Defects in thermosensitive colloidal crystals

Poly-N-Isopropylacrylamide (PNIPAM) colloidal particles form crystal phases that show a thermosensitive behaviour and can be used as atomic model systems. This polymer has both hydrophilic and hydrophobic character and has interesting stimuli-responsive properties in aqueous solution, of which the most important is the temperature response. Above a certain temperature, called Lower Critical Solution Temperature (LCST), the system undergoes a volume phase transition (VPT). Above the LCST, the water is expelled from the polymer network and the swollen state at low temperature transforms into a shrunken state at high temperature. The thermoresponsive behaviour of PNIPAM can be influenced by pH and ionic strength, as well as by the presence of copolymers, such as acrylic acid. In a system formed both by particles of PNIPAM and PNIPAM doped with acrylic acid, one can control the size ratio of the two components by changing the temperature of the mixture, while keeping particle interactions relatively the same. It is therefore possible to obtain thermoresponsive colloidal crystal in which temperature changes induce defects whose formation processes and dynamics can be analysed in an optical microscope at a convenient spatial and temporal scale. The goal of this thesis project was to find the conditions in which such a system could be formed, by using characterization techniques such as Static Light Scattering, Dynamic Light Scattering and Confocal Laser Scanning Microscopy. Two PNIPAM-AAc systems were available, and after characterization it was possible to select a suitable one, on the basis of its low polydispersity and the lack of a VPT, regardless of the external conditions (system JPN_7). The synthesis of a PNIPAM system was attempted, with particles of dimensions matching the JPN_7 system and, unlike JPN_7, displaying a VPT, and one suitable candidate for the mixed system was finally found (system CB_5). The best conditions to obtain thermoresponsive crystal were selected, and the formation and healing of defects were investigated with CLSM temperature scans. The obtained results show that the approach is the correct one and that the present report could represent a useful start for future developments in defect analysis and defect dynamics studies.

La generazione di modelli tridimensionali densi in ambito architettonico mediante la fotogrammetria digitale

The Italian territory offers a wide range of treasures in the field of Cultural Assets. This is a highly relevant property, which needs an accurate management and preservation performed by appropriate tools, also giving attention to the maintenance and safeguard from risk factors. Nowadays the increasing development of new digital technologies, added by remarkable steps forward got by the subject of Geomatic makes possible an efficient integration among different techniques, helped also by spread of solutions to improve the data import-export and transmission between different devices. The main objective of this thesis is to experience the photogrammetric restitution implemented in a commercial software of digital photogrammetry, in order to generate a dense 3D model of the facade of the Basilica Sant'Apollinare Nuovo in Ravenna. The 1st Chapter, after a general introduction regarding the 3D survey of Cultural Heritage and some considerations linked to the use of digital photogrammetry in this field, is focused to analyze the case of stereoscopic and the monoscopic approach. In particular, it develops the theme of close-range photogrammetry. The 2nd Chapter, exposes the theme of digital images, from color theory until their appearing on the monitor. The 3rd Chapter, develops the case study of the Basilica di Sant'Apollinare Nuovo, the historical, architectural and religious of the same. Also, it is examined the issue of photogrammetry and laser scanning of the case study. The final part of the same chapter, treats the processing of data processing the software Agisoft PhotoScan, in order to generate, by means of Structure from Motion technique, a digital geometric 3D model of the Basilica Facade. The digital model has been scaled on the basis of measurements made on the field. With the software it was possible to accomplish the three phases of the photogrammetric data processing: internal orientation, exterior orientation and restitution.

Confronto tra tecniche di remote sensing per la caratterizzazione di un ammasso roccioso presso le Gole di Scascoli, Loiano (BO)

Il versante sinistro delle Gole di Scascoli (BO) è caratterizzato da una marcata tendenza evolutiva per crollo e ribaltamento. Negli ultimi 25 anni si sono verificati eventi parossistici con volumi di roccia coinvolti rispettivamente di 7000 m3, 20000 m3 e 35000 m3. Il sito è di grande rilevanza a causa del forte fattore di rischio rappresentato per la strada di fondovalle ad esso adiacente. Il lavoro di tesi è stato finalizzato allo studio dei fenomeni di versante di una parete rocciosa inaccessibile nota in letteratura come “ex-Mammellone 1” mediante tecniche di telerilevamento quali TLS (Terrestrial Laser Scanning) e CRP (Close Range Photogrammetry) al fine affiancare il rilievo geomeccanico soggettivo dell’area svolto nel 2003 da ENSER Srl in seguito ai fenomeni di crollo del 2002. Lo sviluppo di tecnologie e metodi innovativi per l’analisi territoriale basata sull’impiego di UAV (Unmanned Aerial Vehicle, meglio noti come Droni), associata alle tecniche di fotogrammetria digitale costituisce un elemento di notevole ausilio nelle pratiche di rilevamento in campo di sicurezza e tempi di esecuzione. Il lavoro ha previsto una prima fase di rilevamento areo-fotogrammetrico mediante strumentazione professionale e amatoriale, a cui è seguita l’elaborazione dei rispettivi modelli. I diversi output sono stati confrontati dal punto di vista geomorfologico, geometrico, geomeccanico e di modellazione numerica di caduta massi. Dal lavoro è stato possibile indagare l’evoluzione morfologica del sito in esame negli ultimi 10 anni, confrontare diversi metodi di rilevamento e analisi dati, sperimentare la robustezza e ripetibilità geometrica del metodo fotogrammetrico per il rilievo di fronti rocciosi e mettere a punto un metodo semiautomatico di individuazione e analisi delle giaciture delle discontinuità.

Tecniche geomatiche di monitoraggio delle strutture e dei ponti

Nel presente elaborato vengono analizzate alcune delle più recenti tecniche per eseguire il monitoraggio e il collaudo delle strutture, con attenzione particolare ai ponti. In una prima parte viene spiegata l'importanza di realizzare un sistema di monitoraggio continuo per le opere al fine di evitare danni alle persone e ai beni materiali. In particolare vengono analizzate tre tecniche quali la fibra ottica, laser scanning e fotogrammetria mostrando per ognuna alcuni esempi applicativi al fine di evidenziarne i vantaggi e le condizioni di utilizzo

Outdoor bronze conservation: assessment of protective treatments by accelerated aging and of treatment removal procedures by laser cleaning

Outdoor bronzes exposed to the environment form naturally a layer called patina, which may be able to protect the metallic substrate. However, since the last century, with the appearance of acid rains, a strong change in the nature and properties of the copper based patinas occurred [1]. Studies and general observations have established that bronze corrosion patinas created by acid rain are not only disfiguring in terms of loss of detail and homogeneity, but are also unstable [2]. The unstable patina is partially leached away by rainwater. This leaching is represented by green streaking on bronze monuments [3]. Because of the instability of the patina, conservation techniques are usually required. On a bronze object exposed to the outdoor environment, there are different actions of the rainfall and other atmospheric agents as a function of the monument shape. In fact, we recognize sheltered and unsheltered areas as regards exposure to rainwater [4]. As a consequence of these different actions, two main patina types are formed on monuments exposed to the outdoor environment. These patinas have different electrochemical, morphological and compositional characteristics [1]. In the case of sheltered areas, the patina contains mainly copper products, stratified above a layer strongly enriched in insoluble Sn oxides, located at the interface with the uncorroded metal. Moreover, different colors of the patina result from the exposure geometry. The surface color may be pale green for unsheltered areas, and green and mat black for sheltered areas [4]. Thus, in real outdoor bronze monuments, the corrosion behavior is strongly influenced by the exposure geometry. This must be taken into account when designing conservation procedures, since the patina is in most cases the support on which corrosion inhibitors are applied. Presently, for protecting outdoor bronzes against atmospheric corrosion, inhibitors and protective treatments are used. BTA and its derivatives, which are the most common inhibitors used for copper and its alloy, were found to be toxic for the environment and human health [5, 6]. Moreover, it has been demonstrated that BTA is efficient when applied on bare copper but not as efficient when applied on bare bronze [7]. Thus it was necessary to find alternative compounds. Silane-based inhibitors (already successfully tested on copper and other metallic substrates [8]), were taken into consideration as a non-toxic, environmentally friendly alternative to BTA derivatives for bronze protection. The purpose of this thesis was based on the assessment of the efficiency of a selected compound, to protect the bronze against corrosion, which is the 3-mercapto-propyl-trimethoxy-silane (PropS-SH). It was selected thanks to the collaboration with the Corrosion Studies Centre “Aldo Daccò” at the Università di Ferrara. Since previous studies [9, 10, 11] demonstrated that the addition of nanoparticles to silane-based inhibitors leads to an increase of the protective efficiency, we also wanted to evaluate the influence of the addition of CeO2, La2O3, TiO2 nanoparticles on the protective efficiency of 3-mercapto-propyl-trimethoxy-silane, applied on pre-patinated bronze surfaces. This study is the first section of the thesis. Since restorers have to work on patinated bronzes and not on bare metal (except for contemporary art), it is important to be able to recreate the patina, under laboratory conditions, either in sheltered or unsheltered conditions to test the coating and to obtain reliable results. Therefore, at the University of Bologna, different devices have been designed to simulate the real outdoor conditions and to create a patina which is representative of real application conditions of inhibitor or protective treatments. In particular, accelerated ageing devices by wet & dry (simulating the action of stagnant rain in sheltered areas [12]) and by dropping (simulating the leaching action of the rain in unsheltered areas [1]) tests were used. In the present work, we used the dropping test as a method to produce pre-patinated bronze surfaces for the application of a candidate inhibitor as well as for evaluating its protective efficiency on aged bronze (unsheltered areas). In this thesis, gilded bronzes were also studied. When they are exposed to the outside environment, a corrosion phenomenon appears which is due to the electrochemical couple gold/copper where copper is the anode. In the presence of an electrolyte, this phenomenon results in the formation of corrosion products than will cause a blistering of the gold (or a break-up and loss of the film in some cases). Moreover, because of the diffusion of the copper salts to the surface, aggregates and a greenish film will be formed on the surface of the sample [13]. By coating gilded samples with PropS-SH and PropS-SH containing nano-particles and carrying out accelerated ageing by the dropping test, a discussion is possible on the effectiveness of this coating, either with nano-particles or not, against the corrosion process. This part is the section 2 of this thesis. Finally, a discussion about laser treatment aiming at the assessment of reversibility/re-applicability of the PropS-SH coating can be found in section 3 of this thesis. Because the protective layer loses its efficiency with time, it is necessary to find a way of removing the silane layer, before applying a new one on the “bare” patina. One request is to minimize the damages that a laser treatment would create on the patina. Therefore, different laser fluences (energy/surface) were applied on the sample surface during the treatment process in order to find the best range of fluence. In particular, we made a characterization of surfaces before and after removal of PropS-SH (applied on a naturally patinated surface, and subsequently aged by natural exposure) with laser methods. The laser removal treatment was done by the CNR Institute of Applied Physics “Nello Carrara” of Sesto Fiorentino in Florence. In all the three sections of the thesis, a range of non-destructive spectroscopic methods (Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS), μ-Raman spectroscopy, X-Ray diffractometry (XRD)) were used for characterizing the corroded surfaces. AAS (Atomic Absorption Spectroscopy) was used to analyze the ageing solutions from the dropping test in sections 1 and 2.