Bottom up strategies for the morphology control of BaTiO3 particulates

As propriedades funcionais dos materiais ferroeléctricos tais como a polarização reversível, piroelectricidade, piezoelectricidade, elevada actividade óptica não linear e comportamento dieléctrico não linear são fundamentais para a sua aplicação em sensores, microactuadores, detectores de infravermelhos, filtros de fase de microondas e memórias não-voláteis. Nos últimos anos, motivado pelas necessidades industriais de redução do tamanho dos dispositivos microelectrónicos, aumentando a eficiência volumétrica, tem sido feito um grande esforço ao nível da investigação para desenvolver estruturas ferroeléctricas à escala micro- e nano- métrica. É sabido que a redução de tamanho em materiais ferroeléctricos afecta significamente as suas propriedades. Neste sentido e considerando que foi previsto teoreticamente por cálculos ab initio que estruturas do tipo nanocilindros e nanodiscos apresentariam um novo tipo de ordem ferroeléctrica e, na expectativa de alcançar conhecimento para o desenvolvimento de uma nova geração de dispositivos microelectróncos, existe um grande interesse em desenvolver métodos de fabrico de nanoestruturas ferroeléctricas unidimensionais (1D) tais como nanocilindros e nanotubos. As estratégias de fabrico de nanoestruturas 1D até agora descritas na literatura indicam claramente as dificuldades inerentes à sua preparação. Existem duas grandes vias de síntese destas nanoestruturas: i) o método “topdown” que consiste na redução de tamanho de um dado material até à obtenção duma estrutura 1D; e ii) o método “bottom-up” em que átomos, iões e moléculas são agrupados para formar um material 1D. O método “top down” envolve em geral técnicas de desgaste, como o uso do feixe de electrões, que apesar de permitirem elevada precisão no posicionamento e no controlo do tamanho, falham em termos de resolução, exigem muito tempo e causam facilmente defeitos que deterioram as propriedades físicas destes materiais. Na metodologia “bottom up” a utilização de moléculas ou estruturas “molde” tem sido a mais explorada. As estructuras 1D podem também ser preparadas sem recorrer a “moldes”. Neste caso a agregação orientada é promovida pelo recurso a aditivos que controlam o crescimento dos cristais em direcções preferenciais. Neste contexto, neste trabalho utilizaram-se duas estratégias “bottom up” de baixo custo para a preparação de nanopartículas de titanato de bário (BaTiO3) com morfologia controlada: 1) síntese química (em solução e em fase vapor) com utilização de nanotubos de titanato TiNTs) como “moldes” e precursores de titânio 2) síntese química em solução com presença de aditivos. Os nanotubos de titanato de sódio foram preparados por síntese hidrotermal. Como existiam muitas dúvidas acerca da natureza estrutural e do mecanismo de formação dos NTs, a parte inicial do trabalho foi dedicada à realização de um estudo sistemático dos parâmetros intervenientes na síntese e à caracterização da sua estrutura e microestrutura. Foi demonstrado que os NTs têm a fórmula geral A2Ti2O5 (A = H+ or Na+), e não TiO2 (anátase) com defendido por vários autores na literatura, e podem ser preparados por método hidrotermal em meio fortemente alcalino usando como fonte de titânio TiO2 comercial na forma de anátase ou rútilo. A menor reactividade do rútilo exige temperaturas de síntese superiores ou tempos de reacção mais longos. A forma tubular resulta do tratamento hidrotermal e não de processos de lavagem e neutralização subsequentes. Se os NTs forem tratados após a síntese hidrotérmica em água a 200 ºC, transformam-se em nanocilindros. Uma das partes principais desta tese consistiu na investigação do papel dos NTs de titanato no crescimento anisotrópico de BaTiO3. O potencial funcionamento dos NTs como “moldes” para além de precursores foi testado em reacção com hidróxido de bário em síntese em solução e por reacção com um precursor orgânico de bário em fase vapor. Tendo por base os estudos cinéticos realizados, bem como as alterações estruturais e morfológicas das amostras, é possível concluir que a formação do BaTiO3 a partir de NTs de titanato de sódio, ocorre por dois mecanismos dependendo da temperatura e tempo de reacção. Assim, a baixa temperatura e curto tempo de reacção verifica-se que se formam partículas dendríticas de BaTiO3 cuja superfície é bastante irregular (“wild”) e que apresentam estrutura pseudo-cúbica. Estas partículas formam-se por reacção topotáctica na fronteira dos nanotubos de titanato de sódio. A temperaturas mais altas e/ou reacções mais longas, a reacção é controlada por um mecanismo de dissolução e precipitação com formação de dendrites de BaTiO3 tetragonais com superfície mais regular (“seaweed”). A microscopia de força piezoeléctrica mostrou que as dendrites “seaweeds“ possuem actividade piezoeléctrica superior à das dendrites “wild”, o que confirma o papel desempenhado pela estrutura e pela concentração de defeitos na rede na coerência e ordem ferroeléctrica de nanoestruturas. Os nossos resultados confirmam que os NTs de titanato não actuam facilmente como “moldes” na síntese em solução de BaTiO3 já que a velocidade de dissolução dos NTs em condições alcalinas é superior à velocidade de formação do BaTiO3. Assumindo que a velocidade de reacção dos NTs com o precursor de bário é superior em fase vapor, efectuou-se a deposição de um precursor orgânico de bário por deposição química de vapor sobre um filme de NTs de titnato de sódio depositados por deposição electroforética. Estudou-se a estabilidade dos NTs nas diferentes condições do reactor. Quando os NTs são tratados a temperaturas superiores a 700 ºC, ocorre a transformação dos NTs em nanocilindros de anatase por um mecanismo de agregação orientada. Quando se faz a deposição do precursor de bário, seguida de calcinação a 700 ºC em atmosfera oxidante de O2, verifica-se que a superficie dos NTs fica coberta com nanocristais de BaTiO3 independentemente da concentração de bário. O papel dos NTs de titanato no crescimento anisotrópico de BaTiO3 em fase vapor é assim descrito pela primeira vez. Em relação à metodologias de crescimento de partículas na ausência de “moldes” mas com aditivos fez-se um estudo sistemático utilizando 5 aditivos de natureza differente. As diferenças entre aditivos foram sistematizadas tendo em conta as diferenças estruturais e morfológicas verificadas. Está provado que os aditivos podem funcionar como modificadores de crescimento cristalino por alteração do seu padrão de crescimento ou por alteração da cinética de crescimento das faces cristalográficas do cristal. Entre os aditivos testados verificou-se que o ácido poliacrilíco adsorve em faces específicas do BaTiO3 alterando a cinética de crescimento e induzindo a agregação orientada das partículas. O polivinilpirrolidona, o docecilsulfato de sódio e hidroxipropilmetilcelulose actuam mais como inibidores de crescimento do que como modificadores do tipo de crescimento. A D-frutose aumenta a energia de activação da etapa de nucleação não ocorrendo formação de BaTiO3 para as mesmas condições dos outros aditivos. Esta tese clarifica o papel dos NTs de titanato de sódio enquanto precursores e “moldes” no crescimento anisotrópico de BaTiO3 em solução e em fase vapor. É feita também a abordagem do controlo morfológico do BaTiO3 através do uso de aditivos. As estratégias de preparação de BaTiO3 propostas são de baixo custo, reprodutíveis e fáceis de efectuar. Os resultados contribuem para uma melhor compreensão da relação tamanho – morfologia – propriedade em materiais ferroeléctricos nanométricos com vista à sua potencial aplicação.

Phthalocyanines : interaction with carbon structures and as PDT agents

This dissertation describes the synthesis and characterization of different phthalocyanine (Pc) derivatives, as well as some porphyrins (Pors), for supramolecular interaction with different carbon nanostructures, to evaluate their potential application in electronic nanodevices. Likewise, it is also reported the preparation and biological evaluation of interesting phthalocyanine conjugates for cancer photodynamic therapy (PDT) and microorganisms photodynamic inactivation (PDI). The phthalonitrile precursors were prepared from commercial phthalonitriles by nucleophilic substitution of -NO2, -Cl, or -F groups, present in the phthalonitrile core, by thiol or pyridyl units. After the synthesis of these phthalonitriles, the corresponding Pcs were prepared by ciclotetramerization using a metallic salt as template at high temperatures. A second strategy involved the postfunctionalization of hexadecafluorophthalocyaninato zinc(II) through the adequate substituents of mercaptopyridine or cyclodextrin units on the macrocycle periphery. The different compounds were structurally characterized by diverse spectroscopic techniques, namely 1H, 13C and 19F nuclear magnetic resonance spectroscopies (attending the elemental composition of each structure); absorption and emission spectroscopy, and mass spectrometry. For the specific photophysical studies were also used electrochemical characterization, femtosecond and raman spectroscopy, transmission electron and atomic force microscopy. It was highlighted the noncovalent derivatisation of carbon nanostructures, mainly single wall carbon nanotubes (SWNT) and graphene nanosheets with the prepared Pc conjugates to study the photophysical properties of these supramolecular nanoassemblies. Also, from pyridyl-Pors and ruthenium phthalocyanines (RuPcs) were performed Por-RuPcs arrays via coordination chemistry. The results obtained of the novel supramolecular assemblies showed interesting electron donor-acceptor interactions and might be considered attractive candidates for nanotechnological devices. On the other hand, the amphiphilic phthalocyanine-cyclodextrin (Pc-CD) conjugates were tested in biological trials to assess their ability to inhibit UMUC- 3 human bladder cancer cells. The results obtained demonstrated that these photoactive conjugates are highly phototoxic against human bladder cancer cells and could be applied as promising PDT drugs.

Estudo de defeitos em filmes finos de ZnO depositados por Rf-sputtering

Neste trabalho foram estudados diferentes filmes finos de ZnO depositados por Rf-Sputtering. Filmes finos de ZnO com diferentes propriedades óticas foram obtidos intencionalmente variando os parâmetros de deposição. De modo a correlacionar as propriedades óticas e estruturais com os parâmetros de deposição, foram utilizadas diferentes técnicas de caracterização avançadas, tais como, fotoluminescência, microscopia de força atómica, difração de raios- X e retrodispersão de Rutherford. Este trabalho centra-se na discussão e análise das bandas de emissão vermelha, verde e azul, comumente observadas em amostras de ZnO e cuja natureza tem sido objeto de grande controvérsia na literatura. A utilização de técnicas de caracterização estrutural revelou-se de extrema importância para correlacionar as propriedades físicas de composição e estrutura com os centros óticos observados nos filmes. Nesta base, foram propostos e discutidos diferentes modelos de recombinação ótica associados à qualidade estrutural dos filmes, considerando modelos de camadas que descrevem a heterogeneidade lateral e em profundidade. Desta análise verificou-se a presença de heterogeneidade estrutural e composicional, que aumenta a complexidade na compreensão da correlação dos parâmetros de deposição com as propriedades óticas dos filmes. Foi discutida a limitação e validade de diferentes modelos tendo em conta a presença da heterogeneidade existente nos filmes estudados. Este trabalho contribui assim para uma melhor compreensão da complexidade de interação dos diferentes defeitos e o seu efeito nas propriedades óticas, nomeadamente o papel dos defeitos de interface, na superfície, nas fronteiras de grão e junto ao substrato.

Asymmetric rolling of 5182 aluminium alloy and interstitial free steel sheets

This Ph.D. research focuses on asymmetric rolling (ASR), as an alternative method for improving mechanical responses of aluminium-magnesium alloy and interstitial free (IF) steel regarding industrial requirements. Aluminium alloys are attractive materials in various industries due to their appropriate properties such as low density and corrosion resistance; however, their low formability has limited their applications. As formability of aluminium alloys can be improved through texture development, part of this dissertation is dedicated to producing the desired crystallographic texture with the ASR process. Two types of ASR (i.e. reverse and continuous asymmetric rolling) were investigated. The impact of shear deformation imposed by ASR processes on developing the desirable texture and consequently on mechanical behaviours was observed. The developed shear texture increased the normal and also planar anisotropy. Texture evolution during plastic deformation as well as induced mechanical behaviour were simulated using the “self-consistent” and Taylor models. Interstitial free (IF) steel was the second material selected in this dissertation. Since IF steel is one of the most often used materials in automotive industries it was chosen to investigate the effect of shear deformation through ASR on its properties. Two types of reverse and continuous asymmetric rolling were carried out to deform IF steel sheets. The results of optical microscopy and atomic force microscopy observations showed no significant difference between the grains’ morphology of asymmetric and conventionally rolled samples, whereas the obtained results of transmission electron microscopy indicated that fine and equiaxed dislocation cells were formed through the asymmetric rolling process. This structure is due to imposed shear deformation during the ASR process. Furthermore, the mechanical behaviour of deformed and annealed sheets was evaluated through uniaxial tensile tests. Results showed that at low thickness reductions (18%) the asymmetric rolled sample presented higher stress than that of the conventionally rolled sheet; while for higher thickness reductions (60%) the trend was reversed. The texture analyses indicated that intense rolling texture components which developed through 60% thickness reduction of conventional rolling cause a relatively higher stress; on the contrary the fine structure resulting from ASR appears to be the source of higher stress observed after pre-deformation of 18%.

Ferroelectric : CNTs structures fabrication for advanced functional nano devices

This work is about the combination of functional ferroelectric oxides with Multiwall Carbon Nanotubes for microelectronic applications, as for example potential 3 Dimensional (3D) Non Volatile Ferroelectric Random Access Memories (NVFeRAM). Miniaturized electronics are ubiquitous now. The drive to downsize electronics has been spurred by needs of more performance into smaller packages at lower costs. But the trend of electronics miniaturization challenges board assembly materials, processes, and reliability. Semiconductor device and integrated circuit technology, coupled with its associated electronic packaging, forms the backbone of high-performance miniaturized electronic systems. However, as size decreases and functionalization increases in the modern electronics further size reduction is getting difficult; below a size limit the signal reliability and device performance deteriorate. Hence miniaturization of siliconbased electronics has limitations. On this background the Road Map for Semiconductor Industry (ITRS) suggests since 2011 alternative technologies, designated as More than Moore; being one of them based on carbon (carbon nanotubes (CNTs) and graphene) [1]. CNTs with their unique performance and three dimensionality at the nano-scale have been regarded as promising elements for miniaturized electronics [2]. CNTs are tubular in geometry and possess a unique set of properties, including ballistic electron transportation and a huge current caring capacity, which make them of great interest for future microelectronics [2]. Indeed CNTs might have a key role in the miniaturization of Non Volatile Ferroelectric Random Access Memories (NVFeRAM). Moving from a traditional two dimensional (2D) design (as is the case of thin films) to a 3D structure (based on a tridimensional arrangement of unidimensional structures) will result in the high reliability and sensing of the signals due to the large contribution from the bottom electrode. One way to achieve this 3D design is by using CNTs. Ferroelectrics (FE) are spontaneously polarized and can have high dielectric constants and interesting pyroelectric, piezoelectric, and electrooptic properties, being a key application of FE electronic memories. However, combining CNTs with FE functional oxides is challenging. It starts with materials compatibility, since crystallization temperature of FE and oxidation temperature of CNTs may overlap. In this case low temperature processing of FE is fundamental. Within this context in this work a systematic study on the fabrication of CNTs - FE structures using low cost low temperature methods was carried out. The FE under study are comprised of lead zirconate titanate (Pb1-xZrxTiO3, PZT), barium titanate (BaTiO3, BT) and bismuth ferrite (BiFeO3, BFO). The various aspects related to the fabrication, such as effect on thermal stability of MWCNTs, FE phase formation in presence of MWCNTs and interfaces between the CNTs/FE are addressed in this work. The ferroelectric response locally measured by Piezoresponse Force Microscopy (PFM) clearly evidenced that even at low processing temperatures FE on CNTs retain its ferroelectric nature. The work started by verifying the thermal decomposition behavior under different conditions of the multiwall CNTs (MWCNTs) used in this work. It was verified that purified MWCNTs are stable up to 420 ºC in air, as no weight loss occurs under non isothermal conditions, but morphology changes were observed for isothermal conditions at 400 ºC by Raman spectroscopy and Transmission Electron Microscopy (TEM). In oxygen-rich atmosphere MWCNTs started to oxidized at 200 ºC. However in argon-rich one and under a high heating rate MWCNTs remain stable up to 1300 ºC with a minimum sublimation. The activation energy for the decomposition of MWCNTs in air was calculated to lie between 80 and 108 kJ/mol. These results are relevant for the fabrication of MWCNTs – FE structures. Indeed we demonstrate that PZT can be deposited by sol gel at low temperatures on MWCNTs. And particularly interesting we prove that MWCNTs decrease the temperature and time for formation of PZT by ~100 ºC commensurate with a decrease in activation energy from 68±15 kJ/mol to 27±2 kJ/mol. As a consequence, monophasic PZT was obtained at 575 ºC for MWCNTs - PZT whereas for pure PZT traces of pyrochlore were still present at 650 ºC, where PZT phase formed due to homogeneous nucleation. The piezoelectric nature of MWCNTs - PZT synthesised at 500 ºC for 1 h was proved by PFM. In the continuation of this work we developed a low cost methodology of coating MWCNTs using a hybrid sol-gel / hydrothermal method. In this case the FE used as a proof of concept was BT. BT is a well-known lead free perovskite used in many microelectronic applications. However, synthesis by solid state reaction is typically performed around 1100 to 1300 ºC what jeopardizes the combination with MWCNTs. We also illustrate the ineffectiveness of conventional hydrothermal synthesis in this process due the formation of carbonates, namely BaCO3. The grown MWCNTs - BT structures are ferroelectric and exhibit an electromechanical response (15 pm/V). These results have broad implications since this strategy can also be extended to other compounds of materials with high crystallization temperatures. In addition the coverage of MWCNTs with FE can be optimized, in this case with non covalent functionalization of the tubes, namely with sodium dodecyl sulfate (SDS). MWCNTs were used as templates to grow, in this case single phase multiferroic BFO nanorods. This work shows that the use of nitric solvent results in severe damages of the MWCNTs layers that results in the early oxidation of the tubes during the annealing treatment. It was also observed that the use of nitric solvent results in the partial filling of MWCNTs with BFO due to the low surface tension (<119 mN/m) of the nitric solution. The opening of the caps and filling of the tubes occurs simultaneously during the refluxing step. Furthermore we verified that MWCNTs have a critical role in the fabrication of monophasic BFO; i.e. the oxidation of CNTs during the annealing process causes an oxygen deficient atmosphere that restrains the formation of Bi2O3 and monophasic BFO can be obtained. The morphology of the obtained BFO nano structures indicates that MWCNTs act as template to grow 1D structure of BFO. Magnetic measurements on these BFO nanostructures revealed a week ferromagnetic hysteresis loop with a coercive field of 956 Oe at 5 K. We also exploited the possible use of vertically-aligned multiwall carbon nanotubes (VA-MWCNTs) as bottom electrodes for microelectronics, for example for memory applications. As a proof of concept BiFeO3 (BFO) films were in-situ deposited on the surface of VA-MWCNTs by RF (Radio Frequency) magnetron sputtering. For in situ deposition temperature of 400 ºC and deposition time up to 2 h, BFO films cover the VA-MWCNTs and no damage occurs either in the film or MWCNTs. In spite of the macroscopic lossy polarization behaviour, the ferroelectric nature, domain structure and switching of these conformal BFO films was verified by PFM. A week ferromagnetic ordering loop was proved for BFO films on VA-MWCNTs having a coercive field of 700 Oe. Our systematic work is a significant step forward in the development of 3D memory cells; it clearly demonstrates that CNTs can be combined with FE oxides and can be used, for example, as the next 3D generation of FERAMs, not excluding however other different applications in microelectronics.

Piezoelectricity and ferroelectricity in amino acid glycine

Bioorganic ferroelectrics and piezoelectrics are becoming increasingly important in view of their intrinsic compatibility with biological environment and biofunctionality combined with strong piezoelectric effect and switchable polarization at room temperature. Here we study piezoelectricity and ferroelectricity in the smallest amino acid glycine, representing a broad class of non-centrosymmetric amino acids. Glycine is one of the basic and important elements in biology, as it serves as a building block for proteins. Three polymorphic forms with different physical properties are possible in glycine (α, β and γ), Of special interest for various applications are non-centrosymmetric polymorphs: β-glycine and γ-glycine. The most useful β-polymorph being ferroelectric took much less attention than the other due to its instability under ambient conditions. In this work, we could grow stable microcrystals of β-glycine by the evaporation of aqueous solution on a (111)Pt/Ti/SiO2/Si substrate as a template. The effects of the solution concentration and Pt-assisted nucleation on the crystal growth and phase evolution were characterized by X-ray diffraction analysis and Raman spectroscopy. In addition, spin-coating technique was used for the fabrication of highly aligned nano-islands of β-glycine with regular orientation of the crystallographic axes relative the underlying substrate (Pt). Further we study both as-grown and tip-induced domain structures and polarization switching in the β-glycine molecular systems by Piezoresponse Force Microscopy (PFM) and compare the results with molecular modeling and computer simulations. We show that β-glycine is indeed a room-temperature ferroelectric and polarization can be switched by applying a bias to non-polar cuts via a conducting tip of atomic force microscope (AFM). Dynamics of these in-plane domains is studied as a function of applied voltage and pulse duration. The domain shape is dictated by both internal and external polarization screening mediated by defects and topographic features. Thermodynamic theory is applied to explain the domain propagation induced by the AFM tip. Our findings suggest that β-glycine is a uniaxial ferroelectric with the properties controlled by the charged domain walls which in turn can be manipulated by external bias. Besides, nonlinear optical properties of β-glycine were investigated by a second harmonic generation (SHG) method. SHG method confirmed that the 2-fold symmetry is preserved in as-grown crystals, thus reflecting the expected P21 symmetry of the β-phase. Spontaneous polarization direction is found to be parallel to the monoclinic [010] axis and directed along the crystal length. These data are confirmed by computational molecular modeling. Optical measurements revealed also relatively high values of the nonlinear optical susceptibility (50% greater than in the z-cut quartz). The potential of using stable β-glycine crystals in various applications are discussed in this work.

Multiphysics Simulation of Nanostructured Semiconductor Devices

Thesis (Ph.D.)--University of Washington, 2013

Antifungal nanofibers made by controlled release of sea animal derived peptide

© The Royal Society of Chemistry 2015

Laccase-assisted bio-grafting of polyhydroxy-alkanoates (PHAs) onto the ethyl cellulose (EC) backbone

In the present study, a novel enzyme-based methodology for grafting Polyhydroxyalkanoates (PHAs) onto the ethyl cellulose (EC) as a backbone polymer was developed. Laccase assisted copolymerization was carried out under mild and eco-friendly reaction conditions. The resulting homogeneous composite membranes were characterized by Fourier-transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), and Atomic Force Microscopy (AFM). The FTIR spectra of pure PHAs and PHAs containing graft composites (PHAs-g-EC) showed their strong characteristic bands at 1721 cm1, 1651 cm-1 and 1603 cm-1 respectively. Other accompanying bands in the range of 900-1300 cm-1 correspond to C=O vibration and C-O-C bond stretching, which could be contributed from PHAs and EC, respectively. The high intensity of the 3358 cm-1 band in the graft composite may have corresponded to the degradation of the carboxylic group from PHAs and also showed an increase of hydrogen-bonded groups at that distinct band region. The morphology was examined by SEM, which showed the well dispersed PHAs crystals in the backbone polymer of EC. XRD pattern for PHAs showed distinct peaks at 2-Theta values of 28o, 32o, 34o, 39o, 46o, 57o, 64o, 78o and 84o that represent the crystalline nature of PHAs. In comparison with those of neat PHAs, the degree of crystallinity for PHAs-g-EC decreased and this reduction is mainly because of the new cross-linking of PHAs within the EC backbone that changes the morphology and destroys the crystallites. Improved mechanical properties were observed for the PHAs-g-EC as compared to the individual components due to the impregnation of EC as reinforcement into the PHAs matrix. Improved mechanical strength enhanced thermal properties, along with low crystallinity of the present PHAs-g-EC suggesting its potential for various industrial and bio-medical applications.

DNA interaction and cytotoxicity studies of new ruthenium(II) cyclopentadienyl derivative complexescontaining heteroaromatic ligands

Four ruthenium(II) complexes with the formula [Ru(eta(5)-C(5)H(5))(PP)L][CF(3)SO(3)], being (PP = two triphenylphosphine molecules), L = 1-benzylimidazole, 1; (PP = two triphenylphosphine molecules), L = 2,2'bipyridine, 2; (PP = two triphenylphosphine molecules), L = 4-Methylpyridine, 3; (PP = 1,2-bis(diphenylphosphine) ethane), L = 4-Methylpyridine, 4, were prepared, in view to evaluate their potentialities as antitumor agents. The compounds were completely characterized by NMR spectroscopy and their crystal and molecular structures were determined by X-ray diffraction. Electrochemical studies were carried out giving for all the compounds quasi-reversible processes. The images obtained by atomic force microscopy (AFM) suggest interaction with pBR322 plasmid DNA. Measurements of the viscosity of solutions of free DNA and DNA incubated with different concentrations of the compounds confirmed this interaction. The cytotoxicity of compounds 1234 was much higher than that of cisplatin against human leukemia cancer cells (HL-60 cells). IC(50) values for all the compounds are in the range of submicromolar amounts. Apoptotic death percentage was also studied resulting similar than that of cisplatin. (C) 2010 Elsevier Inc. All rights reserved.

Increasing the wear resistance of molds for injection of glass fiber reinforced plastics

Abrasion by glass fibers during injection molding of fiber reinforced plastics raises new challenges to the wear performance of the molds. In the last few decades, a large number of PVD and CVD coatings have been developed with the aim of minimizing abrasion problems. In this work, two different coatings were tested in order to increase the wear resistance of the surface of a mold used for glass fiber reinforced plastics: TiAlSiN and CrN/CrCN/DLC. TiAlSiN was deposited as a graded monolayer coating while CrN/CrCN/DLC was a nanostructured coating consisting of three distinct layers. Both coatings were produced by PVD unbalanced magnetron sputtering and were characterized using scanning electron microscopy (SEM) provided with energy dispersive spectroscopy (EDS), atomic force microscopy (AFM), micro hardness (MH) and scratch test analysis. Coating morphology, thickness, roughness, chemical composition and structure, hardness and adhesion to the substrate were investigated. Wear resistance was characterized through industrial tests with coated samples and an uncoated reference sample inserted in a feed channel of a plastic injection mold working with 30 wt.% glass fiber reinforced polypropylene. Results after 45,000 injection cycles indicate that the wear resistance of the mold was increased by a factor of 25 and 58, by the TiAlSiN and CrN/CrCN/DLC coatings, respectively, over the uncoated mold steel.

Influence of the abrasive particles size in the micro-abrasion wear tests of TiAlSiN thin coatings

Ball rotating micro-abrasion tribometers are commonly used to carry out wear tests on thin hard coatings. In these tests, different kinds of abrasives were used, as alumina (Al2O3), silicon carbide (SiC) or diamond. In each kind of abrasive, several particle sizes can be used. Some studies were developed in order to evaluate the influence of the abrasive particle shape in the micro-abrasion process. Nevertheless, the particle size was not well correlated with the material removed amount and wear mechanisms. In this work, slurry of SiC abrasive in distilled water was used, with three different particles size. Initial surface topography was accessed by atomic force microscopy (AFM). Coating hardness measurements were performed with a micro-hardness tester. In order to evaluate the wear behaviour, a TiAlSiN thin hard film was used. The micro-abrasion tests were carried out with some different durations. The abrasive effect of the SiC particles was observed by scanning electron microscopy (SEM) both in the films (hard material) as in the substrate (soft material), after coating perforation. Wear grooves and removed material rate were compared and discussed.

Micro-abrasion wear behaviour of TiAlCrSiN nanostructured coatings

The injection process of glass fibres reinforced plastics promotes the moulds surface degradation by erosion. In order to improve its wear resistance, several kinds of PVD thin hard coatings were used. It is well-known that nanostructures present a better compromise between hardness and toughness. Indeed, when the coating is constituted by a large number of ultra-thin different layers, cracks and interface troubles tend to decrease. However, it is not clear that these nanostructures present a better wear behaviour in erosion processes. In order to study its wear behaviour, a sputtered PVD nanostructured TiAlCrSiN coating was used. The substrate and film surfaces topography were analyzed by profilometry and atomic force microscopy techniques. Film adhesion to the substrate was evaluated by scratch tests. The surface hardness was measured with a Vickers micro-hardness tester. The wear resistance was evaluated by micro-abrasion with a rotating ball tribometer tests. Slurry of SiC particles in distilled water was used in order to provoke the surface abrasion. Different duration tests were performed in order to analyze the wear evolution. After these tests, the wear mechanisms developed were analyzed by scanning electron microscopy. Wear craters were measured and the wear rate was calculated and discussed. With the same purpose, coated inserts were mounted in an injection mould working with a 30% glass fibres reinforced polypropylene. After 45 000 cycles no relevant wear was registered.

A biocomposite of collagen nanofibers and nanohydroxyapatite for bone regeneration

This work aims to design a synthetic construct that mimics the natural bone extracellular matrix through innovative approaches based on simultaneous type I collagen electrospinning and nanophased hydroxyapatite (nanoHA) electrospraying using non-denaturating conditions and non-toxic reagents. The morphological results, assessed using scanning electron microscopy and atomic force microscopy (AFM), showed a mesh of collagen nanofibers embedded with crystals of HA with fiber diameters within the nanometer range (30 nm), thus significantly lower than those reported in the literature, over 200 nm. The mechanical properties, assessed by nanoindentation using AFM, exhibited elastic moduli between 0.3 and 2 GPa. Fourier transformed infrared spectrometry confirmed the collagenous integrity as well as the presence of nanoHA in the composite. The network architecture allows cell access to both collagen nanofibers and HA crystals as in the natural bone environment. The inclusion of nanoHA agglomerates by electrospraying in type I collagen nanofibers improved the adhesion and metabolic activity of MC3T3-E1 osteoblasts. This new nanostructured collagen–nanoHA composite holds great potential for healing bone defects or as a functional membrane for guided bone tissue regeneration and in treating bone diseases.

Disposable immunosensor using a simple method for oriented antibody immobilization for label-free real-time detection of an oxidative stress biomarker implicated in cancer diseases

This work proposes a novel approach for a suitable orientation of antibodies (Ab) on an immunosensing platform, applied here to the determination of 8-hydroxy-2′-deoxyguanosine (8OHdG), a biomarker of oxidative stress that has been associated to chronic diseases, such as cancer. The anti-8OHdG was bound to an amine modified gold support through its Fc region after activation of its carboxylic functions. Non-oriented approaches of Ab binding to the platform were tested in parallel, in order to show that the presented methodology favored Ab/Ag affinity and immunodetection of the antigen. The immunosensor design was evaluated by quartz-crystal microbalance with dissipation, atomic force microscopy, electrochemical impedance spectroscopy (EIS) and square-wave voltammetry. EIS was also a suitable technique to follow the analytical behavior of the device against 8OHdG. The affinity binding between 8OHdG and the antibody immobilized in the gold modified platform increased the charge transfer resistance across the electrochemical set-up. The observed behavior was linear from 0.02 to 7.0 ng/mL of 8OHdG concentrations. The interference from glucose, urea and creatinine was found negligible. An attempt of application to synthetic samples was also successfully conducted. Overall, the presented approach enabled the production of suitably oriented Abs over a gold platform by means of a much simpler process than other oriented-Ab binding approaches described in the literature, as far as we know, and was successful in terms of analytical features and sample application.