Controlo da morfologia de filmes de polímeros com potenciais aplicações em células fotovoltaicas

No campo da investigação das células fotovoltaicas orgânicas, a obtenção da camada activa com morfologia “ideal” através de técnicas baratas é ainda um marco não atingido. Este trabalho visa ultrapassar as baixas eficiências que são características destas células, através do desenvolvimento de um método rápido e de baixo custo para preparar camadas activas com morfologia próxima da “ideal”. Tal método permitiu obter filmes estruturados de polímeros conjugados reticulados que constituem um dos componentes da camada activa. O método é baseado no controlo da separação de fases que ocorre durante a deposição de misturas em solução, contendo um polímero conjugado reticulável, um polímero isolador “inerte” e um agente iniciador da reacção de reticulação, por spin coating (técnica rápida e de baixo custo), sobre um substrato que poderá servir de um dos eléctrodos na célula. A posterior irradiação do filme com luz Ultravioleta e o seu aquecimento conduzem à formação de uma “rede” reticulada e insolúvel do polímero conjugado que permite remover o polímero inerte e o agente iniciador por dissolução. Sendo o filme resultante insolúvel, o outro(s) componente(s) da camada activa da célula podem ser também depositados sobre ele a partir de soluções. Foram usados três polímeros conjugados reticuláveis dreivados do poli(dioctil-fluoreno) e um polímero “inerte”, o poliestireno, com diversos pesos moleculares. Demonstrou-se que a variação de condições durante a deposição das misturas e das características das mesmas permite obter filmes com diferentes tipos de morfologia - colunar, bicontínua e porosa - com diferentes dimensões dos “motivos” de polímero. Em particular, obtiveram-se filmes com morfologia colunar, com diâmetro médio de coluna da ordem de 150-200 nm e com morfologia bicontínua com “largura” média de grão de cerca de 200 nm. Demonstrou-se que a utilização dos filmes estruturados é mais vantajosa que a de filmes não estruturados (“planos”), tendo-se obtido valores de 90 a 95% de extinção de fotoluminescência para filmes colunares de um dos polímeros, em que o aceitador de electrões foi depositado em solução. Estes valores são indicativos de um processo de dissociação dos excitões gerados no polímero conjugado muito eficiente, o que permite antever que as camadas activas preparadas possam ser aplicadas em células fotovoltaicas com morfologia optimizada.

The spin polarization of CrO2 revisited

Here, we use Andreev reflection spectroscopy to study the spin polarization of high quality CrO2 films. We study the spin polarization as a function of growth temperature, resulting in grain size and electrical resistivity. In these films low temperature growth appears to be a necessary but not sufficient condition to guarantee the observation of high spin polarization, and this is only observed in conjunction with suppressed superconducting gap values and anomalously low interface properties. We suggest that this combination of observations is a manifestation of the long range spin triplet proximity effect. (C) 2007 American Institute of Physics.

Anti-Corrosion performance of a new silane coating for corrosion protection of AZ31 Magnesium alloy in Hank’s solution

Mg alloys can be used as bioresorsable metallic implants. However, the high corrosion rate of magnesium alloys has limited their biomedical applications. Although Mg ions are essential to the human body, an excess may cause undesirable health effects. Therefore, surface treatments are required to enhance the corrosion resistance of magnesium parts, decreasing its rate to biocompatible levels and allowing its safe application as bioresorbable metallic implants. The application of biocompatible silane coatings is envisaged as a suitable strategy for retarding the corrosion process of magnesium alloys. In the current work, a new glycidoxypropyltrimethoxysilane (GPTMS) based coating was tested on AZ31 magnesium substrates subjected to different surface conditioning procedures before coating deposition. The surface conditioning included a short etching with hydrofluoric acid (HF) or a dc polarisation in alkaline electrolyte. The silane coated samples were immersed in Hank's solution and the protective performance of the coating was studied through electrochemical impedance spectroscopy (EIS). The EIS data was treated by new equivalent circuit models and the results revealed that the surface conditioning process plays a key role in the effectiveness of the silane coating. The HF treated samples led to the highest impedance values and delayed the coating degradation, compared to the mechanically polished samples or to those submitted to dc polarisation.

"In-vitro" corrosion behaviour of the magnesium alloy with Al and Zn (AZ31) protected with a biodegradable polycaprolactone coating loaded with hydroxyapatite and cephalexin

Mg alloys are very susceptible to corrosion in physiological media. This behaviour limits its widespread use in biomedical applications as bioresorbable implants, but it can be controlled by applying protective coatings. On one hand, coatings must delay and control the degradation process of the bare alloy and, on the other hand, they must be functional and biocompatible. In this study a biocompatible polycaprolactone (PCL) coating was functionalised with nano hydroxyapatite (HA) particles for enhanced biocompatibility and with an antibiotic, cephalexin, for anti-bacterial purposes and applied on the AZ31 alloy. The chemical composition and the surface morphology of the coated samples, before and after the corrosion tests, were studied by scanning electron microscopy (SEM) coupled with energy dispersive x-ray analysis (EDX) and Raman. The results showed that the presence of additives induced the formation of agglomerates and defects in the coating that resulted in the formation of pores during immersion in Hanks' solution. The corrosion resistance of the coated samples was studied in Hank's solution by electrochemical impedance spectroscopy (EIS). The results evidenced that all the coatings can provide corrosion protection of the bare alloy. However, in the presence of the additives, corrosion protection decreased. The wetting behaviour of the coating was evaluated by the static contact angle method and it was found that the presence of both hydroxyapatite and cephalexin increased the hydrophilic behaviour of the surface. The results showed that it is possible to tailor a composite coating that can store an antibiotic and nano hydroxyapatite particles, while allowing to control the in-vitro corrosion degradation of the bioresorbable Mg alloy AZ31. (C) 2015 Elsevier Ltd. All rights reserved.

Biofunctional composite coating architectures based on polycaprolactone and nanohydroxyapatite for controlled corrosion activity and enhanced biocompatibility of magnesium AZ31 alloy

In this work a biofunctional composite coating architecture for controlled corrosion activity and enhanced cellular adhesion of AZ31 Mg alloys is proposed. The composite coating consists of a polycaprolactone (PCL) matrix modified with nanohydroxyapatite (HA) applied over a nanometric layer of polyetherimide (PEI). The protective properties of the coating were studied by electrochemical impedance spectroscopy (EIS), a non-disturbing technique, and the coating morphology was investigated by field emission scanning electron microscopy (FE-SEM). The results show that the composite coating protects the AZ31 substrate. The barrier properties of the coating can be optimized by changing the PCL concentration. The presence of nanohydroxyapatite particles influences the coating morphology and decreases the corrosion resistance. The biocompatibility was assessed by studying the response of osteoblastic cells on coated samples through resazurin assay, confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). The results show that the polycaprolactone to hydroxyapatite ratio affects the cell behavior and that the presence of hydroxyapatite induces high osteoblastic differentiation. (C) 2014 Elsevier B.V. All rights reserved.