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名古屋大学年代測定総合研究センターシンポジウム報告

<p>Predmet ovog istraživanja je razvoj nove generacije<br />mineralnih dodataka, dobijenih termičkom i<br />mehanohemijskom aktivacijom kaolinske gline i ispitivanje<br />svojstava kompozita, u kojima je deo portland cementa<br />zamenjen dobijenim pucolanskim materijalima,<br />metakaolinom i amorfnim kaolinom, za različite režime<br />nege. Rezultati su pokazali da su termička i mehanohemijska<br />aktivacija kaolinske gline jednako pogodne metode za<br />dobijanje pucolanskih materijala. Pozitivni efekti na<br />čvrstoće pri pritisku postižu se primenom do 30 %<br />metakaolina u kompozitima pri normalnom režimu nege, a uz<br />dodatno mlevenje, sadržaj metakaolina se može povećati do<br />40 %, uz dodatak CH. Amorfni kaolin se može primeniti u<br />kompozitima, sa stepenom zamene portland cementa do 10 %,<br />pri normalnom i autoklaviranom režimu nege.</p> / <p>The subject of this research is development of a new generation<br />of mineral admixtures, obtained by thermal and<br />mechanochemical activation of kaolin clay, and testing of the<br />properties of the cement based composites, where a part of the<br />portland cement is replaced by pozzolanic materials, metakaolin<br />and amorphous kaolin, for different curing conditions. The<br />results showed that thermal and mechanochemical activation of<br />kaolin clay were equally suitable for obtaining pozzolanic<br />materials. Positive effects on the compressive strength could be<br />achieved by using up to 30 % of MK, and with additional grinding<br />after thermal activation, content of MK could be increased up to<br />40 %, with the addition of CH, under the normal curing<br />conditions. Amorphous kaolin could be used in composites with<br />a cement replacement level of 10 %, under the normal and<br />autoclave curing conditions.</p>

Ces travaux de thèse ont porté sur le développement de nouveaux engrais à relargage contrôlé grâce à la mise en œuvre d’un procédé de mechanosynthèse à partir de mélanges contenant des composés lamellaires soit naturels (montmorillonite, talc et chrysotile) soit synthétiques (les Hydroxydes Doubles Lamellaires (HDL) à base de Mg, d’Al et de Fe) et de monohydrogénophosphate de potassium. Ce sel est déjà utilisé en agriculture en tant que fertilisant conventionnel. Toutefois sa forte solubilité en solution aqueuse induit des pertes importantes lors de l’épandage via des procédés de lixiviation, de volatilisation ou encore de fixation dans les sols, limitant ainsi l’efficacité des nutriments pour les plantes. Il est alors nécessaire d’en utiliser des quantités excessives pour observer une efficacité en agriculture. Aussi la principale alternative est de contrôler l’apport en éléments venant d’une part du sel soluble mais également des constituants chimiques des matrices lamellaires impliquées. Une telle approche pourrait réduire les coûts en permettant une fertilisation accrue tout en en diminuant la solubilité des ions impliqués. La méthode utilisée consiste à broyer les réactifs ensemble en modifiant les conditions de broyage utilisées. Afin d’évaluer les modifications structurales induites par le broyage, les échantillons obtenus sont caractérisés à l’aide de différentes techniques de caractérisation du solide, en fonction des éléments chimiques impliqués. La diffraction des rayons X (PXRD), la microscopie électronique à balayage couplé avec un analyseur (SEM-EDX) et les méthodes spectroscopiques SSNMR, FTIR, RAMAN, RPE…) se sont avérées pertinentes pour réaliser le suivi des réactions de mechanosynthèse et mettre en évidence une amorphisation des matrices précruseurs et éventuellement la formation de nouvelles phases cristallisées. La microscopie montre sytématiquement une modification importante de la taille des particules avec perte de la morphologie des matériaux précurseurs et parfois apparition de nouveaux cristaux de forme bien définie ayant une composition chimique différente. Grâce à la spectroscopie RMN à l’état solide il est possible de mettre en évidence de fortes modifications de l’environnement chimique après mechanosynthèse, suggérant la formation de composés métastables impliquant des cations métalliques issus des phases lamellaires, du phosphore et de l’oxygène. Les composés obtenus ont ensuité été étudiés dans des conditions de relargage mettant en évidence des propriétés de realargage contrôlé quelle que soit la matrice lamellaire précurseur impliquée dans le procédé. La vitesse de relargage des nutriments est influencée par la nature et la composition chimique de la matrices de départ, sachant qu’en fonction de leur composition chimique des produits différents peuvent être formés. / The present work describes the development of slow release fertilizers from the mechanochemical activation of of natural (montmorillonite, talc, chrysotile) and synthetic (Layered Double Hydroxides (LDH) MgAl and MgFe) lamellar matrix mixtures with potassium monohydrogen phosphate. This salt is used in agriculture as a conventional fertilizer and is highly soluble in aqueous solution, which implies large losses due to leaching processes, volatilization or even fixation in the soil, limiting the efficiency of the nutrients for the plants. Due to these characteristics, there is a need to apply large quantities of these products in agriculture. Therefore, the main idea is to control the supply of both the elements coming from the soluble salt as well as the constituting elements of the lamellar matrices. Such approach could reduce costs with exacerbated fertilization, potentiating the use of the products and decreasing the solubility of the ions involved. The methodology used basically consists of the milling of the reagents varying the processing conditions. For the characterization of the samples, several techniques were used according to the nature of the compounds involved. Particularly, PXRD, SEM / EDX and spectroscopic (SSNMR, FTIR, RAMAN, EPR…) techniques proved to be highly efficient for the monitoring of the mechano-chemical reaction, and to highlight the amorphization of the precursors and/or the formation of a distinct crystalline phase. SEM/EDX showed after the mechanochemical activation the changes in particle size, the disappearance of precursor morphologies, and the formation of particles with distinct morphologies and different chemical composition. Using solid state NMR measurements significant changes in the chemical environments involved were evidenced, suggesting the formation of metastable compounds between metal cations from the lamellar matrices, phosphorus and oxygen, as well as other possible compounds as products. After the mechanochemical reaction, in the nutrient release assays, the slow release behavior was observed for all the matrices analyzed. The release rate can be influenced by the chemical composition of the starting matrices, since each matrix can produce similar and distinct products, for example, SiO2 from natural clays which is not possible in the LDH products.

In dieser Arbeit werden das Potential der mechanochemischen Synthesemethode zur Herstellung von metallorganischen Gerüstverbindungen (MOFs) vorgestellt und mögliche Anwendungsgebiete aufgezeigt. Im Forschungsfokus bezüglich schnellerer und effizienterer Darstellungsmethoden ist die Mechanochemie eine aussichtsreiche Alternative. Die Feststoff-Reaktion ist ohne die Verwendung von Lösungsmitteln durchführbar, zeichnet sich durch verkürzte Reaktionszeiten und quantitativen Eduktumsatz aus und gilt somit als Green Chemistry-Methode, die stetig wachsende Bedeutung erlangt. Die Ergebnisse dieser Arbeit belegen, dass über die mechanochemische Synthese metallorganische Verbindungen in allen Dimensionalitäten herstellbar sind. Die Reaktionsparameter sind auf die Herstellung isostruktureller und strukturanaloger Verbindungen übertragbar. Es wurden Synthesebedingungen identifiziert, die die Produktbildung beeinflussen, so dass ihre Kontrolle zur gezielten Herstellung verschiedener Verbindungen diente. Des Weiteren wurden Reaktionsparameter ermittelt, die einen Einfluss auf die Eigenschaften des Produkts ausüben. Im Hinblick auf eine größtmögliche spezifische Oberfläche wurde die Synthese optimiert und eine postsynthetische Aktivierungsprozedur entwickelt, die gemeinsam in einer verbesserten Gasadsorptionskapazität resultieren und auf andere Verbindungen übertragbar sind. Die Ergebnisse zur Gasspeicherung zeigen ein erstes Anwendungspotential für mechanochemisch synthetisierte MOFs auf, die als feine Pulver mit vergrößerter Oberfläche erhalten werden. Weiterhin wurde die Einlagerung von Solvensmolekülen in die Poren eines MOFs untersucht. Dabei zeigte sich, dass das MOF seine Gitterparameter an die jeweiligen Gastmoleküle anpasst. Das Potential zur Interkalation von Feststoffen wird anhand der Einlagerung pharmazeutischer Wirkstoffmoleküle belegt. Katalytische Untersuchungen zeigen eine gute Aktivität des mechanochemisch synthetisierten Rohprodukts. / In this work the potential of mechanochemical synthesis to produce metal-organic frameworks (MOFs) is presented and possible applications for the materials are shown. In the focus of research regarding faster and more efficient methods of synthesis, mechanochemistry is an promising alternative. This solid-state reaction can be carried out without the use of solvent, exhibits shortened reaction times and a quantitative turnover of reactands. Therefore it is a method of green chemistry, and its importance is constantly increasing. The results show that mechanochemical synthesis is capable of producing metal-organic compounds in all dimensionalities. The reaction conditions can be transferred to synthesize isostructural and structural analogous compounds. Parameters influencing the formation of products were identified, and their control led to a well-aimed design of various compounds. In addition, conditions influencing the properties of the product were determined. In terms of a specific surface area as large as possible, the synthesis was optimized and a postsynthetic activation was developed, together resulting in an improved capacity for gas adsorption and transferrable to other compounds. The results concerning gas storage present one possible application of mechanochemically synthesized MOFs, that are produced as fine powders with enlarged surfaces. Furthermore, intercalation of solvent molecules in the pores of a MOF was investigated. It shows that the MOF adjustes its lattice paramters to the guest molecules. The potential to intercalate solid-state compounds is demonstrated using pharmaceutical drug molecules. Catalytic investigations show a good activity of the mechanochemically synthesized raw product.

This thesis is focused at possibilities of preparation and characterization of XRD-amorphous delaminated and dehydroxylated talc phase – meta-talc, which can have its potential application and a starter material for a preparation of magnesium-silicate analogues of geopolymers. Changes in structure and morphology of talc ore were observed during this work. For the purposes of this research, two various talc ores – chloritic and dolomitic were examined. Whole process of meta-talc preparation was examined with whole scale of instrumental techniques such as X-ray diffraction, simultaneous thermogravimetric a differential thermal analysis, infrared spectroscopy, scanning electron microscopy or laser analysis of particle size. Meta-talc can be obtained via mechanochemical activation of talc ore with subsequent calcination. Mechanochemical treatment lead to destruction of original crystal structure and breaking of original bonds, i.e. the product of this treatment was almost amorphous and delaminated. Most of hydroxyl groups were converted to molecules of water which remained adsorbed or coordinated in ore structure. These molecules were removed during calcination step.

This doctoral thesis is focused on the study of reactions in the CaO–SiO2–H2O complex system, primarily to the synthesis of crystalline tobermorite. Hydrothermal conditions are necessary for the formation of crystalline tobermorite, whereas the course of the reaction is influenced by several factors. The main studied factor was the choice of the silica sources differing in means of solubility, crystallinity, particle size distribution, specific surface area, and purity. The water-to-solid ratio turned to be also an important factor as the length of the hydrothermal reaction. The influence of the mechanochemical pretreatment of starting materials to the final phase composition of samples was studied as well. The obtained results show that the crystallinity of the silica source is the main factor influencing the reaction rate and the purity of the synthesized tobermorite. While using the crystalline silica source the shorter silicate chains are formed and the formation of tobermorite structure is easier. Using the amorphous silica sources and the mechanochemical pretreatement of starting materials prolong the hydrothermal reaction. The prepared samples are always the mixture of crystalline or semicrystalline calcium hydrosilicates instead of the phase pure tobermorite.

Nanostructured fayalite (α-Fe2SiO4) with a large volume fraction of interfaces is synthesized for the first time via single-step mechanosynthesis, starting from a 2α-Fe2O3 + 2Fe + 3SiO2 mixture. The nonequilibrium state of the as-prepared silicate is characterized by the presence of deformed polyhedra in the interface/surface regions of nanoparticles. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Vorgestellt werden die gezielte mechanochemische sowie die fluorolytische Sol-Gel-Synthese von fluorierten Koordinationspolymeren mit dem Strukturmotiv einer direkten Metall-Fluor Bindung. Im Vorfeld beschränkten sich die mechanochemischen Synthesen von fluorierten Koordinationspolymeren (FCPs) darauf, Fluor über den organischen Linker im Netzwerk zu integrieren. Auch fehlten Studien, welche die Materialeigenschaften bezüglich der unterschiedlichen Fluorpositionen miteinander verglichen. Es wird die erste mechanochemische Synthese eines Koordinationspolymers mit einer direkten Metall-Fluorid-Bindung (Bariumterephthalatfluorid (BaF(p-BDC)0,5)) vorgestellt. Auch das Strontiumacetatfluorid (SrF(CH3COO)), Bariumacetatfluorid (BaF(CH3COO)) und das Bleiacetatfluorid (PbF(CH3COO) konnten durch unterschiedliche Synthesemethoden dargestellt werden. Die Kristallstrukturen wurden aus den Röntgenpulverdiffraktogrammen bestimmt. Unterstützt werden die Strukturlösungen u. a. durch die chemische Verschiebung in den 19F-MAS-NMR-Spektren, aus denen die Metall-Fluor-Abstände berechnet und mit denen aus den Kristallstrukturen verglichen wurden. Die vorgestellten Koordinationspolymere vervollständigen die Reihe der Verbindungen, welche aus Linkern mit gleichem Kohlenstoffskelett, gleichem Metallkation und ähnlicher chemischer Zusammensetzung, jedoch unterschiedlichen Fluorpositionen bestehen. Die gewählten Koordinationspolymere erlaubten damit den Vergleich der thermischen Stabilität, des Wasserabsorptionsverhaltens, sowie die Acidität der sauren Zentren an der Oberfläche bzgl. der unterschiedlichen Bindungsmotive des Fluors. In Abhängigkeit von der Fluorposition zeigen die Lanthanoid-dotierten Koordinationspolymere unterschiedlich lange Lebenszeiten der angeregten Zustände. Durch das Strukturmotiv der direkten Metall-Fluor-Bindung kann die Abklingzeit der angeregten Zustände des angeregten Lanthanoids deutlich verlängert werden. / The targeted mechanochemical and fluorolytic sol-gel synthesis of fluorinated coordination polymers with the structural motif of a direct metal-fluorine bond are presented. Previously, the mechanochemical syntheses of fluorinated coordination polymers (FCPs) were limited to integrating fluorine into the network via the organic linker. There were also no studies comparing the material properties of the different fluorine positions.The first mechanochemical synthesis of a coordination polymer with a direct metal fluorine bond (barium terephthalate fluoride (BaF(p-BDC)0.5)) is presented. Also the strontium acetate fluoride (SrF(CH3COO)), barium acetate fluoride (BaF(CH3COO)) and lead acetate fluoride (PbF(CH3COO)) can be obtained by different synthesis methods. The crystal structures were determined from the X-ray diffractograms. The structural solutions are supported, among other things, by the chemical shift in the 19F MAS NMR spectra, from which the metal-fluorine distances were calculated and compared with those from the crystal structures. The coordination polymers presented complete the series of compounds consisting of linkers with the same carbon skeleton, the same metal cation and similar chemical composition, but different fluorine positions. The selected coordination polymers thus allowed the comparison of thermal stability, water absorption behaviour and acidity of the acid centres on the surface with respect to the different bonding motives of the fluorine. Depending on the fluorine position, the lanthanide doped coordination polymers show different lifetimes of the excited states. Due to the structural motif of the direct metal-fluorine bond, the decay time of the excited states of the excited lanthanidecan be significantly extended.

This investigation is focused on the understanding of mechanical and chemical reaction behaviors of stoichiometric mixtures of nano- and micro-scale aluminum and hematite (Fe2O3) powders dispersed in epoxy. Epoxy-cast Al+Fe2O3 thermite composites are an example of a structural energetic material that can simultaneously release energy while providing structural strength. The structural and energetic response of this material system is investigated by characterizing the mechanical behavior under high-strain rate and shock loading conditions. The mechanical response and reaction behavior are closely interlinked through deformation characteristics. It is, therefore, desirable to understand the deformation behavior up to and beyond failure and establish the necessary stress and strain states required for initiating chemical reactions. The composite s behavior has been altered by changing two main processing parameters; the reactants particle size and the relative volume fraction of the epoxy matrix. This study also establishes processing techniques necessary for incorporating nanometric-scale reactants into energetic material systems. The mechanochemical behavior of epoxy-cast Al+Fe2O3 composites and the influence of epoxy volume fraction have been evaluated for a variety of loading conditions over a broad range of strain rates, which include low-strain rate or quasistatic loading experiments (10-4 to 10-2 1/s), medium-strain rate Charpy and Taylor impacts (103 to 104 1/s), and high-strain rate parallel-plate impacts (105 to 106 1/s). In general, structural strength and toughness have been observed to improve as the volume fraction of epoxy decreases, regardless of the loading strain rate regime explored. Hugoniot experiments show damage occurring at approximately the same critical impact stress for compositions prepared with significantly different volume fractions of the epoxy binder phase. Additionally, Taylor impact experiments have indicated evidence for strain-induced chemical reactions, which subject the composite to large shear accompanied by temperature increase and associated softening, preceding these reactions. Overall, the work aims to establish an understanding of the microstructural influence on mechanical behavior and chemical reactivity exhibited by epoxy-cast Al+Fe2O3 materials when exposed to high stress and high-strain loading conditions. The understanding of fundamental aspects and the results of impact experiment measurements provide information needed for the design of structural energetic materials.