Este estudo teve como objetivo avaliar os efeitos de variações no protocolo de ativação e envelhecimento acelerado em algumas propriedades de cimentos resinosos de polimerização dual. Adicionalmente, investigaram-se os efeitos da variação da temperatura ambiente e envelhecimento acelerado no tempo de trabalho e tempo de presa dos cimentos quando ativados exclusivamente pela reação química. As propriedades avaliadas foram o grau de conversão, determinado por espectrometria no infravermelho com transformada de Fourier (FTIR-ATR), microdureza Knoop, expressa em KHN, e resistência mecânica à tração expressa em MPa. Os tempos de trabalho e tempos de presa foram determinados por um reômetro oscilatório com controle de temperatura da plataforma de teste estabelecida em 24oC ou 37oC. O envelhecimento acelerado foi determinado pela armazenagem dos cimentos, em suas embalagens originais, e após os testes iniciais, em estufa a 37oC por 12 semanas.A variável de modo de ativação foi determinada em 3 níveis. Os cimentos foram manipulados de acordo com as instruções dos fabricantes e ativados por luz imediatamente (controle), ativados por luz após 10 minutos de reação química no escuro (Exp 1) ou mantidos no escuro por 15 minutos, permitindo a reação química, mas sem fotoativação (Exp 2). Os cimentos tiveram suas propriedades avaliadas em função desses diferentes modos de ativação, antes e após o envelhecimento acelerado. Cimento exclusivamente ativado pela reação química foi empregado como controle quando necessário. Os diversos resultados podem ser resumidos em alguns aspectos de interesse. O tempo de trabalho e o tempo de presa de todos cimentos foram afetados significantemente pela temperatura e envelhecimento (p<0.05). O aumento da temperatura acelerou os tempos de trabalho e presa. Os efeitos do envelhecimento foram materiaisdependentes. Alguns materiais apresentaram redução, enquanto outros apresentaram aumento dos tempos de trabalho e presa, independentemente da variação da temperatura. O modo de ativação e envelhecimento afetaram significantemente as propriedades dos cimentos (p<0.05). Em geral, o grau de conversão aumentou com o tempo após a fotoativação. O retardo da fotoativação por 10 minutos causou alterações no grau de conversão, independentemente do envelhecimento, e para alguns produtos somente. O envelhecimento afetou a cinética da reação química de polimerização dos cimentos. Alguns materiais não apresentaram suficiente reação química após o envelhecimento. As propriedades variaram amplamente de acordo com o modo de ativação e produto. O envelhecimento foi a variável que causou alterações mais significantes e com grande implicação na utilização clínica dos produtos. Alguns materiais se tornaram impróprios para uso após o envelhecimento acelerado. / The study aimed to evaluate the effects of curing protocol and accelerated aging on some properties of dual-cure resin cements. Additionally, the effects of different ambient temperature and aging on the working and setting times were investigated when cements were self-cured only. Properties evaluated were degree of conversion as determined by FTIR-ATR spectroscopy, Knoop microhadness as expressed by KHN, and tensile strength as expressed in MPa. Working time and setting time were determined by an oscilating rheometer with controlled temperature stage at either 24oC or 37oC. Accelerated aging was performed by storing the original product kits in an oven at 37oC for 12 weeks after initial testing had been executed. Different curing protocols were established in 3 levels. Cements were manipulated according to the manufacturers instructions and light-activated immediately (control), light-activated after 10 minutes delay of self-curing in the dark (Exp 1), or simply allowed to self-cure for 15 minutes in the dark (Exp 2). Properties were evaluated according to the different curing protocol and both before and after aging. Exclusively self-curing cement was used as control product when appropriate. The results can be summarized in some aspects of interest. The working time and setting time of all products were significantly affected by temperature and aging (p<0.05). Increased temperature resulted in shorter working time and setting time. The effects of aging were material dependent. Some products presented reduced working and setting times, while others behave otherwise, regardless of the temperature. Curing mode and aging significantly affected the properties of the cements (p<0.05). In general, the degree of conversion increased with time after light-activation. The curing delay for 10 minutes caused alterations in the degree of conversion, regardless of aging, for some products, but not all. Aging affected the curing kinectics and general properties of all cements. Some materials did not present sufficient cure after aging. Properties varied widely according to curing protocol and product. Aging was the variable that most affected the products and the most relevant regarding the clinical use of the materials. Some products were deemed improper for clinical use after accelerated aging.

Ce travail s’inscrit dans le cadre du projet Cigéo (Centre industriel de stockage géologique de déchets radioactifs) et a porté sur la valorisation des argilites du Callovo-Oxfordien sous forme de coulis d’injection activé alcalinement. Cette utilisation requiert un liant présentant une importante durée pratique d’utilisation (~24 heures) et une valeur de pH modérée (10-11). Ainsi l’activation thermique de l’argilite a dû être maitrisée afin d’accroitre la réactivité des espèces argileuses tout en limitant la décarbonatation, pour éviter la présence de calcium réactif. Une solution alcaline silicatée potassique, de réactivité modérée (Si/K = 0,70), a été utilisée pour l’activation alcaline des argilites calcinées. Afin de développer le coulis, il a été nécessaire de favoriser la réactivité de l’argilite par addition de métakaolin et d’incorporer des additifs à base de bore. Un coulis dont les caractéristiques correspondent à celles visées a ainsi été obtenu. Enfin, une étude du liant dans des conditions proches de celles de l’utilisation finale (injection entre la couche géologique d’argilites et le chemisage de déchets radioactifs) a été menée. Pour cela, le liant a été mis en contact avec un bloc d’argilites du Callovo-Oxfordien, à une température de 90 °C (température maximale en condition d’usage). Il a ainsi été mis en évidence qu’à 90 °C le réseau géopolymère se réorganise (intégration du bore dans le réseau et formation éventuelle de zéolite). La mise en contact du liant avec l’argilite géologique a aussi permis d’identifier une diffusion du potassium dans les argilites du Callovo-Oxfordien. / In the context of Cigéo project (geological industrial disposal for radioactive wastes), this work focuses on the valorization of Callovo-Oxfordian argillite by the formulation of an alkali-activated grout. This application required a high setting time (close to 24 hours) and a moderate pH value (10-11). Thus, the argillite thermal treatment has been adapted to alter clays minerals without decomposing carbonate species (to avoid the presence of reactive calcium). A potassium-based silicate solution, with moderated reactivity (Si/K = 0.70), has been used for the alkali-activation step. Concerning the grout formulation, it has been necessary to enhance the argillite reactivity by the insertion of metakaolin and to add boron-based compounds. The resulting grout was in accordance with the specification. Finally, a study of the binder in an environment close to the using conditions (injection between geological layer and a radioactive waste lining) has been investigated. In this aim, the binder has been casted in contact with the geological argillite at 90 °C. It was evidenced a network reorganization at 90 °C (boron integration in the network and possible formation of zeolite). Potassium diffusion from the binder to the argillite has also been observed.

Tato diplomová práce se zabývá aktuálními poznatky, společně s optimalizací oscilačních měření pomocí hybridního reometru, ale hlavně pozorováním změn reologických parametrů v čase past mleté granulované vysokopecní strusky aktivované různými aktivačními roztoky s koncentrací alkálií M: 4 and 7.5 moldm. Výsledky byly pro diskuzi podpořeny výstupy z Vicatovy metody a izotermické kalorimetrie. Nejprve bylo zjištěno, že limit lineární viskoelastické oblasti se zmenšuje v čase. Dále bylo pozorováno, že v time sweep testech vykazovala struska aktivovaná křemičitany nejnižší hodnoty komplexního modulu a struska aktivovaná hydroxidy o koncentraci 4 moldm nejvyšší hodnoty a ostatní pasty vykazovaly hodnoty mezi těmito dvěma extrémy a měly mezi sebou porovnatelné hodnoty. Podobný trend byl pozorován u vývoje kritické meze oscilačního napětí, získaného z amplitude sweep testů (přerušovaně a nepřerušovaně). Oba výše zmíněné parametry, komplexní modul a mez napětí, se vyvíjely v čase. Výsledky všech testů jasně ukázaly, že povrchová chemie hraje roli ve výsledném reologickém chování. Odsud, povaha a koncentrace aktivátoru ovlivňují reologické vlastnosti skrze efekty Na a K iontů, stejně tak skrze koncentraci, která má dopad na elektickou dvojnou vrstvu. Reologické chování může být také ovlivněno dalšími faktory, např. viskozitou aktivačního roztoku a celkovou kinetikou hydratačního procesu.

Youth sport is acknowledged as an ideal setting for promoting positive youth development. In particular, youth sport participation has been linked to life skills development and psychological well-being. The coaching climate has been proposed to play a role in facilitating such positive outcomes. Nonetheless, few measures exist to examine life skills development through sport and it is unclear how positive youth development may be facilitated by the coach. Using existing and newly developed measures, this thesis examined how the coaching climate is related to life skills development and psychological well-being in youth sport participants. Phase 1 of this programme of research investigated Benson and Saito’s (2001) conceptual framework for youth development theory and research within sport. Study 1 examined a model whereby the coaching climate is related to life skills development (personal and social skills, cognitive skills, goal setting, and initiative); which, in turn, is related to participants’ psychological well-being (self-esteem, positive affect, and satisfaction with life). Data from 202 youth sport participants suggested that an autonomy supportive coaching climate was positively related to all four life skills. Further analysis revealed that the development of personal and social skills mediated the relationships between coach autonomy support and all three indices of psychological well-being. However, the validity of the scale used to measure life skills was brought into question during this study. Therefore, the studies which follow developed and validated a new scale which could accurately assess eight key life skills young people learn through sport. Phase 2 of this programme of research involved developing and validating a scale which measures life skills development through sport. Study 2 outlines the initial development of a scale which would assess whether young people learn the following life skills through sport: teamwork, goal setting, time management, emotional skills, interpersonal communication, social skills, leadership, and problem solving and decision making. This study involved defining each of the eight life skills, deciding what components made up each life skill and developing items which could assess each life skill. The initial item pool was reviewed by 39 academics, with between two and seven experts assessing the items for each of the eight life skills. Using the ratings and comments provided by experts, the first version of the Life Skills Scale for Sport (LSSS) was developed. Study 3 reduced the number of items contained within the LSSS from 144 to 47 items using both exploratory factor analysis (EFA) and descriptive statistics. For this task, 338 youth sport participants completed the LSSS. EFA results supported the unidimensional factor structure of each of the eight subscales. Each subscale also displayed adequate internal consistency reliability. Study 4 examined the factor structure of the LSSS using confirmatory factor analysis (CFA) with an independent sample of 223 youth sport participants. After the removal of four emotional skills items, seven of the eight subscales and the revised 43-item scale displayed adequate model fit. Results supported both the convergent and discriminant validity of the LSSS and each of the eight subscales displayed adequate internal consistency reliability. Study 5 assessed the test-retest reliability of the LSSS with an independent sample of 37 youth sport participants. Each participant completed the scale on two occasions which were two weeks apart. Results revealed that time 1 and time 2 scores were relatively unchanged over this two-week period, providing evidence of test-retest reliability. Phase 3 of this programme of research involved re-testing Benson and Saito’s (2001) framework. Study 6 retested the coaching climate – life skills development – psychological well-being model from Study 1 using the LSSS. Data from 326 youth sport participants suggested that an autonomy supportive coaching climate was positively related to young people learning teamwork, goal setting, time management, emotional skills, interpersonal communication, social skills, leadership, and problem solving and decision making. The total amount of life skills a young person developed through sport was positively related to their self-esteem, positive affect and satisfaction with life. Again, the factor structure and reliability of the scale was supported. The findings from this PhD research suggest that the coaching climate plays an important role in young peoples’ development through sport. Specifically, an autonomy supportive coaching climate was positively related to life skills development and psychological well-being in youth sport participants. This thesis also provides researchers with a valid and reliable measure of life skills development through sport. Future research using the LSSS should examine other factors (e.g., peer relationships) which may promote positive youth development through sport. Additionally, future studies can use the LSSS to examine the efficacy of existing programmes (e.g., the SUPER programme) which teach life skills through sport. Such research will help guide coaches and sports programmes efforts to promote positive youth development through sport.

The diploma thesis focuses on the problematics of setting the number of employees in the selected department (team) in a specific company. With respect to the severity of impact of this decision, the diploma thesis choses a sophisticated tool, norms of work consumption. To simplify their utilization a model is created to specify the number of employees. The basis for construction of the model is summarized in the theoretical-methodological part. Practical part of the diploma thesis presents the company, the department and the team and it defines preformed processes. Furthermore, it calculates (determines) individual elements needed for building the required model, namely the time normatives (norms) of the activities, probabilities of occurrence of certain activities and usable time fund of an employee. Lastly, the created model is tested by using real data from the last period and consequent recommendations are presented.