995 resultados para material sciences


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A previous study on the characterization of effective material properties of a d(15) thickness-shear piezoelectric Macro-Fibre Composite (MFC) made of seven layers (Kapton, Acrylic, Electrode, Piezoceramic Fibre and Epoxy Composite, Electrode, Acrylic, Kapton) using a finite element homogenization method has shown that the packaging reduces significantly the shear stiffness of the piezoceramic material and, thus, leads to significantly smaller effective electromechanical coupling coefficient k(15) and piezoelectric stress constant e(15) when compared to the piezoceramic fibre properties. Therefore, the main objective of this work is to perform a parametric analysis in which the effect of the variations of fibre volume fraction, Epoxy elastic modulus, electrode thickness and active layer thickness on the MFC effective material properties is evaluated. Results indicate that an effective d(15) MFC should use relatively thick fibres having relatively high shear modulus and relatively stiff epoxy filler. On the other hand, the electrode thickness does not affect significantly the MFC performance.

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A previous study on the characterization of effective material properties of a d15 thickness-shear piezoelectric Macro-Fibre Composite (MFC) made of seven layers (Kapton, Acrylic, Electrode, Piezoceramic Fibre and Epoxy Composite, Electrode, Acrylic, Kapton) using a finite element homogenization method has shown that the packaging reduces significantly the shear stiffness of the piezoceramic material and, thus, leads to significantly smaller effective electromechanical coupling coefficient k15 and piezoelectric stress constant e15 when compared to the piezoceramic fibre properties. Therefore, the main objective of this work is to perform a parametric analysis in which the effect of the variations of fibre volume fraction, Epoxy elastic modulus, electrode thickness and active layer thickness on the MFC effective material properties is evaluated. Results indicate that an effective d15 MFC should use relatively thick fibres having relatively high shear modulus and relatively stiff epoxy filler. On the other hand, the electrode thickness does not affect significantly the MFC performance.

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Die Isotopenzusammensetzungen des Pitcairn Hotspot (Südpazifik), des Mauna Kea (Hawaii) und der Insel Rurutu (Französisch Polynesien) wurden bestimmt, um Heterogenitäten im Erdmantel zu charakterisieren. Die Bleiisotopenzusammensetzung wurde mit einer Dreiisotopenspiketechnik zur Korrektur der instrumentellen Massenfraktionierung gemessen. An Proben von Pitcairn wurde zusätzlich die Os, Hf, Nd, Sr Isotopenzusammensetzung, sowie die Haupt- und Spurenelementzusammensetzung bestimmt. Die Isotopensignatur des Pitcairn Hotspots kann durch eine Sedimentkomponente in der Magmenquelle erklärt werden. Die Bleiisotopenschwankungen des Mauna Kea in der HSDP-2 Bohrung treten als Oszillationen auf, die sich zu linearen Anordnungen im Bleiisotopenraum zusammensetzen. Das begrenzte zeitliche Auftreten einer linearen Anordnung zeigt, daß die Heterogenitäten mehrere zehner Kilometer Länge im aufsteigenden Mantelmaterial unter dem Vulkan einnehmen. Auch die Bleiisotopenzusammensetzungen der Rurutu-laven zeigen lineare Anordnungen.Diese lineare Anordnungen im Bleiisotopenraum können durch eine vorwiegend binäre Mischung erklärt werden. Ein Bleiisotopenentwicklungsmodell unterstützt, daß die Differenzierung der Ausgangsmaterialien vor weniger als etwa zwei Milliarden Jahren geschah und für Mauna Kea relativ jung sein könnte. Keine der Hotspots weisen identische Mischungsendglieder auf, so daß die Heterogenitäten kleinräumige Merkmale im Erdmantel sind.

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Regenerative medicine claims for a better understanding of the cause-effect relation between cell behaviour and environment signals. The latter encompasses topographical, chemical and mechanical stimuli, electromagnetic fields, gradients of chemo-attractants and haptotaxis. In this perspective, a spatial control of the structures composing the environment is required. In this thesis I describe a novel approach for the multiscale patterning of biocompatible functional materials in order to provide systems able to accurately control cell adhesion and proliferation. The behaviour of different neural cell lines in response to several stimuli, specifically chemical, topographical and electrical gradients is presented. For each of the three kind of signals, I chose properly tailored materials and fabrication and characterization techniques. After a brief introduction on the state of art of nanotechnology, nanofabrication techniques and regenerative medicine in Chapter 1 and a detailed description of the main fabrication and characterization techniques employed in this work in Chapter 2, in Chapter 3 an easy route to obtain accurate control over cell proliferation close to 100% is described (chemical control). In Chapter 4 (topographical control) it is shown how the multiscale patterning of a well-established biocompatible material as titanium dioxide provides a versatile and robust method to study the effect of local topography on cell adhesion and growth. The third signal, viz. electric field, is investigated in Chapter 5 (electrical control), where the very early stages of neural cell adhesion are studied in the presence of modest steady electric fields. In Chapter 6 (appendix) a new patterning technique, called Lithographically Controlled Etching (LCE), is proposed. It is shown how LCE can provide at the same time the micro/nanostructuring and functionalization of a surface with nanosized objects, thus being suitable for applications both in regenerative medicine in biosensing.

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Within this PhD thesis several methods were developed and validated which can find applicationare suitable for environmental sample and material science and should be applicable for monitoring of particular radionuclides and the analysis of the chemical composition of construction materials in the frame of ESS project. The study demonstrated that ICP-MS is a powerful analytical technique for ultrasensitive determination of 129I, 90Sr and lanthanides in both artificial and environmental samples such as water and soil. In particular ICP-MS with collision cell allows measuring extremely low isotope ratios of iodine. It was demonstrated that isotope ratios of 129I/127I as low as 10-7 can be measured with an accuracy and precision suitable for distinguishing sample origins. ICP-MS with collision cell, in particular in combination with cool plasma conditions, reduces the influence of isobaric interferences on m/z = 90 and is therefore well-suited for 90Sr analysis in water samples. However, the applied ICP-CC-QMS in this work is limited for the measurement of 90Sr due to the tailing of 88Sr+ and in particular Daly detector noise. Hyphenation of capillary electrophoresis with ICP-MS was shown to resolve atomic ions of all lanthanides and polyatomic interferences. The elimination of polyatomic and isobaric ICP-MS interferences was accomplished without compromising the sensitivity by the use of a high resolution mode as available on ICP-SFMS. Combination of laser ablation with ICP-MS allowed direct micro and local uranium isotope ratio measurements at the ultratrace concentrations on the surface of biological samples. In particular, the application of a cooled laser ablation chamber improves the precision and accuracy of uranium isotopic ratios measurements in comparison to the non-cooled laser ablation chamber by up to one order of magnitude. In order to reduce the quantification problem, a mono gas on-line solution-based calibration was built based on the insertion of a microflow nebulizer DS-5 directly into the laser ablation chamber. A micro local method to determine the lateral element distribution on NiCrAlY-based alloy and coating after oxidation in air was tested and validated. Calibration procedures involving external calibration, quantification by relative sensitivity coefficients (RSCs) and solution-based calibration were investigated. The analytical method was validated by comparison of the LA-ICP-MS results with data acquired by EDX.

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In der vorliegenden Arbeit werden Experimente beschrieben, die zu einem vertieften Verständnis fundamentaler Prozesse bei der elektrochemischen Herstellung von Dünnschichten, sog. Targets, für kernphysikalische und -chemische Studien führten. Targets wurden mittels 'Molecular Plating' (MP) hergestellt, indem eine Elektrodeposition aus organischem Medium in der Regel bei konstantem Strom in Zwei-Elektroden-Zellen. Die Resultate erlaubten, optimierte Herstellungs-bedingungen zu ermitteln, welche die Produktion deutlich verbesserter Targets erlaubten. MP bei konstantem Strom ist ein massentransportkontrollierter Prozess. Der angelegte Strom wird durch einen konstanten Fluss elektroaktiver Spezies zur Kathode – auf der die Schicht wächst – und Anode aufrechterhalten. Die Untersuchungen zeigten, dass das Zellenpotential des Elektrodepositionsystems immer durch den Ohm'schen Spannungsabfall auf Grund des Widerstandes der verwendeten Lösung dominiert wurde. Dies erlaubte die Herleitung einer Beziehung zwischen dem Zellenpotential und der Konzentration der elektroaktiven Spezies. Die Beziehung erlaubt die Erklärung des gemessenen zeitlichen Verlaufs des Zellenpotentials während der Abscheidung als Funktion der Elektrolytkonzentration. Dies dient als Basis, auf der nun ein umfassenderes Bild der Prozesse, die für die charakteristischen Minima im Potentialverlauf einer Abscheidung verantwortlich sind, gewonnen werden kann. Es konnte gezeigt werden, dass die Minima mit der fast vollständigen Entfernung (durch Abscheidung) der aus einem gelösten Salz erzeugten Nd-Ionen korrespondieren. Die abgeschiedene Spezies wurde als Nd3+ identifiziert, vermutlich als Carboxylat, Oxid oder Hydroxid, was auf Grund der hohen negative Werte des Standardredoxpotentials der Lanthanide verständlich erscheint. Von den vorliegenden elektroaktiven Spezies tragen die Nd3+ Ionen nur zu knapp 20% zum Gesamtstrom bei. Durch Elektrolyse tragen auch die Lösungsmittelkomponenten zu diese Strom bei. Die Gegenwart von elektrolysiertem Lösungsmittel wurde in Analysen der Dünnschichten bestätigt. Diese waren immer mit chemi- und physisorbierten Lösungsmittelmolekülen bedeckt. Die Analyse der Dünnschichten zeigte, dass die Oberflächen von einem furchenartiges Netz durchzogen waren, und dass diese während des Trocknen der Schichten nach dem MP entstanden. Ob die Schichten an Luft oder in inerter Atmosphäre trockneten, hatte keinen Einfluss. Es wurden Experimente mit mehreren Lösungsmitteln durchgeführt, die sich deutlich in ihren physikalischen Eigenschaften, v.a. dem Siedepunkt, unterschieden. Furchenfreie Dünnschichten konnten insbesondere bei MP in N,N-dimethylformamide (DMF) erzeugt werden. Die Verwendung von DMF in Kombination mit einer Abscheidung auf sehr glatten Substraten erlaubte die Produktion von sehr homogenen, glatten und defektfreien Schichten. Diese waren vermutlich geringeren inneren Spannungen während des Trocknens ausgesetzt, als Schichten auf raueren Substraten oder solche, die aus flüchtigeren Lösungsmitteln hergestellt wurden. Die Oberflächenrauigkeit des Substrats und das gewählte Lösungsmittel wurden so als Schlüsselfaktoren für die Produktion hochqualitativer Schichten identifiziert. Es konnte gezeigt werden, dass mit MP eine sehr effiziente Methode zur Herstellung homogener Schichten mit exzellenter Ausbeute ist. In weiteren Experimenten mit dem primordialen Alpha-Emitter 147Sm als Modellisotop wurde die Eignung solcher Schichten als Alpha-Quelle untersucht. Sowohl die Energieauflösung als auch der Anteil der Alpha-Teilchen, die den Detektor erreichten, waren von den Quelleneigenschaften abhängig. Die Effekte wurden verschiedenen Variablen der Dünnschicht zugeordnet, welche die Alpha-Spektren beeinflussten. Dominant war die Wahl des Lösungsmittels und die Rauigkeit des Substrats. Dies beeinflusste Schichtdicke und -morphologie sowie die Art des Schichtwachstums und veränderte die Detektionseffizienz in Alpha-Messungen bis zu 15%. Nur homogene, ebene Schichten, die aus DMF auf glatten Substraten abgeschieden wurden, eignen sich optimal als Alpha-Quelle. Die gewonnenen Ergebnisse erlauben die optimierte Herstellung nuklearer Targets durch MP. Künftige Anwendungen beinhalten insbesondere die Herstellung von Targets für neutroneninduzierte Spaltexperimente und untergrundarmeAlpha-Messungen sehr kleiner Aktivitäten.

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The complementary Watson-Crick base-pairs, A:T and G:C, have long been recognized as pivotal to both the stability of the DNA double helix and replication/transcription. Recently, the replacement of the Watson-Crick base-pairs with other molecular entities has received considerable attention. In this tutorial review we highlight different approaches used to replace natural base-pairs and equip them with novel function. We also discuss the advantages that non-natural base-pairs convey with respect to practical applications.

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Dichelobacter nodosus, the etiological agent of ovine footrot, exists both as virulent and as benign strains, which differ in virulence mainly due to subtle differences in the three subtilisin-like proteases AprV2, AprV5 and BprV found in virulent, and AprB2, AprB5 and BprB in benign strains of D. nodosus. Our objective was a molecular genetic epidemiological analysis of the genes of these proteases by direct sequence analysis from clinical material of sheep from herds with and without history of footrot from 4 different European countries. The data reveal the two proteases known as virulent AprV2 and benign AprB2 to correlate fully to the clinical status of the individuals or the footrot history of the herd. In samples taken from affected herds, the aprV2 gene was found as a single allele whereas in samples from unaffected herds several alleles with minor modifications of the aprB2 gene were detected. The different alleles of aprB2 were related to the herds. The aprV5 and aprB5 genes were found in the form of several alleles scattered without distinction between affected and non-affected herds. However, all different alleles of aprV5 and aprB5 encode the same amino acid sequences, indicating the existence of a single protease isoenzyme 5 in both benign and virulent strains. The genes of the basic proteases BprV and BprB also exist as various alleles. However, differences found in samples from affected versus non-affected herds do not reflect the currently known epitopes that are attributed to differences in biochemical activity. The data of the study confirm the prominent role of AprV2 in the virulence of D. nodosus and shed a new light on the presence of the other protease genes and their allelic variants in clinical samples.

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Phase stability, elastic behavior, and pressure-induced structural evolution of synthetic boron-mullite Al5BO9 (a = 5.6780(7), b = 15.035(6), and c =7.698(3) Å, space group Cmc21, Z = 4) were investigated up to 25.6(1) GPa by in situ single-crystal synchrotron X-ray diffraction with a diamond anvil cell (DAC) under hydrostatic conditions. No evidence of phase transition was observed up to 21.7(1) GPa. At 25.6(1) GPa, the refined unit-cell parameters deviated significantly from the compressional trend, and the diffraction peaks appeared broader than at lower pressure. At 26.7(1) GPa, the diffraction pattern was not indexable, suggesting amorphization of the material or a phase transition to a high-pressure polymorph. Fitting the P–V data up to 21.7(1) GPa with a second-order Birch–Murnaghan Equation-of-State, we obtained a bulk modulus KT0 = 164(1) GPa. The axial compressibilities, here described as linearized bulk moduli, are as follows: KT0(a) = 244(9), KT0(b) = 120(4), and KT0(c) = 166(11) GPa (KT0(a):KT0(b):KT0(c) = 2.03:1:1.38). The structure refinements allowed a description of the main deformation mechanisms in response to the applied pressure. The stiffer crystallographic direction appears to be controlled by the infinite chains of edge-sharing octahedra running along [100], making the structure less compressible along the a-axis than along the b- and c-axis.

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Water flow and solute transport through soils are strongly influenced by the spatial arrangement of soil materials with different hydraulic and chemical properties. Knowing the specific or statistical arrangement of these materials is considered as a key toward improved predictions of solute transport. Our aim was to obtain two-dimensional material maps from photographs of exposed profiles. We developed a segmentation and classification procedure and applied it to the images of a very heterogeneous sand tank, which was used for a series of flow and transport experiments. The segmentation was based on thresholds of soil color, estimated from local median gray values, and of soil texture, estimated from local coefficients of variation of gray values. Important steps were the correction of inhomogeneous illumination and reflection, and the incorporation of prior knowledge in filters used to extract the image features and to smooth the results morphologically. We could check and confirm the success of our mapping by comparing the estimated with the designed sand distribution in the tank. The resulting material map was used later as input to model flow and transport through the sand tank. Similar segmentation procedures may be applied to any high-density raster data, including photographs or spectral scans of field profiles.

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The rate of proteolysis of amino acids was used to assess the nutritional lability of various materials making up estuarine seston in 3 Maine, USA, estuaries. Physical separations of subcellular fractions of phytoplankton cells led to higher proteolysis rate constants for the cytoplasmic fraction (>1.2 h(-1)) than for the membrane fraction (0.2 to 1 h(-1)). Whole cells, copepod fecal pellets, bottom sediments, and estuarine seston had overlapping ranges of rate constants of 0.17 to 1.3 h(-1), which were indistinguishable from one another. Protein pools in the seston of these estuaries throughout the seasons were dominated by phytoplankton production and its fresh detrital products. Inverse relationships between proteolysis rate constants for estuarine seston and the ratios of pheopigments to chlorophyll indicates that the average lability of seston decreases with the disappearance of cytoplasmic material in suspension. This kinetic approach to the quality of food resources implies the existence of different pools of digestible protein for estuarine heterotrophs with different gut residence times. Preferential enrichment of membrane components in sestonic detritus may result from the differential lability of proteins in cytoplasm versus membrane components of cells.

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An identification system for Clostridium chauvoei, using PCR amplification of the 16S rRNA gene (rrs) with specific oligonucleotide primers and subsequent restriction digestion of the amplification product is described. The specific oligonucleotide primers were designed based on the rrs gene sequences of C. chauvoei by comparing it to the DNA sequences of the rrs genes of its most closely related species Clostridium septicum and Clostridium carnis. A subsequent restriction digestion of the 960 bp amplification product was used in order to unambiguously identify C. chauvoei. The developed identification system was evaluated on clinical material during a recent outbreak of blackleg in cattle. Thereby, C. chauvoei was identified as the etiologic agent of the outbreak either directly from clinical samples of muscle, liver, spleen and kidney or from primary cultures made with this material. A comparison of the newly developed method with standard diagnostic tools for C. chauvoei showed that it has advantages over the immunofluorescence and is, therefore, a useful option to it. Moreover, the assay is a valuable tool for the phylogenetic identification of C. chauvoei which can assist to substitute the fastidious traditional identification methods and replace laboratory animal testing currently used.