Point defects in carbon nanostructures studied by in-situ electron microscopy

In the present work, the formation and migration of point defects induced by electron irradiation in carbon nanostructures, including carbon onions, nanotubes and graphene layers, were investigated by in-situ TEM. The mobility of carbon atoms normal to the layers in graphitic nanoparticles, the mobility of carbon interstitials inside SWCNTs, and the migration of foreign atoms in graphene layers or in layers of carbon nanotubes were studied. The diffusion of carbon atoms in carbon onions was investigated by annealing carbon onions and observing the relaxation of the compressed clusters in the temperature range of 1200 – 2000oC. An activation energy of 5.0±0.3 eV was obtained. This rather high activation energy for atom exchange between the layers not only prevents the exchange of carbon atoms between the layers at lower temperature but also explains the high morphological and mechanical stability of graphite nanostructures. The migration of carbon atoms in SWCNTs was investigated quantitatively by cutting SWCNT bundles repeatedly with a focused electron beam at different temperatures. A migration barrier of about 0.25 eV was obtained for the diffusion of carbon atoms inside SWCNTs. This is an experimental confirmation of the high mobility of interstitial atoms inside carbon nanotubes, which corroborates previously developed theoretical models of interstitial diffusivity. Individual Au and Pt atoms in one- or two-layered graphene planes and MWCNTs were monitored in real time at high temperatures by high-resolution TEM. The direct observation of the behavior of Au and Pt atoms in graphenic structures in a temperature range of 600 – 700°C allows us to determine the sites occupied by the metal atoms in the graphene layer and the diffusivities of the metal atoms. It was found that metal atoms were located in single or multiple carbon vacancies, not in off-plane positions, and diffused by site exchange with carbon atoms. Metal atoms showed a tendency to form clusters those were stable for a few seconds. An activation energy of around 2.5 eV was obtained for the in-plane migration of both Au and Pt atoms in graphene (two-dimensional diffusion). The rather high activation energy indicates covalent bonding between metal and carbon atoms. Metal atoms were also observed to diffuse along the open edge of graphene layers (one-dimensional diffusion) with a slightly lower activation energy of about 2.3 eV. It is also found that the diffusion of metal atoms in curved graphenic layers of MWCNTs is slightly faster than in planar graphene.

Ab-initio determination of x-ray absorption near edge structure (xanes) spectra in an ultrasoft and norm conserving pseudopotentials scheme

X-ray absorption spectroscopy (XAS) is a powerful means of investigation of structural and electronic properties in condensed -matter physics. Analysis of the near edge part of the XAS spectrum, the so – called X-ray Absorption Near Edge Structure (XANES), can typically provide the following information on the photoexcited atom: - Oxidation state and coordination environment. - Speciation of transition metal compounds. - Conduction band DOS projected on the excited atomic species (PDOS). Analysis of XANES spectra is greatly aided by simulations; in the most common scheme the multiple scattering framework is used with the muffin tin approximation for the scattering potential and the spectral simulation is based on a hypothetical, reference structure. This approach has the advantage of requiring relatively little computing power but in many cases the assumed structure is quite different from the actual system measured and the muffin tin approximation is not adequate for low symmetry structures or highly directional bonds. It is therefore very interesting and justified to develop alternative methods. In one approach, the spectral simulation is based on atomic coordinates obtained from a DFT (Density Functional Theory) optimized structure. In another approach, which is the object of this thesis, the XANES spectrum is calculated directly based on an ab – initio DFT calculation of the atomic and electronic structure. This method takes full advantage of the real many-electron final wavefunction that can be computed with DFT algorithms that include a core-hole in the absorbing atom to compute the final cross section. To calculate the many-electron final wavefunction the Projector Augmented Wave method (PAW) is used. In this scheme, the absorption cross section is written in function of several contributions as the many-electrons function of the finale state; it is calculated starting from pseudo-wavefunction and performing a reconstruction of the real-wavefunction by using a transform operator which contains some parameters, called partial waves and projector waves. The aim of my thesis is to apply and test the PAW methodology to the calculation of the XANES cross section. I have focused on iron and silicon structures and on some biological molecules target (myoglobin and cytochrome c). Finally other inorganic and biological systems could be taken into account for future applications of this methodology, which could become an important improvement with respect to the multiscattering approach.

Cut-first branch-and-price-second for the capacitated arc-routing problem

This paper presents the first full-fledged branch-and-price (bap) algorithm for the capacitated arc-routing problem (CARP). Prior exact solution techniques either rely on cutting planes or the transformation of the CARP into a node-routing problem. The drawbacks are either models with inherent symmetry, dense underlying networks, or a formulation where edge flows in a potential solution do not allow the reconstruction of unique CARP tours. The proposed algorithm circumvents all these drawbacks by taking the beneficial ingredients from existing CARP methods and combining them in a new way. The first step is the solution of the one-index formulation of the CARP in order to produce strong cuts and an excellent lower bound. It is known that this bound is typically stronger than relaxations of a pure set-partitioning CARP model.rnSuch a set-partitioning master program results from a Dantzig-Wolfe decomposition. In the second phase, the master program is initialized with the strong cuts, CARP tours are iteratively generated by a pricing procedure, and branching is required to produce integer solutions. This is a cut-first bap-second algorithm and its main function is, in fact, the splitting of edge flows into unique CARP tours.

Pre-edge analysis of X-rays absorption spectra in TiO2 modified films

The thesis is mainly focused on the pre-edge analysis of XAS spectra of Ti HCF sample hexacyanocobaltate and hexacyanoferrate samples doped on a Indium Tin Oxide (ITO) thin film. The work is aimed at the determination of Ti oxidation state, as well as indication of various coordination number in the studied samples. The experiment have been conducted using XAFS (X-ray absorption fine structure)beamline at Elettra synchrotron, Trieste (Italy) under supervision of Professor Marco Giorgetti, Department of Industrial Chemistry, University of Bologna. The Master thesis accreditation to fullfill the ASC Master of Advanced Spectroscopy in Chemistry Degree requirement.

Bottom-up solution synthesis of structurally defined graphene nanoribbons

Graphene nanoribbons (GNRs), which are defined as nanometer-wide strips of graphene, are attracting an increasing attention as one on the most promising materials for future nanoelectronics. Unlike zero-bandgap graphene that cannot be switched off in transistors, GNRs possess open bandgaps that critically depend on their width and edge structures. GNRs were predominantly prepared through “top-down” methods such as “cutting” of graphene and “unzipping” of carbon nanotubes, but these methods cannot precisely control the structure of the resulting GNRs. In contrast, “bottom-up” chemical synthetic approach enables fabrication of structurally defined and uniform GNRs from tailor-made polyphenylene precursors. Nevertheless, width and length of the GNRs obtainable by this method were considerably limited. In this study, lateral as well as longitudinal extensions of the GNRs were achieved while preserving the high structural definition, based on the bottom-up solution synthesis. Initially, wider (~2 nm) GNRs were synthesized by using laterally expanded monomers through AA-type Yamamoto polymerization, which proved more efficient than the conventional A2B2-type Suzuki polymerization. The wider GNRs showed broad absorption profile extending to the near-infrared region with a low optical bandgap of 1.12 eV, which indicated a potential of such GNRs for the application in photovoltaic cells. Next, high longitudinal extension of narrow (~1 nm) GNRs over 600 nm was accomplished based on AB-type Diels–Alder polymerization, which provided corresponding polyphenylene precursors with the weight-average molecular weight of larger than 600,000 g/mol. Bulky alkyl chains densely installed on the peripheral positions of these GNRs enhanced their liquid-phase processability, which allowed their formation of highly ordered self-assembled monolayers. Furthermore, non-contact time-resolved terahertz spectroscopy measurements demonstrated high charge-carrier mobility within individual GNRs. Remarkably, lateral extension of the AB-type monomer enabled the fabrication of wider (~2 nm) and long (>100 nm) GNRs through the Diels–Alder polymerization. Such longitudinally extended and structurally well-defined GNRs are expected to allow the fabrication of single-ribbon transistors for the fundamental studies on the electronic properties of the GNRs as well as contribute to the development of future electronic devices.

Valutazione del comportamento di materiali compositi sottoposti ad impatti "near-edge"

I materiali compositi sono largamente utilizzati nel moderno campo ingegneristico e garantiscono una notevole riduzione di peso rispetto ai materiali classici, a parità di caratteristiche meccaniche. Le conoscenze su di essi tuttavia presentano ancora delle lacune: in particolare un aspetto critico di tali materiali è rappresentato dal loro comportamento successivo ad un impatto. Obiettivo della presente tesi è indagare tale problematica mediante la realizzazione di una campagna sperimentale innovativa. Verrà presentata una introduzione generale sui materiali compositi e sulla problematica dei danni da impatto e verrà descritta l'attrezzatura utilizzata per la realizzazione degli impatti, analizzando le problematiche riscontrate e le soluzioni trovate. Dopo un accenno ai Controlli Non Distruttivi effettuabili sui materiali compositi, verrà mostrata l'attrezzatura per la realizzazione di prove a compressione, analizzando le problematiche riscontrate e le soluzioni trovate. Saranno elencati i dati acquisiti durante le prove di impatto e di compressione e, infine, saranno illustrate le conclusioni del lavoro e i possibili sviluppi futuri.

Edge states and zero modes in quadratic fermionic models on a 1-D lattice

In una formulazione rigorosa della teoria quantistica, la definizione della varietà Riemanniana spaziale su cui il sistema è vincolato gioca un ruolo fondamentale. La presenza di un bordo sottolinea l'aspetto quantistico del sistema: l'imposizione di condizioni al contorno determina la discretizzazione degli autovalori del Laplaciano, come accade con condizioni note quali quelle periodiche, di Neumann o di Dirichlet. Tuttavia, non sono le uniche possibili. Qualsiasi condizione al bordo che garantisca l'autoaggiunzione dell' operatore Hamiltoniano è ammissibile. Tutte le possibili boundary conditions possono essere catalogate a partire dalla richiesta di conservazione del flusso al bordo della varietà. Alcune possibili condizioni al contorno, permettono l'esistenza di stati legati al bordo, cioè autostati dell' Hamiltoniana con autovalori negativi, detti edge states. Lo scopo di questa tesi è quello di investigare gli effetti di bordo in sistemi unidimensionali implementati su un reticolo discreto, nella prospettiva di capire come simulare proprietà di edge in un reticolo ottico. Il primo caso considerato è un sistema di elettroni liberi. La presenza di edge states è completamente determinata dai parametri di bordo del Laplaciano discreto. Al massimo due edge states emergono, e possono essere legati all' estremità destra o sinistra della catena a seconda delle condizioni al contorno. Anche il modo in cui decadono dal bordo al bulk e completamente determinato dalla scelta delle condizioni. Ammettendo un' interazione quadratica tra siti primi vicini, un secondo tipo di stati emerge in relazione sia alle condizioni al contorno che ai parametri del bulk. Questi stati sono chiamati zero modes, in quanto esiste la possibilità che siano degeneri con lo stato fondamentale. Per implementare le più generali condizioni al contorno, specialmente nel caso interagente, è necessario utilizzare un metodo generale per la diagonalizzazione, che estende la tecnica di Lieb-Shultz-Mattis per Hamiltoniane quadratiche a matrici complesse.

Valutazione numerica del comportamento di materiali compositi sottoposti ad impatti "near edge"

Simulazione numerica con software Abaqus di impatti a bassa energia su laminati di fibra di carbonio con matrice epossidica per la previsione della formazione di delaminazioni interne. Confronto tra impatti centrali al provino e in prossimità del bordo.

"Cutting for love": genital incisions to enhance sexual desirability and commitment in KwaZulu-Natal, South Africa

Several studies have documented women's use of vaginal practices in South Africa to enhance their desirability to men. This article describes a little known practice of this kind among women in KwaZulu-Natal. It involves the use of small incisions in the genital area (and often abdomen and breasts) to introduce herbal substances, described as love medicines, into the body through the incisions. In-depth interviews were carried out with 20 key informants and 20 women, and eight focus group discussions with women and men, in a rural and urban site in 2005-06. A province-wide household survey was then conducted using a multi-stage cluster sample design among 867 women aged 18-60. Forty-two per cent of the women in the household survey had heard of genital incisions; only 3% had actually used them. The main motivation was the enhancement of sexual attractiveness and long-term partner commitment. It appears to be a very recent practice, but may be an extension of an older healing practice not involving the genitals. It was most prevalent among rural women aged 24-29 (although not significant), those with less education, and those who suspected their partners of having other partners. It is linked to the modern popularity of love medicines, which in turn illustrates the troubling state of gender relations in KwaZulu-Natal today.

Life on the Edge: Patterns of Formal and Informal Help to Older Adults in the United States and Sweden

Objectives Our objective in this study was to compare assistance received by individuals in the United States and Sweden with characteristics associated with low, moderate, or high 1-year placement risk in the United States. Methods We used longitudinal nationally representative data from 4,579 participants aged 75 years and older in the 1992 and 1993 waves of the Medicare Current Beneficiary Survey (MCBS) and cross-sectional data from 1,379 individuals aged 75 years and older in the Swedish Aging at Home (AH) national survey for comparative purposes. We developed a logistic regression equation using U.S. data to identify individuals with 3 levels (low, moderate, or high) of predicted 1-year institutional placement risk. Groups with the same characteristics were identified in the Swedish sample and compared on formal and informal assistance received. Results Formal service utilization was higher in Swedish sample, whereas informal service use is lower overall. Individuals with characteristics associated with high placement risk received more formal and less informal assistance in Sweden relative to the United States. Discussion Differences suggest formal services supplement informal support in the United States and that formal and informal services are complementary in Sweden.