Dealloying refers to the partial, selective dissolution of the less noble component(s) of a binary or ternary alloy precursor, resulting in a noble-rich, porous structure that has high surface area. Such surface structure is beneficial for fuel cells (FC) because FC uses platinum (Pt), a scarce metal, to catalyze the oxygen reduction reaction (ORR) at the cathode surface. In order to characterize the benefit of the dealloying process in FC ORR catalysts with the rotating disk electrode (RDE) technique, a high surface area catalyst support, namely 3M Co’s nanostructured thin film (NSTF), was incorporated into the RDE measurements. NSTF-coated glassy carbon (GC) disks were used in RDE experiments on a Pt/Pt1-xIrx (0.05 < x < 0.3) composition spread. ORR measurements using NSTF-coated GC disks measure the catalytic properties with the same morphology, composition and surface structure as would be found in a fuel cell. A series of Pt1-xCox and Pt1-xNix (0.5 < x < 0.8) dealloy catalyst precursor films were tested using NSTF-coated GC disks in RDE studies. The value of x in Pt1-xMx (M = Ni, Co) was selected to be high in order to examine the dealloying process. The catalyst films were examined by a RDE test protocol that tracked the surface enhancement factor (SEF) and ORR current densities over a large number of test cycles. The aim was to measure the catalytic performance of the Pt-M materials as dealloying took place. The SEF of the PtCo and PtNi materials increased rapidly at the beginning and reached a plateau as high as 50 cm2/cm2 while the specific ORR activities increased as the initial M content in the catalyst precursor increased. The impact of the dealloying process on morphology was examined by completely dealloying a Pt3Ni7 precursor, deposited on mirror-polished GC disks, at a constant potential. As the dealloying process continued, the SEF of the material increased from about 1 cm2/cm2 to > 30 cm2/cm2 and resulted in the formation of whisker-like structures.

Made available in DSpace on 2016-06-02T20:15:28Z (GMT). No. of bitstreams: 1 5177.pdf: 16843754 bytes, checksum: 0b2e8c0ee3f79df315d62b9151b7e100 (MD5) Previous issue date: 2013-04-12 / Universidade Federal de Minas Gerais / Avalanches are sudden dramatic phenomena that occur in nature. The technique of magneto-optical imaging (MOI) has allowed us to observe abrupt flux entrances in superconductors, the so-called ux avalanches, due to thermomagnetic instabilities in the vortex matter. Their morphology is fascinating, especially in superconducting thin films, where they develop in dendritic patterns. From a practical point of view, the flux avalanches undermine applications of superconducting thin films. In the last years, however, several steps have been reached to fully understand the fundamental physics of the phenomenon and also on how to suppress their occurrence. The present thesis deals with the study of flux avalanches in structured superconducting thin films. We have studied crystalline Nb and amorphous Mo79Ge21 thin films decorated with arrays of antidots (ADs or holes) produced by electron beam lithography. The magnetic response of these specimens has been investigated by means of MOI, dc magnetization and ac susceptibility. Firstly, we have established a link among those three techniques in the regime dominated by flux avalanches. We have observed that the reentrant behavior in the ac susceptibility at low temperatures occurs as a consequence of flux avalanches. Essentially, there is reuse of the channels created by the first ac cycle in a regime where the signal is weakly dependent on the temperature. Our results show that measurements of ac susceptibility versus ac field amplitude can be used to detect flux avalanches, since the signature of the flux avalanches appears as noisy curves of both ac susceptibility components. As a consequence, the critical current density as a function of temperature [Jc.T ] obtained by using the Bean model whose validity is assured by Cole-Cole plots is smooth for higher temperatures and, below a certain temperature onset, a non-smooth and noisy behavior takes place due to the avalanches. The temperature dependence of Jc.T,H was determined for different values of the applied magnetic field. The stability/instability frontier was then identified as the limiting temperature below which the curve Jc.T,H becomes noisy, indicating the occurrence of avalanches. Associated with this limiting temperature, the threshold critical current density to trigger avalanches is essentially independent of the magnetic field. This frontier corresponds to the upper threshold limit for the occurrence of avalanches. The effect in a thin film of a graded distribution of ADs which follows nearly the flux profile described by the Bean model has been studied. Compared to the uniform distribution, there is an increase of the critical current density at low fields. Moreover, viii the flux avalanches, highly induced by the presence of an array of ADs, have their activity reduced in temperature and magnetic field. For the first time, flux avalanches have been visualized in amorphous Mo79Ge21 thin film, both in plain and decorated thin films. Finally, we have investigated the influence of the lattice symmetry and AD geometry on the flux avalanche morphology. We have observed avalanches with the habit of forming trees where the trunk is parallel to the main axis of the square lattice and the branches form angles of 45 degrees. In addition to that, we have found an anisotropic penetration in a Nb thin film decorated with a square lattice of triangular ADs. Besides that, a sample having one half of the ADs in the form of squares, and the other half being circles, has been observed to present avalanches of different morphologies on each of its halves. We have also studied an a-MoGe thin film with a centered rectangular 2D Bravais lattice with square ADs which shows penetrations with different angles depending on the edge. The overall features of the avalanches, and in particular the 45-degree direction of the branches, have been confirmed by numerical simulations using the thermomagnetic model. Superconductivity, structured thin films, flux avalanches, magneto-optical imaging. / Avalanches são eventos repentinos e dramáticos que ocorrem na natureza. A técnica de imageamento por magneto-ótica (MOI) tem permitido visualizar a penetração abrupta de fluxo em supercondutores, as chamadas avalanches de fluxo, que ocorrem devido a instabilidades termomagnéticas na matéria de vórtices. A morfologia dessas avalanches de fluxo em filmes finos supercondutores prístinos é singular e se desenvolve de maneira dendrítica, isto é, com ramificações. Do ponto de vista prático, as avalanches de fluxo são prejudiciais para aplicações dos filmes finos supercondutores. Nos últimos anos, no entanto, tem-se alcançado um bom entendimento da física básica do fenômeno, bem como maneiras para suprimir essas avalanches. Esta tese trata do estudo de avalanches de fluxo em filmes finos com uma estrutura de defeitos. Para tal, usamos filmes finos cristalinos de Nb e amorfos da liga Mo79Ge21 decorados com arranjos de antidots (ADs), ou buracos, produzidos por litografia por feixe de elétrons. A resposta magnética desses filmes foi investigada através de MOI, magnetização dc e suscetibilidade ac. Na primeira parte dos resultados, uma conexão entre essas técnicas foi estabelecida no regime de avalanches de fluxo. Foi observado que o comportamento reentrante da suscetibilidade ac em baixas temperaturas ocorre devido `as avalanches de fluxo. Essencialmente, há o reuso dos caminhos ou canais criados pelo primeiro ciclo ac em um regime em que o sinal é fracamente dependente da temperatura. Esses resultados também mostraram que a suscetibilidade ac pode ser usada para detectar avalanches de fluxo, seja pela construção da curva de corrente critica dependente da temperatura Jc.T ou monitorando o ruído nas curvas do tipo Cole-Cole. Assim, a fronteira de instabilidades termomagnéticas/estabilidade foi construída variando-se o campo dc aplicado, tendo sido obtido, um limiar constante de Jc.T para o disparo das avalanches. Essa observação está de acordo com o modelo termomagnético e refere-se ao limite superior da ocorrência das avalanches de fluxo. Também foi estudado o efeito da inserção de um arranjo de antidots distribuídos de maneira gradiente, que segue aproximadamente a distribuição de fluxo descrita pelo Modelo de Bean. Comparada com uma distribuição uniforme, um aumento da densidade de corrente crítica foi observada para a região de baixos campos. Além disso, as avalanches de fluxo, que são altamente induzidas pela presença de ADs, apresentaram uma redução em sua ocorrência, tanto em magnitude do campo magnético aplicado quanto em temperatura. Pela primeira vez, foram observadas avalanches de fluxo em filmes finos amorfos de Mo79Ge21 com e sem uma rede de ADs. x Por fim, a influência da simetria da rede e da geometria do antidot na morfologia das avalanches de fluxo foi investigada. Para filmes finos decorados com uma rede quadrada de ADs quadrados, as avalanches têm o tronco paralelo ao eixo principal da rede de ADs, com ramificações em ângulos de 45 graus como em uma árvore de Natal. Além disso, penetrações abruptas anisotrópicas foram vistas em um filme fino de Nb decorado com uma rede quadrada de ADs triangulares. Uma mudança na morfologia das avalanches também foi observada em um filme com metade dos ADs quadrados e a outra metade circular. Também foram observadas penetrações com diferentes ângulos em uma rede retangular centrada de ADs quadrados dependendo da borda. Por fim, as características gerais das avalanches, em particular a de ramificações em 45 graus, foram confirmadas por simulações numéricas usando o modelo termomagnético.

Title: Nano-structured multicomponent plasma polymers for controlled immobilization of biomolecules Author: Iurii Melnichuk Department / Institute: Department of Macromolecular Physics/Charles University Supervisor of the doctoral thesis: Doc. Ing. Andrey Shukurov, Ph.D. Abstract: The aim of this thesis is to highlight the feasibility of tailored nano- structures in functionalizing surfaces for biointerfacial interactions. Development of new techniques for the production of nanoscaled biomaterials can be of use in a variety of medical and biological applications, e.g. biosensors, microarrays, drug sensors, implants, blood-contacting devices. This thesis first examines the early stages of nano-structured thin film growth fabricated by vapor phase deposition of poly(ethylene). We discuss island growth within a framework of rate equation theory, dynamic scaling theory and capture zone distribution. In a second stage, we test dielectric barrier discharge to activate PE nano-pattern for covalent immobilization of proteins. Finally, we assess cell behavior on surfaces in dependence on morphology and the presence of cell adhesive protein tropoelastin. We employ plasma polymerization to produce ultrathin hydrocarbon layer capable of protein anchoring. The thesis findings for the first time manifest the critical...