Orientadores: Heloise de Oliveira Pastore, Leonardo Marchese / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-16T13:00:02Z (GMT). No. of bitstreams: 1 Superti_GuilhermeBicaleto_D.pdf: 4945691 bytes, checksum: 95096830b37dc8f5ad0537d64a2481e7 (MD5) Previous issue date: 2009 / Resumo: Este trabalho descreve a síntese de dois materiais lamelares, um silicato, a magadiita, e um aluminofosfato, a AlPO-kanemita. No primeiro caso foi feita a substituição isomórfica com alumínio e no segundo com ferro ou vanádio e também se variou os tipos de alquilaminas no espaço interlamelar, alternandose cadeias longas e curtas. A magadiita foi convertida em sua forma ácida por dois métodos diferentes: um pela troca iônica com NH4+ e outro pela troca iônica com HCl. Estudos de DRX em temperaturas crescentes demonstraram que a estabilidade térmica da magadiita não se altera após a introdução de alumínio. A acidez dos materiais foi avaliada pelo monitoramento por FTIR do CO adsorvido e verificou-se que a introdução de alumínio produz sítios de alta acidez, comparável aos zeólitos. A comparação dos dois materiais ácidos diferentes indicou que os sítios produzidos por desamoniação são mais acessíveis ao CO do que os produzidos pela troca com HCl. A AlPO-kanemita foi utilizada na preparação de compósitos poliméricos por dois métodos diferentes, por mistura no estado fundido e polimerização in situ. No primeiro caso os polímeros usados, PP e EVA, não conseguem acessar o espaço interlamelar, enquanto que no segundo caso o PS e a PA6 tem acesso, mas este depende das aminas presentes no espaço interlamelar. As massas moleculares do PS não são afetadas pela presença da AlPO-kan, mas as da PA6 são drasticamente reduzidas. A introdução dos metais de transição tem efeito na decomposição térmica dos polímeros, produzindo uma maior quantidade de um material carbonáceo quando comparada aos análogos sem metal, o que diminui a inflamabilidade do material. / Abstract: This work describes the synthesis of two layered materials, magadiite and AlPOkanemite. The first is a silicate analogous to the natural hydrated layered silicate where isomorphous substitution with aluminum was performed. AlPO-kanemite is an aluminophosphate with the same structure as the hydrated layered silicate kanemite, from the same family as magadiita. It also passed by isomorphous substitution and was also synthesized with different alkylamines at its interlayer space, alternating short and long chains. Magadiite was converted in its acid form by two different methods: ion exchange with NH4+ and themolysis or by ion exchange with HCl. The diffractograms collected in crescent temperatures show that thermal stability of magadiite does not change after introduction of aluminum. The acidity of materials was measured by monitoring the CO adsorption with FTIR and the results shows that the acidity is high, comparable to zeolites. The comparison between the two different acid materials shows that the one produced by desamoniation has acid sites more accessible to probe molecules in respect to the one produced by exchange with HCl. AlPO-kanemite was used to produce polymeric composites by two methods: melt intercalation and in situ polymerization. In the first case the polymers (PP and EVA) were not able to access the interlayer space while at the second one the PS and PA6 were found in theinterlayer space, but their concentration depends on the quantities of the amines present at the material. The molecular mass of PS was not altered by the presence of the AlPO-kan but the PA6 is drastically reduced. The introduction of the metals has effect at thermal decomposition of the polymers, producing a larger quantity of a carbonaceous material when compared to its analogous, but without metals, that diminishes the flammability of the polymer. / Doutorado / Quimica Inorganica / Doutor em Ciências

Orientador: Claudio Airoldi / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T09:24:05Z (GMT). No. of bitstreams: 1 Oliveira_VaeudoValdimiro_D.pdf: 4127433 bytes, checksum: 44acdbe58b130ca68a90c55fc6bf59a7 (MD5) Previous issue date: 2012 / Resumo: Na presente investigação foram sintetizados os híbridos inorgânico-orgânicos micro/mesoestruturados: a) silicato lamelar do tipo kanemita sódica, b) sua forma quimicamente modificada com cobre e c) sílica mesoporosa SBA-16. A combinação dos reagentes Na2SiO3/NaOH/etanol e Na2SiO3/NaOH/Cu(NO3)2/etanol propiciaram a obtenção de kanemita sódica e sua forma contendo o cobre incorporado na estrutura inorgânica, através da substituição isomórfica do silício nas razões molares Si/Cu = 50, 100 e 200. Para as sílicas mesoporosas foram usados sistemas formados por copolímeros F127/TEOS/H2O, F127/TEOS/etanol/H2O e F127/TEOS/butanol/H2O em meio ácido. Os materiais organofuncionalizados previamente intercalado com dimetilsulfóxido (DMSO) e etilenodiamina (EN) formam os sólidos lamelares Na-KN-DMSO, Na-KN-EN e Cu-KN-EN, através do processo de pós-síntese com o agente sililante 3-iodopropiltrimetoxissilano, que reagiu subsequentemente com dietil iminodiacetato e benzidina, formando os híbridos mesoporosos. Os híbridos lamelares foram aplicados na sorção de metais e corantes em soluções aquosas. Dentre os cátions bário, cobalto e cobre, o cobre foi mais facilmente sorvido em Na-KN-EN quando comparado com Na-KN-DMSO. No caso dos corantes verde brilhante e azul reativo 15, o primeiro foi também mais eficiente na sorção. No processo de liberação de fármacos amoxicilina e omeprazol foram utilizados os híbridos mesoporosos. Os dados de liberação mostram que o primeiro fármaco apresentou uma cinética de liberação satisfatória no fluido intestinal simulado (FIS), enquanto que o omeprazol liberou em maior quantidade no fluido gástrico simulado (FGS) / Abstract: The present investigation deals with the syntheses of inorganic-organic nano/mesostrutered hybrids: a) sodic lamellar silicate kanemite, b) its chemically modified form with copper and c) SBA-16 mesoporous silicas. The reagents combination Na2SiO3/NaOH/ethanol and Na2SiO3/NaOH/Cu(NO3)2/ethanol enabled to obtain sodic kanemite and its synthesized form containing incorporated copper in the inorganic structure, through the isomorphic substitution of silicon using the molar ratio Si/Cu = 50, 100 and 200. For mesoporous silicas the copolymers F127/TEOS/H2O, F127/TEOS/ethanol/H2O and F127/TEOS/butanol/H2O in acidic condition were used. The synthesized organofunctionalized materials were previously intercalated with dimethylsulfoxide (DMSO) and ethylenediamine (EN) in the Na-KN-DMSO, Na-KN-EN and Cu-KN-EM lamellar solids, through the post-synthesis process with the silylating agent 3-iodopropyltrimethoxysilane, which subsequently reacted with diethyl iminodiacetate and benzidine. The lamellar hybrids were applied for cation and dye sorption processes. Among barium, cobalt and copper, the last cation was more favorable sorbed in Na-KN-EN, when compared with Na-KN-DMSO. In case of brilliant green and reactive blue 15 dyes, the first one was also more efficient in sorption. The controlled drug delivery process, amoxicillin and omeprazole were applied with mesoporous hybrid systems. The delivery data demonstrated that the first drug presented a satisfactory kinetic in the simulated intestinal fluid (SIF), while omeprazole presented high amount in the simulated gastric fluid (SGF) / Doutorado / Quimica Inorganica / Doutor em Ciências

In this thesis, geometry is used as a basis for conducting experiments aimed at growing and arranging inorganic minerals on curved interfaces. Mineralisation is directed using crystalline and liquid-crystalline metallic soaps and surfactant/water systems as templates.¶ A review of the history, syntheses, structure and liquid crystallinity of metallic soaps and other amphiphiles is presented as a foundation to understanding the interfacial architectures in mesostructured template systems in general.¶ In this study, a range of metallic soaps of varying chain length and cation type are synthesised and characterised to find potentially useful templates for mineral growth. These include alkaline-earth, transition metal, heavy metal and lanthanide soaps. These are systematically characterised using a variety of analytical techniques, including chemical analyses, x-ray diffraction (XRD) infrared spectroscopy (IR) and differential scanning calorimetry (DSC). Their molecular and crystal structures are studied using transmission electron microscopy (TEM), cryo-TEM, electron diffraction (ED), electron paramagnetic spin resonance (EPR), absorption spectroscopy (UV-VIS), high resolution laser spectroscopy, atomic force microscopy (AFM), nuclear magnetic resonance spectroscopy, scanning electron microscopy (SEM), electron dispersive x-ray analysis (EDXA), thermal gravimetric analysis (TGA) and magnetic measurements. Models for the molecular and crystal structures of metallic soaps are proposed. The soaps are predominantly lamellar crystalline or liquid crystalline lamellar rotor phases with tilted and/or untilted molecular constituents. These display evidence of varying degrees of headgroup organisation, including superstructuring and polymerisation. A single crystal structure is presented for a complex of pyridine with cobalt soap. Simple models for their structure are discussed in terms of their swelling properties in water and oils. Experiments are also presented to demonstrate the sorbent properties of aluminium soaps on oil spills.¶ The thermotropic liquid crystallinity of alkaline earth, transition metal, heavy metal and lanthanide soaps is investigated in detail. This is done to assess their suitability as templates, and to document their novel thermotropic behaviour, particularly the relatively unknown lanthanide soaps. Liquid crystalline behaviours are studied using high-temperature XRD (HTXRD), hot-stage optical microscopy and DSC. Models for a liquid crystalline phase progression from crystals to anisotropic liquids are discussed in terms of theories of self-assembly and interfacial curvature. The terminology required for this is drawn from various nomenclature systems for amphiphilic crystals and liquid crystals. General agreement with previous studies is reported for known soaps, while liquid crystallinity is demonstrated in the lanthanide and some non-lanthanide soaps for the first time. A general phase progression of crystalline lamellar through liquid crystalline lamellar to non-lamellar liquid crystalline is discussed in terms of models concerned with the molecular and crystal structures of the soaps and their phase transitions via headgroup and chain re-arrangements.¶ Experiments aimed at guiding growth of metal sulfides using metallic soaps as templates are described, and a model for this growth is discussed. Metal sulfides have been successfully grown by reacting crystalline and liquid crystalline transition metal and heavy metal soaps with H2S gas at room temperature and at elevated temperature. These have been characterised using XRD, TEM, ED and IR. Sulfide growth is demonstrated to be restricted and guided by the reacting soap template architecture. Zinc, cadmium, indium and lead soaps formed confined nanoparticles within the matrix of their reacting soap template. In contrast, curved and flat sheet-like structures, some resembling sponges were found in the products of sulfided iron, cobalt, nickel, copper, tin and bismuth soaps. A model to explain this behaviour is developed in terms of the crystal and liquid crystal structures of the soaps and the crystal structures of the metal sulfide particles.¶ Liquid crystalline iron soaps have been subjected to controlled thermal degradation yielding magnetic iron oxide nanoparticles. Some XRD and TEM evidence has been found for formation of magnetic mesostructures in heat-treated iron soaps. Models for the molecular and liquid crystalline structure of iron soaps, their thermotropic phase progression and eventual conversion to these magnetic products are discussed. Systematic syntheses of mesoporous silicates from sheeted clays are discussed.¶The templates that have been used are cationic surfactants and small, organic molecular salts. Experiments are reported where a cooperative self-assembly of surfactant/water/kanemite plus or minus salt and oils yields 'folded sheet materials' (FSM'S). Templating of kanemite has also been achieved using cobalt cage surfactants. A theoretical prediction of the specific surface areas and specific volumes of homologous sets of FSM's gave excellent agreement with measured values. The geometry and topology of the mesostructures are discussed. A theoretical model is also discussed regarding the curvature found in the sheets of natural clays , and results of templating clays and silica using metallic soaps are presented. Experiments and a model for low temperature nucleation and growth of microporous silicalite-1 are described in terms of silica templating by water clathrates.¶ Finally, the problem of finding minimal surface descriptions of crystal networks is addressed. Combinatoric methods are used to disprove the existence of possible embeddings of type I and II clathrate networks in non-self intersecting periodic minimal surfaces. The crystal network of the clathrate silicate, melanophlogite is successfully embedded in the WI-10 self-intersecting surface. Details of a previously unreported, genus-25 periodic surface with symmetry Im3m are discussed.