Electrolytes for ceramic oxide fuel cells

The main objective of this dissertation is the development and processing of novel ionic conducting ceramic materials for use as electrolytes in proton or oxide-ion conducting solid oxide fuel cells. The research aims to develop new processing routes and/or materials offering superior electrochemical behavior, based on nanometric ceramic oxide powders prepared by mechanochemical processes. Protonic ceramic fuel cells (PCFCs) require electrolyte materials with high proton conductivity at intermediate temperatures, 500-700ºC, such as reported for perovskite zirconate oxides containing alkaline earth metal cations. In the current work, BaZrO3 containing 15 mol% of Y (BZY) was chosen as the base material for further study. Despite offering high bulk proton conductivity the widespread application of this material is limited by its poor sinterability and grain growth. Thus, minor additions of oxides of zinc, phosphorous and boron were studied as possible sintering additives. The introduction of ZnO can produce substantially enhanced densification, compared to the un-doped material, lowering the sintering temperature from 1600ºC to 1300ºC. Thus, the current work discusses the best solid solution mechanism to accommodate this sintering additive. Maximum proton conductivity was shown to be obtained in materials where the Zn additive is intentionally adopted into the base perovskite composition. P2O5 additions were shown to be less effective as a sintering additive. The presence of P2O5 was shown to impair grain growth, despite improving densification of BZY for intermediate concentrations in the range 4 – 8 mol%. Interreaction of BZY with P was also shown to have a highly detrimental effect on its electrical transport properties, decreasing both bulk and grain boundary conductivities. The densification behavior of H3BO3 added BaZrO3 (BZO) shows boron to be a very effective sintering aid. Nonetheless, in the yttrium containing analogue, BaZr0.85Y0.15O3- (BZY) the densification behavior with boron additives was shown to be less successful, yielding impaired levels of densification compared to the plain BZY. This phenomenon was shown to be related to the undesirable formation of barium borate compositions of high melting temperatures. In the last section of the work, the emerging oxide-ion conducting materials, (Ba,Sr)GeO3 doped with K, were studied. Work assessed if these materials could be formed by mechanochemical process and the role of the ionic radius of the alkaline earth metal cation on the crystallographic structure, compositional homogeneity and ionic transport. An abrupt jump in oxide-ion conductivity was shown on increasing operation temperature in both the Sr and Ba analogues.

Development of Zirconia based phosphors for application in lighting and as luminescent bioprobes

The strong progress evidenced in photonic and optoelectronic areas, accompanied by an exponential development in the nanoscience and nanotechnology, gave rise to an increasing demand for efficient luminescent materials with more and more exigent characteristics. In this field, wide band gap hosts doped with lanthanide ions represent a class of luminescent materials with a strong technological importance. Within wide band gap material, zirconia owns a combination of physical and chemical properties that potentiate it as an excellent host for the aforementioned ions, envisaging its use in different areas, including in lighting and optical sensors applications, such as pressure sensors and biosensors. Following the demand for outstanding luminescent materials, there is also a request for fast, economic and an easy scale-up process for their production. Regarding these demands, laser floating zone, solution combustion synthesis and pulsed laser ablation in liquid techniques are explored in this thesis for the production of single crystals, nanopowders and nanoparticles of lanthanides doped zirconia based hosts. Simultaneously, a detailed study of the morphological, structural and optical properties of the produced materials is made. The luminescent characteristics of zirconia and yttria stabilized zirconia (YSZ) doped with different lanthanide ions (Ce3+ (4f1), Pr3+ (4f2), Sm3+ (4f5), Eu3+ (4f6), Tb3+ (4f8), Dy3+ (4f9), Er3+ (4f11), Tm3+ (4f12), Yb3+ (4f13)) and co-doped with Er3+,Yb3+ and Tm3+,Yb3+ are analysed. Besides the Stokes luminescence, the anti- Stokes emission upon infrared excitation (upconversion and black body radiation) is also analysed and discussed. The comparison of the luminescence characteristics in materials with different dimensions allowed to analyse the effect of size in the luminescent properties of the dopant lanthanide ions. The potentialities of application of the produced luminescent materials in solid state light, biosensors and pressure sensors are explored taking into account their studied characteristics.

Tratamento de superfícies metálicas por nanotecnologia

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica

Utilização da Nanotecnologia para o desenvolvimento sustentável na indústria agro-alimentar

O crescimento populacional esperado para os próximos anos conduzirá à necessidade de aumentar a produção agrícola de modo a satisfazer o aumento da procura. Nos últimos anos tem-se assistido a uma evolução tecnológica nos sistemas de produção que tem permitido aumentar a produtividade agrícola, por vezes à custa de elevados consumos de energia e com práticas nem sempre ambientalmente corretas. Os desafios que se colocam atualmente são no sentido de melhorar a conservação de recursos escassos, como o solo e a água, de aumentar a eficiência de uso de fatores de produção, de encontrar novas culturas, do desenvolvimento da biotecnologia, da diminuição dos consumos energéticos e de melhorar ainda mais as tecnologias associadas à produção. De maneira a responder aos desafios emergentes da procura por alimentos, da escassez de terrenos agrícolas aráveis bem como da existência de pragas de insetos e de ervas daninhas, os pesticidas tem vindo a ser usados com maior frequência, tendo-se assistido a uma contaminação dos solos e águas subterrâneas, causando deste modo um risco para a saúde dos seres vivos. Neste sentido, vários fabricantes de pesticidas estão a desenvolver novas formulações contendo pesticidas encapsulados em nanopartículas como modo de aumentar a sua solubilidade em água, biodisponibilidade, volatilidade, estabilidade e eficácia. tendo por objetivo um desenvolvimento sustentável. Neste trabalho, procedeu-se ao estudo do encapsulamento do herbicida Oxadiargil (5-terc-butil-3-[2,4-dicloro-5-(2-propiniloxi)fenil]-1,3,4-oxadiazol-2(3H)-ona) com a 2-hidroxipropil-β-ciclodextrina (HP-β-CD). O estudo da formação do complexo de inclusão Oxadiargil - HP-β-CD foi realizado em diferentes meios, água desionizada, tampão acetato pH = 3,46 e pH = 5,34 e tampão fosfato pH = 7,45, com o objetivo de determinar e comparar a sua constante de estabilidade. Verificou-se, em qualquer dos casos, a ocorrência de uma relação linear entre o aumento da solubilidade do Oxadiargil e o aumento da concentração de HP-β-CD, com um declive inferior a um, o que indicia a formação de um complexo na proporção estequiométrica de 1:1. Os resultados obtidos permitiram concluir que o processo de complexação Oxadiargil - HP-β-CD não é muito influenciado pela constituição e pelo pH do meio. De facto, as constantes de estabilidade obtidas para a água desionizada e soluções-tampão pH = 3,46, pH = 5,34 e pH = 7,45 foram de 919 ± 25, 685 ± 13, 623 ± 17 e 753 ± 9, respetivamente. A solubilidade do complexo obtido nos estudos realizados, em diferentes meios, é cerca de 23 a 32 vezes superior à observada para o Oxadiargil livre. De forma a caracterizar o complexo Oxadiargil - HP-β-CD procedeu-se à sua síntese utilizando o método de “kneading”. O composto obtido foi caracterizado por Ressonância Magnética Nuclear (RMN) tendo-se confirmado a formação de um complexo de inclusão na proporção estequiométrica de 1:1. O complexo obtido é mais solúvel e porventura mais estável quimicamente. O encapsulamento permite uma redução da aplicação dos pesticidas diminuindo assim os custos e o impacto negativo no ambiente. Com a nanotecnologia é possível a libertação controlada dos pesticidas, aumentando a sua eficácia e fornecendo os meios necessários para um desenvolvimento sustentável.

Avaluació tecnològica de les tecnologies convergents : Les NBIC: sinergies entre nanotecnologia, biotecnologia, tecnologies d'informació i comunicació (TIC) i ciències del coneixement

Traducció al català de l’informe “Technology Assessment on Convergent Technologies” elaborat per l’STOA (Science and Technology Options Assessment) per a la Direcció General de Polítiques Interiors del Parlament Europeu, realitzada per la Fundació Catalana per a la Recerca i la Innovació (FCRI).

Nanotecnologia: què és i com ens afectarà?

Informe divulgatiu des d’una perspectiva catalana sobre la nanotecnologia, les seves possibles implicacions econòmiques i socials i el paper de la política pública.

Interfaces e organização da pesquisa no Brasil: da Química à Nanotecnologia

Nanotechnology can be viewed as a powerful tool, capable of shaping the chemistry of atoms and molecules, converting them into exciting nanosized and nanostructured materials, devices and machines. However, in pursuing this task, an exceptional ability is required to deal with complex inter- and multidisciplinary approaches, as imposed by the nanoscale. A new research organization framework, capable of promoting cooperative interactions in many complementary areas, including the industries, is demanded. In this sense, an interesting example are the nanotechnology networks and millenium institutes recently created in Brazil. The highlights and weakness of such cooperative research networks are discussed, in addition to relevant nanotechnology themes focusing on the special needs and resources from the developing nations.

Estratégia supramolecular para a nanotecnologia

Brazilian science is evolving rapidly and steadly in the last 10 years, reaching the 15º place in the international ranking. Research in nanotechnology is following a similar way generating new scientific and technological knowledge in several frontiers but specially in the interfaces of two or more areas, where Chemistry is consolidating itself as a central science. In this context, the supramolecular approach is a very promissing one because it allows the build-up of a chemical inteligence using all the sistematized knowledge for the design and development of new nanomaterials and products. The great challenge of Chemistry is not decrease the dimensionality of the materials but instead find ways to increase the dimensionality and structural complexity keeping strict control on the interactions between the components, in order to generate materials with new properties and functionalities. Unfortunately, the current vigorous advancement of scientific research has not been followed by the transformation of such know-how into patents and produts. Therefore much efforts should be devoted to build a national science and technology program, joining all the segments of the society involved in the technological development (university, institutes of technological research, industry and government) in order to promote the furtherance of the Brazilian technological base. Only in this way it is possible to evolve to a technological society capable to transform the scientific knowledge into wealthy, thus sustaining the socioeconomic development of the country.

Um panorama da nanotecnologia no Brasil (e seus macro-desafios)

The objectives of this essay are to describe the development of nanoscience and nanotechnology (N&N) in Brazil. The analysis shows that Brazilian research in N&N is considered satisfactory and, although under other denominations, dates from at least 20 years. Innovation is still less satisfactory and there are different points of views on the issue. However, there is already a tendency towards the promotion of innovation in nanotechnology in the country. Scientists and the industrial sector have been showing interest in partnerships and some scientific policies stimulate this articulation between academy and companies.

Nanotecnologia: aspectos gerais e potencial de aplicação em catálise

In recent years nanomaterials, such as metallic nanoparticles, nanowires, nanotapes, nanotubes and nanocomposites, have attracted increasing interest for several technological applications. In catalysis, the great potential of nanomaterials is related to the high catalytic activity exhibited by these materials as a function of the high surface/volume ratio when the particles acquire diameter below 5 nm. In this work, a review about concepts and background of nanoscience and nanotechnology is presented with emphasis in catalysis. Special attention is given to gold nanoparticles and carbon nanotubes, focusing the properties and characteristics of these materials in several catalytic reactions.

Patenteamento em nanotecnologia no Brasil: desenvolvimento, potencialidades e reflexões para o meio ambiente e a saúde humana

Nanotechnology developments continue to be produced at exponential rates for a wide and diverse range of applications. In this paper was done a study of technological forecasting in nanotechnology applied to health, based on information drawn in Brazil from 1991 to 2010. The longitudinal evolutions of the number of patent applications, their topics, and their respective patent families have been evaluated for the total global activity. There were obtained 1352 patent applications in this period. It were analyzed the legal nature of the depositors, the year of deposit, depositors' home countries and processes. It has been a goal subsidizes the policy-makers to adapt and modernize the regulatory framework on nanotechnology and risks involving health as a strategic area in the politics of Science.

Impactos da nanotecnologia na saúde: produção de medicamentos

Several studies have described the benefits of nanoscience and nanotechnology (N&N) in different sectors such as agriculture, energy, environmental preservation, and public health. The rapid evolution of N&N can be shown through a panoramic analysis of scientific papers and patents. In the area of public health, it is estimated that the global market for nanotechnology products will expand to 160 billion U.S. dollars in 2015. The Brazilian government has also strengthened its innovative potential in N&N through economic subsidies, as observed for other countries. This review is focused on the current landscape of N&N in a therapeutic context, highlighting the development of nanotech-products produced with biocompatible and biodegradable materials that are already commercially available or under investigation. Most studies under investigation are focused on the development of nanotechnology-based formulations intended for treatment of cancer, inflammatory, cardiovascular, and neurological diseases. Although there are several advantages of N&N in healthcare, many challenges have to be conquered to increase the availability of nanotechnology products in toxicological, preclinical and clinical studies, scale-up, regulatory, and private investments.

Nanotecnologia em medicina: aspectos fundamentais e principais preocupações

The recent advances in the development of nanomaterials have opened new and exciting opportunities for their applications in medicine. These applications include molecular imaging, drug-delivery, and photothermal therapy. Despite the progress in medicinal applications of nanomaterials, several key problems remain unaddressed. Recent advances in this area include the enhancement of sensitivity in early diagnosis and therapy, in addition to investigations into the possible toxicity of nanomaterials. However, since little is known about the toxicity of nanomaterials, the regulation of these materials is a slow and complex process. This paper reviews the current scenario in the applications of nanomaterials in medicine as well as the main concerns and regulatory questions.

A nanotecnologia aplicada à veiculação de fármacos: estudos de desenvolvimento da formulação e caracterização

O ácido azelaico é um fármaco com actividade bacteriostática para muitos microorganismos sendo por isso frequentemente aplicado no tratamento do acne. Porém, às formulações tópicas deste fármaco estão geralmente associados alguns efeitos adversos e fracas adesões à terapêutica. Assim, a nanotecnologia pode ser aqui considerada como uma estratégia inovadora para ultrapassar os obstáculos anteriores. O objectivo deste estudo centrou-se no desenvolvimento e caracterização de nanopartículas de PLGA contendo o ácido azelaico. As nanopartículas foram produzidas através do método modificado de emulsificação/difusão do solvente e posteriormente incluídas num gel de Carbopol 940. Foram caracterizados vários parâmetros da formulação tais como potencial zeta, tamanho da partícula e eficiência de encapsulação. O tamanho médio das partículas foi de 378,63 nm (com I.P. cerca de 0,09) e o potencial zeta foi de -7,82 mV. Aeficiência de encapsulação do ácido azelaico foi de 76 ± 3,81%. Consequentemente, estas nanopartículas poderão ser consideradas ferramentas úteis para a veiculação do ácido azelaico.