COSTA, Erivelton Façanha da. Estudo das propriedades mecânicas de misturas asfálticas por microscopia de força atômica. 2011. 131 f. Tese (Doutorado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2011. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2015-05-05T21:11:07Z No. of bitstreams: 1 2011_tese_efcosta.pdf: 9690898 bytes, checksum: 515b97b02ebfcf8c3652b217cd15491b (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2015-05-07T16:57:29Z (GMT) No. of bitstreams: 1 2011_tese_efcosta.pdf: 9690898 bytes, checksum: 515b97b02ebfcf8c3652b217cd15491b (MD5) / Made available in DSpace on 2015-05-07T16:57:29Z (GMT). No. of bitstreams: 1 2011_tese_efcosta.pdf: 9690898 bytes, checksum: 515b97b02ebfcf8c3652b217cd15491b (MD5) Previous issue date: 2011 / The rheological study of asphalt binders is of great importance for determining its performance in paving construction. Usually, rheological parameters are obtained by a Dynamic Shear Rheometer (DSR). The aim of this work is to study the rheological properties of bitumen using an Atomic Force Microscope (AFM). So, a computational tool caled FVLOAD was used for imaging processing. Five kinds of mathematical models were used in order to analise the force curves colected through AFM: the slope analysis, the Young´s model, the adesion model, the FIEL model (Force Integration to Equal Limits) and the work difference model. Three samples were studied: pure bitumen 50/70, bitumem 50/70 doped with 4% of EVA and bitumem 50/70 doped with 4,5% of SBS. Very thin lms of these materials were prepared on glass slides and lead to an AFM for imaging. The area studied on the sample surface was of 50 m x 50 m. There were colected 1024 force curves for each image. The indentations were carried out in four frequencies: 0,5 Hz, 5 Hz, 14 Hz e 28 Hz. The curves colected were analyzed with the FVLOAD program and once the elastic properties were calculated, they were compared to those obtained in the Dynamic Shear Rheometer. / O estudo reológico do Cimento Asfáltico de Petróleo (CAP) é de fundamental importância para a determinação de sua performance na fabricação de estradas. Usualmente os parâmetros reológicos deste tipo de material são obtidos em ensaios dinâmicos através de um reômetro de cisalhamento. O presente trabalho tem por objetivo estudar as propriedades reológicas do CAP através da técnica de espectroscopia de força utilizando um microscópio de força atômica. Para isso, foi utilizada uma ferramenta computacional desenvolvida para o processamento das imagens de microscopia de força chamada de FVLOAD. Cinco análises foram realizadas com os dados das curvas de força: análise de slope, análise do módulo elástico ou módulo de Young, análise de adesão do filme de CAP, análise FIEL (Force Integration to Equal Limits), Work Difference e Adesão. Três amostras foram utilizadas neste estudo: CAP puro 50/70, CAP com 4% de EVA e CAP com 4,5% de SBS. Filmes dos três tipo de CAP foram confeccionados em lamínulas de vidro e levados ao microscópio de força atômica para obtenção dos dados das curvas de força sobre uma área de 50 μm x 50 μm. Para cada imagem foram coletadas 1024 curvas de força. As indentações com a sonda AFM foram executadas em quatro frequências: 0,5 Hz, 5 Hz, 14 Hz e 28 Hz. Finalizadas as aquisições de dados, estes foram processados no programa FVLOAD. Extraído o módulo elástico das amostras em cada frequência, os dados foram comparados com aqueles obtidos em ensaios dinâmicos através do reômetro de cisalhamento dinâmico.

Les microscopes en champ proche sont très largement utilisés pour caractériser des propriétés physiques à l’échelle du nanomètre. Afin d’assurer la cohérence et l’exactitude des mesures dimensionnelles qu’ils retournent, ces microscopes ont besoin d’être étalonnés périodiquement. Le raccordement à la définition du mètre SI est assuré par le biais d’étalons de transfert dont les caractéristiques dimensionnelles sont étalonnées à l’aide d’un Microscope à Force Atomique métrologique (mAFM).Les travaux de thèse portent sur la contribution à la mise en place du Microscope à Force Atomique métrologique du LNE dans le but de caractériser et réduire l’incertitude de mesure. Une tête AFM passive thermiquement et spécifiquement conçue pour des applications de nanométrologie dimensionnelle a été développée et intégrée au mAFM. Elle comporte un système original pour mesurer les déflexions du levier nécessaire à la détection des forces s’exerçant à l’extrémité de la pointe. Il utilise une évolution de la méthode du levier optique qui permet de déporter les sources de chaleurs à l’extérieur de l’instrument. Pour cela, un nouveau capteur a été développé. Il est basé sur l’utilisation d’un bundle composé de 40 000 microfibres optiques structurées en quatre quadrants. Il remplace avantageusement une photodiode quatre quadrants et permet de transporter le signal lumineux jusqu’à des photodiodes placées à l’extérieur de l’instrument. Ce système a été modélisé, caractérisé et validé expérimentalement. La tête AFM ainsi développée est passive thermiquement. Sa conception repose sur la dissociation complète de la chaine métrologique, constituée en Zerodur, afin de lui conférer une excellente stabilité thermique et mécanique. Pour les mêmes raisons, le châssis de la tête qui supporte l’ensemble des composants et notamment le système de mesure des déflexions du levier est entièrement conçu en Invar. Cette tête repose sur une structure motorisée constituée de trois moteurs à reptation permettant l’approche de pointe mais également le réglage des interféromètres. Après intégration de la tête dans le mAFM, l’ensemble de l’instrument a été caractérisé afin d’établir son bilan d’incertitude. Plusieurs composantes ont ainsi été évaluées expérimentalement comme la non-linéarité et la stabilité de la mesure de position par interférométrie, les rotations parasites du scanner, les erreurs d’Abbe, les défauts de rugosité et de planéité des miroirs ainsi que les erreurs de bras mort. L’impact de chaque composante a été quantifié et listé dans le bilan d’incertitude. Ces travaux ont permis d’avoir une première estimation de l’incertitude de mesure du mAFM. / Scanning probe microscopes are very well used for characterization at the manometer scale. To ensure the measurement coherency and the accuracy of the results, those microscopes need to be periodically calibrated. It’s done thanks to reference standards whose dimensional characteristics are measured by a metrological atomic force microscope (mAFM) for example.The aim of this thesis work is the improvement of the metrological AFM of the LNE in order to reduce the measurement uncertainty. To reach this goal, a thermally passive AFM head has been developed and integrated on the instrument. It contains an original system to measure the cantilever deflexion and thus detect the force acting between the sample and the tip. This system is based on the optical beam deflection method but allow deporting the heat sources outside the instrument. To reach this goal, a new specific sensor has been developed. It is based on a four quadrant optic fibre bundle that contains 40 000 micro-fibre and which is ideal to replace the existing four quadrant photodiode and its conditioning electronic circuit with the bundle and its conditioning electronic circuit placed outside the instrument. This sensor has been modelled, and experimentally validated.The Developed AFM head which integrates the deflection measurement system is then thermally passive. Its design is based on the complete dissociation of the metrological loop and the structural loop. The metrological loop is made of Zerodur® in other to acquire an excellent mechanical and thermal stability and thus reduce the thermal dilatation. For the same reason, the AFM head support frame is fully made of Invar. The AFM head is placed on a motorized frame based on three piezo-leg motors (tripod) to make the tip/sample approach but also to set the interferometer signal quality. The interferometer signal is improved by combining the linear displacements of the three motors to generate small rotations. This allows setting the parallelism of the mirrors linked to the head with those linked to the translation stage.Once the AFM head integrated on the instrument, the assembly is characterized in order to establish the uncertainty budget. Different uncertainty components have been experimentally evaluated as for example: the interferometer non linearity, the drift of the XYZ position, the parasitic rotations of the translation stage, the Abbe error, the roughness and the flatness of the mirrors and the dead path errors. The impact of the each component has been quantified and listed in the uncertainty budget. This allowed getting a first estimation of the combined uncertainty of the instrument.

No description available.

Lipid molecule is well known natural building block to form different supramolecular structures with specific shape, size and functionality. In my thesis work, I have used DC8,9PC 1,2-bis(tricosa-10,12-dinoyl)-sn-glycero-3-phosphocholine), a type of chiral lipid to form the vesicles, tubules and ribbons . By using Atomic Force Microscope, I have studied the morphological features of these particular structures. Also, the mechanical properties of lipid tubules have been studied using AFM. Softlithography has been used to pattern the lipid vesicles and tubules into 2-dimensional and 3-dimensional ordered arrays. The structure of self-assembled hollow spherical vesicles was studied using AFM. The applications of soft lithography in patterning polymerized lipid vesicles of DC8,9PC on glass substrates are reported. It has been demonstrated that the lipid vesicles can be used as a high-molecular weight ink to be transferred from a PDMS stamp onto a glass substrate to form two-dimensional stripes with a controlled separation over a large area. By combining channel flow with dewetting within microfluidic networks, vesicles were assembled into one-dimension lines on a glass substrate. The vesicle lines can also be selectively removed from the substrate with lift-up process. The direct and precise assembly of lipid vesicles on solid substrates will open up the possibility of integrating them in biosensors and microelectronic devices. Lipid tubules and helices are other extremely interesting superstructures that have captured the imagination of scientists in disciplines from biology through material science to chemistry and physics. Lipid tubules are self-assembled hollow cylindrical structures with opened ends, composed of rolled-up bilayers. They have been used as a template for the synthesis of inorganic materials, a substrate for the crystallization of proteins, a controlled release system for drug deliver, and a colorimetric material for chemical sensors. However, due to the high aspect ratio, the formation of ordered arrays of lipid tubules on substrates still remains to be challenging. In this thesis work, the application of well-known soft lithography techniques in assembling and manipulating lipid tubules on substrates has been reported. I show that lipid nano- and microtubules can be assembled into two-dimensional (2-D) parallel arrays with controlled separations by combining fluidic alignment with dewetting, which occur within microchannels. It has also been shown that lipid tubules can be assembled into 3-D crossbar arrays with fluidic alignment, which occurs within microfluidic networks. The deposition experiments with silica colloidal particles show that the 2-D parallel-aligned tubules can be used as a template to synthesize silica films with controlled morphologies and patterns on substrates in a single-step process. Atomic force microscopy studies show that the resulting silica films replicate the shape, orientation, and pattern of aligned tubule templates. Though, the structures of the lipid tubules have been extensively studied, but very little is known about their mechanical properties. In my work, the mechanical properties of the lipid tubules of DC8,9PC were studied with atomic force microscope. The deformation of the lipid tubules with different outer diameters is directly observed in both tapping and contact modes with increasing loading forces.

The precise control of the resonance frequency of plasmonic nanostructures is critical and depends on the size, composition, shape, and dielectric nature of the environment. The ability to control the shape and size of nanomaterials acutely depends on the fabrication technique and material design. We used a cheap and scalable method known as nanosphere lithography (NSL) to fabricate plasmonic nano-prism (NP) on glass and indium tin oxide substrate (ITO). The methods involve substrate hydrophilicity treatment, polystyrene nanosphere masking, metal deposition, and mask removal. The array and specific morphology of the fabricated NP was established using scanning electron microscope (SEM) and atomic force microscope (AFM). Finally, we used UVVis spectroscopy to determine the plasmonic resonance frequencies of fabricated NP on different substrates. The results reported herein have potential applications in surface-enhanced Raman spectroscopy (SERS), and biosensing. We also used scanning tunneling microscope to obtain high spatial resolution images of supramolecular trigrams.

No description available.

The abiotic oxidation of pyrite requires the supply of oxygen and water only. In abiotic systems, pyrite oxidation may proceed via several paths, with multiple steps in each of the paths. Defect sites (S-deficient, Fe3+ bearing sites) on the pyrite surface have been shown reported to be the initial reaction sites on pristine pyrite surfaces. In neutral to slightly acidic solutions (3.5<pH<7), ferric iron hydroxide patches will form on the surface. These patches have been shown to be the predominant sites for electron exchange. Efforts were undertaken to suppress the electron transfer at these sites to inhibit pyrite oxidation. It has been shown that pyrite oxidation can be controlled by exposing the pyrite to phosphate under relatively high pH values (pH above 5.0). However, phosphate ceases to function as an inhibitor under lower pHs. The use of two-tail phospholipids instead of phosphate to inhibit the pyrite oxidation proved to be very effective under abiotic conditions. The purpose of the present study is to determine if the use of two-tail phospholipids can be extended to systems that have bacteria present. Batch experiments were conducted in which pyrite slurries were treated with two-tailed lipid either before or after exposure to bacteria. Iron release into the solution was used as a reaction progress variable and Atomic Force Microscopy was used to study the distribution of lipids and bacteria on the pyrite surface. AFM images showed that the formation of 7nm lipid bilayers contributes to the majority of lipid structures on pyrite surface. The bilayers render the pyrite surface hydrophobic and inhibit the reaction of water with the surface, which is known to be a critical reactant. AFM images also showed that phospholipids are capable of displacing a large fraction of bacteria attached to pyrite, reducing the oxidation rate of the mineral. However, addition of heterotrophic bacterial (Acidiphilum acidophilum) to the system resulted in the increase in pyrite oxidation rate again. Cross-linking of the 23:2 dyne phospholipids by exposing the lipid to UV light greatly enhanced the stability of the lipid in the presence of the heterotrophic bacteria. UV pretreated lipid layers reduced pyrite oxidation in the presence of heterotrophic bacteria for up to 30 days. / Chemistry

Graphene, one-atom-thick planar sheet of carbon atoms densely packed in a honeycomb crystal lattice, has grabbed appreciable attention due to its exceptional electronic, mechanical and optical properties. Chemical functionalization schemes are needed to integrate graphene with the different materials required for potential applications. Molecular self-assembly behavior on graphene is a key method to investigate the mechanism of interaction between molecules and graphene and the promising applications related to molecular devices. In this thesis, we report the molecular self-assembly behavior of phenyl-C61-butyric acid methyl ester (PCBM), C60, perylenetetracarboxylic dianhydride (PTCDA) and Gd3N@C80 on flat and rippled graphene 2D material by the experimental methods of scanning tunneling microscope (STM) and atomic force microscope (AFM) and by the theoretical method of density functional theory (DFT). We found that molecules form ordered structures on flat graphene, while they form disordered structure on rippled graphene. For example, PCBM forms bilayer and monolayer structures, C60 and Gd3N@C80 form hexagonal close packed (hcp) structure on flat graphene and PTCDA forms herringbone structure on flat graphene surface. Although C60 and Gd3N@C80 both form hcp structure, C60 forms a highly ordered hcp structure over large areas with little defects and Gd3N@C80 forms hcp structure only over small areas with many defects. These differences of structure that forms on flat graphene is mainly due to the molecule-molecule interactions and the shape of the molecules. We find that the spherical C60 molecules form a quasi-hexagonal close packed (hcp) structure, while the planar PTCDA molecules form a disordered herringbone structure. From DFT calculations, we found that molecules are more effected by the morphology of rippled graphene than the molecule-molecule interaction, while the molecule-molecule interaction plays a main role during the formation process on flat graphene. The results of this study clearly illustrate significant differences in C60 and PTCDA molecular packing on rippled graphene surfaces. / Doctor of Philosophy / As the first physical isolated two-dimensional (2D) material, graphene has attracted exceptional scientific attention. Due to its impressive properties including high carrier density, flexibility and transparency, graphene has numerous potential applications, such as solar cell, sensors and electronics. 2D molecular self-assembly is an area that focuses on organization and interaction between self-assembly behaviors of molecules on surface. Graphene is an excellent substrate for the study of molecular self-assembly behavior, and study of molecular study is very important for graphene due to potential applications of molecules on graphene. In this thesis, we present investigations of the molecular self-assembly of PCBM, C60, PTCDA and Gd3N@C80 on graphene substrate. First, we report the two types of bilayer PCBM configuration on HOPG with a step height of 1.68 nm and 1.23 nm, as well as two types of monolayer PCBM configuration with a step height of 0.7 nm and 0.88 nm, respectively. On graphene, PCBM forms one type of PCBM bilayer with a step height of 1.37 nm and one type of PCBM monolayer with a step height of 0.87 nm. By building and analyzing the models of PCBM bilayers and monolayers, we believe the main differences between two configurations of PCBM bilayer and monolayer is the tilt angle between PCBM and HOPG, which makes type I configuration the higher molecule density and binding energy. Secondly, we report the investigation of self-assembly behaviors of C60 and PTCDA on flat graphene and rippled graphene by experimental scanning tunneling microscope (STM) and theoretical density functional theory (DFT). On flat graphene, C60 forms hexagon close pack (hcp) structure, while PTCDA forms herringbone structure. On rippled graphene, C60 forms quasi-hcp structure while PTCDA forms disordered herringbone structure. By DFT calculation, we study the effect of graphene curvature on spherical C60 and planar PTCDA. Finally, we report a STM study of a monolayer of Gd3N@C80 on graphene substrate. Gd3N@C80 forms hcp structure in a small domain with a step height of 0.88 nm and lattice constant of 1.15 nm. According to our DFT calculation, for the optimal organization of Gd3N@C80 and graphene, the gap between Gd3N@C80 and graphene is 3.3 Å and the binding energy is 0.95 eV. Besides, the distance between Gd3N@C80 and Gd3N@C80 is 3.5 Å and the binding energy is 0.32 eV.

Yes / Plasma technology has been widely used to increase the surface energy of the polymer surfaces for many industrial applications; in particular to increase in wettability. The present work was carried out to investigate how surface modification using plasma treatment modifies the surface energy of micro-injection moulded microneedles and its influence on drug delivery. Microneedles of polyether ether ketone and polycarbonate and have been manufactured using micro-injection moulding and samples from each production batch have been subsequently subjected to a range of plasma treatment. These samples were coated with bovine serum albumin to study the protein adsorption on these treated polymer surfaces. Sample surfaces structures, before and after treatment, were studied using atomic force microscope and surface energies have been obtained using contact angle measurement and calculated using the Owens-Wendt theory. Adsorption performance of bovine serum albumin and release kinetics for each sample set was assessed using a Franz diffusion cell. Results indicate that plasma treatment significantly increases the surface energy and roughness of the microneedles resulting in better adsorption and release of BSA.

O clareamento dental é o meio disponível mais simples, comum e conservador para o cirurgião-dentista proporcionar aos pacientes o padrão de cor de seus dentes mais desejado. Em alguns casos, os dentes que vão ser clareados podem apresentar restaurações realizadas com compósitos dentais, que são mais suscetíveis a alterações químicas, quando comparados a outros materiais restauradores. Alguns estudos mostraram que diferentes concentrações de agentes clareadores levaram a um aumento significativo da rugosidade superficial e das porosidades em compósitos dentais. Este estudo avaliou o efeito de dois agentes clareadores (Whiteness HP Blue 20%, Whiteness HP Max) sobre a rugosidade superficial de dois compósitos dentais, um micro-híbrido (Esthet X, Denstply) e outro nanoparticulado (Z 350, 3M ESPE). Um total de oito corpos de prova (9 x 2 mm) foram confeccionados com auxílio de uma matriz de teflon, sendo divididos em 4 grupos (Esthet X + Whiteness HP Blue 20%; Esthet X + Whiteness HP Max; Z 350 + Whiteness HP Blue 20%; Z 350 + Whiteness HP Max), sendo n=2. Os corpos de prova foram armazenados em saliva artificial neutra e, após 24 horas, foram polidos com discos de óxido de Alumínio (Sof-lex, 3M ESPE). Após sete dias de imersão salivar, cada corpo de prova foi levado a um microscópio de força atômica para obtenção do valor inicial de rugosidade superficial (Ra em nm). Em seguida, sem remover o corpo de prova do microscópio, o agente clareador foi aplicado sobre a superfície do corpo de prova, segundo as instruções do fabricante, de modo que permitisse uma posterior observação da mesma área do corpo de prova observada inicialmente, para obtenção do valor final de rugosidade superficial. Imagens em duas e três dimensões foram obtidas de cada corpo de prova para observação de alterações da topografia. Os resultados foram tratados estatisticamente por ANOVA e pelo teste de contraste Student-Newman-Keuls (p < 0,05). Não houve alteração significativa na rugosidade superficial (Ra) dos corpos da prova de compósitos micro-híbrido e nanoparticulado, submetidos aos agentes clareadores Whiteness HP Blue 20% e Whiteness HP Maxx. No entanto, independente do agente clareador utilizado, foram observadas maiores alterações topográficas nas imagens de microscopia de força atômica da superfície do compósito micro-híbrido do que nas imagens do nanoparticulado. / Dental bleaching is the simplest, the most common and conservative available way for dentists to offer their patients the standard color of teeth more desired. In some cases, the teeth that will be bleached may include restorations made of resin composites, which are more prone to chemical alteration compared with other restoration materials. Some studies have showed that different concentrations of bleaching gels might lead to a significant increase in surface roughness and amount of porosities in composite resins. This study evaluated the effect of two bleaching gels (Whiteness HP Blue 20%, Whiteness HP Max) on surface roughness of two resin composites, micro-hybrid (Esthet X, Denstply) and nanoparticled (Z350, 3M ESPE). A total of eight specimens (9 x 2 mm) were produced with a Teflon mold help, and were divided into four groups (Esthet X + Whiteness HP Blue 20%; Esthet X + Whiteness HP Max; Z 350 + Whiteness HP Blue 20%; Z 350 + Whiteness HP Max), with n=2. They were stored in neutral artificial saliva and, after 24 hours, were polished with aluminium oxide discs (Sof-lex, 3M ESPE). After seven days of salivary immersion, each specimen was taken to an atomic force microscope for recording initial value of surface roughness (Ra in nm). After that procedure, without removing the specimen from microscope, the bleaching gel was applied on the surface of the specimen, following manufacturers instructions, in order to allow posterior observation of the same area of the specimen initially observed, for recording the final value of surface roughness. Two-dimensional and 3D images were taken from each specimen group for observation of surface alterations. The results were statistically analyzed by ANOVA and the SNK test (p< 0.05). There were no statistically significant differences in the surface roughness (Ra) for specimens of micro-hybrid and nanoparticled composites, submitted to the bleaching agents Whiteness HP Blue 20% and Whiteness HP Maxx. However, there were noticed larger surface alterations in atomic force microscope images on the surface of micro-hybrid composites than on the nanoparticled, independently of the bleaching agent used.