On the Chemical Signature and Origin of Dicoppertrihydroxyformate (Cu2(OH)3HCOO) Formed on Copper Miniatures of 17th and 18th centuries

A corrosion product rarely reported in the literature has been found on the copper support of three miniature paintings of the 17th and 18th centuries. This product, which has been identified as dicoppertrihydroxyformate (Cu2(OH)3HCOO), is an unusual basic copper formate found on copper artifacts. The identification and characterization of dicoppertrihydroxyformate was carried out directly over the corroded surface of the objects, using a nondestructive approach, which combines the integrated use of various microanalytical techniques. Using this approach, it was possible to obtain a set of new reference data about the natural form of Cu2(OH)3HCOO, that will enable its unambiguous identification in other similar objects. In this work, the probable causes that may have contributed to its formation are also discussed.

Variedades e estilos na obra atribuída a Frei Carlos: novas perspetivas

Este trabalho de investigação centra-se no contributo dos exames de superfície e nas análises micro-analíticas no estudo de vinte e uma pinturas atribuídas à oficina de Frei Carlos, um dos grandes Mestres Luso-Flamengos ativos em território Nacional durante a primeira metade do século XVI. A "Pintura Luso-Flamenga" é uma expressão comummente usada na história da pintura Portuguesa do primeiro terço do século XVI e no seu sentido mais básico designa o trabalho de mestres flamengos que se instalaram em Portugal durante o reinado de D. Manuel I (1495- 1521) contribuindo decisivamente para o processo de renovação da pintura Portuguesa na época. O estudo integrado combina a pesquisa histórica em fontes documentais com exames de superfície e de caracterização material das obras de arte. O estudo material das pinturas foi realizado através de microscopia ótica, microscopia de infravermelhos com transformada de Fourier, espectroscopia de micro-Raman, microscopia eletrónica de varrimento acoplada com espectrometria de energia dispersiva de raios X, micro- difração de raios-X, cromatografia líquida de alta eficiência e pirólise acoplada à cromatografia gasosa /espectrometria de massa. Esta investigação envolveu técnicas complementares de análise de superfície e de ponto no estudo técnico e material das preparações, imprimitura, desenho subjacente, camadas pictóricas e sucessões estratigráficas, dando a conhecer os materiais utilizados na execução técnica das pinturas e evidenciando especificidades técnicas da produção artística. Este estudo pretende inclusivamente evidenciar alguns detalhes técnicos do artista que possivelmente estão relacionados com a herança das práticas Flamengas. O conhecimento de algumas particularidades da técnica deste Mestre também permitiu estabelecer comparações com duas pinturas que haviam sido atribuídas, com algumas reservas, a esta oficina de pintura Luso-Flamenga. Mais recentemente, como resultado de um estudo colaborativo, foi realizada uma ampla campanha de reflectografia infravermelhos, introduzindo novos dados acerca da execução técnica do desenho subjacente, o que contribuiu para diferenciar, nestas duas pinturas, outra "mão", atribuída então a um seguidor de Frei Carlos. Esta investigação introduz um novo e profundo conhecimento sobre a Oficina de Frei Carlos, permitindo estabelecer comparações com a obra do seu seguidor e com uma pintura também atribuída a esta oficina e que incorpora o Museu da National Gallery (NG5594), evidenciando os materiais utilizados na técnica de produção artística e especificidades técnicas aliadas aos processos criativos/ construtivos que permitem estabelecer os pontos de contacto e de diferenciação entre estas obras; Varieties and styles in the works attributed to Frei Carlos - new perspectives Abstract: This investigation is focused on the contributions of surface exams and micro-analytical research in the study of twenty one paintings attributed to Frei Carlos workshop, one of the most important Portuguese-Flemish painters active in our country during the first half of sixteen Century. "Portuguese-Flemish Painting" is a common expression used in the history of Portuguese painting of the first third of the sixteenth century and in its most basic meaning designates the work of Flemish masters who settled in Portugal during the reign of King Manuel I (1495-1521) contributing decisively to the process of renewal of Portuguese painting at the time. The integrated approach combines historical research on documental sources with surface examination and material characterization of the paintings by using state-of-art analytical techniques. Microanalysis was carried out by optical microscopy, micro-Fourier-transform infrared-spectroscopy, micro-Raman spectroscopy, scanning electron microscopy coupled with energy dispersive X-ray spectrometry, micro-X-ray diffraction analysis, high performance liquid chromatography and Pyrolysis gas chromatography mass spectrometry. This complementary surface and analytical research was involved in the technical and material characterization of grounds, underdrawings, primings, paint layers and its multi-layered build-up, providing access to the painter´s materials used in the technical execution of the paintings and details of the technique of artistic production. This study also intends to expose some usual details of the artist’s technique which are possibly related to the Master´s Flemish influence. The knowledge of some particularities of the Master´s technique also allowed a new comparison with two paintings that had been attributed with some reserves to this Portuguese-Flemish workshop. More recently, as a result of a collaborative study, an extensive infrared reflectography campaign was made, giving new data concerning underdrawings technical execution and contributing to differentiate, in these two paintings, another “hand”, attributed to a follower of Frei Carlos. Complementary analytical research also added a new and deep insight into Frei Carlos workshop, his follower and a panel that still attributed to Frei Carlos workshop that integrates the National Gallery´s Museum (NG5594), evidencing the materials used in technical production, their models and sources of artistic inspiration, techniques and pictorial construction procedures that could specifically relate or distinguish between them.

Testing the cleaning effectiveness of new ecological aqueousdispersions applied on old icons

Adherent deposits are very aggressive towards ancient heritage paintings since they affect the varnish and the painting’s layers, sometimes reaching the preparative layers. The biggest problem to the restorer is their removal without affecting the patina, the transparent varnish (well preserved) and fine colour glazes made during painting. Therefore, their removal requires preliminary cleaning tests that allow the optimization of the cleaning system composition that is going to be used. The study was focused on organic natural systems, as colourless supernatants, some of them used during ages, but insufficiently studied. The paper presents an evaluation of the effectiveness of cleaning varnished icons of the nineteenth century, with complex conservation cases using supernatants derived from aqueous dispersions extracted from vegetables and dry indigenous herbal infusions. Best results, after six consecutive cleaning steps, on tempera old icon was obtained for a mixture made of mature white onion juice + extract of Soapwort flowers + corn silk tea + acacia tea. As a best result after just one cleaning step was obtained for a quaternary mixture composed from mature white onion juice + mature carrot juice + corn silk tea + aqueous extract of Soapwort flowers.

Do Espírito do Lugar - Música, Estética, Silêncio, Espaço, Luz I e II Residências Cistercienses de São Bento de Cástris (2013, 2014).

As Residências Cistercienses em S. Bento de Cástris que se vêm realizando desde 2013 têm como primeiro objectivo reinventar na contemporaneidade a densidade histórica do discurso cisterciense, integrando a realidade deste mosteiro tanto numa ampla geografia da Ordem de Cister em Portugal e na Europa, como na história da região e do país. Inspiradas nas questões da História, da Arte, da Arquitectura, da Música, do Património e da Paisagem, as Residências Cistercienses em Cástris vêm apostando no debate de questões actuais ligadas aos espaços monásticos e ao seu futuro, nomeadamente os cistercienses. Esta aposta concretiza-se também no presente trabalho, DO ESPÍRITO DO LUGAR. ESTÉTICA. SILÊNCIO, ESPAÇO, LUZ, resultado das I e II Residências Cistercienses (2013 e 2014), e integra estudos que se reportam especialmente ao Silêncio e às suas várias linguagens e significados e às dimensões da Estética monástico-religiosa, com algum privilégio para as temáticas da Música. A apropriação do mosteiro pelo silêncio e pela música e a apreciação do espólio musical e instrumental de S. Bento de Cástris permitem uma melhor percepção das diversidades conjunturais e dos seus ritmos, aliando-se às dimensões de valorização patrimonial, eacompanhando-as de sugestões estéticas na pintura, escultura, pintura mural, azulejaria…, no sentido da fruição plena dos espaços. A riqueza deste evento, a Residência Cisterciense no mosteiro de S. Bento de Cástris, permitirá que o futuro deste património, de tanta diversidade e espessura histórico-cultural, continue a ser debatido e a justificar edições futuras resultantes dos trabalhos de investigação aí apresentados e debatidos.

Uncover the mantle: rediscovering Gregório Lopes palette and technique with a study on the painting “Mater Misericordiae”

Grego´rio Lopes (c. 1490–1550) was one of the most prominent painters of the renaissance and Mannerism in Portugal. The painting “Mater Misericordiae” made for the Sesimbra Holy House of Mercy, circa 1535–1538, is one of the most significant works of the artist, and his only painting on this theme, being also one of the most significant Portuguese paintings of sixteenth century. The recent restoration provided the possibility to study materially the painting for the first time, with a multianalytical methodology incorporating portable energy-dispersive X-ray fluorescence spectroscopy, scanning electron microscopy–energy-dispersive spectroscopy, micro-X-ray diffraction, micro-Raman spectroscopy and high-performance liquid chromatography coupled to diode array and mass spectrometry detectors. The analytical study was complemented by infrared reflectography, allowing the study of the underdrawing technique and also by dendrochronology to confirm the date of the wooden panels (1535–1538). The results of this study were compared with previous ones on the painter’s workshop, and significant differences and similitudes were found in the materials and techniques used

Evaluation of portable Raman spectroscopy and handheld X-ray fluorescence analysis (hXRF) for the direct analysis of glyptics

In archaeometry, the advantages of a combined use of Raman spectroscopy and X-ray fluorescence spectroscopy are extensively discussed for applications such as the analysis of paintings, manuscripts, pottery, etc. Here, we demonstrate for the first time the advantage of using both techniques for analysing glyptics. These engraved gemstones or glass materials were originally used as stamps, to identify the owner, for instance on letters, but also on wine vessels. For this research, a set of 64 glyptics (42 Roman glass specimens and 22 modern ones), belonging to the collection of the museum ‘Quinta das Cruzes’ in Funchal (Madeira, Portugal), was analysed with portable Raman spectroscopy and handheld X-ray fluorescence (hXRF). These techniques were also used to confirm the gemological identification of these precious objects and can give extra information about the glass composition. Raman spectroscopy identifies the molecular composition as well as on the crystalline phases present. On the other hand, hXRF results show that the antique Roman glass samples are characterised with low Pb and Sn levels and that the modern specimens can be discriminated in two groups: lead-based and non-lead-based ones.

Calcium sulfate fillers and binders in Portuguese 15th and 16th centuries: Ground layers from a family painting workshop — Study by multianalytical spectroscopic techniques

This study presents results on a developed methodology to characterize ground layers in Portuguese workshops. In this work a set of altarpieces of the 15th and 16th centuries, assigned to Coimbra painting workshop was studied, overall the masters Vicente Gil (doc. Coimbra 1498–1525), Manuel Vicente (doc. Coimbra 1521–1530) and Bernardo Manuel (act. c. 1559–94), father, son and grandson, encompassing from late gothic to mannerist periods. The aim of the study is to compare ground layers, fillers and binders of Coimbra workshop, and to correlate their characteristics to understand the technical evolution of this family of painters, using complementary microscopic techniques. The cross-sections from the groups of paintings were examined by optical microscopy and the results were integrated through the analysis obtained by μ-X–ray diffraction, scanning electron microscopy with energy dispersive X–ray Spectrometry, μ-confocal Raman and occasionally with μ-Fourier transform infrared spectroscopy imaging. Ground layers are of calcium sulfate, present as gesso grosso (mainly anhydrite with small amounts of gypsum) in the first and last phases of the workshop and gesso mate (mainly gypsum with small amounts of anhydrite) in an intermediate period. Binders have protein and oleic characteristics.

Advanced Spectroscopy for the Study of Colourants in Cultural Heritage

Colourants are substances used to change the colour of something, and are classified in three typology of colorants: a) pigments, b) dyes, and c) lakes and hybrid pigments. Their identification is very important when studying cultural heritage; it gives information about the artistic technique, can help in dating, and offers insights on the condition of the object. Besides, the study of the degradation phenomena constitutes a framework for the preventive conservation strategies, provides evidence of the object's original appearance, and contributes to the authentication of works of art. However, the complexity of these systems makes it impossible to achieve a complete understanding using a single technique, making necessary a multi-analytical approach. This work focuses on the set-up and application of advanced spectroscopic methods for the study of colourants in cultural heritage. The first chapter presents the identification of modern synthetic organic pigments using Metal Underlayer-ATR (MU-ATR), and the characterization of synthetic dyes extracted from wool fibres using a combination of Thin Layer Chromatography (TLC) coupled to MU-ATR using AgI@Au plates. The second chapter presents the study of the effect of metallic Ag in the photo-oxidation process of orpiment, and the influence of the different factors, such as light and relative humidity. We used a combination of vibrational and synchrotron radiation-based X-ray microspectroscopy techniques: µ-ATR-FT-IR, µ-Raman, SR-µ-XRF, µ-XANES at S K-, Ag L3- and As K-edges and SR-µ-XRD. The third chapter presents the study of metal carboxylates in paintings, specifically on the formation of Zn and Pb carboxylates in three different binders: stand linseed oil, whole egg, and beeswax. We used micro-ATR-FT-IR, macro FT-IR in total reflection (rMA-FT-IR), portable Near-Infrared spectroscopy (NIR), macro X-ray Powder Diffraction (MA-XRPD), XRPD, and Gas Chromatography Mass-Spectrometry (GC-MS). For the data processing, we explored the data from rMA-FT-IR and NIR with the Principal Component Analysis (PCA).

I Malvezzi della Ca' Grande: genesi, sviluppo e dispersione di una quadreria bolognese del Settecento

La ricerca ricostruisce e analizza la storia della raccolta d’arte appartenuta al ramo senatorio della famiglia Malvezzi della Ca’ Grande all’interno del variegato panorama collezionistico bolognese settecentesco. La volontà di indagarne lo sviluppo è motivata sia dalla sua esemplarità che dal suo carattere eccezionale. Fondata da Piriteo III (1658-1728) con l’acquisto e la commissione di una cinquantina di dipinti, sia di artisti contemporanei sia di maestri antichi, a cui si aggiungono le opere ereditate dagli antenati, la raccolta fu accresciuta nell’arco di sole tre generazioni. Il principale artefice dell’ampliamento del patrimonio pittorico del casato fu il figlio Sigismondo III (1703-1787), tramite il quale confluì nella quadreria anche l’importante collezione del marchese Paolo Magnani, suo zio materno. Compiendo scelte collezionistiche originali rispetto a quelle d’ordine marcatamente municipalistico, Sigismondo raccolse per la galleria della Ca’ Grande numerose opere di artisti stranieri, glorificati e ricercati in campo europeo, ma estranei di norma al gusto petroniano dell’epoca. Al marchese spetta, inoltre, l’acquisizione del celebre nucleo di opere tre-quattrocentesche, che andò a formare la Camera degli Antichi. Secondo principi illuministici, questi mirava a possedere una sorta di ideale museo privato, ove fosse possibile ammirare il progresso dell’arte petroniana dalle origini sino alla modernità e istituire paragoni fra le più importanti scuole pittoriche. Anche l’erede Piriteo IV (1734-1806) continuò ad ampliare la collezione, compiendo acquisti più limitati, ma non per questo meno significativi. Alla sua morte si estinse la linea maschile del ramo senatorio, per cui la prestigiosa quadreria fu divisa tra le figlie Maria (1780-1865) e Teresa (1782-1811). La raccolta Malvezzi non ebbe la fortuna di confluire entro collezioni durature, cosicché in cinquant’anni quella che fu una delle più importanti gallerie della Bologna settecentesca è stata irrimediabilmente dispersa.

Percorsi urbani e percorsi narrativi: il "racconto dei racconti" di via Zamboni a Bologna

La percezione dello spazio urbano, nella sua complessità, risente inevitabilmente dello stratificarsi, nel tempo, di significati storici, ideologie, archetipi e utopie attraverso i quali la società, nei suoi diversi stadi di sviluppo, ha consolidato l'idea di centro abitato. Nel mondo contemporaneo, la città narrata si sovrappone sempre di più a quella reale, organizzando e sintetizzando i processi interpretativi dei circuiti urbani: al cityscape, il panorama fisico della città, si antepone il suo mindscape, il panorama dell'anima e delle culture urbane. In sintonia con tali prospettive, la presente ricerca si propone di analizzare i processi comunicativi e i paradigmi mediatici che attraversano e ridefiniscono le dinamiche urbane, prendendo in esame gli strumenti e i linguaggi che concorrono a disegnare e raccontare l'immagine di una città. In tale contesto, il progetto prende in considerazione come case study la singolare situazione del distretto universitario intorno a via Zamboni a Bologna: un'arteria di straordinaria bellezza e vitalità, cui tuttavia non corrisponde un'immagine pubblica altrettanto positiva. La tesi ha analizzato in particolare l’immagine pubblica e la percezione di via Zamboni e di piazza Verdi dai primi del Novecento a oggi, in relazione ai principali eventi che le hanno viste come scenari privilegiati. Prendendo in considerazione un arco di tempo di oltre un secolo, sono stati selezionati alcuni momenti topici, occasioni culturali o accadimenti con una forte connotazione simbolica: dalla Liberazione alle manifestazioni del ’77, dalle storiche ‘prime’ del Teatro Comunale agli allestimenti della Pinacoteca, dalle lezioni di professori universitari di chiara fama alle più recenti contestazioni studentesche. Il risultato è un racconto stratificato che attraversa segni e immagini per ricostruire l’iconografia del quartiere attraverso testi, fotografie, filmati, opere d’arte o prodotti multimediali.

Development of new immunochemical and spectroscopic analytical methods for the characterization and conservation of works of art

Cultural heritage is constituted by complex and heterogenous materials, such as paintings but also ancient remains. However, all ancient materials are exposed to external environment and their interaction produces different changes due to chemical, physical and biological phenomena. The organic fraction, especially the proteinaceous one, has a crucial role in all these materials: in archaeology proteins reveal human habits, in artworks they disclose technics and help for a correct restoration. For these reasons the development of methods that allow the preservation of the sample as much as possible and a deeper knowledge of the deterioration processes is fundamental. The research activities presented in this PhD thesis have been focused on the development of new immunochemical and spectroscopic approaches in order to detect and identify organic substances in artistic and archaeological samples. Organic components could be present in different cultural heritage materials as constituent element (e.g., binders in paintings, collagen in bones) and their knowledge is fundamental for a complete understanding of past life, degradation processes and appropriate restauration approaches. The combination of immunological approach with a chemiluminescence detection and Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry allowed a sensitive and selective localization of collagen and elements in ancient bones and teeth. Near-infrared spectrometer and hyper spectral imaging have been applied in combination with chemometric data analysis as non-destructive methods for bones prescreening for the localization of collagen. Moreover, an investigation of amino acids in enamel has been proposed, in order to clarify teeth biomolecules survival overtime through the optimization and application of High-Performance Liquid Chromatography on modern and ancient enamel powder. New portable biosensors were developed for ovalbumin identification in paintings, thanks to the combination between biocompatible Gellan gel and electro-immunochemical sensors, to extract and identify painting binders with the contact only between gel and painting and between gel and electrodes.

Essential oils and hydrolates as potential tools for integrated prevention of bacterial diseases in plants

The present work aims to investigate the potential use of natural substances against bacterial plant pathogens. Microdilution tests were therefore carried out in vitro to identify the minimum inhibitory and bactericidal concentrations (MIC and MBC) of several EOs and Hys against selected bacterial pathogens. Commercial products based on a mixture of EOs were in addition assayed with macrodilution experiments against Erwinia amylovora (Ea-causal agent of fire blight). Subsequently, using selected EOs, Hys, and commercial products, ex vivo tests on disease incidence and Ea population dynamics were carried out; the latter experiment was followed by SEM observations. In addition, in vivo resistance induction test was carried out against bacterial leaf of tomato, caused by Xanthomonas vesicatoria (Xv). EOs and Hys showed high bactericidal activity in vitro (MBC <0.1 and <10% for the most active EOs and Hys: Origanum compactum and Thymus vulgaris EOs and Citrus aurantium var. amara Hy, respectively), but they were not effective ex vivo, while resulted very active when used in vivo as resistance inducers in the tomato-Xv pathosystem (relative protection >40%). Differently, commercial products resulted active in all tests, but not as resistance inducers against Xv. An open field trial with commercial products was carried out on strawberry plants naturally infected with Xanthomonas fragariae; the results showed discrete relative protection, concerning that provided by the conventional products based on copper; mostly, the disease severity reduction on those plants treated with EOs commercial products was significant when disease severity resulted high. The papers already published described in the present work investigate (1)the activity of Hys in comparison to EOs with respect to their active volatile content; (2) the potential use of EOs and Hys in cultural heritage; for the restoration of paintings; (3) the induction of resistance caused by plasma-activated water-based root treatments.

Benedetto Gennari ritrattista e pittore di corte in Europa tra Sei e Settecento. I dipinti, la committenza e il diario di lavoro

Cresciuto in una delle botteghe artistiche più prolifiche e illustri della Bologna di metà Seicento, Benedetto Gennari riuscì a distinguersi più degli altri collaboratori del Guercino per una brillante carriera all’estero internazionale che lo portò prima in Francia e poi in Inghilterra, dove seppe ritagliarsi uno spazio di rilievo tra i ranghi della corte, ottenendo finanche la nomina di primo pittore di Giacomo II Stuart. Partendo dall’analisi dei suoi Memoriali, dalla loro natura e dalle ragioni della loro compilazione, il presente studio intende indagare e restituire il profilo dell’artista. Attraverso l’analisi critica della documentazione autografa, di testimonianze edite e inedite e di informazione sui suoi guadagni e sul metodo di lavoro, il lavoro traccia le tappe della lunga attività del pittore, contraddistinta da commissioni di rilievo per importanti mecenati e collezionisti italiani e stranieri. Ben lontano dall’essere un semplice imitatore di provincia, Benedetto divenne un artista di corte, maturando un linguaggio raffinato e a tratti irriverente, che si configura come una personale variante del classicismo bolognese. Su questi aspetti fa luce l’apparato catalografico in cui trovano posto anche opere inedite, riletture iconografiche di quadri noti e indagini tecnico-diagnostiche effettuate, su due dipinti significativi, dal Laboratorio Diagnostico per i Beni Culturali del Dipartimento di Beni Culturali dell’Università di Bologna al fine di documentare la tecnica pittorica dell’artista dopo il suo trasferimento all’estero.

Towards a sustainable approach for Cultural Heritage Conservation: developing micro-structured green materials and analytical protocols for their performance assessment

Cleaning is one of the most important and delicate procedures that are part of the restoration process. When developing new systems, it is fundamental to consider its selectivity towards the layer to-be-removed, non-invasiveness towards the one to-be-preserved, its sustainability and non-toxicity. Besides assessing its efficacy, it is important to understand its mechanism by analytical protocols that strike a balance between cost, practicality, and reliable interpretation of results. In this thesis, the development of cleaning systems based on the coupling of electrospun fabrics (ES) and greener organic solvents is proposed. Electrospinning is a versatile technique that allows the production of micro/nanostructured non-woven mats, which have already been used as absorbents in various scientific fields, but to date, not in the restoration field. The systems produced proved to be effective for the removal of dammar varnish from paintings, where the ES not only act as solvent-binding agents but also as adsorbents towards the partially solubilised varnish due to capillary rise, thus enabling a one-step procedure. They have also been successfully applied for the removal of spray varnish from marble substrates and wall paintings. Due to the materials' complexity, the procedure had to be adapted case-by-case and mechanical action was still necessary. According to the spinning solution, three types of ES mats have been produced: polyamide 6,6, pullulan and pullulan with melanin nanoparticles. The latter, under irradiation, allows for a localised temperature increase accelerating and facilitating the removal of less soluble layers (e.g. reticulated alkyd-based paints). All the systems produced, and the mock-ups used were extensively characterised using multi-analytical protocols. Finally, a monitoring protocol and image treatment based on photoluminescence macro-imaging is proposed. This set-up allowed the study of the removal mechanism of dammar varnish and semi-quantify its residues. These initial results form the basis for optimising the acquisition set-up and data processing.

Moodle

Desenvolver uma compreensão básica de conceitos que serão utilizados frequentemente durante o curso, como por exemplo, Ensino a Distância (EAD), Ambiente Virtual de Aprendizagem (AVA), Moodle, Fórum, Mural, Chat. Diferenciar as ferramentas síncronas das assíncronas. Introduzir as ferramentas funcionais que serão utilizadas durante o curso.