Evolution of the functional properties of titanium–silver thin films for biomedical applications: Influence of in-vacuum annealing

In this work, the thermal stability of TiAgx thin films, deposited by magnetron sputtering, was evaluated, envisaging their application in biomedical devices, namely as electrodes for biosignal acquisition. Based on the composition and microstructural characterization, a set of four representative TiAgx thin films was selected in order to infer whether they are thermally stable in terms of functional properties. In order to achieve this purpose, the structural and morphological evolution of the films with annealing temperature was correlated with their electrical, mechanical and thermal properties. Two distinct zones were identified and two samples from each zone were extensively analysed. In the first zone (zone I), Ti was the main component (Ti-rich zone) while in the second, zone II, the Ag content was more significant. The selected samples were annealed in vacuum at four different temperatures up to 500 oC. For the samples produced within zone I, small microstructural changes were observed due to the recrystallization of the Ti structure and grain size increment. Also, no significant changes were observed with annealing temperature regarding the f l ’ functional properties, being thermally stable up to 500 oC. For higher Ag contents (zone II) the energy supplied by thermal treatments was sufficient to activate the crystallization of Ti-Ag intermetallic phases. A strong increase of the grain size of these phases was also reported. The structural and morphological organization proved to be determinant for the physical responses of the TiAgx system. The hardness and Y g’s modulus were significantly improved with the formation of the intermetallic phases. The silver addition and annealing treatments also played an important role in the electrical conductivity of the films, which was once again improved by the formation of Ti-Ag phases. The thermal diffusivity of the films was practically unchanged with the heat-treatment. This set of results shows that this intermetallic-like thin film system has good thermal stability up to high temperatures (as high as 500 oC), which in case of the highest Ag content zone is particularly evident for electrical and mechanical properties, showing an important improvement. Hardness increases about three times, while resistivity values become half of those from the lowest Ag contents zone. These set of characteristics are consistent with the targeted applications, namely in terms of biomedical sensing devices.

Particle transport in fouling caused by kaolin-water suspensions on copper tubes

Particulate fouling tests were carried out using kaolin-water suspensions flowing through an annular heat exchanger with a copper inner tube. The flow rate was changed from test to test, but the fluid temperature and pH, as well as the particle concentration, were maintained constant. In the lower range of fluid velocities (<0.5 m/s), the deposition process seemed to be controlled by mass transfer. The corresponding experimental transport fluxes were compared to the predictions obtained with several models, showing that diffusion governed particle transport. The absolute values of the mass transfer fluxes and their dependences on the Reynolds number were satisfactorily predicted by some of the models.

Evolution of the surface plasmon resonance of Au:TiO2 nanocomposite thin films with annealing temperature

This paper reports on the changes in the structural and morphological features occurring in a particular type of nanocomposite thin-film system, composed of Au nanoparticles (NPs) dispersed in a host TiO2 dielectric matrix. The structural and morphological changes, promoted by in-vacuum annealing experiments of the as-deposited thin films at different temperatures (ranging from 200 to 800 C), resulted in a well-known localized surface plasmon resonance (LSPR) phenomenon, which gave rise to a set of different optical responses that can be tailored for a wide number of applications, including those for optical-based sensors. The results show that the annealing experiments enabled a gradual increase of the mean grain size of the Au NPs (from 2 to 23 nm), and changes in their distributions and separations within the dielectric matrix. For higher annealing temperatures of the as-deposited films, a broad size distribution of Au NPs was found (sizes up to 100 nm). The structural conditions necessary to produce LSPR activity were found to occur for annealing experiments above 300 C, which corresponded to the crystallization of the gold NPs, with an average size strongly dependent on the annealing temperature itself. The main factor for the promotion of LSPR was the growth of gold NPs and their redistribution throughout the host matrix. On the other hand, the host matrix started to crystallize at an annealing temperature of about 500 C, which is an important parameter to explain the shift of the LSPR peak position to longer wavelengths, i.e. a red-shift.

Methodology for real-time adaptation of tunnels support using the observational method

The observational method in tunnel engineering allows the evaluation in real time of the actual conditions of the ground and to take measures if its behavior deviates considerably from predictions. However, it lacks a consistent and structured methodology to use the monitoring data to adapt the support system in real time. The definition of limit criteria above which adaptation is required are not defined and complex inverse analysis procedures (Rechea et al. 2008, Levasseur et al. 2010, Zentar et al. 2001, Lecampion et al. 2002, Finno and Calvello 2005, Goh 1999, Cui and Pan 2012, Deng et al. 2010, Mathew and Lehane 2013, Sharifzadeh et al. 2012, 2013) may be needed to consistently analyze the problem. In this paper a methodology for the real time adaptation of the support systems during tunneling is presented. In a first step limit criteria for displacements and stresses are proposed. The methodology uses graphics that are constructed during the project stage based on parametric calculations to assist in the process and when these graphics are not available, since it is not possible to predict every possible scenario, inverse analysis calculations are carried out. The methodology is applied to the “Bois de Peu” tunnel which is composed by two tubes with over 500 m long. High uncertainty levels existed concerning the heterogeneity of the soil and consequently in the geomechanical design parameters. The methodology was applied in four sections and the results focus on two of them. It is shown that the methodology has potential to be applied in real cases contributing for a consistent approach of a real time adaptation of the support system and highlight the importance of the existence of good quality and specific monitoring data to improve the inverse analysis procedure.

Effect of annealing temperature on photoluminescence and resistive switching characteristics of ZnO/Al2O3 multilayer nanostructures

This work demonstrates the role of defects generated during rapid thermal annealing of pulsed laser deposited ZnO/Al2O3 multilayer nanostructures in presence of vacuum at different temperatures (Ta) (500–900 C) on their electrical conductance and optical characteristics. Photoluminescence (PL) emissions show the stronger green emission at Ta 600 C and violet–blue emission at TaP800 C, and are attributed to oxygen vacancies and zinc related defects (zinc vacancies and interstitials) respectively. Current–voltage (I–V) characteristics of nanostructures with rich oxygen vacancies and zinc related defects display the electroforming free resistive switching (RS) characteristics. Nanostructures with rich oxygen vacancies exhibit conventional and stable RS behavior with high and low resistance states (HRS/LRS) ratio 104 during the retention test. Besides, the dominant conduction mechanism of HRS and LRS is explained by trap-controlled-space-charge limited conduction mechanism, where the oxygen vacancies act as traps. On the other hand, nanostructures with rich zinc related defects show a diode-like RS behavior. The rectifying ratio is found to be sensitive on the zinc interstitials concentration. It is assumed that the rectifying behavior is due to the electrically formed interface layer ZnAl2O4 at the Zn defects rich ZnO crystals – Al2O3 x interface and the switching behavior is attributed to the electron trapping/de-trapping process at zinc vacancies.

Local non-negative initial data scalar characterization of the Kerr solution

For any vacuum initial data set, we define a local, non-negative scalar quantity which vanishes at every point of the data hypersurface if and only if the data are Kerr initial data. Our scalar quantity only depends on the quantities used to construct the vacuum initial data set which are the Riemannian metric defined on the initial data hypersurface and a symmetric tensor which plays the role of the second fundamental form of the embedded initial data hypersurface. The dependency is algorithmic in the sense that given the initial data one can compute the scalar quantity by algebraic and differential manipulations, being thus suitable for an implementation in a numerical code. The scalar could also be useful in studies of the non-linear stability of the Kerr solution because it serves to measure the deviation of a vacuum initial data set from the Kerr initial data in a local and algorithmic way.

Assessing the application of polypropylene multifilament yarns in brain phantoms

The currently available clinical imaging methods do not provide highly detailed information about location and severity of axonal injury or the expected recovery time of patients with traumatic brain injury [1]. High-Definition Fiber Tractography (HDFT) is a novel imaging modality that allows visualizing and quantifying, directly, the degree of axons damage, predicting functional deficits due to traumatic axonal injury and loss of cortical projections. This imaging modality is based on diffusion technology [2]. The inexistence of a phantom able to mimic properly the human brain hinders the possibility of testing, calibrating and validating these medical imaging techniques. Most research done in this area fails in key points, such as the size limit reproduced of the brain fibers and the quick and easy reproducibility of phantoms [3]. For that reason, it is necessary to develop similar structures matching the micron scale of axon tubes. Flexible textiles can play an important role since they allow producing controlled packing densities and crossing structures that match closely the human crossing patterns of the brain. To build a brain phantom, several parameters must be taken into account in what concerns to the materials selection, like hydrophobicity, density and fiber diameter, since these factors influence directly the values of fractional anisotropy. Fiber cross-section shape is other important parameter. Earlier studies showed that synthetic fibrous materials are a good choice for building a brain phantom [4]. The present work is integrated in a broader project that aims to develop a brain phantom made by fibrous materials to validate and calibrate HDFT. Due to the similarity between thousands of hollow multifilaments in a fibrous arrangement, like a yarn, and the axons, low twist polypropylene multifilament yarns were selected for this development. In this sense, extruded hollow filaments were analysed in scanning electron microscope to characterize their main dimensions and shape. In order to approximate the dimensional scale to human axons, five types of polypropylene yarns with different linear density (denier) were used, aiming to understand the effect of linear density on the filament inner and outer areas. Moreover, in order to achieve the required dimensions, the polypropylene filaments cross-section was diminished in a drawing stage of a filament extrusion line. Subsequently, tensile tests were performed to characterize the mechanical behaviour of hollow filaments and to evaluate the differences between stretched and non-stretched filaments. In general, an increase of the linear density causes the increase in the size of the filament cross section. With the increase of structure orientation of filaments, induced by stretching, breaking tenacity increases and elongation at break decreases. The production of hollow fibers, with the required characteristics, is one of the key steps to create a brain phantom that properly mimics the human brain that may be used for the validation and calibration of HDFT, an imaging approach that is expected to contribute significantly to the areas of brain related research.

Cylindrically symmetric models of gravitational collapse to black holes: a short review

We survey results about exact cylindrically symmetric models of gravitational collapse in General Relativity. We focus on models which result from the matching of two spacetimes having collapsing interiors which develop trapped surfaces and vacuum exteriors containing gravitational waves. We collect some theorems from the literature which help to decide a priori about eventual spacetime matchings. We revise, in more detail, some toy models which include some of the main mathematical and physical issues that arise in this context, and compute the gravitational energy flux through the matching boundary of a particular collapsing region. Along the way, we point out several interesting open problems.

Biological behaviour of thin films consisting of Au nanoparticles dispersed in a TiO2 dielectric matrix

In this work it was studied the possible use of thin films, composed of Au nanoparticles (NPs) embedded in a TiO2 matrix, in biological applications, by evaluating their interaction with a well-known protein, Bovine Serum Albumin (BSA), as well as with microbial cells (Candida albicans). The films were produced by one-step reactive DC magnetron sputtering followed by heat-treatment. The samples revealed a composition of 8.3 at.% of Au and a stoichiometric TiO2 matrix. The annealing promoted grain size increase of the Au NPs from 3 nm (at 300 °C) to 7 nm (at 500 °C) and a progressive crystallization of the TiO2 matrix to anatase. A broad localized surface plasmon resonance (LSPR) absorption band (λ = 580–720 nm) was clearly observed in the sample annealed at 500 °C, being less intense at 300 °C. The biological tests indicated that the BSA adhesion is dependent on surface nanostructure morphology, which in turn depends on the annealing temperature that changed the roughness and wettability of the films. The Au:TiO2 thin films also induced a significant change of the microbial cell membrane integrity, and ultimately the cell viability, which in turn affected the adhesion on its surface. The microstructural changes (structure, grain size and surface morphology) of the Au:TiO2 films promoted by heat-treatment shaped the amount of BSA adhered and affected cell viability.

Multifunctional Ti–Me (Me=Al, Cu) thin film systems for biomedical sensing devices

Ti-Me binary intermetallic thin films based on a titanium matrix doped with increasing amounts of Me (Me = Al, Cu) were prepared by magnetron sputtering (under similar conditions), aiming their application in biomedical sensing devices. The differences observed on the composition and on the micro(structural) features of the films, attributed to changes in the discharge characteristics, were correlated with the electrical properties of the intermetallic systems (Ti-Al and Ti-Cu). For the same Me exposed areas placed on the Ti target (ranging from 0.25 cm2 to 20 cm2) the Cu content increased from 3.5 at.% to 71.7 at.% in the Ti-Cu system and the Al content, in Ti-Al films, ranged from 11 to 45 at.%. The structural characterization evidenced the formation of metastable Ti-Me intermetallic phases for Al/Ti atomic ratios above 0.20 and for Cu/Ti ratios above 0.25. For lower Me concentrations, the effect of the α-Ti(Me) structure domains the overall structure. With the increase amount of the Me into Ti structure a clear trend for amorphization was observed. For both systems it was observed a significant decrease of the electrical resistivity with increasing Me/Ti atomic ratios (higher than 0.5 for Al/Ti atomic ratio and higher than 1.3 for Cu/Ti atomic ratio). Although similar trends were observed in the resistivity evolution for both systems, the Ti-Cu films presented lower resistivity values in comparison to Ti-Al system.

Simulação numérica do comportamento ao impacto de componentes metálicos para aplicações de crashworthiness utilizando iniciadores de deformação configuráveis

Dissertação de mestrado integrado em Engenharia Mecânica

Processamento e caracterização de compósitos de Ti-HAP para aplicações biomédicas

Dissertação de mestrado integrado em Engenharia de Materiais

Ultrasound enhances lipase-catalyzed synthesis of poly (ethylene glutarate)

The present work explores the best conditions for the enzymatic synthesis of poly (ethylene glutarate) for the first time. The start-up materials are the liquids; diethyl glutarate and ethylene glycol diacetate, without the need of addition of extra solvent. The reactions are catalyzed by lipase B from Candida antarctica immobilized on glycidyl methacrylate-ter-divinylbenzene-ter-ethylene glycol dimethacrylate at 40 °C during 18 h in water bath with mechanical stirring or 1 h in ultrasonic bath followed by 6 h in vacuum in both the cases for evaporation of ethyl acetate. The application of ultrasound significantly intensified the polyesterification reaction with reduction of the processing time from 24 to 7 h. The same degree of polymerization was obtained for the same enzyme loading in less time of reaction when using the ultrasound treatment. The degree of polymerization for long-term polyesterification was improved approximately 8-fold due to the presence of sonication during the reaction. The highest degree of polymerization achieved was 31, with a monomer conversion of 96.77%. The ultrasound treatment demonstrated to be an effective green approach to intensify the polyesterification reaction with enhanced initial kinetics and high degree of polymerization.

Flexible thin-film lithium battery

Tese de Doutoramento Programa Doutoral em Engenharia Electrónica e Computadores.

Bio-detoxification of mycotoxins by lactic acid bacteria from different food matrices

Lactic acid bacteria (LAB) play a key role in the biopreservation of a wide range of fermented food products, such as yogurt, cheese, fermented milks, meat, fish, vegetables (sauerkraut, olives and pickles), certain beer brands, wines and silage, allowing their safe consumption, which gave to these bacteria a GRAS (Generally Recognised as Safe) status. Besides that, the use of LAB in food and feed is a promising strategy to reduce the exposure to dietary mycotoxins, improving their shelf life and reducing health risks, given the unique mycotoxin decontaminating characteristic of some LAB. Mycotoxins present carcinogenic, mutagenic, teratogenic, neurotoxic and immunosuppressive effects over animals and Humans, being the most important ochratoxin A (OTA), aflatoxins (AFB1), trichothecenes, zearalenone (ZEA), fumonisin (FUM) and patulin. In a previous work of our group it was observed OTA biodegradation by some strains of Pediococcus parvulus isolated from Douro wines. So, the aim of this study was to enlarge the screening of the biodetoxification over more mycotoxins besides OTA, including AFB1, and ZEA. This ability was checked in a collection of LAB isolated from vegetable (wine, olives, fruits and silage) and animal (milk and dairy products, sausages) sources. All LAB strains were characterized phenotypically (Gram, catalase) and genotypically. Molecular characterisation of all LAB strains was performed using genomic fingerprinting by MSP- PCR with (GTG)5 and csM13 primers. The identification of the isolates was confirmed by 16S rDNA sequencing. To study the ability of LAB strains to degrade OTA, AFB1 and ZEA, a MRS broth medium was supplemented with 2.0 g/mL of each mycotoxin. For each strain, 2 mL of MRS supplemented with the mycotoxins was inoculated in triplicate with 109 CFU/mL. The culture media and bacterial cells were extracted by the addition of an equal volume of acetonitrile/methanol/acetic acid (78:20:2 v/v/v) to the culture tubes. A 2 mL sample was then collected and filtered into a clean 2 mL vial using PP filters with 0.45 m pores. The samples were preserved at 4 °C until HPLC analysis. Among LAB tested, 10 strains isolated from milk were able to eliminate AFB1, belonging to Lactobacillus casei (7), Lb. paracasei (1), Lb. plantarum (1) and 1 to Leuconostoc mesenteroides. Two strains of Enterococcus faecium and one of Ec. faecalis from sausage eliminated ZEA. Concerning to strains of vegetal origin, one Lb. plantarum isolated from elderberry fruit, one Lb. buchnerii and one Lb. parafarraginis both isolated from silage eliminated ZEA. Other 2 strains of Lb. plantarum from silage were able to degrade both ZEA and OTA, and 1 Lb. buchnerii showed activity over AFB1. These enzymatic activities were also verified genotypically through specific gene PCR and posteriorly confirmed by sequencing analysis. In conclusion, due the ability of some strains of LAB isolated from different sources to eliminate OTA, AFB1 and ZEA one can recognize their potential biotechnological application to reduce the health hazards associated with these mycotoxins. They may be suitable as silage inoculants or as feed additives or even in food industry.