This thesis is focused on the principles of behavior of shrinkage reducing agents (SRA) in alkali-activated materials based on blast furnace slag. The main focus of this work is selecting the most suitable admixture based on experiments, by which will be achieved through minimal shrinkage and will have negative effect on the properties of alkali-activated blast furnace slag at the same time. In experimental section of this work, the surface tension as individual additives as their mixtures with pore solution were measured primarily. Then the testing samples composed of blast furnace slag, water glass and addition of SRA were prepared. Of these samples was measured shrinkage and weight loss. Moreover, their mechanical properties such as flexural and compressive strength were monitored. Next, the beginning and the end of solidification was studied using the Vicat device and last but not least workability. The hydration process of alkali-activated materials with SRA was measured calorimetrically. Finally the microstructure in prepared samples was observed using scanning electron microscopy (SEM-EDS) and the total porosity was determined by mercury porosimeter.

A novel crown ether precursor was developed in which a rigid 4-oxahexacyclo (5.4.1.26.3,10.05,9.08,11) dodecyl cage moiety ("cage functionality") was incorporated.

The technique to produce pulp has improved and become more complex throughout the years. The purpose of pulping is to liberate the wood fibers and it can be done in two ways, either by chemically or mechanically separating the fibers. This thesis will focus on the commonly used kraft pulping process for eucalyptus and especially on the impregnation stage and how it affects kappa number and alkali consumption. This is done by studying the alkali charge, impregnation time and temperature for the impregnation stage while maintaining constant cooking parameters. This project has shown that the impregnation temperature affects the alkali consumption more than the impregnation time. A correlation between alkali consumption in the impregnation and the kraft cook was seen. When the consumption is high in the impregnation stage, a lower consumption was observed in the cooking stage. / Tekniken för framställningen av trämassa har utvecklats och blivit mer komplex genom åren. Massaframsställningens syfte är att separera träfibrerna ifrån varandra vilket kan utföras på två sätt, antingen på kemisk eller mekanisk väg. Denna studie kommer att fokusera på den beprövade sulfatkokningen och då i synnerhet hur impregneringssteget påverkar kappa numret och alkali konsumtion. För att uppnå detta studeras basningen för alkalin, impregneringstid och temperatur under impregneringen samtidigt som de övriga parametrarna hålls konstanta. Detta projekt har visat att impregneringstemperaturen påverkar alkali konsumtionen mer än tiden den impregneras. Andra studier som exempelvis Weiping Ban and Lucian A. Lucia 2003 och Joni Lehto & Raimo Alén 2013 har har också påvisat denna relation mellan alkali konsumtion och impregneringstemperaturen. Denna studie har även visat en alkali konsumtionstrend mellan impregneringen och sulfatkoket. När konsumtionen är hög under impregneringen så är den lägre i koket.

Die individuelle Hautempfindlichkeit stellt einen bedeutsamen Risikofaktor für die Entwicklung von berufsbedingten Hauterkrankungen dar. Zur Beurteilung der Hautempfindlichkeit hat sich in der Berufsdermatologie der Alkaliresistenztest als Standardverfahren etabliert. Er wird heute in vielen methodischen Varianten durchgeführt, was eine einheitliche Beurteilung und Begutachtung von Versicherten mit Berufsdermatosen wesentlich erschwert. Außerdem fehlt trotz bestehender Standardisierungs- und Qualitätskriterien eine allgemeingültige Standardisierung der Hautirritabilitätsdiagnostik im Sinne einer Leitlinie. Das Ziel der vorliegenden Arbeit war zum einen, die aktuelle Hautempfindlichkeitsdiagnostik bundesweit zu vereinheitlichen, zum anderen, neue Testverfahren zu entwickeln, die nicht nur schneller durchzuführen sind, sondern auch mit weniger Belastungen für die Patienten einhergehen. Der Schnelle Modifizierte Alkali-Resistenz-Test (SMART) und der Differenzielle IrritationsTest (DIT) wurden im Rahmen einer Multicenter-Studie hinsichtlich der Praktikabilität im Einsatz bei den berufsdermatologischen Routineuntersuchungen evaluiert. Die Studie zeigte, dass weder klinische noch hautphysiologische Testergebnisse von den erfassten Umgebungsfaktoren wesentlich beeinflusst werden. Auf der Grundlage der vorliegenden Ergebnisse können der SMART und der DIT sowohl zur Identifizierung vermehrter konstitutioneller Risiken als auch zur Objektivierung einer resultierenden subklinischen Minderbelastbarkeit der Haut der Hände nach früherem, abgeheiltem Berufsekzem eingesetzt werden. In der zweiten Studie wurden immunologische Ursachen individueller Hautempfindlichkeit mittels der Abrissmethode untersucht. Auf der Basis der Ergebnisse dieser Studie lässt sich schlussfolgern, dass es noch nicht möglich ist, anhand eines Tesafilmabrisses eine Aussage zur individuellen Hautempfindlichkeit zu erhalten. Hierzu erscheinen weitere Forschungsprojekte mit größeren Stichproben erforderlich.

Cette thèse vise à étudier l'interaction résonante d'un rayonnement laser avec une couche mince d'épaisseur sub-longueur d'onde de vapeur alcaline atomique confinée en nanocellule ; et les applications de détection qui en émergent.Nous nous concentrons sur la réflexion sélective se produisant à l'interface entre une fenêtre diélectrique et une vapeur résonante, et montrons que la dérivée des spectres de réflexion sélective est composée de résonances étroites dont les maxima correspondent aux positions des transitions atomiques. Ces résonances sont observées avec une largeur spectrale jusqu'à quinze fois plus fine que la largeur Doppler du milieu, et leurs amplitudes évoluent de façon linéaire avec celles des transitions. Grâce à ces propriétés et aux faibles épaisseurs de cellule pouvant être sondées, nous examinons les interactions atome-surface et mesurons le coefficient C3 de l'interaction de van der Waals.Nous présentons un modèle théorique décrivant l'interaction entre lumière quasi-résonante et nanocellule remplie d'une vapeur alcaline sous champ magnétique statique. Ce modèle se montre en excellent accord avec les résultats expérimentaux pour une large gamme de champs magnétiques depuis le régime Zeeman jusqu'au régime Paschen-Back. Au vu de ces résultats, nous proposons un concept de magnétomètre optique basé sur les nanocellules. Une preuve de faisabilité est présentée et une analyse en performance révèle un coefficient de variation des mesures de champs magnétiques inférieur à 5 % dans la gamme 0,4 - 2 kG. / This thesis is aimed at studying the resonant interaction of a laser radiation with an atomic alkali vapor layer of wavelength-scale thickness confined in an optical nanocell; and emerging sensing applications.We focus our attention on the selective reflection arising at the interface between a dielectric window and a resonant alkali vapor, and show that the derivative of selective reflection spectra exhibit narrow resonances whose maxima are located exactly at atomic resonance frequencies. These resonances are observed with a spectral linewidth up to fifteen times smaller than the Doppler linewidth of the medium and their amplitudes scale linearly with respect to the transitions ones. Owing to these properties and the possibility to probe thin atomic layers, we investigate atom-surface interaction and measure the C3 coefficient of the van der Waals interaction.We present a theoretical model describing the interaction of near-resonant laser light with alkali vapor-filled nanocell in the presence of an external static magnetic field. We show an excellent agreement between recorded and calculated spectra in a wide range of magnetic fields spanning from Zeeman to Paschen-Back regimes. Following these results, we propose a concept for a nanocell-based optical magnetometer. A proof of feasibility is presented and a performance analysis reveals a coefficient of variation for the magnetic field measurements less than 5% in the range 0.4 - 2 kG.

abstract: This dissertation aims at developing novel materials and processing routes using alkali activated aluminosilicate binders for porous (lightweight) geopolymer matrices and 3D-printing concrete applications. The major research objectives are executed in different stages. Stage 1 includes developing synthesis routes, microstructural characterization, and performance characterization of a family of economical, multifunctional porous ceramics developed through geopolymerization of an abundant volcanic tuff (aluminosilicate mineral) as the primary source material. Metakaolin, silica fume, alumina powder, and pure silicon powder are also used as additional ingredients when necessary and activated by potassium-based alkaline agents. In Stage 2, a processing route was developed to synthesize lightweight geopolymer matrices from fly ash through carbonate-based activation. Sodium carbonate (Na2CO3) was used in this study to produce controlled pores through the release of CO2 during the low-temperature decomposition of Na2CO3. Stage 3 focuses on 3D printing of binders using geopolymeric binders along with several OPC-based 3D printable binders. In Stage 4, synthesis and characterization of 3D-printable foamed fly ash-based geopolymer matrices for thermal insulation is the focus. A surfactant-based foaming process, multi-step mixing that ensures foam jamming transition and thus a dry foam, and microstructural packing to ensure adequate skeletal density are implemented to develop foamed suspensions amenable to 3D-printing. The last stage of this research develops 3D-printable alkali-activated ground granulated blast furnace slag mixture. Slag is used as the source of aluminosilicate and shows excellent mechanical properties when activated by highly alkaline activator (NaOH + sodium silicate solution). However, alkali activated slag sets and hardens rapidly which is undesirable for 3D printing. Thus, a novel mixing procedure is developed to significantly extend the setting time of slag activated with an alkaline activator to suit 3D printing applications without the use of any retarding admixtures. This dissertation, thus advances the field of sustainable and 3D-printable matrices and opens up a new avenue for faster and economical construction using specialized materials. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2019

Alkali-Aggregate Reaction (AAR) is one of the most harmful distress mechanisms affecting the serviceability and durability of concrete critical infrastructure worldwide. Over the past decades, several approaches and recommendations have been developed to assess the potential reactivity of aggregates in the laboratory and the efficiency of preventive measures (e.g., supplementary cementing materials – SCMs) to mitigate ASR in the field. Yet, recent findings suggest that the appropriate use of SCMs “only” delayed and does not entirely prevent ASR occurrence. Moreover, once ASR starts in the field, there is no “universal” solution that should be applied in various cases, and each situation should be evaluated as “unique”. Nevertheless, artificially triggering healing agents have been studied in the late years, thus presenting an interesting “physical” solution to reduce the ingress of water and recover damaged concrete elements, which could present an interesting solution for durability-related distress due to ASR. This Ph.D. project focuses on detailed laboratory investigations aiming first to understand the self-healing process of concrete (i.e., by the natural or engineered process). Then, its further influence on ASR-induced expansion and deterioration, either applied internally or externally to the concrete. To achieve this goal, concrete mixtures presenting a wide range of binder compositions, using distinct types of chemical admixtures (e.g., crystalline self-healing), and incorporating five different types/nature of highly reactive aggregates (i.e., coarse and fine) were combined to manufactured concrete specimens in the laboratory. Otherwise, in aging specimens, concrete samples were designed only with GU-cement as the binder material but incorporated two different types/nature of highly reactive aggregates. Then, the samples were exposed to ASR-induced development until they reached pre-determined expansion levels, in which a wide range of sealers and coating materials were applied on the surface of the affected specimens. Mechanical (i.e., stiffness damage test, modulus of elasticity, micro indentation, shear and compressive strengths) and microscopic (damage rating index and scanning electron microscopy) tests were performed on samples at different ages (up to two years of accelerated ASR development). The results show that besides changing AAR-kinetics, the different binder compositions or the chemical admixtures could modify the distress mechanism due to AAR. The addition of crystalline healing agents or their combination with SCMs in concrete not only delayed the development of inner damage but significantly lowered the compressive strength loss at equivalent expansion amplitudes than control specimens. Moreover, the combination of different binder materials modified the chemical and mechanical properties of the ASR-gel, changing its swelling properties and the further damage development in concrete. On the other hand, the wide range of surface treatments used were not able to alter ASR distress mechanism; yet, they changed ASR-kinetics. Moreover, their effectiveness to slower the reaction shows to be significantly influenced by the damage degree to which the surface treatment is applied. Finally, a comprehensive framework enabling the optimized selection of raw materials to prevent or mitigate ASR development is proposed.

Over the last decades, researchers have proposed a number of tools for the condition assessment of concrete infrastructure affected by alkali-silica reaction (ASR). Amongst those, increasing attention has been given to the Stiffness Damage Test (SDT), Damage Rating Index (DRI), and Residual Expansion (RE) laboratory test procedures that aim to determine the cause and extent (i.e., diagnosis) of damage along with the potential of further deterioration (i.e., prognosis) of affected concrete. Yet, most of the data gathered so far while using the aforementioned tools has been obtained on laboratory test specimens presenting distinct conditions from affected structural members in the field, especially regarding restraint effects. This work aims to understand the impact of restraint on ASR-induced expansion and damage. Thirty-two 450 mm by 450 mm by 675 mm concrete blocks with various reinforcement configurations (i.e., unreinforced, 1D and 2D reinforcement) and incorporating highly reactive coarse and fine aggregates (i.e., Springhill coarse and Texas sand) were manufactured and stored in conditions enabling ASR-induced development (i.e., 38°C and 100 R.H). Two expansion levels were selected for analysis (i.e., 0.08% and 0.15%); once reached, cores were extracted from three different directions (i.e., longitudinal, transversal and vertical) of all blocks and mechanical (i.e., SDT and compressive strength), microscopic (i.e., DRI, scanning electron microscope, etc.) and expansion (i.e., RE) test procedures were conducted on the concrete cores. Results suggest that the presence of restraint influences the induced expansion, resulting in an anisotropic response of the specimens. Furthermore, similar to the expansion behavior, an anisotropic distribution of induced damage and mechanical properties reduction are observed for the restrained concrete blocks in which the restraint configuration seems to significantly affect ASR-induced damage development and features. This led to the observation of a higher number of damage features, ASR development and mechanical properties reduction in cores obtained from unrestrained directions. Yet, some anticipated results from the current research will be studied in detail in the near future where the reliability of the existing techniques (i.e., residual expansion and soluble alkalis) for appraising ASR potential for further induced development and distress (i.e., prognosis) in affected concrete presenting distinct restraint scenarios will be evaluated.

This thesis examines the possibility of creating composite mainly from waste materials. The matrix of this composite was prepared from fly ash type F, which was activated by sodium water glass. Wood chips were used as a filler. This thesis includes theoretical and experimental parts. The theoretical part deals with the most important issues of wood composites with an inorganic matrix as well as basic components of investigated composite, ie alkaline activated fly ash and wood. In the experimental part, the fly ash pastes were prepared, from which the most suitable mixture was chosen for the composite preparation. Properties of wood composite with alkali activated fly ash matrix were investigated depending on the dose of wood chips.

Final publication is available at http://link.springer.com/article/10.1007%2Fs10856-015-5612-2 / 京都大学 / 0048 / 新制・課程博士 / 博士(医学) / 甲第19566号 / 医博第4073号 / 新制||医||1013(附属図書館) / 32602 / 京都大学大学院医学研究科医学専攻 / (主査)教授 安達 泰治, 教授 戸口田 淳也, 教授 鈴木 茂彦 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM