Magnetic properties of acicular Fe1-xREx (RE = Nd, Sm, Eu, Tb; x=0, 0.05, 0.10) metallic nanoparticles

Acicular monodispersed Fe1-xREx (RE= Nd, Sm,Eu,Tb;x=0, 0.05, 0.10) metallic nanoparticles (60 +/- 5 nm in length and axial ratio similar to6) obtained by reduction of alumina-coated goethite nanoparticles-containing rare earth (RE) under hydrogen flow are reported. Alumina and maghemite thin layers on particle surface were used to protect the goethite particles against sintering and oxidation, respectively. Al and RE additions were obtained by successive heterocoagulation reactions. Aluminum sulfate (10 at.% based on Fe) was dissolved in water and the pH adjusted to 12.5 with NaOH solution. Goethite particles were suspended in this solution and CO2 gas was blown into the slurry to neutralize it to a pH 8.5 or less. Particles were purified and dehydrated to effect transformation to alumina-coated hematite nanoparticles, which were re-suspended in aqueous solution in which RE sulfate (0-0.15 at.% based on Fe) has been dissolved, and the pH increased by ammonia aqueous solution addition. Resulted alumina-coated RE-doped hematite nanoparticles were reduced to metal at 450 degreesC/12 h under hydrogen flow and passivated with nitrogen-containing ethanol vapor at room temperature. Acicular monodispersed metallic nanoparticle systems were obtained and the presence of Al and RE were confirmed by induced-coupled plasma spectrometry analysis. X-ray diffraction, Mossbauer spectroscopy, and magnetization data are in agreement with the nanosized alpha-Fe core in a bcc structure, having a spinel structure, gammaFe(2)O(3), with thickness similar to1.5 run on particle surface. Main magnetic parameters showed saturation magnetization decreases and significant increasing in the coercive field with the RE composition increases. Magnetic properties of these particles, similar to40% smaller than those commercially available, suggest a decrease in the bit-size for high-density magnetic or magneto-optics recording media application. (C) 2004 Published by Elsevier B.V.

Microleakage in primary teeth restored by conventional or bonded amalgam technique.

The aim of this in vitro study was to evaluate marginal leakage in class V restorations in primary teeth restored with amalgam, using three different techniques. Thirty maxillary anterior primary teeth, clinically sound and naturally exfoliated, were used. In group 1 (n = 10), two thin layers of a copal varnish (Cavitine) were applied. In group 2 (n = 10), Scotchbond Multi-Purpose Plus, a dual adhesive system, was used according to manufacturer instructions. In group 3 (n = 10), One-Step adhesive system in combination with a low-viscosity resin (Resinomer) were used according to manufacturer instructions. All samples were restored with a high-copper dental amalgam alloy (GS 80, SDI). After restoration, the samples were stored in normal saline at 37 degrees C for 72 h. The specimens were polished, thermocycled (500 cycles, 5 degrees and 55 degrees C, 30-s dwell time) and impermeabilized with fingernail polish to within 1.0 mm of the restoration margins. The teeth were then placed in 0.5% methylene blue for 4 h. Finally, the samples were sectioned and evaluated for marginal leakage. The Kruskal-Wallis test showed that the filled adhesive resin (group 3) had the least microleakage. There was no significant difference between groups 1 and 2.

Nova contribuiçao ao conhecimento da formação Rio Claro (T) na Folha Rio Claro (SP)

The Rio Claro Formation mainly occurs in the county of Rio Claro (SP) lying unconformably on Paleozoic and Mesozoic rocks. Its thickness is 30-40 m. It shows fine to coarse, regular to poor sorted, Triable sandstones and conglomerates with quartzite and quartz clasts in the base. Thin layers of mudstone occur interbeded. Stratigraphic maps had been elaborated in recent analyses allowing to improve the knowledge about the formation. The biggest thicknesses occur on the east part of the studied area. The coarse/fine clastic ratio map demonstrates that fine sediments are concentrated in the east side, and suggests the existence of barriers which conditioned perennial water body (or bodies) where decantation took place (east, south and southeast sides). The structural contour map of the Rio Claro Formation base indicates a NW/SE trough which was the main depositional axis. The integrated analysis demonstrates that the formation is formed by lacustrine, fluvial and debris flows deposits whose source area was located on NW side, with coalescent alluvial fans from where braided to psamitic meandering fluvial channels came. The location of the source area suggests no link with the Corumbataf River paleo-terraces.

Role of the range of the dipole function in the classical dynamics of molecular dissociation

The dissociation dynamics of heteronuclear diatomic molecules induced by infrared laser pulses is investigated within the framework of the classical driven Morse oscillator. The interaction between the molecule and the laser field described in the dipole formulation is given by the product of a time-dependent external field with a position-dependent permanent dipole function. The effects of changing the spatial range of the dipole function in the classical dissociation dynamics of large ensembles of trajectories are studied. Numerical calculations have been performed for distinct amplitudes and carrier frequencies of the external pulses and also for ensembles with different initial energies. It is found that there exist a set of values of the dipole range for which the dissociation probability can be completely suppressed. The dependence of the dissociation on the dipole range is explained through the examination of the Fourier series coefficients of the dipole function in the angle variable of the free system. In particular, the suppression of dissociation corresponds to dipole ranges for which the Fourier coefficients associated with nonlinear resonances are null and the chaotic region in the phase space is reduced to thin layers. In this context, it is shown that the suppression of dissociation of heteronuclear molecules for certain frequencies of the external field is a consequence of the finite range of the corresponding permanent dipole. © 2013 American Physical Society.

Quantification of water in ethanol using a photothermal transparent transducer

Ethanol with added water may be found during the process of assessing its physical and chemical properties. This addition can damage automotive vehicle engines and also may contribute to tax evasion. The present contribution describes a method based on a photothermal transparent transducer to determine the water content in ethanol. A chamber with a window of lithium tantalate coated with a thin layer of indium tin oxide was used, and a 1450-nm laser diode was employed as the excitation source. The results indicated a nearly linear response of the apparatus, as a function of the water content in water/ethanol solutions ranging from 0 to 100 (vol.%). The results for the dependency of the photothermal signal on the laser power and chopping frequency suggested that reliable results can be obtained using laser power and chopping rates above 100 mW and 10 Hz, respectively. The results reported here may be useful in the development of an alternative method that can provide real-time data on the water concentration in ethanol in a rapid, portable and unambiguous way, and that can be easily used in laboratory analyses or in gas stations. © 2013 Elsevier B.V.

Preparação e caracterização estrutural e elétrica de células solares sensibilizadas por corantes empregando anodos nanoestruturados à base de 'TiO IND. 2'

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Modelagem numérica da influência do eletrojato equatorial em dados magnetotelúricos produzidos por estruturas tridimensionais

A América do Sul apresenta várias peculiaridades geomagnéticas, uma delas, é a presença do Eletrojato Equatorial, o qual se estende de leste para oeste no Brasil ao longo de aproximadamente 3500 km. Considerando-se o fato de que a influência do Eletrojato Equatorial pode ser detectada a grandes distâncias do seu centro, isto suscita o interesse em se estudar os seus efeitos na exploração magnetotelúrica no Brasil. A influência do eletrojato equatorial na prospecção magnetotelúrica tem sido modelada para meios geológicos uni e bidimensionais valendo-se para isto de soluções analíticas fechadas e de técnicas numéricas tais como elementos finitos e diferenças finitas. Em relação aos meios geológicos tridimensionais, eles tem sido modelados na forma de "camadas finas", usando o algoritmo "thin sheet". As fontes indutoras utilizadas para simular o eletrojato equatorial nestes trabalhos, tem sido linhas de corrente, eletrojatos gaussianos e eletrojatos ondulantes. Por outro lado, o objetivo principal da nossa tese foi o modelamento dos efeitos que o eletrojato equatorial provoca em estruturas tridimensionais próprias da geofísica da prospecção. Com tal finalidade, utilizamos o esquema numérico da equação integral, com as fontes indutoras antes mencionadas. De maneira similar aos trabalhos anteriores, os nossos resultados mostram que a influência do eletrojato equatorial somente acontece em frequências menores que 10^-1 Hz. Este efeito decresce com a distância, mantendo-se até uns 3000 km do centro do eletrojato. Assim sendo, a presença de grandes picos nos perfis da resistividade aparente de um semi-espaço homogêneo, indica que a influência do eletrojato é notável neste tipo de meio. Estes picos se mostram com diferente magnitude para cada eletrojato simulado, sendo que a sua localização também muda de um eletrojato para outro. Entretanto, quando se utilizam modelos geo-elétricos unidimensionais mais de acordo com a realidade, tais como os meios estratificados, percebe-se que a resposta dos eletrojatos se amortece significativamente e não mostra muitas diferenças entre os diferentes tipos de eletrojato. Isto acontece por causa da dissipação da energia eletromagnética devido à presença da estratificação e de camadas condutivas. Dentro do intervalo de 3000 km, a resposta eletromagnética tridimensional pode ser deslocada para cima ou para baixo da resposta da onda plana, dependendo da localização do corpo, da frequência, do tipo de eletrojato e do meio geológico. Quando a resposta aparece deslocada para cima, existe um afastamento entre as sondagens uni e tridimensionais devidas ao eletrojato, assim como um alargamento da anomalia dos perfis que registra a presença da heterogeneidade tridimensional. Quando a resposta aparece deslocada para baixo, no entanto, há uma aproximação entre estes dois tipos de sondagens e um estreitamento da anomalia dos perfis. Por outro lado, a fase se mostra geralmente, de uma forma invertida em relação à resistividade aparente. Isto significa que quando uma sobe a outra desce, e vice-versa. Da mesma forma, comumente nas altas frequências as respostas uni e tridimensionais aparecem deslocadas, enquanto que nas baixas frequências se mostram com os mesmos valores, com exceção dos eletrojatos ondulantes com parâmetros de ondulação α = —2 e —3. Nossos resultados também mostram que características geométricas próprias das estruturas tridimensionais, tais como sua orientação em relação à direção do eletrojato e a dimensão da sua direção principal, afetam a resposta devido ao eletrojato em comparação com os resultados da onda plana. Desta forma, quando a estrutura tridimensional é rotacionada de 90°, em relação à direção do eletrojato e em torno do eixo z, existe uma troca de polarizações nas resistividades dos resultados, mas não existem mudanças nos valores da resistividade aparente no centro da estrutura. Ao redor da mesma, porém, se percebe facilmente alterações nos contornos dos mapas de resistividade aparente, ao serem comparadas com os mapas da estrutura na sua posição original. Isto se deve à persistência dos efeitos galvânicos no centro da estrutura e à presença de efeitos indutivos ao redor do corpo tridimensional. Ao alongar a direção principal da estrutura tridimensional, as sondagens magnetotelúricas vão se aproximando das sondagens das estruturas bidimensionais, principalmente na polarização XY. Mesmo assim, as respostas dos modelos testados estão muito longe de se considerar próximas das respostas de estruturas quase-bidimensionais. Porém, os efeitos do eletrojato em estruturas com direção principal alongada, são muito parecidos com aqueles presentes nas estruturas menores, considerando-se as diferenças entre as sondagens de ambos tipos de estruturas. Por outro lado, os mapas de resistividade aparente deste tipo de estrutura alongada, revelam um grande aumento nos extremos da estrutura, tanto para a onda plana como para o eletrojato. Este efeito é causado pelo acanalamento das correntes ao longo da direção principal da estrutura. O modelamento de estruturas geológicas da Bacia de Marajó confirma que os efeitos do eletrojato podem ser detetados em estruturas pequenas do tipo "horst" ou "graben", a grandes distâncias do centro do mesmo. Assim, os efeitos do eletrojato podem ser percebidos tanto nos meios estratificados como tridimensionais, em duas faixas de freqüência (nas proximidades de 10^-1 Hz e para freqüências menores que 10^-3 Hz), possivelmente influenciados pela presença do embasamento cristalino e a crosta inferior, respectivamente. Desta maneira, os resultados utilizando o eletrojato como fonte indutora, mostram que nas baixas freqüências as sondagens magnetotelúricas podem ser fortemente distorcidas, tanto pelos efeitos galvânicos da estrutura tridimensional como pela presença da influência do eletrojato. Conseqüêntemente, interpretações errôneas dos dados de campo podem ser cometidas, se não se corrigirem os efeitos do eletrojato equatorial ou, da mesma forma, não se utilisarem algoritmos tridimensionais para interpretar os dados, no lugar do usual modelo unidimensional de Tikhonov - Cagniard.

The mineralogy and chemistry of the German and Portuguese tiles used to face a historic building in the Amazon region and their natural susceptibility to tropical weathering

As proeminentes edificações da cidade de Belém foram revestidas durante o século 19 com azulejos produzidos em Portugal e Alemanha que já apresentam distintos graus de degradação. O Palacete Pinho é uma das mais importantes destas edificações e foi selecionado para se investigar a ação do clima tropical amazônico sobre a degradação destes azulejos. Para atingir estes objetivos mapearam-se os azulejos desta edificação visando identificar as modificações de origem orgânica e inorgânica e coletas de amostras para análises. Os minerais foram determinados por DRX, a composição química por métodos clássicos úmidos e MEV/SED e os micro-organismos por microscopia. Os resultados obtidos mostram que os azulejos Portugueses e Alemães são distintos entre si. Enquanto o biscoito é composto de SiO₂ e Al₂O₃, CaO foi encontrado apenas nos Portugueses. Os baixos conteúdos de Na₂O e K₂O indicam adição de materiais para redução da temperatura de fusão. SiO₂ e PbO compõem o vidrado, já CoO e FeO foram adicionados como pigmentos. O biscoito dos azulejos Alemães é constituído de quartzo, mullita e cristobalita, ao contrário do Português com quartzo, gehlenita, diopsídio, calcita e feldspatos. Os vidrados são amorfos ao DRX. As diferenças químicas e mineralógicas entre os azulejos Portugueses e Alemães indicam que foram produzidos por matéria prima distinta, bem como processo termal. As alterações relacionadas com o intemperismo são as finas camadas de detritos (nos Alemães), manchas de oxidação, manchas escuras, descolamento do azulejo (no Português); perda de vidrado e biscoito tornando-se pulverulento como consequência do estabelecimento de Cyanophyta e bacillariophyta (Português). As distintas feições de degradação dos azulejos refletem as suas diferenças mineralógicas e químicas expostas ao clima tropical Amazônico.

Melhoramento da resolução para camadas delgadas de perfilagens existentes em áreas específicas de produção-exploração

No campo da perfilagem de poço existe um grande interesse voltado para as técnicas que melhorem a resolução vertical das respostas das ferramentas. Neste trabalho, optamos por desenvolver uma técnica de aumento de resolução vertical dos perfis obtidos com a ferramenta de indução denominada na bibliografia de 6FF40, através de um algoritmo que utiliza as técnicas de estimativa dos mínimos quadrados. Este método torna possível o processamento dos dados registrados de uma maneira computacionalmente eficiente. O algoritmo apresentado necessita apenas dos dados registrados, dos valores adotados como coeficientes da ferramenta, e de uma estimativa dos ruídos existentes. Como ilustração foram utilizados trechos de um perfil de uma área que reconhecidamente apresenta problemas relacionados à resolução vertical da ferramenta 6FF40. Com o objetivo de verificar a eficiência do algoritmo utilizado, os perfis processados foram correlacionados com os perfis de raio gama e com os perfis esféricos focalizados do poço 7-LOR-18-RN, perfis estes que possuem resolução vertical maior do que os perfis convencionais de indução, comprovando a individualização das camadas delgadas que antes do processamento não eram facilmente reconhecidas no perfil original. O algoritmo foi também testado com dados sintéticos demonstrando sua eficiência na recuperação de valores mais representativos para R_t.

Photo-Induced Conductivity of Heterojunction GaAs/Rare-Earth Doped SnO2

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Sucessão estratigráfica e tratos de sistemas do Membro Romualdo, porção leste da Bacia do Araripe, nordeste do Brasil

Located in northeastern Brazil, the evolution of Araripe Basin has been associated with the fragmentation of Gondwana and opening of the South Atlantic. The Santana Formation belongs to the post-rift sequence of the basin and is characterized by the presence of laminated limestones in the lower portion (Mb. Crato), evaporite (Ipubi) and siliciclastics (Mb. Romualdo). For better understanding of the Romualdo's stratigraphy, depositional environments and tract of systems, a stratigraphic analysis was made with representative columnar sections of the unit. Sedimentary facies have been described in detail, as well as paleocurrents measured at different stratigraphic levels. It was found that the contact of Mb. Romualdo with the carbonate-evaporite section (Mbs. Crato and Ipubi) is a unconformity, evidenced by residual lags and thin layers of conglomerates above the contact. Above the conglomeratic levels predominate fine sandstones / medium interlayered with calciferous green shales. The percentage of shales increases towards the top, featuring retrogradational stacking culminating in layers of coquinas, excellent stratigraphic mark in the basin. Thin layers of coquins of gastropods comprising equinoids, located on the shale section, present in three sections marine deposits are associated with surfaces ravine. The upper section is characterized by recurrent facies of green shales, sandstones intercalated with sandstones progressively become more frequent towards the top of the unit, featuring the regressive part of the cycle. The sandstones present cross-stratification, often with mud clasts and clay layers in the foresets, and beddings of flaser type and wavy in heterolitic facies, suggesting the action of tidal currents. Paleocurrents measured in the sandstones show gaps with opposite flow directions outlining bipolar standards, which reinforce the interpretation of shallow marine environment influenced by tides during the sedimentation...

Application of FTIR microscopy to cultural heritage materials

Research in art conservation has been developed from the early 1950s, giving a significant contribution to the conservation-restoration of cultural heritage artefacts. In fact, only through a profound knowledge about the nature and conditions of constituent materials, suitable decisions on the conservation and restoration measures can thus be adopted and preservation practices enhanced. The study of ancient artworks is particularly challenging as they can be considered as heterogeneous and multilayered systems where numerous interactions between the different components as well as degradation and ageing phenomena take place. However, difficulties to physically separate the different layers due to their thickness (1-200 µm) can result in the inaccurate attribution of the identified compounds to a specific layer. Therefore, details can only be analysed when the sample preparation method leaves the layer structure intact, as for example the preparation of embedding cross sections in synthetic resins. Hence, spatially resolved analytical techniques are required not only to exactly characterize the nature of the compounds but also to obtain precise chemical and physical information about ongoing changes. This thesis focuses on the application of FTIR microspectroscopic techniques for cultural heritage materials. The first section is aimed at introducing the use of FTIR microscopy in conservation science with a particular attention to the sampling criteria and sample preparation methods. The second section is aimed at evaluating and validating the use of different FTIR microscopic analytical methods applied to the study of different art conservation issues which may be encountered dealing with cultural heritage artefacts: the characterisation of the artistic execution technique (chapter II-1), the studies on degradation phenomena (chapter II-2) and finally the evaluation of protective treatments (chapter II-3). The third and last section is divided into three chapters which underline recent developments in FTIR spectroscopy for the characterisation of paint cross sections and in particular thin organic layers: a newly developed preparation method with embedding systems in infrared transparent salts (chapter III-1), the new opportunities offered by macro-ATR imaging spectroscopy (chapter III-2) and the possibilities achieved with the different FTIR microspectroscopic techniques nowadays available (chapter III-3). In chapter II-1, FTIR microspectroscopy as molecular analysis, is presented in an integrated approach with other analytical techniques. The proposed sequence is optimized in function of the limited quantity of sample available and this methodology permits to identify the painting materials and characterise the adopted execution technique and state of conservation. Chapter II-2 describes the characterisation of the degradation products with FTIR microscopy since the investigation on the ageing processes encountered in old artefacts represents one of the most important issues in conservation research. Metal carboxylates resulting from the interaction between pigments and binding media are characterized using synthesised metal palmitates and their production is detected on copper-, zinc-, manganese- and lead- (associated with lead carbonate) based pigments dispersed either in oil or egg tempera. Moreover, significant effects seem to be obtained with iron and cobalt (acceleration of the triglycerides hydrolysis). For the first time on sienna and umber paints, manganese carboxylates are also observed. Finally in chapter II-3, FTIR microscopy is combined with further elemental analyses to characterise and estimate the performances and stability of newly developed treatments, which should better fit conservation-restoration problems. In the second part, in chapter III-1, an innovative embedding system in potassium bromide is reported focusing on the characterisation and localisation of organic substances in cross sections. Not only the identification but also the distribution of proteinaceous, lipidic or resinaceous materials, are evidenced directly on different paint cross sections, especially in thin layers of the order of 10 µm. Chapter III-2 describes the use of a conventional diamond ATR accessory coupled with a focal plane array to obtain chemical images of multi-layered paint cross sections. A rapid and simple identification of the different compounds is achieved without the use of any infrared microscope objectives. Finally, the latest FTIR techniques available are highlighted in chapter III-3 in a comparative study for the characterisation of paint cross sections. Results in terms of spatial resolution, data quality and chemical information obtained are presented and in particular, a new FTIR microscope equipped with a linear array detector, which permits reducing the spatial resolution limit to approximately 5 µm, provides very promising results and may represent a good alternative to either mapping or imaging systems.

Noble-metal nanoparticles produced with colloidal lithography: fabrication, optical properties and applications

In this work, metal nanoparticles produced by nanosphere lithography were studied in terms of their optical properties (in connection to their plasmon resonances), their potential application in sensing platforms - for thin layer sensing and bio-recognition events -, and for a particular case (the nanocrescents), for enhanced spectroscopy studies. The general preparation procedures introduced early in 2005 by Shumaker-Parry et al. to produce metallic nanocrescents were extended to give rise to more complex (isolated) structures, and also, by combining colloidal monolayer fabrication and plasma etching techniques, to arrays of them. The fabrication methods presented in this work were extended not only to new shapes or arrangements of particles, but included also a targeted surface tailoring of the substrates and the structures, using different thiol and silane compounds as linkers for further attachment of, i.e. polyelectrolyte layers, which allow for a controlled tailoring of their nanoenvironment. The optical properties of the nanocrescents were studied with conventional transmission spectroscopy; a simple multipole model was adapted to explain their behaviour qualitatively. In terms of applications, the results on thin film sensing using these particles show that the crescents present an interesting mode-dependent sensitivity and spatial extension. Parallel to this, the penetrations depths were modeled with two simplified schemes, obtaining good agreement with theory. The multiple modes of the particles with their characteristic decay lengths and sensitivities represent a major improvement for particle-sensing platforms compared to previous single resonance systems. The nanocrescents were also used to alter the emission properties of fluorophores placed close to them. In this work, green emitting dyes were placed at controlled distances from the structures and excited using a pulsed laser emitting in the near infrared. The fluorescence signal obtained in this manner should be connected to a two-photon processes triggered by these structures; obtaining first insight into plasmon-mediated enhancement phenomena. An even simpler and faster approach to produce plasmonic structures than that for the crescents was tested. Metallic nanodiscs and nanoellipses were produced by means of nanosphere lithography, extending a procedure reported in the literature to new shapes and optical properties. The optical properties of these particles were characterized by extinction spectroscopy and compared to results from the literature. Their major advantage is that they present a polarization-dependent response, like the nanocrescents, but are much simpler to fabricate, and the resonances can be tailored in the visible with relative ease. The sensing capabilities of the metallic nanodiscs were explored in the same manner as for the nanocrescents, meaning their response to thin layers and to bio-recognition events on their surface. The sensitivity of these nanostructures to thin films proved to be lower than that of the crescents, though in the same order of magnitude. Experimental information about the near field extension for the Au nanodiscs of different sizes was also extracted from these measurements. Further resonance-tailoring approaches based on electrochemical deposition of metals on the nanodiscs were explored, as a means of modifying plasmon resonances by changing surface properties of the nanoparticles. First results on these experiments would indicate that the deposition of Ag on Au on a submonolayer coverage level can lead to important blue-shifts in the resonances, which would open a simple way to tailor resonances by changing material properties in a local manner.

Studies of degradation of organic solar cell materials using electrical scanning probe microscopy

Intense research is being done in the field of organic photovoltaics in order to synthesize low band-gap organic molecules. These molecules are electron donors which feature in combination with acceptor molecules, typically fullerene derivarntives, forming an active blend. This active blend has phase separated bicontinuous morphology on a nanometer scale. The highest recorded power conversionrnefficiencies for such cells have been 10.6%. Organic semiconductors differ from inorganic ones due to the presence of tightly bonded excitons (electron-hole pairs)resulting from their low dielectric constant (εr ≈2-4). An additional driving force is required to separate such Frenkel excitons since their binding energy (0.3-1 eV) is too large to be dissociated by an electric field alone. This additional driving force arises from the energy difference between the lowest unoccupied molecular orbital (LUMO) of the donor and the acceptor materials. Moreover, the efficiency of the cells also depends on the difference between the highest occupied molecular orbital (HOMO) of the donor and LUMO of the acceptor. Therefore, a precise control and estimation of these energy levels are required. Furthermore any external influences that change the energy levels will cause a degradation of the power conversion efficiency of organic solar cell materials. In particular, the role of photo-induced degradation on the morphology and electrical performance is a major contribution to degradation and needs to be understood on a nanometer scale. Scanning Probe Microscopy (SPM) offers the resolution to image the nanometer scale bicontinuous morphology. In addition SPM can be operated to measure the local contact potential difference (CPD) of materials from which energy levels in the materials can be derived. Thus SPM is an unique method for the characterization of surface morphology, potential changes and conductivity changes under operating conditions. In the present work, I describe investigations of organic photovoltaic materials upon photo-oxidation which is one of the major causes of degradation of these solar cell materials. SPM, Nuclear Magnetic Resonance (NMR) and UV-Vis spectroscopy studies allowed me to identify the chemical reactions occurring inside the active layer upon photo-oxidation. From the measured data, it was possible to deduce the energy levels and explain the various shifts which gave a better understanding of the physics of the device. In addition, I was able to quantify the degradation by correlating the local changes in the CPD and conductivity to the device characteristics, i.e., open circuit voltage and short circuit current. Furthermore, time-resolved electrostatic force microscopy (tr-EFM) allowed us to probe dynamic processes like the charging rate of the individual donor and acceptor domains within the active blend. Upon photo-oxidation, it was observed, that the acceptor molecules got oxidized first preventing the donor polymer from degrading. Work functions of electrodes can be tailored by modifying the interface with monomolecular thin layers of molecules which are made by a chemical reaction in liquids. These modifications in the work function are particularly attractive for opto-electronic devices whose performance depends on the band alignment between the electrodes and the active material. In order to measure the shift in work function on a nanometer scale, I used KPFM in situ, which means in liquids, to follow changes in the work function of Au upon hexadecanethiol adsorption from decane. All the above investigations give us a better understanding of the photo-degradation processes of the active material at the nanoscale. Also, a method to compare various new materials used for organic solar cells for stability is proposed which eliminates the requirement to make fully functional devices saving time and additional engineering efforts.

3D-Druck von Kunststoff-Medizinprodukten

Das Additive Manufacturing gewinnt im Bereich der Medizintechnik zur Herstellung von Prototypen bis hin zu Endprodukten zunehmend an Bedeutung. Ein großes Hemmnis stellen allerdings die relativ hohen Fertigungskosten dar. Hier bietet der verstärkte Einsatz der 3D-Drucktechnologie (3D Printing) ein erhebliches Potential zur Reduktion der Kosten. Aus dieser Motivation heraus wurde ein 3D-Druckverfahren zur Herstellung biokompatibler, sterilisierbarer Kunststoffmodelle entwickelt. Beim 3D-Druck-Verfahren handelt es sich um einen pulverbasierten Prozess zur schichtweisen Herstellung von Modellen direkt aus Computerdaten. Dabei werden dünne Schichten eines Pulvers auf eine Grundplatte aufgebracht, die dann durch gezielte Binderzugabe entsprechend des aktuellen Bauteilquerschnitts verfestigt werden. Ausgangsmaterial für diesen Prozess ist ein Granulatgemisch auf Basis von PMMA (Polymethylmethacrylat). Als Binderflüssigkeit wird ein Lösungsmittel eingesetzt. Die 3D gedruckten Modelle werden nach einer entsprechenden Trocknungszeit im Pulverbett entpackt und warmgelagert, um das Abdampfen des Lösungsmittels zu beschleunigen. Der Nachweis der Biokompatibilität der hergestellten Modelle erfolgte durch einen Test nach DIN EN ISO 10993-5. In Kooperation mit Anwendern wurden verschiedene Anwendungsbeispiele wie Bohrschablonen, Otoplastiken, Gebissmodelle und Modelle für die präoperative Planung realisiert und charakterisiert.