Development of PVD-coated and nanostructured reactive multilayer films

This dissertation addresses nanoscale reactive multilayer films (RMFs) for the purpose of storing chemical energy as heat and supplying localized heat for joining and other industrial applications. Here, self-propagating reactions were analyzed for magnetron sputtered deposited binary Ti-Al, Zr-Al and ternary Ti-Al-Si RMF systems as a function of different Al-molar ratios, bilayer thicknesses and layer sequences. Reaction properties, namely reaction front velocity, temperature, and heat vary quantitatively over a wide range. The maximum reaction temperature of ~ 1800 °C has been achieved in ternary RMFs. This work also highlights the effects of oxidation and the unsteady propagation on the reaction properties. The scalability concept of RMFs was improved and ternary Ti/Si/Ti/Al RMFs were applied in the reactive joining. This dissertation provides new insights into multilayer modulation and opens more freedom to design ternary RMFs by controlling both, diffusion interfaces and distances. It is further shown that the development processes, simulation and experimental analysis are beneficial to design and to synthesize application tailored new RMFs.Als eine neue Klasse von energetischen Materialien speichern die reaktiven Multilagensysteme die chemische Energie. Sie setzen eine große Menge der Energie durch eine schnelle Reaktionspropagation nach einer Aktivierung in der Form von Wärme frei. Im Zusammenhang mit dem zunehmenden Potenzial in den hochmodernen Fügetechnologien und den anderen Industrieanwendungen finden solche Typen von reaktiven Mehrschichtensystemen große Aufmerksamkeit. Das hohe Interesse konzentriert sich auf die Anwendung der sehr schnellen und lokalisierten Energie Freisetzung. Die Kenntnisse über die Materialkombinationen und Morphologie spielt eine wichtige Rolle, um reaktive Mehrschichtensysteme mit entsprechenden Reaktionseigenschaften und Wärmemenge herzustellen. Im Mittelpunkt dieser Arbeit stehen daher die Entwicklung der Schichtweise abgeschiedenen reaktiven Multilagenschichten und die Charakterisierung der Reaktionseigenschaften. Die eingestellten Bereiche können wie folgt zusammengefasst werden; • Die reaktiven Multilagenschichten von binären Ti-Al, Zr-Al und ternären Ti-Al-Si Kombinationen wurden mittels Magnetronsputtern-Deposition produziert, die zu der niedrigen - Medium oder hohen Energieklasse gehören. • Die selbstverbreitenden Reaktionseigenschaften wurden in Bezug auf Wärme, Temperatur, Reaktionsgeschwindigkeit und Propagationsweisen charakterisiert. • Herstellung der großflächigen freistehenden reaktiven Folien wurde aufgezeigt. Für die Bestimmung der Reaktionswärme wurde die Standardbildungsenthalpie zu Beginn der Arbeit durch thermodynamische Simulationen mit Thermo-Calc 3.1 berechnet. Die Menge der Reaktionswärme hängt von der chemischen Zusammensetzung des Ti-Al-, Zr-Al- und Ti-Si Systems ab. Dann wurden Ti/Al, Zr/Al und Ti/Si/Ti/nAl Multilagenschichten für unterschiedliche Periodendicken, Molverhältnisse und Multischichtaufbau abgeschieden. Die Ti/nAl (n = 1-3) reaktiven Multilagenschichten wurden mit verschiedenen Al-Molverhältnissen hergestellt. Die Reaktionsgeschwindigkeit änderte sich zwischen (0.68±0.4) m/s und (2.57±0.6) m/s. Die Reaktionstemperatur änderte sich im Bereich 1215-1298 °C. Die 1Ti/3Al Schicht zeigt auch eine instationäre Reaktionspropagation mit der Kräuselungsbandbildung. Außerdem wurden der Temperaturfluss und die chemische Vermischung in nanoskalige Schichten von 1Ti/1Al Zusammensetzung (für 20 nm Periodendicke) erstmals mittels Strömung Simulation berechnet. Die Ergebnisse zeigten, dass der Temperaturfluss viel schneller als das chemische Mischen während der fortschreitenden Reaktion ist. Die 1Zr/1Al Schichten wurden mit der verschiedenen Periodendicken von 20 nm bis 55 nm untersucht. Die Reaktionsgeschwindigkeit und Reaktionstemperatur änderten sich im Bereich 0.23-1.22 m/s und 1581-1707 °C. Hier wurde auch die Oxidationsreaktion während der fortschreitenden Reaktion aufgezeigt. Zum ersten Mal wurden ternäre Multilagenschichten von Ti, Si und Al-Reaktanten für verschiedene Schichtenanordnung (Si/Ti/Al/Si und Ti/Si/Ti/nAl, n = 1- 3) abgeschieden. Hier, Reaktionseigenschaften hängten von Schichtenanordnung und Al-Molverhältnissen ab. Für den Ti/Si/Ti/Al Schicht konnte eine maximale Reaktionspropagation von (9.2±2) m/s und eine Reaktionstemperatur von (1807±30) °C bestimmt werden. Danach wurden die vorgenannten ternären Folien erstmals in einem reaktiven Fügeprozess eingesetzt. Für die Herstellung großflächiger freistehenden RMS, würde der Einfluss der Substratwerkstoffe in Hinblick auf der Ablöseverhalten nach der Beschichtung untersucht. Die Verwendung des Kupfersubstrats zeigt eine einfache und schnelle Weise, freistehende Folie zu produzieren. Diese Methode ermöglicht die Produktion von freistehenden 1Zr/1Al und 1Ti/1Si/1Ti/Al Folien mit der großen Fläche von 11 cm × 2 cm × 45 µm und 8 cm × 4 cm × 52 µm. Außerdem zeigt diese Arbeit einen verbesserten Herstellungsprozess mit der Skalierbarkeit und homogenen Mikrostrukturen von Multilagenschichten. Die Untersuchungen in dieser Arbeit zeigen, dass die Zusammensetzung und Morphologie die Reaktionseigenschaften unmittelbar beeinflussen und bieten potenzielle Möglichkeiten als eine kontrollierbare Wärmequelle auf der Basis Ti/Al-, Zr/Al- und Ti/Si/Al RMS zur Verfügung stellen. Andererseits schließt die Reaktion die Effekte der Oxidation und instationären Reaktionspropagation ein, die dabei hilfreich wären, die Reaktionskinetik zu verstehen. Die Ergebnisse in dieser Arbeit können als ein Beitrag zu einem Modell um ideale RMS in Bezug auf Reaktionseigenschaften zu entwickeln.As a new class of energetic materials, reactive multilayer systems store chemical energy. They release a large amount of energy in the form of heat by fast reaction propagation after activation. In connection with increasing potentiality in advanced joining technology and other industrial applications, such type of reactive multilayer systems pay attention. The high interests focus on the utilization of very fast and localized heat. The knowledge about material combination, morphology plays an important role to design reactive multilayer systems with an appropriate reaction propagation and heat release. Therefore, this research attributes the development of layer-by-layer-deposited planar reactive multilayer film and characterizing corresponding self-propagating reaction properties. The focused areas are summarized as follows; • Reactive multilayer films of binary Ti-Al, Zr-Al and ternary Ti-Al-Si combinations were produced by Magnetron Sputter Ion Platting process, which belong to different energy classed reactive systems. • The self-propagating exothermic reaction properties were characterized in terms of heat flow, temperature, reaction propagation velocity and propagation modes. • The fabrication concept of freestanding foils with large surface was demonstrated. In connection with the reaction heat, standard heat of formation was initially calculated by using Thermo-Calc 3.1 simulation. The amount of heat released has been influenced by the chemical compositions. Then Ti/Al, Zr/Al und Ti/Si/Ti/nAl reactive films were deposited for different bilayers, molar ratios and multilayer design. The Ti/nAl (n = 1-3) reactive films with different Al-molar ratios were investigated. The reaction speed varies between (0.68±0.4) m/s and (2.57±0.6) m/s. The maximum reaction temperature varies in the range of 1215-1298 °C. The 1Ti/3Al film exhibits unsteady propagation with ripple band formation. Moreover, temperature flow and atomic mixing were characterized by using computational fluid dynamics simulation in 1Ti/1Al reactive foil for 20 nm bilayer thickness for the first time. The results show that the temperature flow is much faster than the chemical mixing during an exothermic reaction. Zr/Al reactive films with different bilayer thicknesses of 20-55 nm were deposited. Here, reaction speed and maximum temperature were found in the range of 0.23-1.22 m/s and 1581-1707 °C, respectively. Oxidation characteristic during a self-propagating reaction was also shown. For the first time the ternary reactive films were investigated for two different multilayer design and Al- molar ratios (Si/Ti/Al/Si und Ti/Si/Ti/nAl, n = 1- 3). Reaction properties depend on chemical compositions. For Ti/Si/Ti/Al reactive film, a maximum reaction propagation of (9.2±2) m/s and temperature (1807±30) °C was estimated. Then reactive joining was attempt first time by using this ternary film. For the production of large-area freestanding RMS, the influence of the substrates with regard to the peel behavior was investigated. In that case, selection of a proper and cost effective substrate and developing synthesis methods are of great interest for large size films. The use of copper substrate shows a simple and efficient way to produce freestanding films. This work assures the production of 1Zr/1Al und 1Ti/1Si/1Ti/Al freestanding films with the size of ~ 11 cm × 2 cm × 45 µm und ~ 8 cm × 4 cm × 52 µm. Furthermore, this work shows an improved fabrication process of reactive films with scalability and uniform microstructure throughout the cross-section. Then reactive joining of steels was performed by using developed ternary reactive films. The experimental results in this work predict composition and morphology dependent reaction properties and offer the potential use of Ti/Al-, Zr/Al- and Ti/Si/Ti/Al reactive films as controllable heat source due to their wide range of reaction properties. On the other hand, the reaction propagation includes the effects of oxidation and unsteady reaction, which will help to understand the reaction kinetics. The achieved results can be used as a contribution to model an ideal reactive multilayer film in terms of reaction properties

The first structure of polarity suppression protein, Psu from enterobacteria phage P4, reveals a novel fold and a knotted dimer

Psu is a capsid decoration protein of bacteriophage P4 and acts as an antiterminator of Rho-dependent transcription termination in bacteria. So far, no structures have been reported for the Psu protein or its homologues. Here, we report the first structure of Psu solved by the Hg2+ single wavelength anomalous dispersion method, which reveals that Psu exists as a knotted homodimer and is first of its kind in nature. Each monomer of Psu attains a novel fold around a tight coiled-coil motif. CD spectroscopy and the structure of an engineered disulfide-bridged Psu derivative reveal that the protein folds reversibly and reassembles by itself into the knotted dimeric conformation without the requirement of any chaperone. This structure would help to explain the functional properties of the protein and can be used as a template to design a minimal peptide fragment that can be used as a drug against Rho-dependent transcription termination in bacteria

Measurement of the cross-section and charge asymmetry of WW bosons produced in proton-proton collisions at s=8\sqrt{s}=8 TeV with the ATLAS detector

This paper presents measurements of the $W^+ \rightarrow \mu^+\nu$ and $W^- \rightarrow \mu^-\nu$ cross-sections and the associated charge asymmetry as a function of the absolute pseudorapidity of the decay muon. The data were collected in proton--proton collisions at a centre-of-mass energy of 8 TeV with the ATLAS experiment at the LHC and correspond to a total integrated luminosity of 20.2~\mbox{fb^{-1}}. The precision of the cross-section measurements varies between 0.8% to 1.5% as a function of the pseudorapidity, excluding the 1.9% uncertainty on the integrated luminosity. The charge asymmetry is measured with an uncertainty between 0.002 and 0.003. The results are compared with predictions based on next-to-next-to-leading-order calculations with various parton distribution functions and have the sensitivity to discriminate between them.Comment: 38 pages in total, author list starting page 22, 5 figures, 4 tables, submitted to EPJC. All figures including auxiliary figures are available at https://atlas.web.cern.ch/Atlas/GROUPS/PHYSICS/PAPERS/STDM-2017-13

Search for new phenomena in final states with an energetic jet and large missing transverse momentum in pp collisions at √ s = 8 TeV with the ATLAS detector

Results of a search for new phenomena in final states with an energetic jet and large missing transverse momentum are reported. The search uses 20.3 fb−1 of √ s = 8 TeV data collected in 2012 with the ATLAS detector at the LHC. Events are required to have at least one jet with pT > 120 GeV and no leptons. Nine signal regions are considered with increasing missing transverse momentum requirements between Emiss T > 150 GeV and Emiss T > 700 GeV. Good agreement is observed between the number of events in data and Standard Model expectations. The results are translated into exclusion limits on models with either large extra spatial dimensions, pair production of weakly interacting dark matter candidates, or production of very light gravitinos in a gauge-mediated supersymmetric model. In addition, limits on the production of an invisibly decaying Higgs-like boson leading to similar topologies in the final state are presente

Search for direct stau production in events with two hadronic tau-leptons in root s=13 TeV pp collisions with the ATLAS detector

A search for the direct production of the supersymmetric partners ofτ-leptons (staus) in final stateswith two hadronically decayingτ-leptons is presented. The analysis uses a dataset of pp collisions corresponding to an integrated luminosity of139fb−1, recorded with the ATLAS detector at the LargeHadron Collider at a center-of-mass energy of 13 TeV. No significant deviation from the expected StandardModel background is observed. Limits are derived in scenarios of direct production of stau pairs with eachstau decaying into the stable lightest neutralino and oneτ-lepton in simplified models where the two staumass eigenstates are degenerate. Stau masses from 120 GeV to 390 GeV are excluded at 95% confidencelevel for a massless lightest neutralino

Search for chargino-neutralino production with mass splittings near the electroweak scale in three-lepton final states in √s=13 TeV pp collisions with the ATLAS detector

A search for supersymmetry through the pair production of electroweakinos with mass splittings near the electroweak scale and decaying via on-shell W and Z bosons is presented for a three-lepton final state. The analyzed proton-proton collision data taken at a center-of-mass energy of √s=13  TeV were collected between 2015 and 2018 by the ATLAS experiment at the Large Hadron Collider, corresponding to an integrated luminosity of 139  fb−1. A search, emulating the recursive jigsaw reconstruction technique with easily reproducible laboratory-frame variables, is performed. The two excesses observed in the 2015–2016 data recursive jigsaw analysis in the low-mass three-lepton phase space are reproduced. Results with the full data set are in agreement with the Standard Model expectations. They are interpreted to set exclusion limits at the 95% confidence level on simplified models of chargino-neutralino pair production for masses up to 345 GeV

Antioxidant and cytotoxic activities of sulfated polysaccharides from five different edible seaweeds

In recent times, there has been a growing interest in the exploration of antioxidants and global trend toward the usage of seaweeds in the food industries. The low molecular weight up to 14 kDa sulfated polysaccharides of seaweeds (Portieria hornemannii, Spyridia hypnoides, Asparagopsis taxiformis, Centroceras clavulatum and Padina pavonica) were evaluated for in vitro antioxidant activities and cytotoxic assay using HeLa cell line and also characterized by FTIR. The high yield (7.74% alga dry wt.) of sulfated polysaccharide was observed in P. hornemannii followed by S. hypnoides (0.69%), C. clavulaum (0.55%) and A. taxiformis (0.17%). In the brown seaweed P. pavonica, the sulfated polysaccharide yield was 2.07%. High amount of sulfate was recorded in the polysaccharide of A. taxiformis followed by C. clavulaum, P. pavonica, S. hypnoides and P. hornemannii as indicative for bioactivity. The FTIR spectroscopic analysis supports the sulfated polysaccharides of S. hypnoides, C. clavulatum and A. taxiformis are similar to agar polymer whereas the spectral characteristics of P. hornemannii have similarities to carrageenan. The higher DPPH activity and reducing power were recorded in the polysaccharide of brown seaweed P. pavonica than the red seaweeds as follows: DPPH activities: S. hypnoides > A. taxiformis > C. clavulatum > P. hornimanii; Reducing power: A. taxiformis > P. hornimanii > S. hypnoides > C. clavulatum. The polysaccharide fractions contain up to 14 kDa from red seaweeds P. hornemannii and S. hypnoides followed by brown seaweed P. pavonica exhibit cytotoxic activity in HeLa cancer cell line (and are similar to structural properties of carrageenan extracted from P. hornemannii). The low molecular weight agar like polymer of S. hypnoides and alginate like brown seaweed P. pavonica showing better in vitro antioxidant activities that are capable of exhibiting cytotoxicity against HeLa cell line can be taken up further in-depth investigation for nutraceutical study.University of Algarve: DL 57/2016info:eu-repo/semantics/publishedVersio