one temperature (41°C) and time (72 h). In the third experiment, the same species and seed lots used in experiment one at their original seed moisture content (SMC) were tested for conductivity after soaking in deionised water for 4, 8, 12, 16, 20 and 24 h. They were then re-tested after the SMC had been adjusted to 8.5%. In the fourth experiment, three seed lots of forage rape and three seed lots of Asian kale were graded into three seed size categories; large (retained on a 2.0 mm screen), medium (retained on a 1.7 mm screen) and small (passed through a 1.7 mm screen). Graded seeds were then tested for standard germination, AA (41°C/48 h) and conductivity (measured at 16 and 24 h). In the final experiment, the relationships between laboratory tests for the six species (each consisting of three seed lots), field emergence from three sowings, and cold room emergence were evaluated. Both time and temperature influenced post-AA germination. Increasing the ageing period from 48 to 72 hours at 41°C, and 24 to 48 hours at 42°C resulted in decreased mean germination percentage for all species but not always clear separation of seed lots. While there were sometimes few differences between ageing at 41°C and 42°C, the former is preferred because it is already the temperature used for other species. For Asian rape, choisum and turnip, the previously recommended testing conditions of 41°C/72 h provided good seed lot separation, but for Asian kale and turnip rape hybrid, AA testing at 41°C/48 h provided better results. Seed moisture content after ageing ranged from 29-37% depending on species. Fungal growth on seeds during the ageing period appeared to reduce post-ageing germination in some seed lots . Substituting saturated salts for distilled water did not stress seed lots in the AA test, due to the lowered RH%, the exception being seed lots 1210 and 1296. For forage and Asian species, seed lot germination mostly remained above 90% when aged for 72 h at lowered RH%. Increasing the ageing duration from 72 to 96 hours resulted in some decreases in post-AA germination but no clear separation of seed lots. Surface sterilising the seeds prior to the AA test resulted in a lower incidence of contaminant fungi which was associated with a lower percentage of abnormal seedlings. The conductivity test was mostly able to identify vigour differences among forage and Asian vegetable brassica seed lots. Differences in conductivity readings were observed among seed lots in all species. Increasing the period of imbibition resulted in increased conductivity from most seed lots but radicle emergence occurred after 16-20 h of imbibition. Variation was observed in the time to reach 95% maximum of the imbibition curve for most species. Conductivity readings at 16 h would avoid possible influences of radicle emergence on results. Adjusting the SMC to 8.5% resulted in reduced variation in conductivity among replicates of seed lots, due to a reduction in imbibition damage. Seed size had a significant effect on both post-AA germination and conductivity results. In forage rape, large size seeds had higher post-AA germination cf. medium cf. small size seeds. In Asian kale, large size seeds had higher post-AA germination compared with small size seeds. For both forage rape and Asian kale, large size seeds had lower conductivity readings cf. small size seeds. The correlation analyses demonstrated significant relationships between AA testing and field emergence parameters (percentage emergence, emergence index and emergence rate). Significant relationships were also observed between conductivity testing and these field emergence parameters. Based on the correlation analysis, AA testing at 41°C/48 hand/or 42°C/48 h could be recommended to be used as an AA test for turnip and Asian rape; and 41°C/48 hand/or 41°C/72 h for Asian kale and choisum. Based on the correlation analysis, conductivity testing at 16 h can be used to predict the field emergence potential of forage and Asian vegetable seed lots. Vigour tests were consistently able to provide better indicators of field perfonnance than the standard germination test, although these relationships did vary with the different field sowings.

Estudos anteriores utilizando matriz cimentícia reforçada exclusivamente com fibras vegetais propiciaram a produção de telhas com desempenho aceitável nas idades iniciais. Porém, com o envelhecimento natural, as telhas apresentaram significativa redução do desempenho mecânico, fato este atribuído principalmente ao ataque alcalino da matriz cimentícia. A presente pesquisa teve como objetivo o aprimoramento de telhas onduladas de fibrocimento sem amianto, a partir de processo automatizado. A primeira etapa do trabalho consistiu na avaliação do efeito da intensidade de refino da polpa Kraft de sisal (Agave sisalana) nas propriedades mecânicas e físicas de placas planas baseadas em matriz de cimento Portland, e o uso conjunto com fibras de poliproprileno (PP). Esta etapa envolveu também a caracterização dos principais atributos das polpas celulósicas refinadas, bem como a caracterização microestrutural (microscopia eletrônica de varredura e porosimetria por intrusão de mercúrio) do material resultante após envelhecimento acelerado e em ambiente natural. Na segunda etapa, séries de telhas onduladas de fibrocimento foram produzidas por técnica de sucção do excesso de água e prensagem, utilizando os melhores parâmetros definidos na etapa anterior. Os efeitos da cura acelerada em autoclave e dos envelhecimentos acelerados (carbonatação acelerada, imersão-secagem e calor-chuva) nas propriedades mecânicas e físicas das telhas foram avaliados. Os resultados obtidos mostraram a grande contribuição do refino da polpa celulósica na melhoria da resistência dos compósitos. Altas intensidades de refino apresentaram os melhores resultados para compósitos reforçados somente com polpa celulósica, mesmo após os envelhecimentos, porém intensidades intermediárias em compósitos híbridos mostraram-se suficientes. A adição das fibras de polipropileno como reforço híbrido teve como ponto forte a manutenção da resistência ao impacto, propriedade esta fortemente afetada pelo envelhecimento acelerado nos compósitos reforçados somente com polpa de sisal. As telhas produzidas mostraram-se mais eficientes no amortecimento térmico do que telhas comerciais de fibrocimento amianto. Melhorias no processo de produção das telhas mostraram efetiva contribuição no desempenho mecânico em relação aos trabalhos anteriores, tanto no curto como no longo prazo. Os resultados também indicaram a utilização da carbonatação acelerada como um procedimento eficiente na mitigação da degradação sofrida pelas fibras celulósicas em meios menos agressivos, no caminho para tornar viáveis os materiais reforçados com fibras vegetais. / Previous studies using exclusively vegetal fibres as the sole reinforcement of cement matrix have propitiated the production of roofing tiles with acceptable performance at the first ages. However, with the natural ageing, the roofing tiles have presented significant reduction in the mechanical performance, attributed to the alkaline attack of the cimentitious matrix mainly. The present research had as objective the improvement of undulate fibrecement roofing tiles without asbestos with automated equipment for production. The study also evaluated the physical, mechanical and microstructural behaviour of the obtained composites. The first stage consisted of evaluating the refinement effect of sisal Kraft pulp on mechanical and physical properties of flat pads based on Ordinay Portland cement and the jointly use of polypropylene fibres (PP). This stage also involved the characterization of the main attributes of refined cellulosic pulps, as well as the microstructural characterization (scanning electron microscopy and mercury intrusion porosimetry) of the resultant material after the accelerated and natural ageing. In the second stage, series of fibrecement roofing tiles were produced by slurry dewatering technique and pressing, using the best parameters of the first stage. Efects of autoclaved curing and accelerated ageing (accelerated carbonation, soak-dry and heat-rain) on mechanical and physical properties of tiles were evaluated. Results showed the great contribution of pulp refinement on mechanical strengh improvement. Higher intensities of refinement provided the best results for composites only reinforced with sisal pulp, despite ageing mechanism. Intermediate refinement revealed to be enough for hybrid composites. Adition of polypropylene fibres as hybrid reinforcement provided toughness maintenance after ageing, which was strongly affected only in sisal reinforced composites. Asbestos free tiles showed to be more efficient on thermal insulating properties than commercial asbestos cement. Improvements on tiles production process showed effective contribution on mechanical performance in relation to the previous works, both at initial ages and after ageing. The results have also indicated the utilization of accelerated carbonation as an effective procedure to mitigate the degradation suffered by the cellulosic fibres in the less aggressive medium, in way of the viability of the cement based materials reinforced by vegetal fibres.

Strategies to improve stem yield and juice quality in sweet sorghum were investigated in this study. Seed quality of sixty five accessions (landraces) from Botswana was investigated. Standard germination tests revealed that only 66% of the accessions had germination percentages in excess of 85%. The Accelerated Ageing test showed that only 50%of the 26 accessions had germination percentages above 80%. The results indicated that Botswana sweet sorghum seed quality is generally poor. Seed development and maturity observations demonstrated that maximum seed quality occurred 14 to 17 days after mass maturity (physiological maturity) and this coincided with maximum seed germination. These results suggest that harvesting sweet sorghum seed prior to mass maturity can lower seed quality. Farmers should, therefore be advised to select plants intended for seed harvesting and allow them to mature properly before the seeds are harvested. Differences in seed colour, shape and compactness of the inflorescences were observed amongst the 65 landraces collected from farmers in Botswana. Ten landraces were characterised and from the results it was evident that there was a range of genetic diversity which can be utilized in the improvement of the crop. Large panicles were characteristic of most sweet sorghum landraces, the effect of tiller, panicle and floret removal on juice quality was consequently studied. Removal of panicles and florets significantly improved juice quality whilst removal of tillers did not. Selection and breeding of genotypes with small panicles and male sterile varieties may improve juice quality and should be investigated. Effect of planting date, spacing and nitrogen were investigated. Early planting (October) resulted in increased stem yields but reduced juice quality. A 30 cm intra-row spacing resulted in high stem yields per plant and good juice quality. Nitrogen fertilisation increased stem yield and improved juice quality. On the bases of the results obtained from this study, early planting (October), application of 60 kg N ha-¹, and 30 cm intra-row spacing could be recommended for sweet sorghum production in pure stands. In pure stands yields of more than 37 000 stems (per hectare) of good quality can be attained. These could be sold at an estimated price of P2.00 (R2.25) per stem indicating the potential of sweet sorghum as a cash crop. However, its economic viability depends on the price elasticity in the supply - demand function. / Dissertation (PHD)--University of Pretoria, 2003. / Plant Production and Soil Science / unrestricted

AR-Glas wird in Form von Multifilamentgarn zur Verstärkung in textilbewehrtem Beton eingesetzt. Während des Herstellungsprozesses wird auf die AR-Glasfilamente die Schlichte aufgebracht, deren chemische Zusammensetzung maßgeblich die Qualität der Filament-Matrix-Grenzschicht bestimmt, sowie die chemische Beständigkeit im alkalischen Milieu gewährleistet. Zur Beurteilung der chemischen Beständigkeit in alkalischer Umgebung werden beschleunigte Alterungsversuche in wässrigen, alkalischen Lösungen durchgeführt. Die Reaktion von Hydroxid-Ionen mit dem Si-O-Si-Gruppen des Glasnetzwerkes führt zur Ausbildung hydratisierter Oberflächen und gelösten Silikaten. Das Ausmaß der Glaskorrosion ist von der chemischen Zusammensetzung der Glasfaser, der Schlichte bzw. Beschichtung und der alkalischen Lösung sowie von Zeit und Temperatur abhängig. Die beschleunigte Alterung von verschiedenen AR-Glasfasern in NaOH-Lösung sowie Zementlösung zeigt, dass sich der Korrosionsmechanismus aufgrund der vorhandenen Calcium-Ionen unterscheidet. Die Filamentbruchspannung wird anhand der Weibull-Verteilungsfunktion analysiert. Das mechanische Verhalten hängt deutlich von der chemischen Zusammensetzung der Alterungslösung ab, was zu unterschiedlichen Parametern der Weibull-Verteilungsfunktion sowie vermengten Verteilungen führen kann. Die Alterung in NaOH-Lösung führt zur Ausbildung einer korrodierten Schicht an der Filamentoberfläche. In Ca-haltigen Zementlösungen kommt es dagegen zu einer lokal begrenzten Korrosion. Für die Beurteilung verschiedener Polymerbeschichtungen werden Betonverbunde bei unterschiedlichen Temperaturen und Umgebungsfeuchten gelagert, wodurch geeignete Alterungsbedingungen evaluiert werden und den Vergleich der chemischen Beständigkeit unterschiedlicher Beschichtungen ermöglichen. / Rovings made of AR-glass are used in textile reinforced concrete. During the manufacturing process the sizing is applied on the AR-glass filaments. The chemical constitution of the sizing determines the quality of the filament-matrix-interface but also the chemical durability of the glass filaments in alkaline environment. The durability is evaluated by accelerated ageing tests in aqueous, alkaline solutions. In alkaline solutions, the reaction of hydroxyl ions with Si-O-Si-groups of the glass network leads to the formation of hydrated surfaces and dissolved silicate. The rate of this corrosion depends on the chemical constitution of the fibre and the alkaline solution as well as on time and temperature. The investigation of the ageing of glass fibres with different chemical constitutions in NaOH and cement solutions shows that the corrosion mechanism changes due to the inhibiting effect of calcium ions. The strength distributions have been evaluated using a Weibull distribution function. The mechanical behaviour strongly depends on the chemistry of the solution and determines the parameters of the Weibull distribution function in terms of either single or mixed distributions. The corrosion in NaOH solution leads to a strong dissolution of the outer layer of the glass fibres, whereas during aging in cement solution at the same pH-value a limited, local attack was revealed. The evaluation of polymer coatings is realised by the ageing of concrete composites at different temperatures and humidities to deduce adequate ageing conditions for the comparison of different coatings.

In alkalischen Lösungen führt die Reaktion von Hydroxylionen mit den Si-O-Si-Bindungen des Glasnetzwerks zur Bildung hydratisierter Oberflächen und gelöstem Silikat. Der Grad der Korrosion bzw. der Alterung der Glasfaser ist abhängig von der chemischen Zusammensetzung des Glases und Korrosionslösung sowie von Zeit und Temperatur. Die Untersuchung von Glasfasern verschiedener chemischer Zusammensetzung in NaOH- sowie Zementlösungen zeigte, dass die inhibierende Wirkung von Ca-Ionen zu einem veränderten Korrosionsmechanismus führt. Dies konnte anhand der mechanischen Eigenschaften der Glasfasern sowie rasterelektronenmikroskopischen Untersuchungen gezeigt werden. Während die Korrosion in NaOH-Lösung zu einer ausgeprägten Umwandlung der gesamten äußeren Glasfaserschicht in Reaktionsprodukte führte, zeigten Glasfasern in Zementlösung bei gleichem pH-Wert einen stark lokal begrenzten, punktförmigen Angriff. Daraus resultieren unterschiedliche mechanische Eigenschaften der Glasfasern in Abhängigkeit von der gewählten Korrosionslösung.

The physical complications of Type 1 diabetes mellitus (T1DM) have been understood as an accelerated ageing process (Morley, 2008). Do people with T1DM also experience accelerated cognitive and brain ageing? Using findings from research of the normal cognitive and brain ageing process and conceptualized in theories of the functional brain changes in cognitive ageing, a combination of cognitive testing and functional magnetic resonance imaging (fMRI) techniques were used to evaluate evidence of accelerated cognitive and brain ageing in middle-aged adults with T1DM. The first part of this thesis comprises a cognitive study of 94 adults (≥ 45 years of age) with long duration (≥ 10 years) of T1DM. Participants completed cognitive assessment and questionnaires on general mood and feelings about living with diabetes. Findings highlighted the importance of microvascular disease (specifically retinopathy) as an independent predictor of cognitive function. The incidence and predictors of mild cognitive impairment (MCI) were then explored. Results indicate a higher percentage of the group met criteria for MCI than expected based on incidence rates in the general population, providing initial evidence of accelerated cognitive ageing. Psychological factors were explored next. The relationship between the measures of well-being, diabetes health, and cognitive function highlighted the need for attention to patient's psychological well-being in diabetes care. Finally, a subgroup of 30 participants between the ages of 45 and 65 who differed on severity of retinopathy were selected to take part in an fMRI study. Blood oxygen level dependent (BOLD) activity was evaluated while participants were engaged in cognitive tasks and during rest. The findings provided evidence that the pattern of BOLD activation and functional connectivity for those with high severity of retinopathy are similar to patterns found in adults over the age of 65. In line with the theories of cognitive ageing, functional brain changes appear to maintain a level of cognitive function. Evidence of accelerated brain ageing in this primarily middle-aged group, emphasizes the importance of treatments and regimens to prevent or minimize microvascular complications.

Le domaine aéronautique connait de nos jours un engouement sans précédent autour de l’avion plus électrique. L’importance du nombre d’équipements électriques est à un tel point que l’amélioration de leur fiabilité devient incontournable. Actuellement, les composants passifs occupent 75 % des éléments électroniques utilisés en avionique dont la moitié correspond à des condensateurs. Ces derniers doivent donc répondre aux exigences environnementales avioniques assez contraignantes. C’est dans ce contexte que nous nous sommes intéressés particulièrement à l’étude des condensateurs à technologie film utilisant le polypropylène ou le polyester comme diélectrique. Afin de mieux comprendre le comportement fréquentiel de cette technologie, deux modèles fins de condensateurs films ont été développés, permettant ainsi de suivre les évolutions de leurs grandeurs électriques dans des conditions cohérentes avec l’application. Dans un deuxième temps, l’effet des contraintes en tension et en température constantes a été étudié sous la forme de facteurs d’accélération du vieillissement. Cela a été établi par l’intermédiaire de plusieurs essais, permettant d’établir les lois d’évolutions temporelles des paramètres électriques des condensateurs. Comme ces contraintes constantes ne sont pas toujours représentatives des conditions réelles d’utilisation, les cinétiques de dégradation ont été comparées à celles où les condensateurs sont sollicités par de fortes ondulations de courant, seules ou associées à une tension continue. Enfin, la dernière partie de notre travail expose l’utilisation des données expérimentales issues des essais de vieillissement dans un objectif de diagnostic en ligne. Les techniques utilisées assurent l'analyse de la dégradation de ces composants, étape essentielle dans la prédiction de l’état de santé des condensateurs en ligne / Nowadays, aeronautic research field is moving towards a more electric aircraft. Although this evolutionary path offers many advantages from a financial and ecological point of view, the increased power source usage sets additional constraints on the different electrical systems used onboard. Currently, passive components occupy 75% of the overall electronic equipments used in avionics, whose 50% corresponds to capacitors. Consequently, these latter must be able to withstand the harsh avionic operating conditions. In this thesis we were particularly interested in the study of metallized film capacitors technology using polyester or polypropylene as dielectric. A first approach consisted on the modeling of these components as function of frequency in order to study the evolution of their electrical parameters under consistent avionic stresses. These models were also developed on the purpose of tracking the degradation of the capacitors parameters over time. This operation was done by the means of accelerated floating ageing tests, where capacitors were subjected to different constant voltages and temperatures. Original capacitance ageing laws were thus proposed based on the identification of voltage and temperature degradation kinetics. However, since traditional floating ageing tests, do not reflects the normal ageing of the component, degradation kinetics of metallized films capacitors under high ripple currents, alone or combined with a DC voltage across the devices terminals where also studied, and the associated failure mechanisms were identified. A final step consisted on the health monitoring of metallized film capacitors online based on the experimental ageing data

In recent years, due to growing environmental awareness, considerable attention has been given to the development and production of natural fibre reinforced polymer (both thermoset and thermoplastic) composites. The main objective of this study was to reinforce epoxy and polylactic acid (PLA) with hemp fibre to produce improved composites by optimising the fibre treatment methods, composite processing methods, and fibre/matrix interfacial bonding. An investigation was conducted to obtain a suitable fibre alkali treatment method to: (i) remove non-cellulosic fibre components such as lignin (sensitive to ultra violet (UV) radiation) and hemicelluloses (sensitive to moisture) to improve long term composites stability (ii) roughen fibre surface to obtain mechanical interlocking with matrices (iii)expose cellulose hydroxyl groups to obtain hydrogen and covalent bonding with matrices (iv) separate the fibres from their fibre bundles to make the fibre surface available for bonding with matrices (v) retain tensile strength by keeping fibre damage to a minimum level and (vi) increase crystalline cellulose by better packing of cellulose chains to enhance the thermal stability of the fibres. An empirical model was developed for fibre tensile strength (TS) obtained with different treatment conditions (different sodium hydroxide (NaOH) and sodium sulphite (Na2SO3) concentrations, treatment temperatures, and digestion times) by a partial factorial design. Upon analysis of the alkali fibre treatments by single fibre tensile testing (SFTT), scanning electron microscopy (SEM), zeta potential measurements, differential thermal analysis/thermogravimetric analysis (DTA/TGA), wide angle X-ray diffraction (WAXRD), lignin analysis and Fourier transform infrared (FTIR) spectroscopy, a treatment consisting of 5 wt% NaOH and 2 wt% Na2SO3 concentrations, with a treatment temperature of 120oC and a digestion time of 60 minutes, was found to give the best combination of the required properties. This alkali treatment produced fibres with an average TS and Young's modulus (YM) of 463 MPa and 33 GPa respectively. The fibres obtained with the optimised alkali treatment were further treated with acetic anhydride and phenyltrimethoxy silane. However, acetylated and silane treated fibres were not found to give overall performance improvement. Cure kinetics of the neat epoxy (NE) and 40 wt% untreated fibre/epoxy (UTFE) composites were studied and it was found that the addition of fibres into epoxy resin increased the reaction rate and decreased the curing time. An increase in the nucleophilic activity of the amine groups in the presence of fibres is believed to have increased the reaction rate of the fibre/epoxy resin system and hence reduced the activation energies compared to NE. The highest interfacial shear strength (IFSS) value for alkali treated fibre/epoxy (ATFE) samples was 5.2 MPa which was larger than the highest value of 2.7 MPa for UTFE samples supporting that there was a stronger interface between alkali treated fibre and epoxy resin. The best fibre/epoxy bonding was found for an epoxy to curing agent ratio of 1:1 (E1C1) followed by epoxy to curing agent ratios of 1:1.2 (E1C1.2), 1: 0.8 (E1C0.8), and finally for 1:0.6 (E1C0.6). Long and short fibre reinforced epoxy composites were produced with various processing conditions using vacuum bag and compression moulding. A 65 wt% untreated long fibre/epoxy (UTLFE) composite produced by compression moulding at 70oC with a TS of 165 MPa, YM of 17 GPa, flexural strength of 180 MPa, flexural modulus of 10.1 GPa, impact energy (IE) of 14.5 kJ/m2, and fracture toughness (KIc) of 5 MPa.m1/2 was found to be the best in contrast to the trend of increased IFSS for ATFE samples. This is considered to be due to stress concentration as a result of increased fibre/fibre contact with the increased fibre content in the ATFE composites compared to the UTFE composites. Hygrothermal ageing of 65 wt% untreated and alkali treated long and short fibre/epoxy composites (produced by curing at 70oC) showed that long fibre/epoxy composites were more resistant than short fibre/epoxy composites and ATFE composites were more resistant than UTFE composites towards hygrothermal ageing environments as revealed from diffusion coefficients and tensile, flexural, impact, fracture toughness, SEM, TGA, and WAXRD test results. Accelerated ageing of 65 wt% UTLFE and alkali treated long fibre/epoxy (ATLFE) composites (produced by curing at 70oC) showed that ATLFE composites were more resistant than UTLFE composites towards hygrothermal ageing environments as revealed from tensile, flexural, impact, KIc, SEM, TGA, WAXRD, FTIR test results. IFSS obtained with untreated fibre/PLA (UFPLA) and alkali treated fibre/PLA (ATPLA) samples showed that ATPLA samples had greater IFSS than that of UFPLA samples. The increase in the formation of hydrogen bonding and mechanical interlocking of the alkali treated fibres with PLA could be responsible for the increased IFSS for ATPLA system compared to UFPLA system. Long and short fibre reinforced PLA composites were also produced with various processing conditions using compression moulding. A 32 wt% alkali treated long fibre PLA composite produced by film stacking with a TS of 83 MPa, YM of 11 GPa, flexural strength of 143 MPa, flexural modulus of 6.5 GPa, IE of 9 kJ/m2, and KIc of 3 MPa.m1/2 was found to be the best. This could be due to the better bonding of the alkali treated fibres with PLA. The mechanical properties of this composite have been found to be the best compared to the available literature. Hygrothermal and accelerated ageing of 32 wt% untreated and alkali treated long fibre/PLA composites ATPLA composites were more resistant than UFPLA composites towards hygrothermal and accelerated ageing environments as revealed from diffusion coefficients and tensile, flexural, impact, KIc, SEM, differential scanning calorimetry (DSC), WAXRD, and FTIR results. Increased potential hydrogen bond formation and mechanical interlocking of the alkali treated fibres with PLA could be responsible for the increased resistance of the ATPLA composites. Based on the present study, it can be said that the performance of natural fibre composites largely depend on fibre properties (e.g. length and orientation), matrix properties (e.g. cure kinetics and crystallinity), fibre treatment and processing methods, and composite processing methods.

Chromatography and extraction techniques, and also chemiluminescence have been utilized to develop new rapid and informative tools in the evaluation of long-term properties and environmental effects of polymeric materials. Methods were developed for classification of materials and for early and rapid degradation detection. Degradable polyethylene films were classified on the basis of their incorporated prooxidant systems using chromatographic fingerprinting of carboxylic acids, the dominating type of degradation product. The fingerprints were also shown to be useful for prediction of the degradation states and evaluation of the degradation mechanisms. Classification and prediction models were obtained by Multivariate Data Analysis, where the diacids were grouped according to both their type of prooxidant system and their state of degradation. The use of total luminescence intensity (TLI) measurements was also investigated as a means of classifying films and for the early detection of degradation. Comparisons were carried out with common techniques, e.g. FTIR and DSC, after both thermal and UV oxidation. TLI gave an earlier detection of degradation and was more sensitive than carbonyl index and crystallinity measurements to relative differences in degradation between the materials. It furthermore offered complementary information regarding changes in activation energies during the course of the degradation. The results were compared with the chromatographic fingerprints. A new way to evaluate the low temperature long-term stabilisation efficiency of antioxidants was investigated. A prooxidant was used to obtain catalytic oxidation, instead of using thermal acceleration, to evaluate the stabilisation efficiency of antioxidants at low temperatures but still during reasonably short aging times. Comparisons were made between polypropylene films stabilised with primary antioxidants (Irganox 1076, Irganox 1010 and α-tocopherol) with and without the prooxidant manganese stearate at different temperatures. The relative efficiencies of the antioxidants obtained under prooxidant acceleration test correlated better than thermal acceleration test with the results of a long-term low temperature test. Additives in plastic packaging materials may affect the environment after migration from the packaging to e.g. their contents, especially if they consist of organic aqueous solutions or oils. The use of Solid-Phase Microextraction (SPME) for the specific task of extraction from an organic aqueous solution such as a simulated food or pharmaceutical solution consisting of 10 vol-% ethanol in water was investigated. Methods were developed and evaluated for extraction both with direct sampling and with headspace sampling. If the extraction method and temperature were selected to suit the concentration levels of the analytes, it was possible to quantify several degradation products simultaneously. Comparisons made with Solid Phase Extraction showed the advantage of SPME for this purpose. / QC 20100929