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.

A new class of bragg stacks and its principle application

This work is focused on the development of high quality nanoporous 1D photonic crystals –so called Bragg stacks – made by spin-coating of approximately 25 nm large SiO2 and TiO2 nanoparticles bearing interparticle voids large enough to infiltrate reactive species. Therefore, the first part of this work describes the synthesis of well-dispersed TiO2 nanoparticles in this size range (the corresponding SiO2 nanoparticles are commercially available). In the second part, a protocol was developed to prepare nanoporous Bragg stacks of up to 12 bilayers with high quality and precision. Tailor-made Bragg stacks were prepared for different applications such as (i) a surface emitting feedback laser with a FWHM of only 6 nm and (ii) an electrochromic device with absorption reversibly switchable by an external electrical bias independently of the Bragg reflection. In the last chapter, the approach to 1D photonic crystals is transferred to 1D phononic crystals. Contrast in the modulus is achieved by spin-coating SiO2 and PMMA as high and low moduli material. This system showed a band gap of fg = 12.6 GHz with a width of Dfg/fg = 4.5 GHz.

Kolloide und ihre Überstrukturen als Bausteine zur Herstellung funktioneller Materialien

In dieser Arbeit wird die Synthese von Polymerkolloiden mit unterschiedlichen Formen und Funktionalitäten sowie deren Verwendung zur Herstellung kolloidaler Überstrukturen beschrieben. Über emulgatorfreie Emulsionspolymerisation (SFEP) erzeugte monodisperse sphärische Kolloide dienen als Bausteine von Polymeropalen, die durch die Selbstorganisation dieser Kolloide über vertikale Kristallisation (mit Hilfe einer Ziehmaschine) oder horizontale Kristallisation (durch Aufschleudern oder Aufpipettieren) entstehen. Durch die Kontrolle der Kugelgröße über die Parameter der Emulsionspolymerisation sowie die Einstellung der Schichtdicke der Kolloidkristalle über die Anpassung der Kristallisationsparameter ist die Erzeugung von qualitativ hochwertigen Opalen mit definierter Reflektionswellenlänge möglich. Darüber hinaus kann die chemische und thermische Beständigkeit der Opale durch den Einbau von Vernetzern oder vernetzbaren Gruppen in die Polymere erhöht werden. Die Opalfilme können als wellenlängenselektive Reflektoren in auf Fluoreszenzkonzentratoren basierenden Solarzellensystemen eingesetzt werden, um Lichtverluste in diesen Systemen zu reduzieren. Sie können auch als Template für die Herstellung invertierter Opale aus verschiedenen anorganischen Oxiden (TiO2, Al2O3, ZnO) dienen. Über einen CVD-Prozess erzeugte ZnO-Replika besitzen dabei den Vorteil, dass sie nicht nur eine hohe optische Qualität sondern auch eine elektrische Leitfähigkeit aufweisen. Dies ermöglicht sowohl deren Einsatz als Zwischenreflektor in Tandemsolarzellen als auch die Herstellung hierarchischer Strukturen über die Elektroabscheidung von Nanokristallen. In einem weiteren Teil der Arbeit wird die Herstellung funktioneller formanisotroper Partikel behandelt. Durch die Entmischung von mit Monomer gequollenen vernetzten Partikeln in einer Saatpolymerisation sind mehrere Mikrometer große Kolloide zugänglich, die aus zwei interpenetrierenden Halbkugeln aus gleichen oder verschiedenen Polymeren bestehen. Dadurch sind unter anderem Glycidyl-, Alkin- und Carbonsäuregruppen in die eine oder die andere Halbkugel integrierbar. Diese funktionellen Gruppen erlauben die Markierung bestimmter Partikelhälften mit Farbstoffen, die Beschichtung von Partikelbereichen mit anorganischen Oxiden wie SiO2 sowie die Erzeugung amphiphiler formanisotroper Partikel, die sich an Grenzflächen ausrichten lassen. Das Synthesekonzept kann - ausgehend von mittels SFEP erzeugten stark vernetzten PMMA-Partikeln - auch auf kleine Kolloide mit Größen von mehreren hundert Nanometern übertragen werden.

Caratterizzazione geochimica dei sedimenti nel sito Caretti di Ferrara

Lo studio riguarda la caratterizzazione geochimica dei sedimenti del sito Caretti, situato a est del comune di Ferrara, interessato da un forte caso di contaminazione dovuto alla presenza di due discariche municipali non controllate risalenti agli anni '60-'70. L'obiettivo del lavoro è quello di valutare la geochimica dei sedimenti e delle acque prelevate nel sito al fine di individuare eventuali relazioni tra il chimismo delle due matrici. Inoltre, i dati dell' analisi dei sedimenti sono stati confrontati con quelli di letteratura per delinearne aspetti di provenienza. I dati geochimici dei sedimenti sono stati ottenuti mediante fluorescenza a raggi X (XRF) e sono stati elaborati graficamente e statisticamente, mediante software di analisi statistica (GCDkit). La composizione geochimica delle acque è stata ottenuta mediante tecniche di cromatografia ionica e spettroscopia di assorbimento atomico. La geochimica dei sedimenti ha evidenziato che la composizione chimica mostra associazioni di elementi legate a una componente tessiturale del sedimento. In particolare si rilevano concentrazioni elevate di Fe2O3, Al2O3, TiO2, Cr, Ni, e V in sedimenti a granulometria fine, a differenza delle concentrazioni di SiO2 e Na2O elevate in sedimenti sabbiosi. La distribuzione statistica degli elementi nei sedimenti e nelle acque ha permesso di effettuare una valutazione delle caratteristiche geochimiche dei principali corpi idrogeologici. La caratterizzazione geochimica ha fornito, inoltre, indicazioni sull'origine dei sedimenti. Cromo e Nichel, tra gli elementi in traccia, sono particolarmente efficaci nella valutazione della provenienza permettendo, all'interno del sito Caretti, una distinzione tra popolazioni di provenienza appenninica (bassi valori Cr-Ni) e padana (alti valori Cr-Ni).

Studio dell'interazione di etanolo con catalizzatori TiO2-CeOx.

Due to the limited availability of natural oil and the harmful effects of its usage, the industry has focused in searching for sustainable types of raw materials for the production of chemicals. The bioethanol, obtained by fermentation of biomass, has gained particular importance in recent years both as a biofuel, and as a “building block” molecule because it can be considered as a starting reagent to obtain other added value chemical compounds, such as ethylene, acetaldehyde, butadiene and ethyl acetate. The goal of this research was the study of the interaction of ethanol with catalysts based on TiO2-CeOX. Since the electronic properties have implications on the catalytic activity, the idea was to understand if the TiO2-CeOX systems have different reactivity from that of ceria and rutile alone, or an intermediate between them. The study was focused on the characterization of the adsorbed species on the catalysts surface after ethanol adsorption through an in-situ spectroscopic technique (DRIFTS) that allowed us to extract information that could be helpful for the understanding of the processes at the molecular level. The mass spectrometry was used to monitor on-line the desorbed products. Furthermore, reactivity tests in a flow reactor were performed, in order to verify the catalytic behavior of the samples in conditions which are more similar to those applied at an industrial scale. The samples showed to behave in different way depending on the conditions used and the thermal treatment. The particular behavior of the mixed samples with respect to the single oxides is interpreted for each case according to the spectroscopic information collected.

Microscopic Picture of Aging in SiO2

We investigate the aging dynamics of amorphous SiO2 via molecular dynamics simulations of a quench from a high temperature Ti to a lower temperature Tf.We obtain a microscopic picture of aging dynamics by analyzing single particle trajectories, identifying jump events when a particle escapes the cage formed by its neighbors, and determining how these jumps depend on the waiting time tw, the time elapsed since the temperature quench to Tf. We find that the only tw-dependent microscopic quantity is the number of jumping particles per unit time, which decreases with age. Similar to previous studies for fragile glass formers, we show here for the strong glass former SiO2 that neither the distribution of jump lengths nor the distribution of times spent in the cage are tw dependent.We conclude that the microscopic aging dynamics is surprisingly similar for fragile and strong glass formers.

Temperature-Dependent Defect Dynamics in the Network Glass SiO2

We investigate the long time dynamics of a strong glass former, SiO2, below the glass transition temperature by averaging single-particle trajectories over time windows which comprise roughly 100 particle oscillations. The structure on this coarse-grained time scale is very well defined in terms of coordination numbers, allowing us to identify ill-coordinated atoms, which are called defects in the following. The most numerous defects are O-O neighbors, whose lifetimes are comparable to the equilibration time at low temperature. On the other hand, SiO and OSi defects are very rare and short lived. The lifetime of defects is found to be strongly temperature dependent, consistent with activated processes. Single-particle jumps give rise to local structural rearrangements. We show that in SiO2 these structural rearrangements are coupled to the creation or annihilation of defects, giving rise to very strong correlations of jumping atoms and defects.

Determining the optical properties of a gelatin-TiO2 phantom at 780 nm

Tissue phantoms play a central role in validating biomedical imaging techniques. Here we employ a series of methods that aim to fully determine the optical properties, i.e., the refractive index n, absorption coefficient μa, transport mean free path ℓ∗, and scattering coefficient μs of a TiO2 in gelatin phantom intended for use in optoacoustic imaging. For the determination of the key parameters μa and ℓ∗, we employ a variant of time of flight measurements, where fiber optodes are immersed into the phantom to minimize the influence of boundaries. The robustness of the method was verified with Monte Carlo simulations, where the experimentally obtained values served as input parameters for the simulations. The excellent agreement between simulations and experiments confirmed the reliability of the results. The parameters determined at 780 nm are n=1.359(±0.002), μ′s=1/ℓ∗=0.22(±0.02) mm-1, μa= 0.0053(+0.0006-0.0003) mm-1, and μs=2.86(±0.04) mm-1. The asymmetry parameter g obtained from the parameters ℓ∗ and μ′s is 0.93, which indicates that the scattering entities are not bare TiO2 particles but large sparse clusters. The interaction between the scattering particles and the gelatin matrix should be taken into account when developing such phantoms.

Glycosylation and pyranose-furanose isomerization of carbohydrates using HClO4-SiO2: Synthesis of oligosaccharides containing galactofuranose

A series of di- and trisaccharides containing galactofuranose were synthesized using HClO4-SiO2 catalyzed glycosylation and ring transformation for the conversion of galactopyranose to galactofuranose. Yields in glycosylations and ring transformation reactions were excellent.

A thermodynamic model for di-trioctahedral chlorite from experimental and natural data in the system MgO-FeO-Al2O3-SiO2-H2O. Applications to P-T sections and geothermometry

We present a new thermodynamic activity-composition model for di-trioctahedral chlorite in the system FeO–MgO–Al2O3–SiO2–H2O that is based on the Holland–Powell internally consistent thermodynamic data set. The model is formulated in terms of four linearly independent end-members, which are amesite, clinochlore, daphnite and sudoite. These account for the most important crystal-chemical substitutions in chlorite, the Fe–Mg, Tschermak and di-trioctahedral substitution. The ideal part of end-member activities is modeled with a mixing-on-site formalism, and non-ideality is described by a macroscopic symmetric (regular) formalism. The symmetric interaction parameters were calibrated using a set of 271 published chlorite analyses for which robust independent temperature estimates are available. In addition, adjustment of the standard state thermodynamic properties of sudoite was required to accurately reproduce experimental brackets involving sudoite. This new model was tested by calculating representative P–T sections for metasediments at low temperatures (<400 °C), in particular sudoite and chlorite bearing metapelites from Crete. Comparison between the calculated mineral assemblages and field data shows that the new model is able to predict the coexistence of chlorite and sudoite at low metamorphic temperatures. The predicted lower limit of the chloritoid stability field is also in better agreement with petrological observations. For practical applications to metamorphic and hydrothermal environments, two new semi-empirical chlorite geothermometers named Chl(1) and Chl(2) were calibrated based on the chlorite + quartz + water equilibrium (2 clinochlore + 3 sudoite = 4 amesite + 4 H2O + 7 quartz). The Chl(1) thermometer requires knowledge of the (Fe3+/ΣFe) ratio in chlorite and predicts correct temperatures for a range of redox conditions. The Chl(2) geothermometer which assumes that all iron in chlorite is ferrous has been applied to partially recrystallized detrital chlorite from the Zone houillère in the French Western Alps.

The triplite–triploidite supergroup: structural modulation in wagnerite, discreditation of magniotriplite, and the new mineral hydroxylwagnerite

Electron-microprobe analysis, single-crystal X-ray diffraction with an area detector, and high-resolution transmission electron microscopy show that minerals related to wagnerite, triplite and triploidite, which are monoclinic Mg, Fe and Mn phosphates with the formula Me2+ 2PO4(F,OH), constitute a modulated series based on the average triplite structure. Modulation occurs along b and may be commensurate with (2b periodicity) or incommensurate but generally close to integer values (∼3b, ∼5b, ∼7b, ∼9b), i.e. close to polytypic behaviour. As a result, the Mg- and F-dominant minerals magniotriplite and wagnerite can no longer be considered polymorphs of Mg2PO4F, i.e., there is no basis for recognizing them as distinct species. Given that wagnerite has priority (1821 vs. 1951), the name magniotriplite should be discarded in favour of wagnerite. Hydroxylwagnerite, end-member Mg2PO4OH, occurs in pyrope megablasts along with talc, clinochlore, kyanite, rutile and secondary apatite in two samples from lenses of pyrope–kyanite–phengite–quartz-schist within metagranite in the coesite-bearing ultrahigh-pressure metamorphic unit of the Dora-Maira Massif, western Alps, Vallone di Gilba, Val Varaita, Piemonte, Italy. Electron microprobe analyses of holotype hydroxylwagnerite and of the crystal with the lowest F content gave in wt%: P2O5 44.14, 43.99; SiO2 0.28, 0.02; SO3 –, 0.01; TiO2 0.20, 0.16; Al2O3 0.06, 0.03; MgO 48.82, 49.12; FeO 0.33, 0.48; MnO 0.01, 0.02; CaO 0.12, 0.10; Na2O 0.01, –; F 5.58, 4.67; H2O (calc) 2.94, 3.36; –O = F 2.35, 1.97; Sum 100.14, 99.98, corresponding to (Mg1.954Fe0.007Ca0.003Ti0.004Al0.002Na0.001)Σ=1.971(P1.003Si0.008)Σ=1.011O4(OH0.526F0.474)Σ=1 and (Mg1.971Fe0.011Ca0.003Ti0.003Al0.001)Σ=1.989(P1.002Si0.001)Σ=1.003O4(OH0.603F0.397)Σ=1, respectively. Due to the paucity of material, H2O could not be measured, so OH was calculated from the deficit in F assuming stoichiometry, i.e., by assuming F + OH = 1 per formula unit. Holotype hydroxylwagnerite is optically biaxial (+), α 1.584(1), β 1.586(1), γ 1.587(1) (589 nm); 2V Z(meas.) = 43(2)°; orientation Y = b. Single-crystal X-ray diffraction gives monoclinic symmetry, space group P21/c, a = 9.646(3) Å, b = 12.7314(16) Å, c = 11.980(4) Å, β = 108.38(4) , V = 1396.2(8) Å3, Z = 16, i.e., hydroxylwagnerite is the OH-dominant analogue of wagnerite [β-Mg2PO4(OH)] and a high-pressure polymorph of althausite, holtedahlite, and α- and ε-Mg2PO4(OH). We suggest that the group of minerals related to wagnerite, triplite and triploidite constitutes a triplite–triploidite super-group that can be divided into F-dominant phosphates (triplite group), OH-dominant phosphates (triploidite group), O-dominant phosphates (staněkite group) and an OH-dominant arsenate (sarkinite). The distinction among the three groups and a potential fourth group is based only on chemical features, i.e., occupancy of anion or cation sites. The structures of these minerals are all based on the average triplite structure, with a modulation controlled by the ratio of Mg, Fe2+, Fe3+ and Mn2+ ionic radii to (O,OH,F) ionic radii.

Sand geochemistry on sediment core CRP-3 from the Ross Sea, Antarctica

A total of 167 samples distubuted throughout the CRP-3 drillhole from 5.77 to 787.68 mbsf and representing fine to coarse sandstones have been analysed by X-ray fluorescence spectrometry (XRF) Bulk sample geochemistry (major and trace elements) indicates a dominant provenance of detritus from the Ferrar Supergroup in the uppermost 200 mbsf of the core. A markedly increased contribution from the Beacon sandstones is recognized below 200 mbsf and down to 600 mbsf. In the lower part of CRP-3, down to 787.68 mbsf, geochemical evidence for influxes of Ferrar materials is again recorded. On the basis of preliminary magnetostratigraphic data reported for the lower 447 mbsf of the drillhole, we tentatively evaluated the main periodicities modulating the geochemical records. Our results identify a possible influence of the precession, obliquity and long-eccentricity astronomical components (21, 41, and 400 ky frequency bands) on the deposition mechanisms of the studied glaciomarine sediments.