The effect of linseed oil on the properties of lime-based restoration mortars

The traditional lime mortar is composed of hydrated lime, sand and water. Besides these constituents it may also contain additives aiming to modify fresh mortar´s properties and/or to improve hardened mortar´s strength and durability. Already in the first civilizations various additives were used to enhance mortar´s quality, among the organic additives, linseed oil was one of the most common. From literature we know that it was used already in Roman period to reduce water permeability of a mortar, but the mechanism and the technology, e.g. effects of different dosages, are not clearly explained. There are only few works studying the effect of oil experimentally. Knowing the function of oil in historical mortars is important for designing a new compatible repair mortar. Moreover, linseed oil addition could increase the sometimes insufficient durability of lime-based mortars used for reparation and it could be a natural alternative to synthetic additives. In the present study, the effect of linseed oil on the properties of six various lime-based mortars has been studied. Mortars´ compositions have been selected with respect to composition of historical mortars, but also mortars used in a modern restoration practise have been tested. Oil was added in two different concentrations – 1% and 3% by the weight of binder. The addition of 1% of linseed oil has proved to have positive effect on mortars´ properties. It improves mechanical characteristics and limits water absorption into mortar without affecting significantly the total open porosity or decreasing the degree of carbonation. On the other hand, the 3% addition of linseed oil is making mortar to be almost hydrophobic, but it markedly decreases mortars´ strength. However, all types of tested lime-based mortars with the oil addition showed significantly decreased water and salt solution absorption by capillary rise. Addition of oil into mortars is also decreasing the proportion of pores which are easily accessible to water. Furthermore, mortars with linseed oil showed significantly improved resistance to salt crystallization and freeze-thaw cycles. On the base of the obtained results, the addition of 1% of linseed oil can be taken into consideration in the design of mortars meant to repair or replace historic mortars.

Durability of monumental stones treated with siloxane-based water repellents

The thesis investigates the effect of siloxane-based water repellents on the durability of monumental stones. Laspra, a micritic limestone typical for the Spanish region of Asturias, and Repedea, an oolitic limestone from Moldavia, Romania were selected for the present study, due to their regional / national significance and level of usage. As for the siloxane-based water repellents, three worldwide used products, namely Lotexan-N, Silres® BS 290 and Tegosivin HL 100 and a newly synthesized nanocomposite material, TMSPMA, obtained starting from the 3(trimethoxysilyl)propyl methacrylate as a precursor were investigated. The limestones and the water repellents were thoroughly characterized using specific techniques. The coating of the two monumental stones with the mentioned products and the investigation of coating efficiency yielded to the conclusion that all treatments induce good water repellent properties. The treated limestones were afterwards submitted to different artificially accelerated ageing tests – resistance against UV irradiation, resistance to salt mist action and resistance to SO2 action in the presence of humidity –, the results being analyzed according to standardized evaluation methods. The durability of the treated stones was proved to depend on both stone characteristics and water repellent chemical structure. All four water repellents induced a good protection against UV irradiation, no significant differences among them being noticed. As far as the resistance to salt mist action is concerned, the product that afforded the best results when applied on Laspra was TMSPMA, and on Repedea, Silres® BS 290 or / and TMSPMA showed the highest efficiency. The best resistance to SO2 action in the presence of humidity was conferred by Tegosivin HL 100 and TMSPMA when applied on Laspra, while Silres® BS 290 and TMSPMA afforded better results in the case of Repedea.

Study of the building and decorative materials and techniques used in Hungarian Roman sites

The aims of this research were: - To identify the characteristics, properties and provenance of the building and decorative material found in three Hungarian Roman sites: Nagyharsány, Nemesvámos-Balácapuszta and Aquincum - To provide a database of information on the different sites - To have an overview of main conservation strategies applied in Hungary. Geological studies, macroscopical and microscopical observations, XRD investigations, physical and chemical analyses allowed us to define the characteristics and properties of the different kinds of collected materials. Building stones sampled from Nagyharsány site showed two different kinds of massive limestone belonging to the areas surrounding the villa. Also Building stones sampled from Nemesvámos-Balácapuszta Roman villa proved to be compatible with limestone belonging to local sources. Mural painting fragments show that all samples are units composed of multilayered structures. Mosaic tesserae can be classified as following: -Pale yellow , blackish and pink tesserae are comparable with local limestone; -White tessera, composed of marble, was probably imported from distant regions of the Empire, as the usual practice of Romans. Mortars present different characteristics according to the age, the site and the functions: -Building mortars are generally lime based, white or pale yellow in colour, present a high percentage of aggregates represented by fine sand; -Supporting mortars from both mosaics and mural paintings are reddish or pinkish in colour, due to the presence of high percentage of brick dust and tiles fragments, and present a higher content of MgO. Although the condition of the sites, there is an insignificant content of soluble salts. Database The whole study has allowed us to provide work sheets for each samples, including all characteristics and properties. Furthermore, all sites included in the frame of the research have been described and illustrated on the base of their floor plans, material and construction methodologies. It can be concluded that: 1. In Nagyharsány Archaeological site, it is possible to define a sequence of different construction phases on the base of the study of building material and mortars. The results are comparable with the chronology of the site provided by the archaeologists 2. The material used for construction was of local origin while the more precious ones, used for decorative elements, were probably imported from long distance 3. Construction techniques in Hungary mainly refer to the usual Roman knowledge and practice (Vitruvius); few differences have been found 4. The database will represent an archive for Archaeologists, Historians and Conservators dealing with Roman period in Hungary.

The Effect of Preservative Interventions on the Chemical- Physical and Structural Characteristics of Panel Painting

This work studies the impact of two traditional Romanian treatments, Red Petroleum and Propolis, in terms of real efficiency and consequence on the wooden artifacts. The application of these solutions is still a widely adopted and popular technique in preservative conservation but the impact of these solutions is not well known. It is important to know the effect of treatments on chemical-physical and structural characteristics of the artifacts, not only for understanding the influence on present conditions but also for foreseeing the future behavior. These treatments with Romanian traditional products are compared with a commercial antifungal product, Biotin R, which is utilized as reference to control the effectiveness of Red Petroleum and Propolis. Red Petroleum and Propolis are not active against mould while Biotin R is very active. Mould attack is mostly concentrated in the painted layer, where the tempera, containing glue and egg, enhance nutrition availability for moulds. Biotin R, even if is not a real insecticide but a fungicide, was the most active product against insect attack of the three products, followed by Red Petroleum, Propolis and untreated reference. As for colour, it did not change so much after the application of Red Petroleum and Biotin R and the colour difference was almost not perceptible. On the contrary, Propolis affected the colour a lot. During the exposure at different RH, the colour changes significantly at 100% RH at equilibrium and this is mainly due to the mould attack. Red Petroleum penetrates deeply into wood, while Propolis does not penetrate and remains only on the surface. However, Red Petroleum does not interact chemically with wood substance and it is easy volatilized in oven-dry condition. On the contrary Propolis interacts chemically with wood substance and hardly volatilized, even in oven-dry condition and consequently Propolis remains where it penetrated, mostly on the surface. Treatment by immersion has impact on wood physical parameters while treatment by brushing does not have significant impact. Especially Red Petroleum has an apparent impact on moisture content (MC) due to the penetration of solution, while Propolis does not penetrate so much and remains only on surface therefore Propolis does not have so much impact as Red Petroleum. However, if the weight of the solution penetrated in wood is eliminated, there is not significant difference in MC between treated and untreated samples. Considering physical parameters, dimensional stability is an important parameter. The variation of wood moisture content causes shrinkages/swelling of the wood that polychrome layer can only partially follow. The dimension of wooden supports varied under different moisture conditioning; the painted layer cannot completely follow this deformation, and consequently a degradation and deterioration caused by detachment, occurs. That detachment affects the polychrome stratification of the panel painting and eventually the connections between the different layer compositions of the panel painting.

Durability of crystalline monumental stones in terms of their petrophysical characteristics

The durability of stone building materials is an issue of utmost importance in the field of monument conservation. In order to be able to preserve our built cultural heritage, the thorough knowledge of its constituent materials and the understanding of the processes that affect them are indispensable. The main objective of this research was to evaluate the durability of a special stone type, the crystalline stones, in correlation with their intrinsic characteristics, the petrophysical properties. The crystalline stones are differentiated from the cemented stones on the basis of textural features. Their most important specific property is the usually low, fissure-like porosity. Stone types of significant monumental importance, like the marble or granite belong to this group. The selected materials for this investigation, indeed, are a marble (Macael marble, Spain) and a granite (Silvestre Vilachán granite, Spain). In addition, an andesite (Szob andesite, Hungary) also of significant monumental importance was selected. This way a wide range of crystalline rocks is covered in terms of petrogenesis: stones of metamorphic, magmatic and volcanic origin, which can be of importance in terms of mineralogical, petrological or physical characteristics. After the detailed characterization of the petrophysical properties of the selected stones, their durability was assessed by means of artificial ageing. The applied ageing tests were: the salt crystallization, the frost resistance in pure water and in the presence of soluble salts, the salt mist and the action of SO2 in the presence of humidity. The research aimed at the understanding of the mechanisms of each weathering process and at finding the petrophysical properties most decisive in the degradation of these materials. Among the several weathering mechanisms, the most important ones were found to be the physical stress due to crystallization pressure of both salt and ice, the thermal fatigue due to cyclic temperature changes and the chemical reactions (mostly the acidic attack) between the mineral phases and the external fluids. The properties that fundamentally control the degradation processes, and thus the durability of stones were found to be: the mineralogical and chemical composition; the hydraulic properties especially the water uptake, the permeability and the drying; the void space structure, especially the void size and aperture size distribution and the connectivity of the porous space; and the thermal and mechanical properties. Because of the complexity of the processes and the high number of determining properties, no mechanisms or characteristics could be identified as typical for crystalline stones. The durability or alterability of each stone type must be assessed according to its properties and not according to the textural or petrophysical classification they belong to. Finally, a critical review of standardized methods is presented, based on which an attempt was made for recommendations of the most adequate methodology for the characterization and durability assessment of crystalline stones.

Un piano territoriale per la riduzione della concentrazione di CO2 nell'atmosfera e la produzione energetica da fonti rinnovabili per mezzo della filiera delle biomasse

Il progetto propone uno studio per verificare la fattibilita' di un piano territoriale (ideato per il bacino del Po ma di fatto estendibile a tutti i bacini fluviali) per la creazione di una filiera di colture bioenergetiche (biomasse) che, trasportate per mezzo della navigazione fluviale (uno dei mezzi di trasporto a minore emissione di CO2), alimentino una o piu' centrali a nuova tecnologia che associno alla produzione di calore (teleriscaldamento e raffreddamento) e di energia la separazione dei fumi. La CO2 catturata dalla crescita delle biomasse e recuperata dalla combustione, puo' quindi essere segregata nel sottosuolo di aree costiere subsidenti contrastando il fenomeno dell’abbassamento del suolo. Ricavando benefici in tutti i passaggi di attuazione del piano territoriale (lancio dell'agricoltura bioenergetica, rilancio della navigazione a corrente libera, avvio di una economia legata alla logistica del trasporto e dello stoccaggio delle biomasse, generazione di energia pulita, lotta alla subsidenza) il progetto, di fatto, consente di catturare ingenti quantitativi di CO2 dall'atmosfera e di segregarli nel sottosuolo, riducendo l'effetto serra. Nel corso del Dottorato e' stata sviluppata una metodologia di valutazione della sostenibilita' economica ed ambientale del progetto ad un bacino fluviale, che consta di una modulistica di raccolta dei dati di base e di una procedura informatizzata di analisi.

Chemical characterization of atmospheric secondary organic aerosol of biogenic and anthropogenic origin

The main objective of this thesis was the chemical characterization of synthetic secondary organic aerosol (SOA) produced from atmospherically relevant anthropogenic and biogenic VOCs during reaction chamber experiments. In parallel, the resulting chemical features of these laboratory-SOA were used to interpret the composition of ambient samples of atmospheric fine particulate matter collected at several sites in Europe, in order to determine the fraction of ambient aerosol organic mass accounted for by biogenic and anthropogenic SOA.

Collective effects for the LHC injectors: non-ultrarelativistic approaches

The upgrade of the CERN accelerator complex has been planned in order to further increase the LHC performances in exploring new physics frontiers. One of the main limitations to the upgrade is represented by the collective instabilities. These are intensity dependent phenomena triggered by electromagnetic fields excited by the interaction of the beam with its surrounding. These fields are represented via wake fields in time domain or impedances in frequency domain. Impedances are usually studied assuming ultrarelativistic bunches while we mainly explored low and medium energy regimes in the LHC injector chain. In a non-ultrarelativistic framework we carried out a complete study of the impedance structure of the PSB which accelerates proton bunches up to 1.4 GeV. We measured the imaginary part of the impedance which creates betatron tune shift. We introduced a parabolic bunch model which together with dedicated measurements allowed us to point to the resistive wall impedance as the source of one of the main PSB instability. These results are particularly useful for the design of efficient transverse instability dampers. We developed a macroparticle code to study the effect of the space charge on intensity dependent instabilities. Carrying out the analysis of the bunch modes we proved that the damping effects caused by the space charge, which has been modelled with semi-analytical method and using symplectic high order schemes, can increase the bunch intensity threshold. Numerical libraries have been also developed in order to study, via numerical simulations of the bunches, the impedance of the whole CERN accelerator complex. On a different note, the experiment CNGS at CERN, requires high-intensity beams. We calculated the interpolating Hamiltonian of the beam for highly non-linear lattices. These calculations provide the ground for theoretical and numerical studies aiming to improve the CNGS beam extraction from the PS to the SPS.

Conoscere per Conservare, Conservare per Conoscere. Ipotesi di conservazione e restauro della facciata di Palazzo Guidi a Cesena e della Rocca Malatestiana a Verucchio.

Il mio percorso universitario presso la Facoltà di Architettura di Cesena ha inizio nell’anno accademico 2006-2007. Il titolo della tesi “Conoscere per conservare3, conservare per conoscere” sintetizza l’importanza di offrire una spiegazione della tematica della conoscenza e della sua necessità, la quale risulta essere indispensabile per ottenere un buon progetto di restauro. Progettare un edificio senza conoscerlo appare una scelta ingiustificabile, è tuttavia necessario che la raccolta di dati analitici non sia fine a se stessa e solo finalizzata a donare una facciata di rispettabilità all’architetto e alle sue operazioni progettuali. A partire da questa riflessione si arriva inevitabilmente a parlare di “ricerca della metodologia del restauro” e delle tecniche con il quale questo deve venire affrontato in termini di “piccolo restauro” (ossia restauro delle superfici). Nonostante infatti ogni cantiere di restauro abbia una sua particolare storia è comunque necessario un metodo chiaro e ordinato, di procedure collaudate e di tecniche ben sperimentate. Alla luce di tali osservazioni i temi di seguito proposti sono occasione di una riflessione nel contempo teorica e pratica, con particolare riferimento al restauro e alla conservazione delle superfici; gli edifici scelti appartengono a temi molto differenti l’uno dell’altro e per entrambi verrà proposta una ipotesi di conservazione e restauro delle superfici. Il primo, Palazzo Guidi, è un palazzo settecentesco sito all’interno del centro storico della città di Cesena; il secondo, la Rocca Malatestiana, costruita a partire dal 1100 dalla famiglia dei Malatesta trova la sua ubicazione in cima a una roccia nella alta Valmarecchia. Il progetto per la conservazione ed il restauro di Palazzo Guidi risulta essere la sintesi degli apprendimenti ricevuti nei precedenti anni accademici in due diverse discipline quali: “Rilievo architettonico” e “Laboratorio di restauro architettonico”. Per quanto concerne la Rocca Malatestiana il tema proposto nasce invece a partire dal progetto del “LSF. Archeologia e progetto di architettura” il quale è stato maggiormente approfondito riguardo le tematiche del restauro con la collaborazione del Prof. Arch. Andrea Ugolini e con l’ausilio del corso di “Conservazione e trattamento dei materiali” seguito presso la Facoltà di Conservazione dei Beni Culturali di Ravenna.

Performance evaluation of detectors for digital radiography

To date the hospital radiological workflow is completing a transition from analog to digital technology. Since the X-rays digital detection technologies have become mature, hospitals are trading on the natural devices turnover to replace the conventional screen film devices with digital ones. The transition process is complex and involves not just the equipment replacement but also new arrangements for image transmission, display (and reporting) and storage. This work is focused on 2D digital detector’s characterization with a concern to specific clinical application; the systems features linked to the image quality are analyzed to assess the clinical performances, the conversion efficiency, and the minimum dose necessary to get an acceptable image. The first section overviews the digital detector technologies focusing on the recent and promising technological developments. The second section contains a description of the characterization methods considered in this thesis categorized in physical, psychophysical and clinical; theory, models and procedures are described as well. The third section contains a set of characterizations performed on new equipments that appears to be some of the most advanced technologies available to date. The fourth section deals with some procedures and schemes employed for quality assurance programs.

An advanced analytical study on linseed oil paint binder

Drying oils, and in particular linseed oil, were the most common binding media employed in painting between XVI and XIX centuries. Artists usually operated some pre-treatments on the oils to obtain binders with modified properties, such as different handling qualities or colour. Oil processing has a key role on the subsequent ageing of and degradation of linseed oil paints. In this thesis a multi-analytical approach was adopted to investigate the drying, polymerization and oxidative degradation of the linseed oil paints. In particular, thermogravimetry analysis (TGA), yielding information on the macromolecular scale, were compared with gas-chromatography mass-spectrometry (GC-MS) and direct exposure mass spectrometry (DEMS) providing information on the molecular scale. The study was performed on linseed oils and paint reconstructions prepared according to an accurate historical description of the painting techniques of the 19th century. TGA revealed that during ageing the molecular weight of the oils changes and that higher molecular weight fractions formed. TGA proved to be an excellent tool to compare the oils and paint reconstructions. This technique is able to highlight the different physical behaviour of oils that were processed using different methods and of paint layers on the basis of the different processed oil and /or the pigment used. GC/MS and DE-MS were used to characterise the soluble and non-polymeric fraction of the oils and paint reconstructions. GC/MS allowed us to calculate the ratios of palmitic to stearic acid (P/S), and azelaic to palmitic acid (A/P) and to evaluate effects produced by oil pre-treatments and the presence of different pigments. This helps to understand the role of the pre-treatments and of the pigments on the oxidative degradation undergone by siccative oils during ageing. DE-MS enabled the various molecular weight fractions of the samples to be simultaneously studied, and thus helped to highlight the presence of oxidation and hydrolysis reactions, and the formation of carboxylates that occur during ageing and with the changing of the oil pre-treatments and the pigments. The combination of thermal analysis with molecular techniques such as GC-MS, DEMS and FTIR enabled a model to be developed, for unravelling some crucial issues: 1) how oil pre-treatments produce binders with different physical-chemical qualities, and how this can influence the ageing of an oil paint film; 2) which is the role of the interaction between oil and pigments in the ageing and degradation process.

Produzione e circolazione delle anfore greco italiche in area Adriatica

The present study, being part of a wide research program carried by the University of Bologna (Dipartimento di Scienze della Terra e Geo-Ambientali and Dipartimento di Archeologia) together with the Soprintendenze of Emilia-Romagna and Veneto, is aimed at examining the manufacturing and circulation of Greek Italic amphorae in the Adriatic area. This represents an essential step for the historical and archaeological reconstructions and in particular for: - the identification of local manufacturing though the archaeometric comparisons between ceramic samples and raw materials - the reconstruction of the ancient routes connecting different areas of the Roman world The examined archaeologic sites are representative of the main manufacturing areas in the Adriatic region both along the Italian and Albanian coasts: Adria, Cattolica, Rimini, Spina , Suasa and Phoinike. Notably, the Adriatic region not only represents the manufacturing area, but also coincides with the source area where the raw materials were collected. Archaeometric analyses of representative samples from the different areas of interests, were performed adapting the analytical tecniques used in mineralogy, petrography and geochemistry, to the study of ancient archaeological finds. These data were combined with the ones obtained from the analysis of clays, aimed at characterizing the nature of the raw materials. As a whole, an integration of these data with the available archaeologic observations led to significant advances in the scientific knowledge about of the main types of amphoric manufacturing and distribution in the Adriatic region. In particular, a local manufacturing is suggested for all the archaeological finds from Cattolica and for the main part of the archaeological finds from Suasa. Moreover, the occurrence of commercial routes between the sites of Rimini and Suasa and between Adria, Spina and Suasa is evidenced. On the contrary, for the amphorae from Phoinike a provenance from the examined sites is very unlikely.

Sustainability indicators for environmental management and decision making

The general objective of this research is to explore theories and methodologies of sustainability indicators, environmental management and decision making disciplines with the operational purpose of producing scientific, robust and relevant information for supporting system understanding and decision making in real case studies. Several tools have been applied in order to increase the understanding of socio-ecological systems as well as providing relevant information on the choice between alternatives. These tools have always been applied having in mind the complexity of the issues and the uncertainty tied to the partial knowledge of the systems under study. Two case studies with specific application to performances measurement (environmental performances in the case of the K8 approach and sustainable development performances in the case of the EU Sustainable Development Strategy) and a case study about the selection of sustainable development indicators amongst Municipalities in Scotland, are discussed in the first part of the work. In the second part of the work, the common denominator among subjects consists in the application of spatial indices and indicators to address operational problems in land use management within the territory of the Ravenna province (Italy). The main conclusion of the thesis is that a ‘perfect’ methodological approach which always produces the best results in assessing sustainability performances does not exist. Rather, there is a pool of correct approaches answering different evaluation questions, to be used when methodologies fit the purpose of the analysis. For this reason, methodological limits and conceptual assumptions as well as consistency and transparency of the assessment, become the key factors for assessing the quality of the analysis.