443 resultados para Tailoring.


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In the field of organic thin films, manipulation at the nanoscale can be obtained by immobilization of different materials on platforms designed to enhance a specific property via the layer-by-layer technique. In this paper we describe the fabrication of nanostructured films containing cobalt tetrasulfonated phthalocyanine (CoTsPc) obtained through the layer-by-layer architecture and assembled with linear poly(allylamine hydrochloride) (PAH) and poly(amidoamine) dendrimer (PAMAM) polyelectrolytes. Film growth was monitored by UV-vis spectroscopy following the Q band of CoTsPc and revealed a linear growth for both systems. Fourier transform infrared (FTIR) spectroscopy showed that the driving force keeping the structure of the films was achieved upon interactions of CoTsPc sulfonic groups with protonated amine groups present in the positive polyelectrolyte. A comprehensive SPR investigation on film growth reproduced the deposition process dynamically and provided an estimation of the thicknesses of the layers. Both FTIR and SPR techniques suggested a preferential orientation of the Pc ring parallel to the substrate. The electrical conductivity of the PAH films deposited on interdigitated electrodes was found to be very sensitive to water vapor. These results point to the development of a phthalocyanine-based humidity sensor obtained from a simple thin film deposition technique, whose ability to tailor molecular organization was crucial to achieve high sensitivity.

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Spark Plasma Sintering (SPS) is a promising rapid consolidation technique that allows a better understanding and manipulating of sintering kinetics and therefore makes it possible to obtain Si3N4-based ceramics with tailored microstructures, consisting of grains with either equiaxed or elongated morphology. The presence of an extra liquid phase is necessary for forming tough interlocking microstructures in Yb/Y-stabilised α-sialon by HP. The liquid is introduced by a new method, namely by increasing the O/N ratio in the general formula RExSi12-(3x+n)Al3x+nOnN16-n while keeping the cation ratios of RE, Si and Al constant. Monophasic α-sialon ceramics with tailored microstructures, consisting of either fine equiaxed or elongated grains, have been obtained by using SPS, whether or not such an extra liquid phase is involved. The three processes, namely densification, phase transformation and grain growth, which usually occur simultaneously during conventional HP consolidation of Si3N4-based ceramics, have been precisely followed and separately investigated in the SPS process. The enhanced densification is attributed to the non-equilibrium nature of the liquid phase formed during heating. The dominating mechanism during densification is the enhanced grain boundary sliding accompanied by diffusion- and/or reaction-controlled processes. The rapid grain growth is ascribed to a dynamic ripening mechanism based on the formation of a liquid phase that is grossly out of equilibrium, which in turn generates an extra chemical driving force for mass transfer. Monophasic α-sialon ceramics with interlocking microstructures exhibit improved damage tolerance. Y/Yb- stabilised monophasic α-sialon ceramics containing approximately 3 vol% liquid with refined interlocking microstructures have excellent thermal-shock resistance, comparable to the best β-sialon ceramics with 20 vol% additional liquid phase prepared by HP. The obtained sialon ceramics with fine-grained microstructure show formidably improved superplasticity in the presence of an electric field. The compressive strain rate reaches the order of 10-2 s-1 at temperatures above 1500oC, that is, two orders of magnitude higher than that has been realised so far by any other conventional approaches. The high deformation rate recorded in this work opens up possibilities for making ceramic components with complex shapes through super-plastic forming.

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I test di qualifica a vibrazioni vengono usati in fase di progettazione di un componente per verificarne la resistenza meccanica alle sollecitazioni dinamiche (di natura vibratoria) applicate durante la sua vita utile. La durata delle vibrazioni applicate al componente durante la sua vita utile (migliaia di ore) deve essere ridotta al fine di realizzare test fattibili in laboratorio, condotti in genere utilizzando uno shaker elettrodinamico. L’idea è quella di aumentare l’intensità delle vibrazioni riducendone la durata. Esistono diverse procedure di Test Tailoring che tramite un metodo di sintesi definiscono un profilo vibratorio da applicare in laboratorio a partire dalle reali vibrazioni applicate al componente: una delle metodologie più comuni si basa sull’equivalenza del danno a fatica prodotto dalle reali vibrazioni e dalle vibrazioni sintetizzate. Questo approccio è piuttosto diffuso tuttavia all’autore non risulta presente nessun riferimento in letteratura che ne certifichi la validità tramite evidenza sperimentalmente. L’obiettivo dell’attività di ricerca è stato di verificare la validità del metodo tramite una campagna sperimentale condotta su opportuni provini. Il metodo viene inizialmente usato per sintetizzare un profilo vibratorio (random stazionario) avente la stessa durata di un profilo vibratorio non stazionario acquisito in condizioni reali. Il danno a fatica prodotto dalla vibrazione sintetizzata è stato confrontato con quello della vibrazione reale in termini di tempo di rottura dei provini. I risultati mostrano che il danno prodotto dalla vibrazione sintetizzata è sovrastimato, quindi l’equivalenza non è rispettata. Sono stati individuati alcuni punti critici e sono state proposte alcune modifiche al metodo per rendere la teoria più robusta. Il metodo è stato verificato con altri test e i risultati confermano la validità del metodo a condizione che i punti critici individuati siano correttamente analizzati.

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Self-assembled molecular structures were investigated on insulating substrate surfaces using non-contact atomic force microscopy. Both, substrate preparation and molecule deposition, took place under ultra-high vacuum conditions. First, C60 molecules were investigated on the TiO2 (110) surface. This surface exhibits parallel running troughs at the nanometer scale, which strongly steer the assembly of the molecules. This is in contrast to the second investigated surface. The CaF2 (111) surface is atomically flat and the molecular assemblyrnwas observed to be far less affected by the surface. Basically different island structures were observed to what is typically know. Based on extensive experimental studies and theoretical considerations, a comprehensive picture of the processes responsible for the island formation of C60 molecules on this insulating surfaces was developed. The key process for the emergence of the observed novel island structures was made out to be the dewetting of molecules from the substrate. This new knowledge allows to further understand andrnexploit self-assembly techniques in structure fabrication on insulating substrate surfaces. To alter island formation and island structure, C60 molecules were codeposited with second molecule species (PTCDI and SubPc) on the CaF2 (111) surface. Depending on the order of deposition, quiet different structures were observed to arise. Thus, these are the first steps towards more complex functional arrangements consisting of two molecule species on insulating surfaces.

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In der vorliegenden Arbeit wurden Struktur-Eigenschaftsbeziehungen des konjugierten Modell-Polymers MEH-PPV untersucht. Dazu wurde Fällungs-fraktionierung eingesetzt, um MEH-PPV mit unterschiedlichem Molekulargewicht (Mw) zu erhalten, insbesondere MEH-PPV mit niedrigem Mw, da dieses für optische Wellenleiterbauelemente optimal geeignet ist Wir konnten feststellen, dass die Präparation einer ausreichenden Menge von MEH-PPV mit niedrigem Mw und geringer Mw-Verteilung wesentlich von der geeigneten Wahl des Lösungsmittels und der Temperatur während der Zugabe des Fällungsmittels abhängt. Alternativ dazu wurden UV-induzierte Kettenspaltungseffekte untersucht. Wir folgern aus dem Vergleich beider Vorgehensweisen, dass die Fällungsfraktionierung verglichen mit der UV-Behandlung besser geeignet ist zur Herstellung von MEH-PPV mit spezifischem Mw, da das UV-Licht Kettendefekte längs des Polymerrückgrats erzeugt. 1H NMR and FTIR Spektroskopie wurden zur Untersuchung dieser Kettendefekte herangezogen. Wir konnten außerdem beobachten, dass die Wellenlängen der Absorptionsmaxima der MEH-PPV Fraktionen mit der Kettenlänge zunehmen bis die Zahl der Wiederholeinheiten n  110 erreicht ist. Dieser Wert ist signifikant größer als früher berichtet. rnOptische Eigenschaften von MEH-PPV Wellenleitern wurden untersucht und es konnte gezeigt werden, dass sich die optischen Konstanten ausgezeichnet reproduzieren lassen. Wir haben die Einflüsse der Lösungsmittel und Temperatur beim Spincoaten auf Schichtdicke, Oberflächenrauigkeit, Brechungsindex, Doppelbrechung und Wellenleiter-Dämpfungsverlust untersucht. Wir fanden, dass mit der Erhöhung der Siedetemperatur der Lösungsmittel die Schichtdicke und die Rauigkeit kleiner werden, während Brechungsindex, Doppelbrechung sowie Wellenleiter-Dämpfungsverluste zunahmen. Wir schließen daraus, dass hohe Siedetemperaturen der Lösungsmittel niedrige Verdampfungsraten erzeugen, was die Aggregatbildung während des Spincoatings begünstigt. Hingegen bewirkt eine erhöhte Temperatur während der Schichtpräparation eine Erhöhung von Schichtdicke und Rauhigkeit. Jedoch nehmen Brechungsindex und der Doppelbrechung dabei ab.rn Für die Schichtpräparation auf Glassubstraten und Quarzglas-Fasern kam das Dip-Coating Verfahren zum Einsatz. Die Schichtdicke der Filme hängt ab von Konzentration der Lösung, Transfergeschwindigkeit und Immersionszeit. Mit Tauchbeschichtung haben wir Schichten von MEH-PPV auf Flaschen-Mikroresonatoren aufgebracht zur Untersuchung von rein-optischen Schaltprozessen. Dieses Verfahren erweist sich insbesondere für MEH-PPV mit niedrigem Mw als vielversprechend für die rein-optische Signalverarbeitung mit großer Bandbreite.rn Zusätzlich wurde auch die Morphologie dünner Schichten aus anderen PPV-Derivaten mit Hilfe von FTIR Spektroskopie untersucht. Wir konnten herausfinden, dass der Alkyl-Substitutionsgrad einen starken Einfluss auf die mittlere Orientierung der Polymerrückgrate in dünnen Filmen hat.rn

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The functionalization of substrates through the application of nanostructured coatings allows to create new materials, with enhanced properties. In this work, the development of self-cleaning and antibacterial textiles, through the application of TiO2 and Ag based nanostructured coatings was carried out. The production of TiO2 and Ag functionalized materials was achieved both by the classical dip-padding-curing method and by the innovative electrospinning process to obtain nanofibers doped with nano-TiO2 and nano-Ag. In order to optimize the production of functionalized textiles, the study focused on the comprehension of mechanisms involved in the photocatalytic and antibacterial processes and on the real applicability of the products. In particular, a deep investigation on the relationship between nanosol physicochemical characteristics, nanocoating properties and their performances was accomplished. Self-cleaning textiles with optimized properties were obtained by properly purifying and applying commercial TiO2 nanosol while the studies on the photocatalytic mechanism operating in self-cleaning application demonstrated the strong influence of hydrophilic properties and of interaction surface/radicals on final performance. Moreover, a study about the safety in handling of nano-TiO2 was carried out and risk remediation strategies, based on “safety by design” approach, were developed. In particular, the coating of TiO2 nanoparticles by a SiO2 shell was demonstrated to be the best risk remediation strategy in term of biological response and preserving of photoreactivity. The obtained results were confirmed determining the reactive oxygen species production by a multiple approach. Antibacterial textiles for biotechnological applications were also studied and Ag-coated cotton materials, with significant anti-bacterial properties, were produced. Finally, composite nanofibers were obtained merging biopolymer processing and sol-gel techniques. Indeed, electrospun nanofibers embedded with TiO2 and Ag NPs, starting from aqueous keratin based formulation were produced and the photocatalytic and antibacterial properties were assessed. The results confirmed the capability of electrospun keratin nanofibers matrix to preserve nanoparticle properties.

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Organic molecular semiconductors are subject of intense research for their crucial role as key components of new generation low cost, flexible, and large area electronic devices such as displays, thin-film transistors, solar cells, sensors and logic circuits. In particular, small molecular thienoimide (TI) based materials are emerging as novel multifunctional materials combining a good processability together to ambipolar or n-type charge transport and electroluminescence at the solid state, thus enabling the fabrication of integrated devices like organic field effect transistors (OFETs) and light emitting transistor (OLETs). Given this peculiar combination of characteristics, they also constitute the ideal substrates for fundamental studies on the structure-property relationships in multifunctional molecular systems. In this scenario, this thesis work is focused on the synthesis of new thienoimide based materials with tunable optical, packing, morphology, charge transport and electroluminescence properties by following a fine molecular tailoring, thus optimizing their performances in device as well as investigating and enabling new applications. Investigation on their structure-property relationships has been carried out and in particular, the effect of different π-conjugated cores (heterocycles, length) and alkyl end chain (shape, length) changes have been studied, obtaining materials with enhanced electron transport capability end electroluminescence suitable for the realization of OFETs and single layer OLETs. Moreover, control on the polymorphic behaviour characterizing thienoimide materials has been reached by synthetic and post-synthetic methodologies, developing multifunctional materials from a single polymorphic compound. Finally, with the aim of synthesizing highly pure materials, simplifying the purification steps and avoiding organometallic residues, procedures based on direct arylation reactions replacing conventional cross-couplings have been investigated and applied to different classes of molecules, bearing thienoimidic core or ends, as well as thiophene and anthracene derivatives, validating this approach as a clean alternative for the synthesis of several molecular materials.

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High-performance thermoplastics including polyetheretherketone (PEEK) are key biomaterials for load-bearing implants. Plasma treatment of implants surfaces has been shown to chemically activate its surface, which is a prerequisite to achieve proper cell attachment. Oxygen plasma treatment of PEEK films results in very reproducible surface nanostructures and has been reported in the literature. Our goal is to apply the plasma treatment to another promising polymer, polyetherketoneketone (PEKK), and compare its characteristics to the ones of PEEK. Oxygen plasma treatments of plasma powers between 25 and 150 W were applied on 60 μm-thick PEKK and 100 μm-thick PEEK films. Analysis of the nanostructures by atomic force microscopy showed that the roughness increased and island density decreased with plasma power for both PEKK and PEEK films correlating with contact angle values without affecting bulk properties of the used films. Thermal analysis of the plasma-treated films shows that the plasma treatment does not change the bulk properties of the PEKK and PEEK films.

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Software Product Line Engineering (SPLE) is becoming widely used due to the improvement it means when developing software products of the same family. However, SPLE demands long-term investment on a product-line platform that might not be profitable due to rapid changing business settings. Since Agile Software Development (ASD) approaches are being successfully applied in volatile markets, several companies have suggested the idea of integrating SPLE and ASD when a family product has to be developed. Agile Product Line Engineering (APLE) advocates the integration of SPLE and ASD to address their lacks when they are individually applied to software development. A previous literature re-view of experiences and practices on APLE revealed important challenges about how to fully put APLE into practice. Our contribution address several of these challenges by tailoring the agile method Scrum by means of three concepts that we have defined: plastic partial components, working PL-architectures, and reactive reuse.

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Irradiation with swift heavy ions (SHI), roughly defined as those having atomic masses larger than 15 and energies exceeding 1 MeV/amu, may lead to significant modification of the irradiated material in a nanometric region around the (straight) ion trajectory (i.e., latent tracks). In the case of amorphous silica it has been reported that SHI irradiation originates nano-tracks of either higher density than the virgin material (for low electronic stopping powers, Se < 7 keV/nm) [1] or having a low-density core and a dense shell (Se > 12 keV/nm) [2]. The intermediate region has not been studied in detail but we will show in this work that essentially no changes in density occur in this zone. An interesting effect of the compaction is that the refractive index is increased with respect to that of the surroundings. In the first Se region it is clear that track overlapping leads to continuous amorphous layers that present a significant contrast with respect to the pristine substrate and this has been used to produce optical waveguides. The optical effects of intermediate and high stopping powers, on the other hand, are largely unknown so far. In this work we have studied theoretically (molecular dynamics and optical simulations) and experimentally (irradiation with SHI and optical characterization) the dependence of the macroscopic optical properties (i.e., the refractive index of the effective medium, n_EMA) on the electronic stopping power of the incoming ions. Our results show that the refractive index of the irradiated silica is not increased in the intermediate region, as expected; however, the core-shell tracks of the high-Se region produce a quite effective enhancement of n_EMA that could prove attractive for the fabrication of optical waveguides at ultralow fluences (as low as 1E11 cm^-2). 1. J. Manzano, J. Olivares, F. Agulló-López, M. L. Crespillo, A. Moroño, and E. Hodgson, "Optical waveguides obtained by swift-ion irradiation on silica (a-SiO2)," Nucl. Instrum. Meth. B 268, 3147-3150 (2010). 2. P. Kluth, C. S. Schnohr, O. H. Pakarinen, F. Djurabekova, D. J. Sprouster, R. Giulian, M. C. Ridgway, A. P. Byrne, C. Trautmann, D. J. Cookson, K. Nordlund, and M. Toulemonde, "Fine structure in swift heavy ion tracks in amorphous SiO2," Phys. Rev. Lett. 101, 175503 (2008).

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We report the magnetic anisotropy and domain configuration of cosputtered TbFeGa alloys. The layers were deposited from two targets with compositions TbFe2 and Fe3Ga, respectively. The structural and magnetic properties do not only depend on the composition but also on the growth conditions. Alloys with the same composition but deposited using a DC or a pulsed power source in the TbFe2 target exhibit a different magnetic anisotropy. The perpendicular magnetic anisotropy, the size and topology of domain patterns can be tailored by changing the evaporation parameters of TbFe2. The width of the stripe domain increases from 235 to 835 nm when using the DC source in the TbFe2. We correlate this effect with Tb enrichment of the TbxFe1−x phases present in the samples.

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One option to optimize carbon materials for supercapacitor applications is the generation of surface functional groups that contribute to the pseudocapacitance without losing the designed physical properties. This requires suitable functionalization techniques able to selectively introduce a given amount of electroactive oxygen groups. In this work, the influence of the chemical and electrochemical oxidation methods, on the chemical and physical properties of a zeolite templated carbon (ZTC), as a model carbon material, have been studied and compared. Although both oxidation methods generally produce a loss of the original ZTC physical properties with increasing amount of oxidation, the electrochemical method shows much better controllability and, unlike chemical treatments, enables the generation of a large number of oxygen groups (O = 11000- 3300 μmol/g), with a higher proportion of active functionalities, while retaining a high surface area (ranging between 1900-3500 m2/g), a high microporosity and an ordered 3-D structure.