Characterization and modeling of the barrier properties in nanostructured systems

The object of the present study is the process of gas transport in nano-sized materials, i.e. systems having structural elements of the order of nanometers. The aim of this work is to advance the understanding of the gas transport mechanism in such materials, for which traditional models are not often suitable, by providing a correct interpretation of the relationship between diffusive phenomena and structural features. This result would allow the development new materials with permeation properties tailored on the specific application, especially in packaging systems. The methods used to achieve this goal were a detailed experimental characterization and different simulation methods. The experimental campaign regarded the determination of oxygen permeability and diffusivity in different sets of organic-inorganic hybrid coatings prepared via sol-gel technique. The polymeric samples coated with these hybrid layers experienced a remarkable enhancement of the barrier properties, which was explained by the strong interconnection at the nano-scale between the organic moiety and silica domains. An analogous characterization was performed on microfibrillated cellulose films, which presented remarkable barrier effect toward oxygen when it is dry, while in the presence of water the performance significantly drops. The very low value of water diffusivity at low activities is also an interesting characteristic which deals with its structural properties. Two different approaches of simulation were then considered: the diffusion of oxygen through polymer-layered silicates was modeled on a continuum scale with a CFD software, while the properties of n-alkanthiolate self assembled monolayers on gold were analyzed from a molecular point of view by means of a molecular dynamics algorithm. Modeling transport properties in layered nanocomposites, resulting from the ordered dispersion of impermeable flakes in a 2-D matrix, allowed the calculation of the enhancement of barrier effect in relation with platelets structural parameters leading to derive a new expression. On this basis, randomly distributed systems were simulated and the results were analyzed to evaluate the different contributions to the overall effect. The study of more realistic three-dimensional geometries revealed a prefect correspondence with the 2-D approximation. A completely different approach was applied to simulate the effect of temperature on the oxygen transport through self assembled monolayers; the structural information obtained from equilibrium MD simulations showed that raising the temperature, makes the monolayer less ordered and consequently less crystalline. This disorder produces a decrease in the barrier free energy and it lowers the overall resistance to oxygen diffusion, making the monolayer more permeable to small molecules.

Thermodynamic concepts in adaptive resolution simulations

This thesis work is devoted to the conceptual and technical development of the Adaptive Resolution Scheme (AdResS), a molecular dynamics method that allows the simulation of a system with different levels of resolution simultaneously. The simulation domain is divided into high and low resolution zones and a transition region that links them, through which molecules can freely diffuse.rnThe first issue of this work regards the thermodynamic consistency of the method, which is tested and verified in a model liquid of tetrahedral molecules. The results allow the introduction of the concept of the Thermodynamic Force, an external field able to correct spurious density fluctuations present in the transition region in usual AdResS simulations.rnThe AdResS is also applied to a system where two different representations with the same degree of resolution are confronted. This simple test extends the method from an Adaptive Resolution Scheme to an Adaptive Representation Scheme, providing a way of coupling different force fields based on thermodynamic consistency arguments. The Thermodynamic Force is successfully applied to the example described in this work as well.rnAn alternative approach of deducing the Thermodynamic Force from pressure consistency considerations allows the interpretation of AdResS as a first step towards a molecular dynamics simulation in the Grand Canonical ensemble. Additionally, such a definition leads to a practical way of determining the Thermodynamic Force, tested in the well studied tetrahedral liquid. The effects of AdResS and this correction on the atomistic domain are analyzed by inspecting the local distribution of velocities, radial distribution functions, pressure and particle number fluctuation. Their comparison with analogous results coming from purely atomistic simulations shows good agreement, which is greatly improved under the effect of the external field.rnA further step in the development of AdResS, necessary for several applications in biophysics and material science, consists of its application to multicomponent systems. To this aim, the high-resolution representation of a model binary mixture is confronted with its coarse-grained representation systematically parametrized. The Thermodynamic Force, whose development requires a more delicate treatment, also gives satisfactory results.rnFinally, AdResS is tested in systems including two-body bonded forces, through the simulation of a model polymer allowed to adaptively change its representation. It is shown that the distribution functions that characterize the polymer structure are in practice not affected by the change of resolution.rnThe technical details of the implementation of AdResS in the ESPResSo package conclude this thesis work.

Ab-initio study of hydrogen technology materials for hydrogen storage and proton conduction

This dissertation deals with two specific aspects of a potential hydrogen-based energy economy, namely the problems of energy storage and energy conversion. In order to contribute to the solution of these problems, the structural and dynamical properties of two promising materials for hydrogen storage (lithium imide/amide) and proton conduction (poly[vinyl phosphonic acid]) are modeled on an atomistic scale by means of first principles molecular dynamics simulation methods.rnrnrnIn the case of the hydrogen storage system lithium amide/imide (LiNH_2/Li_2NH), the focus was on the interplay of structural features and nuclear quantum effects. For these calculations, Path-Integral Molecular Dynamics (PIMD) simulations were used. The structures of these materials at room temperature were elucidated; in collaboration with an experimental group, a very good agreement between calculated and experimental solid-state 1H-NMR chemical shifts was observed. Specifically, the structure of Li_2NH features a disordered arrangement of the Li lattice, which was not reported in previous studies. In addition, a persistent precession of the NH bonds was observed in our simulations. We provide evidence that this precession is the consequence of a toroid-shaped effective potential, in which the protons in the material are immersed. This potential is essentially flat along the torus azimuthal angle, which might lead to important quantum delocalization effects of the protons over the torus.rnrnOn the energy conversion side, the dynamics of protons in a proton conducting polymer (poly[vinyl phosphonic acid], PVPA) was studied by means of a steered ab-initio Molecular Dynamics approach applied on a simplified polymer model. The focus was put on understanding the microscopic proton transport mechanism in polymer membranes, and on characterizing the relevance of the local environment. This covers particularly the effect of water molecules, which participate in the hydrogen bonding network in the material. The results indicate that these water molecules are essential for the effectiveness of proton conduction. A water-mediated Grotthuss mechanism is identified as the main contributor to proton conduction, which agrees with the experimentally observed decay on conductivity for the same material in the absence of water molecules.rnrnThe gain in understanding the microscopic processes and structures present in this materials can help the development of new materials with improved properties, thus contributing to the solution of problems in the implementation of fuel cells.

Changing the Face of Traditional Education

At large, research universities, a common approach for teaching hundreds of undergraduate students at one time is the traditional, large, lecture-based course. Trends indicate that over the next decade there will be an increase in the number of large, campus courses being offered as well as larger enrollments in courses currently offered. As universities investigate alternative means to accommodate more students and their learning needs, Web-based instruction provides an attractive delivery mode for teaching large, on-campus courses. This article explores a theoretical approach regarding how Web-based instruction can be designed and developed to provide quality education for traditional, on-campus, undergraduate students. The academic debate over the merit of Web-based instruction for traditional, on-campus students has not been resolved. This study identifies and discusses instructional design theory for adapting a large, lecture-based course to the Web.

Is There a Net Gener in the House? Dispelling a Mystification

The subject of this essay is the so-called ‘net generation’, the ‘generation @’, or the ‘millennials’ and the speculations about the importance of this generation for teaching. This essay represents both a critical analysis of such allegations and assumptions and a discourse, from the perspective of socialization, on the use of media in teaching.

Generisches Framework Studi-App

Mit der Idee eines generischen, an vielfältige Hochschulanforderungen anpassbaren Studierenden-App-Frameworks haben sich innerhalb des Arbeitskreises Web der ZKI ca. 30 Hochschulen zu einem Entwicklungsverbund zusammengefunden. Ziel ist es, an den beteiligten Einrichtungen eine umfassende Zusammenstellung aller elektronischen Studienservices zu evaluieren, übergreifende Daten- und Metadatenmodelle für die Beschreibung dieser Dienste zu erstellen und Schnittstellen zu den gängigen Campusmanagementsystemen sowie zu Infrastrukturen der elektronischen Lehre (LMS, Druckdienste, elektronischen Katalogen usw.) zu entwickeln. In einem abschließenden Schritt werden auf dieser Middleware aufsetzende Studienmanagement-Apps für Studierende erstellt, die die verschiedenen Daten- und Kommunikationsströme der standardisierten Dienste und Kommunikationskanäle bündeln und in eine für den Studierenden leicht zu durchschauende, navigationsfreundliche Aufbereitung kanalisiert. Mit der Konzeption eines dezentralen, über eine Vielzahl von Hochschulen verteilten Entwicklungsprojektes unter einer zentralen Projektleitung wird sichergestellt, dass redundante Entwicklungen vermieden, bundesweit standardisierte Serviceangebote angeboten und Wissenstransferprozesse zwischen einer Vielzahl von Hochschulen zur Nutzung mobiler Devices (Smartphones, Tablets und entsprechende Apps) angeregt werden können. Die Unterstützung der Realisierung klarer Schnittstellenspezifikationen zu Campusmanagementsystemen durch deren Anbieter kann durch diese breite Interessensgemeinschaft ebenfalls gestärkt werden. Weiterhin zentraler Planungsinhalt ist ein Angebot für den App-Nutzer zum Aufbau eines datenschutzrechtlich integeren, persönlichen E-Portfolios. Details finden sich im Kapitel Projektziele weiter unten.

Mathe-Üben in Studium und Abitur

Fehlende Grundkenntnisse in der Mathematik zählen zu den größten Hindernissen für einen erfolgreichen Start in ein Hochschulstudium. Studienanfänger in einem MINT-Studium bringen inzwischen deutlich unterschiedliche Vorrausetzungen mit: „Mathe-Angst“ gilt als typisches Phänomen und der Übergang in ein selbstbestimmtes Lernverhalten stellt eine große Herausforderung dar. Diese Fall-Studie beschreibt, wie mit Hilfe einer Mathe-App bereits zu Beginn des Studiums aktives Lernen unterstützt und selbstbestimmtes Lernen eingeübt werden kann. Das neue Kurskonzept mit App-Unterstützung stößt an der Hochschule Offenburg auf breite Akzeptanz. Der mobile BYOD-Ansatz ermöglicht Lern-Szenarien, die über PC- bzw.- Laptop-gebundene eLearning-Lösungen nicht realisierbar sind. Der Inhalt des MassMatics-Vorbereitungskurs orientiert sich am Mindestanforderungskatalog des cosh-Arbeitskreises für den Übergang Schule-Hochschule. In der Zwischenzeit wurde der App-gestützte Kurs mit seinen über 500 Aufgaben von mehr als 1000 Studierenden besucht.

Building an Academic Cloud for 500,000 Users

Under the brand name “sciebo – the Campuscloud” (derived from “science box”) a consortium of more than 20 research and applied science universities started a large scale cloud service for about 500,000 students and researchers in North Rhine-Westphalia, Germany’s most populous state. Starting with the much anticipated data privacy compliant sync & share functionality, sciebo offers the potential to become a more general cloud platform for collaboration and research data management which will be actively pursued in upcoming scientific and infrastructural projects. This project report describes the formation of the venture, its targets and the technical and the legal solution as well as the current status and the next steps.

Performance Analysis and Comparison between Legacy-PSM and U-APSD

This paper evaluates the performance of the most popular power saving mechanisms defined in the IEEE 802.11 standard, namely the Power Save Mode (Legacy-PSM) and the Unscheduled Automatic Power Save Delivery (U-APSD). The assessment comprises a detailed study concerning energy efficiency and capability to guarantee the required Quality of Service (QoS) for a certain application. The results, obtained in the OMNeT++ simulator, showed that U-APSD is more energy efficient than Legacy-PSM without compromising the end-to- end delay. Both U-APSD and Legacy-PSM revealed capability to guarantee the application QoS requirements in all the studied scenarios. However, unlike U-APSD, when Legacy-PSM is used in the presence of QoS demanding applications, all the stations connected to the network through the same access point will consume noticeable additional energy.

Computational and experimental methodology for site-matched investigations of the influence of mineral mass fraction and collagen orientation on the axial indentation modulus of lamellar bone

Relationships between mineralization, collagen orientation and indentation modulus were investigated in bone structural units from the mid-shaft of human femora using a site-matched design. Mineral mass fraction, collagen fibril angle and indentation moduli were measured in registered anatomical sites using backscattered electron imaging, polarized light microscopy and nano-indentation, respectively. Theoretical indentation moduli were calculated with a homogenization model from the quantified mineral densities and mean collagen fibril orientations. The average indentation moduli predicted based on local mineralization and collagen fibers arrangement were not significantly different from the average measured experimentally with nanoindentation (p=0.9). Surprisingly, no substantial correlation of the measured indentation moduli with tissue mineralization and/or collagen fiber arrangement was found. Nano-porosity, micro-damage, collagen cross-links, non-collagenous proteins or other parameters affect the indentation measurements. Additional testing/simulation methods need to be considered to properly understand the variability of indentation moduli, beyond the mineralization and collagen arrangement in bone structural units.

Knowledge transfer in software-maintenance offshore outsourcing

Software-maintenance offshore outsourcing (SMOO) projects have been plagued by tedious knowledge transfer during the service transition to the vendor. Vendor engineers risk being over-strained by the high amounts of novel information, resulting in extra costs that may erode the business case behind offshoring. Although stakeholders may desire to avoid these extra costs by implementing appropriate knowledge transfer practices, little is known on how effective knowledge transfer can be designed and managed in light of the high cognitive loads in SMOO transitions. The dissertation at hand addresses this research gap by presenting and integrating four studies. The studies draw on cognitive load theory, attributional theory, and control theory and they apply qualitative, quantitative, and simulation methods to qualitative data from eight in-depth longitudinal cases. The results suggest that the choice of appropriate learning tasks may be more central to knowledge transfer than the amount of information shared with vendor engineers. Moreover, because vendor staff may not be able to and not dare to effectively self-manage learn-ing tasks during early transition, client-driven controls may be initially required and subsequently faded out. Collectively, the results call for people-based rather than codification-based knowledge management strategies in at least moderately specific and complex software environments.