Preparation and characterization of novel nanocomposites of inorganic/polysaccharide type

O uso de polímeros naturais no âmbito da preparação de nanocompósitos não tem sido tão amplamente estudado quando comparado com os polímeros sintéticos. Assim, esta tese tem como objectivo estudar metodologias para a preparação de novos materiais nanocompósitos sob a forma de dispersões e filmes utilizando polissacarídeos como matriz. A tese está dividida em cinco capítulos sendo o último capítulo dedicado às conclusões gerais e a sugestões para trabalhos futuros. Inicialmente é apresentada uma breve revisão bibliográfica sobre os principais temas colocando esta tese em contexto. Considerações sobre o uso de polímeros naturais e a sua combinação com a utilização de nanopartículas inorgânicas para a fabricação de novos bionanocomposites são descritas e os objectivos e outline da tese são também apresentados. No segundo capítulo, a preparação de partículas de sílica puras ou modificadas bem como a sua caracterização por FTIR, SEM, TEM, TGA, DLS (tamanho e potencial zeta) e medições de ângulo de contacto são discutidas. De modo a melhorar a compatibilidade da sílica com os polissacarídeos, as partículas SiO2 foram modificados com dois compostos do tipo organosilano: 3- metacril-oxipropil-trimetoxissilano (MPS) e 3-aminopropil-trimetoxissilano (APS). As partículas SiO2@MPS foram posteriormente encapsuladas com de poli(metacrilato de glicidilo) utilizando a técnica de polimerização em emulsão. A utilização dos nanocompósitos resultantes na preparação de dispersões de bionanocompósitos não foi bem sucedida e por esse motivo não os estudos não foram prosseguidos. O uso de SiO2@APS na preparação de dispersões bionanocomposite foi eficiente. No terceiro capítulo é apresentada uma revisão sobre dispersões bionanocompósitas e respectiva caracterização destacando aspectos fundamentais sobre reologia e microestrutura. Em seguida, é discutido o estudo sistemático realizado sobre o comportamento reológico de dispersões de SiO2 utilizando três polissacarídeos distintos no que concerne a carga e as características gelificantes: a goma de alfarroba (não iónica), o quitosano (catiónico) e a goma xantana (aniónica) cujas propriedades reológicas são amplamente conhecidas. Os estudos reológicos realizados sob diferentes condições demonstraram que a formação de géis frágeis e/ou bem estruturados depende do tamanho SiO2, da concentração, do pH e da força iónica. Estes estudos foram confirmados por análises microestruturais usando a microscopia electrónica a baixas temperaturas (Cryo-SEM). No quarto capítulo, são apresentados os estudos relativos à preparação e caracterização de filmes bionanocompósitos utilizando quitosano como matriz. Primeiramente é apresentada uma revisão sobre filmes de bionanocompósitos e os aspectos fundamentais das técnicas de caracterização utilizadas. A escolha do plasticizante e da sua concentração são discutidas com base nas propriedades de filmes de quitosano preparados. Em seguida, o efeito da concentração de sílica e dos métodos utilizados para a dispersar na matriz de polissacarídeo, bem como o efeito da modificação da superfície da sílica é avaliado. As características da superfície e as propriedades de barreira, mecânicas e térmicas são discutidas para cada conjunto de filmes preparados antes e após a sua neutralização. Os resultados obtidos mostraram que a dispersão das cargas no plasticizante e posterior adição à matriz polissacarídica resultaram apenas em pequenas melhorias já que o problema da agregação de sílica não foi ultrapassado. Por esse motivo foram preparados filmes com SiO2@APS os quais apresentaram propriedades melhores apesar da agregação das partículas não ter sido completamente impedida. Tal pode estar relacionado com o processo de secagem dos filmes. Finalmente, no capítulo 5, são apresentadas as principais conclusões obtidas e algumas sugestões para trabalho futuro.

Structural and chemical characterization of corals grown under present day and naturally elevated pCO2 conditions in Papua New Guinea - a window into the future

Dissertação de mestrado, Biologia Marinha, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2015

Characterization on ferrite microstructure evolution during large strain warm torsion testing of plain low carbon steel

Ferrite grain/subgrain structures evolution during the extended dynamic softening of a plain low carbon steel was investigated throughout the large strain warm deformation by hot torsion. Microstructural analysis with electron back-scattering diffraction (EBSD) scanning electron microscope (FEG/SEM) was carried out on the ferrite microstructural parameters. The results showed that the warm flow stress–strain curves are similar to those affected only by dynamic softening and an extended warm flow softening is seen during large strain deformation up to 30. Furthermore, with an increase in strain up to ~ vert, similar1 the grain size of ferrite, misorientation angle and fraction of high-angle boundaries gradually decrease and fraction of low-angle boundaries increases. With a further increase in the strain beyond ~, vert, similar2, these parameters remain approximately unchanged. No evidence of discontinuous dynamic recrystallisation involving nucleation and growth of new grains was found within ferrite. Therefore, the dynamic softening mechanism observed during large strain ferritic deformation is explained by continuous dynamic recrystallization (CDRX).

Polymeric precursor method to the synthesis of XWO(4) (X = Ca and Sr) thin films-Structural, microstructural and spectroscopic investigations

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Characterization of the columbite precursor and (1-x)PMN-xPT powders prepared by Ti-modified columbite route

This study proposes to synthesize (1-x)PMN-xPT powders, where 0.10 < x < 0.45, using the T-modified columbite route. This methodology consists in the preparation of the MNT columbite precursor via the polymeric precursor method, followed by the solid state reaction with PbO to get the PMN-PT powders. It was verified that from 15 mol% of Ti, the MNT presents the coexistence of two main phases with different crystal symmetry: Rutile and Columbite. However, the synthesis of (1-x)PMN-xPT powders is not affected by this event. A detailed study of structural effects in MNT and PMN-PT powders as function of Ti content was made using the Rietveld method. It was also demonstrated that powders possess high chemical and microstructural homogeneity.

Microstructural, dielectric and ferroelectric properties of calcium-modified lead titanate thin films derived by chemical processes

Ferroelectric Pb1-xCaxTiO3 (x = 0.24) thin films were formed on a Pt/Ti/SiO2/Si substrate by the polymeric precursor method using the dip-coating technique for their deposition. Characterization of the films bq X-ray diffraction showed a perovskite single phase with a tetragonal structure after annealing at 700 degreesC. Atomic force microscopy (AFM) analyses showed that the film had a smooth and crack-free surface with low surface roughness. In addition, the PCT thin film had a granular structure with an 80 nm grain size. The thickness of the films observed by the scanning electron microscopy (SEM) is 550 nm and there is a good adhesion between the film and substrate. For the electrical measurements metal-ferroelectric-metal of the type capacitors were obtained, where the thin films showed good dielectric and ferroelectric properties. The dielectric constant and dissipation factor at 1 kHz and measured at room temperature were found to be 457 and 0.03. respectively. The remanent polarization and coercive field for the: deposited films were P-r = 17 muC/cm(2) and E-c = 75 kV/cm, respectively. Moreover. The 550-nm-thick film showed a current density in the order of 10(-8) A/cm(2) at the applied voltage of 2 V. The high values of the thin film's dielectric properties are attributed to its excellent microstructural quality and the chemical homogeneity obtained by the polymeric precursor method. (C) 2001 Elsevier science Ltd. All rights reserved.

Characterization of ZnO-degraded varistors used in high-tension devices

The effects of the degradation process on the structural, microstructural and electrical properties of ZnO-based varistors were analyzed. Rietveld refinement showed that the BiO2-x phase is affected by the degradation process. Besides the changes in the spinel phase, the degradation process also affects the lattice microstrain in the ZnO phase. Scanning electron microscopy analysis showed electrode-melting failure, while wavelength dispersive X-ray spectroscopy qualitative analysis showed deficiency of oxygen species at the grain boundaries in the degraded samples. Atomic force microscopy using electrostatic mode force illustrated a decrease in the charge density at the grain boundaries of the degraded sample. Transmission electron microscopy showed submicrometric spinel grains embedded in a ZnO matrix, but their average grain size is smaller in the degraded sample than in the standard one. Long pulses appeared to be more harmful for the varistors' properties than short ones, causing higher leakage current values. The electrical characteristics of the degraded sample are partially restored after heat treatment in an oxygen-rich atmosphere. (C) 2006 Elsevier Ltd. All rights reserved.

Preparation, structural and optical characterization of BaWO4 and PbWO4 thin films prepared by a chemical route

Polycrystalline BaWO4 and PbWO4 thin films having a tetragonal scheelite structure were prepared at different temperatures. Soluble precursors such as barium carbonate, lead acetate trihydrate and tungstic acid, as starting materials, were mixed in aqueous solution. The thin films were deposited on silicon, platinum-coated silicon and quartz substrates by means of the spinning technique. The surface morphology and crystal structure of the thin films were investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction, and specular reflectance infrared Fourier transform spectroscopy, respectively. Nucleation stages and surface morphology evolution of thin films on silicon substrates have been studied by atomic force microscopy. XRD characterization of these films showed that BaWO4 and PbWO4 phase crystallize at 500 degreesC from an inorganic amorphous phase. FTIR spectra revealed the complete decomposition of the organic ligands at 500 degreesC and the appearance of two sharp and intense bands between 1000 and 600 cm(-1) assigned to vibrations of the antisymmetric stretches resulting from the high crystallinity of both thin films. The optical properties were also studied. It was found that BaWO4 and PbWO4 thin films have Eg = 5.78 eV and 4.20 eV, respectively, of a direct transition nature. The excellent microstructural quality and chemical homogeneity results confirmed that soft solution processing provides an inexpensive and environmentally friendly route for the preparation of BaWO4 and PbWO4 thin films. (C) 2003 Elsevier Ltd. All rights reserved.

Synthesis and characterization of 9.5/65/35 PLZT prepared from the polymeric precursors

The 9.5/65/35 PLZT was prepared from the polymeric precursors (the Pechini and partial oxalate process) and by sintering in two stages in an oxygen atmosphere. After thermal treatment at 400 degreesC, the powders were calcinated and sintered at 1200 degreesC with slow heating and cooling rates. The second stage of sintering consisted of hot pressing at the same temperature in oxygen atmosphere. After calcination of PLZT powders obtained by both methods, as well as after sintering of PLZT obtained by Pechini process, the paraelectric cubic phase was formed. After sintering of PLZT obtained by partial oxalate procedure, small tetragonality of crystal structure was observed. After hot pressing PLZT was pseudocubic. SEM microstructural analyses were carried out of the sintering and hot pressed samples and indicated the small grain size less than 2 mum. (C) 2001 Elsevier B.V. B.V. All rights reserved.

From tin oxalate to (Fe, Co, Nb)-doped SnO(2): Sintering behavior, microstructural and electrical features

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Characterization of nanosized ZnAl2O4 spinel synthesized by the sol-gel method

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The effect of TiO(2) on the microstructural and electrical properties of low voltage varistor based on (Sn,Ti)O(2) ceramics

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Influence of TiO2 and AI(2)O(3) on the electrical and microstructural properties of SnO2 ceramics obtained by the Pechini method

Tin oxide has wakened up great scientific and technological interest for its potential use in varistors production and as gas sensor. In order to improve the microstructural and electrical properties in SnO2 varistor ceramics, the influence of differents dopants used, like TiO2 and Al2O3, is under research. The effect of TiO2 and Al2O3 on the properties of Sn-Co-Nb varistor systems obtained by the Pechini method has been investigated in this work. Characterization of synthesized raw material was performed by X-Ray Diffraction (XRD) and Scanning Electronic Microscopy (SEM). The microstructural and electrical characterization of sintered samples show that the TiO2 favors the grain growth and the Al2O3 contributes to the decrease it, effect that is manifested in the Sn-Co-Nb varistor systems. Breakdown field increase up to 6300V/cm with increasing Al2O3 content and non-linear coefficients with alpha=22 were obtained.

Temperature and stoichiometry effect on microstructural and ferroelectric properties of Pb(Zr1-xTix)O3 thin films prepared by chemical soulution deposition

Lead zirconate titanate (PZT) solutions were prepared using a polymeric precursor method, Zr n-propoxide and Ti i-propoxide were used as starting materials with ethylene glycol and water as solvents. The PZT solution was spin-coated on Pt/Ti/SiO2/Si substrates, baked on a hot plate, and finally heat-treated in a tube furnace between 400 and 800°C. The surface morphology and grain size of the films were characterized by atomic force microscopy (AFM), using a tapping mode with amplitude modulation. The films, thermal annealed at temperatures higher than 500°C, exhibited a dense microstructure, without noticeable cracks or voids. Electrical properties were investigated as a function of composition and annealing temperature.

Soft-chemical synthesis, characterization and humidity sensing behavior of WO3/TiO2 nanopowders

Tungsten oxide/titania (WO3/TiO2) nanopowders were synthesized by the polymeric precursor method which varied the WO3 content between 0 and 10 mol%. The powders were thermally treated in a conventional furnace and their structural, microstructural and electric properties were evaluated by X-ray diffraction (XRD), Raman spectrometry, N 2 physisorption, NH3 chemisorption, temperature-programmed reduction (TPR), X-ray absorption near-edge spectroscopy (XANES) in situ XANES and extended X-ray absorption fine structure spectroscopy (EXAFS) and transmission electron microscopy (TEM). XRD and Raman spectrometry confirmed the homogeneous distribution of an amorphous WO3 phase in the TiO 2 matrix which stabilized the anatase phase through the generation of [TiO5·V0] or [TiO5·V 0] complex sites. Conventional TPR-H2 (temperature programmed reduction) along with XANES TPR-H2 and XANES TPR-EtOH showed that WO3/TiO2 sample reduction occurs through the formation of these complex clusters. Moreover, the addition of WO3 promoted an increase in the surface acidity of doped samples as revealed by NH3 chemisorption. The WO3/TiO2 bulk-ceramic samples were further used to estimate their potential application in a humidity sensor in the range of 15-85% relative humidity. Probable reasons that lead to the different humidity sensor responses of samples were given based on the structural and surface characterizations. Correlation between the sensing performance of the sensor and its structural features are also discussed. Although all samples responded as a humidity sensor, the W2T sample (2 mol% added WO3) excelled for sensitivity due to the increase in acid sites, optimum mean pore size and pore size distribution. © 2013 Elsevier B.V.