The present thesis work is focused on the low-temperature transformation of food industry wastes like mussel shells into nanocrystalline ions-substituted hydroxyapatite powder, having similarities with natural bone apatite, on the consolidation of such powder by cold sintering, and on the physicochemical characterization of the raw materials, synthesised powders and sintered pellets. Nonetheless the evaluation of the mechanical and biological properties was carried out to address cold sintered bodies to possible scaffolds for bone tissue engineering applications. Mussel shells, like other biogenic source of calcium carbonate/phosphate, have the attractive of being a “zero”-cost raw material because they are a waste, but also of having trace elements (Mg, Na, Sr, etc.) which, if found in a bioceramic, have a positive effect on the biological properties. Therefore, mussel shell-derived hydroxyapatite could resemble the mineralized bone tissue, being natural apatite nanometric, ion substituted and with low crystalline tenor. In the first part of the manuscript, two production methods were explored: mechanochemistry and dissolution-precipitation synthesis. Mechanochemistry was carried out at room temperature by directly mixing crushed mussel shells with phosphoric acid in a ball mill. Nanocrystalline multi-ions substituted hydroxyapatite was produced after 4 h of milling and drying at 150°C. Conversely, dissolution-precipitation synthesis was carried out in two steps: the dissolution of crushed mussel shells by adding phosphoric and chloric acid occurred at room temperature, whereas the precipitation of calcium phosphates induced by soda solution, occurred at 45°C. Dissolution-precipitation was further implemented to produce a homogeneous composite material in a single-step by introducing chitosan (in a 2/5/10 wt%) during the dissolution step. The idea was to produce a composite material able to mimic the natural bone tissue composition. In the second part of the manuscript, cold sintering was investigated for the consolidation of the synthesised hydroxyapatite and hydroxyapatite-based composites at a maximum temperature of 200 °C to avoid phase transformation, limit grain growth and preserve the osteoconduction of the bioceramic materials. The effect of the main process parameters such as solvent amount, pressure, temperature and holding time was discussed. Pressure-solution creep and plastic deformation were pointed out as the fundamental consolidation mechanisms in cold sintering, the pressure playing the major role. With a synergistic combination of pressure (600 MPa), temperature (200°C) and liquid phase (20 wt%) it was possible to consolidate hydroxyapatite above 80% relative density in only 15 min. Furthermore, pressure and temperature act a complementary agent during cold sintering. In fact, it was possible to consolidate nanometric HAp and HAp/chitosan composites above 90% relative density by increasing the applied pressure up to 1.5 GPa at room temperature. The mechanical properties of cold sintered pellets were investigated, and resulted in a flexural bending strength and Vickers microhardness, respectively, of 45 MPa and 1.1 GPa for pure hydroxyapatite and of 55 MPa and 0.8 GPa for HAp/chitosan composite. In the frame of bone tissue engineering applications, cold sintered bodies were also preliminarily tested in vitro to establish their bioactivity, their cellular viability through cytotoxicity assessment, and the ability to sustain cells adhesion, osteogenic differentiation. And extracellular matrix mineralization.

The demand for efficient and clean fuel alternatives has been increasing in recent years and is expected to become more pronounced in the future. Utilization of hydrogen as a fuel is one of the most promising energy resources due to its easy production, abundance, regeneration and not creation of greenhouse gases during its combustion. Although gaseous hydrogen has a very high energy content per unit weight, its volumetric energy density is rather low. The large scale use of hydrogen as a fuel crucially depends on the development of compact hydrogen storage materials with a high mass content of hydrogen relative to total mass and to volume. Certain metals and alloys are capable of reversibly absorbing large amounts of hydrogen to form metal hydrides. They exhibit the highest volumetric densities of hydrogen and are very promising for hydrogen storage because of their efficiency, cost and safety. Some of the metal hydride families can also be used in hydrogen compressors. The objective of this work is to investigate the synthesis and characterization behavior of intermetallic alloys (ZrMn2, ZrNi) for hydrogen compression and of complex hydrides (Zn(BH4)2 ) for on-board hydrogen storage. An overview of hydrogen as a fuel and its storage means is provided, synthesis and characterization methods of metal hydrides are presented and the effect of mechanical milling and the catalytic doping of metal/complex hydrides are investigated in detail. The hydrogen storage alloys (hydrides) are extensively characterized using various analytical tools such as: XRD, SEM, EDS, TCD, FTIR and GC/MS. The thermal (heat flow and weight loss) and volumetric (storage capacity, kinetics, cycle life, etc) analysis have been carried out via DSC/TGA and high pressure PCT apparatus. Finally conclusions and recommendations for future work are provided to improve the absorption/desorption cycle of hydrogen storage in the compounds under investigation.

Previous work has shown that when inorganic compounds are milled with quartz in a high energy ball mill the elements are sequestered into the quartz matrix and cannot be easily recovered by simple extraction methods. In this study lead (II) oxide, copper (II) oxide, magnesium oxide, zinc oxide and sodium hydroxide were milled with quartz sand and the recoveries of the metals investigated in detail. The standard EPA3050B method (acid digestion of sediments, sludge and soils) for extractable metals was compared to exhaustive HF digestion method based on ASTM C146-94a (test methods for chemical analysis of glass sand) and UDC 666.123:543.06 (chemical analysis of soda-lime and borosilicate glass). From these two analyses the total recovery of metals was determined. It was found that the elements extracted by the EPA3050B method decreased in an approximately logarithmic way with milling time. The metals are apparently strongly sequestered into the fractured quartz. Total HF digestion of the insoluble matrix gave good recovery of the “lost” elements. A reliable analytical procedure has been developed and the mechanisms leading to this sequestering are discussed. Particle size analysis and electron microscopy of milled samples support a process of brittle alloy formation as the proposed mechanism whereby the elements are sequestered into the milled quartz.

The aim of this study was to investigate synthesis of lithium borides by mechanochemical synthesis from oxides. Lithium borides have promising properties in the area of high energy additives and hydrogen storage. Lithium oxide (Li2O), boron oxide (B2O3) and Mg were used to synthesize lithium borides. Experiments were conducted in a planetary ball mill under argon atmosphere. Analyses of the products were done by X-ray diffraction and scanning electron microscopy. Trilithium tetradecaboride (Li3B14) peaks were observed in the product powder. Removal of other phases that were formed during experiments was done by leaching in HCl/water solution. Leaching in 0.5 M HCl/water solution for 10 minutes was found to be sufficient to remove / iron (Fe) and magnesium oxide (MgO). Effects of ball milling parameters such as milling speed, ball to powder ratio, milling duration were investigated and milling for 20 hours with 300 rpm and 30:1 ball to powder ratio was found to be the optimum conditions. Syntheses of other lithium borides (LiB4, Li2B6, LiB13) were also experimented with the same milling parameters. Formation of LiB4, Li2B6 and LiB13 was not observed in the product powders. However, the results of LiB4 and LiB13 production experiments showed also Li3B14 peaks in the product. Li2B6 synthesis experiments resulted in Li2B9 peaks in the product powders.

Previous work has shown that when inorganic compounds are milled with quartz in a high energy ball mill the elements are sequestered into the quartz matrix and cannot be easily recovered by simple extraction methods. In this study lead (II) oxide, copper (II) oxide, magnesium oxide, zinc oxide and sodium hydroxide were milled with quartz sand and the recoveries of the metals investigated in detail. The standard EPA3050B method (acid digestion of sediments, sludge and soils) for extractable metals was compared to exhaustive HF digestion method based on ASTM C146-94a (test methods for chemical analysis of glass sand) and UDC 666.123:543.06 (chemical analysis of soda-lime and borosilicate glass). From these two analyses the total recovery of metals was determined. It was found that the elements extracted by the EPA3050B method decreased in an approximately logarithmic way with milling time. The metals are apparently strongly sequestered into the fractured quartz. Total HF digestion of the insoluble matrix gave good recovery of the “lost” elements. A reliable analytical procedure has been developed and the mechanisms leading to this sequestering are discussed. Particle size analysis and electron microscopy of milled samples support a process of brittle alloy formation as the proposed mechanism whereby the elements are sequestered into the milled quartz.

Orientador: Prof. Dr. Fabio Furlan Ferreira / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2017. / A malária, apesar de ser uma doença tratável, ainda continua causando um grande número de mortes, principalmente no continente africano, sendo considerada uma das doenças parasitárias mais prevalecentes no mundo. A recomendação da organização mundial da saúde (OMS) para o tratamento da malária consiste na utilização de terapia combinada de artemisinina (artemisinin combined therapy - ACT). A ACT visa combinar a artemisinina ou um derivado com outro fármaco antimalárico que tenha um maior tempo de meia-vida e, assim, tornar o tratamento mais eficaz e evitar o aparecimento de resistência dos parasitas aos antimaláricos. O MEFAS é um novo sal híbrido derivado do artesunato e da mefloquina ¿ dois compostos antimaláricos ¿ que apresenta dois mecanismos de ação diferentes e promissoras características que viabiliza a sua utilização no tratamento da malária. Neste contexto, foi realizado um estudo estrutural do MEFAS em estado sólido e foi proposta uma síntese mecanoquímica para sua obtenção. Com o uso da difração de raios X por policristais (DRXP) foi verificado que uma das amostras de MEFAS estudadas, apresenta uma fase amorfa. A estabilidade química do MEFAS também foi estudada, visto que fases amorfas tendem a ser instáveis; os resultados mostraram que o MEFAS se degradou após dezoito meses de armazenamento, formando a diidroartemisinina (DHA). Isto foi evidenciado com o uso das técnicas de espectroscopia vibracional na região do infravermelho por transformada de Fourier (FTIR), ressonância magnética nuclear de estado sólido (RMN) e também pelos dados de DRXP e método de Rietveld. A estabilidade química do MEFAS em solventes orgânicos também foi estudada. Para os solventes testados, o MEFAS demonstrou ser estável quimicamente apenas em éter etílico. Por fim, uma rota de síntese via mecanoquímica é proposta para a obtenção do MEFAS, com a possibilidade de utilização de pequenas quantidades de solventes. Essa é uma boa estratégia, pois é uma rota de síntese mais rápida, comparada com a obtenção do MEFAS via reação química em solução, e ainda é uma síntese considerada "química verde", ou seja, um método sustentável. Os resultados obtidos pelas técnicas de FTIR e RMN indicaram que a síntese mecanoquímica foi promissora na formação do MEFAS, sendo que após quinze minutos de moagem foi obtido o sal hibrido desejado. / Malaria, despite being a treatable disease, still continues to cause a large number of deaths, especially on the African continent, and is considered one of the most prevalent parasitic diseases in the world. The recommendation of the World Health Organization (WHO) for the treatment of malaria is the use of artemisinin combination therapy ¿ ACT. ACT aims to combine artemisinin or derivative with another antimalarial drug that has a longer half-life and thus make treatment more effective and prevent the emergence of parasite resistance to antimalarials. The MEFAS, a new hybrid salt derived from artesunate and mefloquine ¿ two antimalarials compounds ¿ has two different mechanisms of action and presents promising characteristics that make its use feasible in the treatment of malaria. In this context, a structural study of MEFAS in solid state was performed and a mechanochemical synthesis was proposed to obtain this hybrid salt. With the use of X-ray powder diffraction data (XRPD) it was verified that the MEFAS is in the amorphous form. The chemical stability of MEFAS has also been studied, since that the amorphous phases tend to be unstable; the results showed that MEFAS degraded after eighteen months of storage. When degradation of this hybrid salt occurs, dihydroartemisinin (DHA) is formed. This was evidenced by Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) as well as by the Rietveld method with X-ray powder diffraction data. Finally, a route of synthesis via mechanochemistry is proposed to obtain the MEFAS, with the possibility of using catalytic amounts of solvents. This is a good strategy and is still a synthesis considered "green chemistry", that is, a more ecologically correct method. The results obtained by FTIR and NMR techniques indicated that the mechanochemical synthesis was promising in the formation of MEFAS, after fifteen minutes of milling the desired hybrid salt was obtained.

No / Mechanochemical synthesis has been applied to the rapid synthesis of Deep Eutectic Solvents (DESs), including Reline 200 (choline chloride : urea, 1 : 2), in a continuous flow methodology by Twin Screw Extrusion (TSE). This gave products in higher purity and with Space Time Yields (STYs), four orders of magnitude greater than for batch methods

Mechanochemically synthesized cobalt oxide-based particles are employed for the catalytic reduction of 4-nitrophenol (4NP), a toxic water contaminant. This reduction produces 4‑aminophenol (4AP), a less toxic, pharmaceutical precursor for drugs such as paracetamol. The indicated reduction has been completed previously using noble metals and/or catalysts requiring extensive solvent use, and time as part of their preparation. The cost and synthesis of these noble metal catalysts hinders the sustainable broad scale application as an environmental remediation solution. The catalyst synthesis explored in this study utilizes the green chemistry technique of vibratory ball-milling and annealing cobalt oxide-based particles at different temperatures, producing unique agglomerates with differing surface structure and catalytic properties. Additional investigation into the mechanism through temperature, pH, and change in pressure over the reaction is completed. Further analysis shows that these catalysts are efficient for the reduction of 4-amino-3-nitrophenol and 2-amino-5-nitrophenol with unique catalytic rates. Finally, it is found that the application of this reduction in a flow process has potential for use on a broader scale.

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.

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.