Marcia Vilarigues - Academia.edu (original) (raw)

Papers by Marcia Vilarigues

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2013

The present paper describes the main results obtained from the characterization of a wide range o... more The present paper describes the main results obtained from the characterization of a wide range of natural and synthetic ochre samples used in Portugal from the 19th to the 20th century, including powder and oil painting samples. The powder ochre samples came from several commercial distributors and from the collection of Joaquim Rodrigo (1912-1997), a leading Portuguese artist, particularly active during the sixties and seventies. The micro-samples of oil painting tubes came from the Museu Nacional de Arte Contemporânea-Museu do Chiado (National Museum of Contemporary Art-Chiado Museum) in Lisbon and were used by Columbano Bordalo Pinheiro (1857-1929), one of the most prominent naturalist Portuguese painters. These tubes were produced by the main 19th century colourmen: Winsor & Newton, Morin et Janet, Maison Merlin, and Lefranc. The samples have been studied using μ-Fourier Transform Infrared Spectroscopy (μ-FTIR), Raman microscopy, μ-Energy Dispersive X-ray fluorescence (μ-EDXRF), and X-ray diffraction (XRD). The analyzed ochres were found to be a mixture of several components: iron oxides and hydroxides in matrixes with kaolinite, gypsum and chalk. The results obtained allowed to identify and characterize the ochres according to their matrix and chromophores. The main chromophores where identified by Raman microscopy as being hematite, goethite and magnetite. The infrared analysis of the ochre samples allowed to divide them into groups, according to the composition of the matrix. It was possible to separate ochres containing kaolinite matrix and/or sulfate matrix from ochres where only iron oxides and/or hydroxides were detected. μ-EDXRF and Raman were the best techniques to identify umber, since the presence of elements such as manganese is characteristic of these pigments. μ-EDXRF also revealed the presence of significant amounts of arsenic in all Sienna tube paints.

Vacuum, 2009

In this paper we present a study of boron-doped nc-Si:H films prepared by PECVD at high depositio... more In this paper we present a study of boron-doped nc-Si:H films prepared by PECVD at high deposition pressure (!4 mbar), high plasma power and low substrate temperature ( 200 C) using trimethylboron (TMB) as a dopant gas. The influence of deposition parameters on electrical, structural and optical properties is investigated. We determine the deposition conditions that lead to the formation of p-type nanocrystalline silicon thin films with very high crystallinity, high value of dark conductivity (>7 (U cm) À1 ) and high optical band gap (!1.7 eV). Modeling of ellipsometry spectra reveals that the film growth mechanism should proceed through a sub-surface layer mechanism that leads to silicon crystallization. The obtained films are very good candidates for application in amorphous and nanocrystalline silicon solar cells as a p-type window layer.

Corrosion crusts, composed mainly of calcium salts, are one of the main problems that can be foun... more Corrosion crusts, composed mainly of calcium salts, are one of the main problems that can be found on the surface of stained glass. In this study, chemical characterization of corrosion products was performed on the 15th-century stained-glass panel S07c, Figura Aureolada, from the Monastery of Santa Maria da Vitória, in Batalha, Portugal, and the use of ionic liquids was assessed as an alternative to conventional cleaning methods. For better characterization and analysis of the experimental procedures, several analytical techniques were used, including optical microscopy (OM), energy dispersive X-ray fluorescence (ED-XRF), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The experiments revealed that some of the ionic liquids studied can be a good alternative to current cleaning methods applied to stained glass, as they reveal good properties in the removal of corrosion crusts. Nevertheless, this is preliminary work and further studies and experimental testing are in progress; more results are needed before this method can be considered safe for the cleaning of stained glass.

... The obtained results also indicate that the yellow silver stain produced by the workshop of R... more ... The obtained results also indicate that the yellow silver stain produced by the workshop of Ricardo Leone is richer in Cu, with ... Veritá, Composition, structure et mécanisme de détérioration des grisailles, Grisaille, Jaune d'argent, Sanguine, Email et Peinture à Froid, Dossier de la ...

The present work aims to give new insights into the study of blue enamels applied on stained glas... more The present work aims to give new insights into the study of blue enamels applied on stained glass. Selected blue enamel recipes from the treatise The Handmaid to the Arts (1758) by Robert Dossie were reproduced. Components such as lead can influence the fnal colour and appearance. Its use was important to the adhesion between the enamel layer and the glass surface. Colouring agents can also have an effect on the outcome. Powdered glass such as smalt can lead to a more predictable fnal colour, allowing the glass painter to foresee the result before fring the paint. The colour of the enamels was characterized by means of fbre optic reflectance spectroscopy (FORS), comparing the results with the ones obtained for four stained-glass panels from the Pena National Palace. The FORS technique was a good frst approach for enamel characterisation, when is not possible to collect a sample for analysis.

A pintura sobre vitral apresenta um desafo para a conservação-restauro dada a sua fragilidade. Os... more A pintura sobre vitral apresenta um desafo para a conservação-restauro dada a sua fragilidade. Os materiais modernos utilizados para a pintura do vitral não reflectem as antigas tecnologias e matérias primas e por esse motivo não podem ser utilizados como materiais de referência em estudos de mecanismos de degradação e de implementação de medidas de conservação. Neste contexto, o conhecimento das técnicas de pintura histórica revela-se fundamental para uma melhor compreensão dos diferentes mecanismos que levam à sua degradação e constitui ainda uma oportunidade de melhor compreender a história desta disciplina artística.
*
The painting applied on stained glass presents a challenge for conservation-restoration due to its fragility. Modern materials used for stained glass painting do not reflect the old technologies and raw materials and therefore cannot be used as reference materials in studies of mechanisms of degradation and implementation of conservation measures. In this context, knowledge of historical painting techniques is fundamental for a better understanding of the different mechanisms that lead to their degradation and an opportunity to better understand the history of this artistic discipline.

Journal of Cultural …, 2008

... The obtained results also indicate that the yellow silver stain produced by the workshop of R... more ... The obtained results also indicate that the yellow silver stain produced by the workshop of Ricardo Leone is richer in Cu, with ... Veritá, Composition, structure et mécanisme de détérioration des grisailles, Grisaille, Jaune d'argent, Sanguine, Email et Peinture à Froid, Dossier de la ...

Nuclear Instruments & Methods in Physics Research Section B-beam Interactions With Materials and Atoms, 2011

Yellow decoration effects in stained glasses using silver staining were first applied in the begi... more Yellow decoration effects in stained glasses using silver staining were first applied in the beginning of the 14th century. The glass piece being decorated was usually painted on its side intended to be facing the exterior environment, and then fired to temperatures between 500 and 650 °C, resulting in colours ranging from pale lemon to deep orange. Stained glass fragments painted by this process and belonging to the Convento de Cristo, in Tomar, Portugal, were characterised using micro-PIXE, and complemented with other analytical techniques, namely UV–Vis spectroscopy and XRF. Preliminary analysis showed that a mixture of Ag and Cu was used for the production of the yellow staining.In order to understand this staining process and the influence of the firing temperature on the resulting colours, several soda and potash glasses with compositions similar to those of medieval glasses were produced and characterised. The role played by the addition of Cu in the final colours was also investigated.

In this study façon-de-Venise glass objects from several Portuguese archaeological sites were stu... more In this study façon-de-Venise glass objects from several Portuguese archaeological sites were studied aiming at
characterising their chemical composition, discussing the raw materials and possible provenance. These objects
were found during four archaeological excavations performed in Portugal (at Santa Clara-a-Velha Monastery
(SCV) in Coimbra, São João de Tarouca Monastery in Lamego (SJT), Miguel Fernandes Square in Beja (PMF)
and at the courtyard of the University of Coimbra (CPU)). Most fragments are dated to the 17th century, with
only two objects being dated between the 14th and 15th centuries. These last two fragments, due to chronological
reasons, can't be attributed to a façon de Venise production, but were included in this study for comparison.
The glass compositionwas characterised bymeans of particle induced X-ray emission (μ-PIXE), laser ablation inductively
coupled plasma mass spectrometry (LA-ICP-MS), and UV–Vis reflectance spectroscopy. All thirty-one
objects are composed by soda–lime–silica glass and the use of coastal plants as raw materials is suggested by
the contents of MgO, K2O, P2O5 and chlorine. The observed greyish/bluish glass hue was also investigated and
UV–Vis analysis allowed one to identify Co and Fe as the cations responsible for that hue.
Through the analysis of silica trace elements and of the flux agents it was possible to associate four objects, from
the Santa Clara-a-Velha Monastery assemblage, to Venetian production (three objects of cristallo and one object
of vitrum blanchum) and to identify two other distinct production lines.
One group comprising fragments from São João de TaroucaMonastery, presented medium alumina contents, differing
from known façon-de-Venise production centres. The other group includes most fragments from Miguel
Fernandes Square assemblage and has high alumina values, which, once again, is not consistent with any of the
known façon-de-Venise production centres. For these reasons, the existence of new façon-de-Venise production centres
is proposed.

Dissertação apresentada para obtenção do Grau de Doutor em Conservação e Restauro, especialidade ... more Dissertação apresentada para obtenção do Grau de Doutor em Conservação e Restauro, especialidade em Ciências da Conservação, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia. LISBOA 2008 Agradecimentos iii Agradecimentos O meu primeiro agradecimento vai para o Professor Doutor Rui Coelho da Silva pela amizade, orientação, apoio, incentivo e disponibilidade constantes ao longo deste trabalho. Um agradecimento ao Professor Doutor António Pires e Matos por ter aceite entrar neste barco e pelas sempre boas sugestões dadas. Ao Professor Doutor Fernando Pina que me disse "A Márcia se quer continuar a fazer investigação tem de escolher um assunto", tendo-me assim feito procurar e encontrar esta área do conhecimento que me tem dado muito prazer. À Professora Doutora Maria João Melo cuja dinâmica, motivação e procura pela excelência são sempre um exemplo a seguir. Uma palavra especial de agradecimento ao Dr. Pedro Redol pela amizade, sugestões e disponibilização das amostras dos vitrais do Mosteiro de Santa Maria da Vitória (Batalha). Ao Luís Cerqueira do ITN pela amizade, apoio, sugestões e constante disponibilidade manifestadas para as análises de microssonda iónica. Gostava também de expressar os meus agradecimentos aos meus colegas do DCR e do Centro do Vidro pela amizade, camaradagem e bom ambiente de trabalho que me foram proporcionados. À Ana Maria por estar sempre presente, tornando melhores os dias no DCR. Por fim um agradecimento especial ao Matthias e à minha família pelo apoio e incentivo constantes. Agradecimentos iv Sumário v Sumário Fragmentos de vitrais do séc. XV, provenientes do Mosteiro de Santa Maria da Vitória (Batalha), foram analisados pela primeira vez, de forma sistemática, de forma a obter-se um termo de referência para o estudo da corrosão de vidros potássicos antigos. Pare este estudo recorreu-se às espectroscopias de feixes de iões e de infravermelhos, tendo-se determinado que os vidros de base são formados por misturas de óxidos de Si, K, Ca, e de óxidos de Mn, Fe e Cu, usados como corantes, em composições que estão de acordo com o receituário da época. As grisalhas revelaram-se misturas de óxidos de Si e Pb, com elevadas concentrações de Fe e Cu, e também de Zn, cuja presença é notável uma vez que não se encontra habitualmente associado com aqueles metais. A camada de corrosão mostrou-se formada por carbonatos e oxalatos de Ca. Estabelecida a composição de referência, pretendeu-se estudar neste trabalho o efeito da introdução de elementos de coloração na deterioração de vidro potássico em presença de água, para compreender os mecanismos de corrosão dos vitrais medievais, essencial a um trabalho de conservação adequado. Assim, produziram-se vidros modelo com composições SiO 2 −CaO−K 2 O semelhantes às encontradas nos vitrais do Mosteiro da Batalha, a que foram adicionados óxidos de Cu, Fe ou Mn, isoladamente ou em combinação. Estes vidros foram sujeitos a ensaios de imersão em água de forma a simular ambientes de elevada humidade. A corrosão e a sua progressão foram caracterizadas por técnicas espectroscópicas de feixes de iões e de infravermelhos com transformada de Fourier, e por microscopia óptica, em combinação com a avaliação das alterações da solução aquosa, em particular o seu pH. As condições de testes exploradas, com e sem agitação do meio, conduziram a diferentes morfologias de superfície associadas com as diferentes taxas da corrosão. Mostra-se que se formam camadas superficiais de carbonato de Ca, e uma camada rica em Si nos períodos mais longos da imersão. Para além destas, encontram-se camadas Sumário vi enriquecidas nos elementos da transição, e uma corrosão inicial mais rápida nos vidros dopados com Cu. Este trabalho mostra que as condições experimentais escolhidas reproduzem bem a forma de corrosão encontrada nos vidros antigos de composição similar e sujeitos às condições atmosféricas ao longo de cinco séculos, e que o pH pode ser um bom parâmetro para estudar as cinéticas da corrosão em condições de humidade elevada.

Corrosion crusts, composed mainly of calcium salts, are one of the main problems that can be foun... more Corrosion crusts, composed mainly of calcium salts, are one of the main problems that can be found on the surface of stained glass. In this study, chemical characterization of corrosion products was performed on the 15th-century stained-glass panel S07c, Figura Aureolada, from the Monastery of Santa Maria da Vitória, in Batalha, Portugal, and the use of ionic liquids was assessed as an alternative to conventional cleaning methods. For better characterization and analysis of the experimental procedures, several analytical techniques were used, including optical microscopy (OM), energy dispersive X-ray fluorescence (ED-XRF), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and inductively coupled plasma atomic emission spectroscopy (ICP‑AES). The experiments revealed that some of the ionic liquids studied can be a good alternative to current cleaning methods applied to stained glass, as they reveal good properties in the removal of corrosion crusts. N...

All the glasses were found to be of soda-­‐lime-­‐silica type. The relatively high amounts of K 2... more All the glasses were found to be of soda-­‐lime-­‐silica type. The relatively high amounts of K 2 O, MgO , P 2 O 5 and the presence of chlorine suggest the use of coastal plants as the source of alkali. µ-­‐PIXE analysis also allowed to distinguish three groups regarding the alumina contents where it was possible to identify a group with low alumina contents (Al 2 O 3 < 2 wt%), a group with high alumina contents (3< Al 2 O 3 <6wt%) and a group with very high alumina contents (Al 2 O 3 > 6 wt%). This alumina content clustering suggests the use of three different silica sources which can be related to the existence of different production centers. Results will be further compared with glass compositions dating to the same period from Portugal and from several European centers , highlighting differences and similarities , and discussing the possible origin of the finds. With the aim of studying and characterizing this collection , thirty-­‐six glass fragments were sampled a...

Applied Physics A: Materials Science & Processing, 2004

Applied Physics A m. vilarigues 1,u r.c. da silva 2 Ion beam and infrared analysis of medieval st... more Applied Physics A m. vilarigues 1,u r.c. da silva 2 Ion beam and infrared analysis of medieval stained glass ABSTRACT Ion beam analysis and Fourier Transform Infrared (FTIR) spectroscopy were used to characterize 15 th century stained glass fragments from Batalha Monastery. This information is being used to help establish their origins as well as the art schools and artistic trends involved in the manufacture of these panels.

A group of late medieval and early modern glass fragments from an archaeological excavation that ... more A group of late medieval and early modern glass fragments from an archaeological excavation that took place at Avenida Miguel Fernandes in Beja, a town located in the South of Portugal, was chemically characterised by means of PIXE, micro-EDXRF and UV-Vis absorption spectroscopy. PIXE and micro-EDXRF analysis enabled the determination of the chemical composition (major, minor and trace elements) and UV-Vis absorption spectroscopy was used as a complementary technique to identify the transition metals responsible for the different colours observed in the glass objects. During the archaeological intervention, a set of 137 silos was discovered. They were used as storage containers for food during the 14th and the 15th centuries. After the end of this function, they served as rubbish pits. The glass objects were found inside these silos together with ceramics, faunal remains, coins, and metal and bone artefacts. They can be dated from the 14th to 17th century, thus providing an overview...

Organic pollutants such as formic acid , acetic acid and formaldehyde released by some materials ... more Organic pollutants such as formic acid , acetic acid and formaldehyde released by some materials (mainly wood) used for storage and display can play an important role on the alteration of the glass structure due to the alkali leaching process. It as been determined that formic acid when present inside storage or display cabinets is the one that affects most glass integrity , accelerating and deepening the alkali leaching from the silica matrix. As this situation can affect many museums on their glass collections , monitoring this compound would be of great importance for indoor preservation purposes. An optical sensor based on the layer-­‐by-­‐layer (LbL) electrostatic self-­‐assembly process is under development to identify indoor formic acid based on the immobilization of chemo-­‐responsive dyes in polymeric structures. The sensors are based on an optical response resulting from the reaction between immobilized dyes and the referred organic pollutant .

In 2008 an external ion microbeam analytical end-station became operational at the ion microprobe... more In 2008 an external ion microbeam analytical end-station became operational at the ion microprobe facility of the Laboratório de Feixe de Iões at Instituto Tecnológico e Nuclear, Portugal. Its availability adds a set of valuable analytical techniques for the community involved in the study and conservation of Cultural Heritage. With the external ion microbeam it is possible to analyze the elemental composition (in point, line or areal maps modes) and perform structural studies of different objects, large or small, using Ion Beam Analysis techniques in open air or helium atmosphere – i.e. without vacuum conditions – and without the need of sampling or any special preparation. In this article, the details concerning the external beam set-up and a selection of the results obtained from selected analyzed objects will be presented. These objects include glass fragments from a Roman villa and religious gilt objects from the XVI-XVIII centuries.

Amadeo de Souza Cardoso (1887-1918) is one of the most important Portuguese modernist artists. In... more Amadeo de Souza Cardoso (1887-1918) is one of the most important Portuguese modernist artists. In his short life he explored and combined different influences, particularly when he lived in Paris, where he was in contact with the avant-garde artists. The materials and techniques used by Amadeo are studied in the project Crossing Borders- History, materials and techniques of Portuguese painters from 1850-1918 which aims at the conservation, valorization, and access to Portuguese artists. Texture, composition and, above all, colour are the crucial features that should be explored to analyze his work. Indeed, as expressed by Gonçalves: “the impact of his [Amadeo’s] paint stems, largely, from the combination of the maximum energy of the forms with the maximum power of colours...” [1]. The goal of this work was to investigate the colorimetric properties of a representative number of paintings of Amadeo preserved at the Center of Modern Arts of the Gulbenkian Foundation, in Lisbon. Twenty...

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2013

The present paper describes the main results obtained from the characterization of a wide range o... more The present paper describes the main results obtained from the characterization of a wide range of natural and synthetic ochre samples used in Portugal from the 19th to the 20th century, including powder and oil painting samples. The powder ochre samples came from several commercial distributors and from the collection of Joaquim Rodrigo (1912-1997), a leading Portuguese artist, particularly active during the sixties and seventies. The micro-samples of oil painting tubes came from the Museu Nacional de Arte Contemporânea-Museu do Chiado (National Museum of Contemporary Art-Chiado Museum) in Lisbon and were used by Columbano Bordalo Pinheiro (1857-1929), one of the most prominent naturalist Portuguese painters. These tubes were produced by the main 19th century colourmen: Winsor &amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp; Newton, Morin et Janet, Maison Merlin, and Lefranc. The samples have been studied using μ-Fourier Transform Infrared Spectroscopy (μ-FTIR), Raman microscopy, μ-Energy Dispersive X-ray fluorescence (μ-EDXRF), and X-ray diffraction (XRD). The analyzed ochres were found to be a mixture of several components: iron oxides and hydroxides in matrixes with kaolinite, gypsum and chalk. The results obtained allowed to identify and characterize the ochres according to their matrix and chromophores. The main chromophores where identified by Raman microscopy as being hematite, goethite and magnetite. The infrared analysis of the ochre samples allowed to divide them into groups, according to the composition of the matrix. It was possible to separate ochres containing kaolinite matrix and/or sulfate matrix from ochres where only iron oxides and/or hydroxides were detected. μ-EDXRF and Raman were the best techniques to identify umber, since the presence of elements such as manganese is characteristic of these pigments. μ-EDXRF also revealed the presence of significant amounts of arsenic in all Sienna tube paints.

Vacuum, 2009

In this paper we present a study of boron-doped nc-Si:H films prepared by PECVD at high depositio... more In this paper we present a study of boron-doped nc-Si:H films prepared by PECVD at high deposition pressure (!4 mbar), high plasma power and low substrate temperature ( 200 C) using trimethylboron (TMB) as a dopant gas. The influence of deposition parameters on electrical, structural and optical properties is investigated. We determine the deposition conditions that lead to the formation of p-type nanocrystalline silicon thin films with very high crystallinity, high value of dark conductivity (>7 (U cm) À1 ) and high optical band gap (!1.7 eV). Modeling of ellipsometry spectra reveals that the film growth mechanism should proceed through a sub-surface layer mechanism that leads to silicon crystallization. The obtained films are very good candidates for application in amorphous and nanocrystalline silicon solar cells as a p-type window layer.

Corrosion crusts, composed mainly of calcium salts, are one of the main problems that can be foun... more Corrosion crusts, composed mainly of calcium salts, are one of the main problems that can be found on the surface of stained glass. In this study, chemical characterization of corrosion products was performed on the 15th-century stained-glass panel S07c, Figura Aureolada, from the Monastery of Santa Maria da Vitória, in Batalha, Portugal, and the use of ionic liquids was assessed as an alternative to conventional cleaning methods. For better characterization and analysis of the experimental procedures, several analytical techniques were used, including optical microscopy (OM), energy dispersive X-ray fluorescence (ED-XRF), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The experiments revealed that some of the ionic liquids studied can be a good alternative to current cleaning methods applied to stained glass, as they reveal good properties in the removal of corrosion crusts. Nevertheless, this is preliminary work and further studies and experimental testing are in progress; more results are needed before this method can be considered safe for the cleaning of stained glass.

... The obtained results also indicate that the yellow silver stain produced by the workshop of R... more ... The obtained results also indicate that the yellow silver stain produced by the workshop of Ricardo Leone is richer in Cu, with ... Veritá, Composition, structure et mécanisme de détérioration des grisailles, Grisaille, Jaune d&#x27;argent, Sanguine, Email et Peinture à Froid, Dossier de la ...

The present work aims to give new insights into the study of blue enamels applied on stained glas... more The present work aims to give new insights into the study of blue enamels applied on stained glass. Selected blue enamel recipes from the treatise The Handmaid to the Arts (1758) by Robert Dossie were reproduced. Components such as lead can influence the fnal colour and appearance. Its use was important to the adhesion between the enamel layer and the glass surface. Colouring agents can also have an effect on the outcome. Powdered glass such as smalt can lead to a more predictable fnal colour, allowing the glass painter to foresee the result before fring the paint. The colour of the enamels was characterized by means of fbre optic reflectance spectroscopy (FORS), comparing the results with the ones obtained for four stained-glass panels from the Pena National Palace. The FORS technique was a good frst approach for enamel characterisation, when is not possible to collect a sample for analysis.

A pintura sobre vitral apresenta um desafo para a conservação-restauro dada a sua fragilidade. Os... more A pintura sobre vitral apresenta um desafo para a conservação-restauro dada a sua fragilidade. Os materiais modernos utilizados para a pintura do vitral não reflectem as antigas tecnologias e matérias primas e por esse motivo não podem ser utilizados como materiais de referência em estudos de mecanismos de degradação e de implementação de medidas de conservação. Neste contexto, o conhecimento das técnicas de pintura histórica revela-se fundamental para uma melhor compreensão dos diferentes mecanismos que levam à sua degradação e constitui ainda uma oportunidade de melhor compreender a história desta disciplina artística.
*
The painting applied on stained glass presents a challenge for conservation-restoration due to its fragility. Modern materials used for stained glass painting do not reflect the old technologies and raw materials and therefore cannot be used as reference materials in studies of mechanisms of degradation and implementation of conservation measures. In this context, knowledge of historical painting techniques is fundamental for a better understanding of the different mechanisms that lead to their degradation and an opportunity to better understand the history of this artistic discipline.

Journal of Cultural …, 2008

... The obtained results also indicate that the yellow silver stain produced by the workshop of R... more ... The obtained results also indicate that the yellow silver stain produced by the workshop of Ricardo Leone is richer in Cu, with ... Veritá, Composition, structure et mécanisme de détérioration des grisailles, Grisaille, Jaune d&#x27;argent, Sanguine, Email et Peinture à Froid, Dossier de la ...

Nuclear Instruments & Methods in Physics Research Section B-beam Interactions With Materials and Atoms, 2011

Yellow decoration effects in stained glasses using silver staining were first applied in the begi... more Yellow decoration effects in stained glasses using silver staining were first applied in the beginning of the 14th century. The glass piece being decorated was usually painted on its side intended to be facing the exterior environment, and then fired to temperatures between 500 and 650 °C, resulting in colours ranging from pale lemon to deep orange. Stained glass fragments painted by this process and belonging to the Convento de Cristo, in Tomar, Portugal, were characterised using micro-PIXE, and complemented with other analytical techniques, namely UV–Vis spectroscopy and XRF. Preliminary analysis showed that a mixture of Ag and Cu was used for the production of the yellow staining.In order to understand this staining process and the influence of the firing temperature on the resulting colours, several soda and potash glasses with compositions similar to those of medieval glasses were produced and characterised. The role played by the addition of Cu in the final colours was also investigated.

In this study façon-de-Venise glass objects from several Portuguese archaeological sites were stu... more In this study façon-de-Venise glass objects from several Portuguese archaeological sites were studied aiming at
characterising their chemical composition, discussing the raw materials and possible provenance. These objects
were found during four archaeological excavations performed in Portugal (at Santa Clara-a-Velha Monastery
(SCV) in Coimbra, São João de Tarouca Monastery in Lamego (SJT), Miguel Fernandes Square in Beja (PMF)
and at the courtyard of the University of Coimbra (CPU)). Most fragments are dated to the 17th century, with
only two objects being dated between the 14th and 15th centuries. These last two fragments, due to chronological
reasons, can't be attributed to a façon de Venise production, but were included in this study for comparison.
The glass compositionwas characterised bymeans of particle induced X-ray emission (μ-PIXE), laser ablation inductively
coupled plasma mass spectrometry (LA-ICP-MS), and UV–Vis reflectance spectroscopy. All thirty-one
objects are composed by soda–lime–silica glass and the use of coastal plants as raw materials is suggested by
the contents of MgO, K2O, P2O5 and chlorine. The observed greyish/bluish glass hue was also investigated and
UV–Vis analysis allowed one to identify Co and Fe as the cations responsible for that hue.
Through the analysis of silica trace elements and of the flux agents it was possible to associate four objects, from
the Santa Clara-a-Velha Monastery assemblage, to Venetian production (three objects of cristallo and one object
of vitrum blanchum) and to identify two other distinct production lines.
One group comprising fragments from São João de TaroucaMonastery, presented medium alumina contents, differing
from known façon-de-Venise production centres. The other group includes most fragments from Miguel
Fernandes Square assemblage and has high alumina values, which, once again, is not consistent with any of the
known façon-de-Venise production centres. For these reasons, the existence of new façon-de-Venise production centres
is proposed.

Dissertação apresentada para obtenção do Grau de Doutor em Conservação e Restauro, especialidade ... more Dissertação apresentada para obtenção do Grau de Doutor em Conservação e Restauro, especialidade em Ciências da Conservação, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia. LISBOA 2008 Agradecimentos iii Agradecimentos O meu primeiro agradecimento vai para o Professor Doutor Rui Coelho da Silva pela amizade, orientação, apoio, incentivo e disponibilidade constantes ao longo deste trabalho. Um agradecimento ao Professor Doutor António Pires e Matos por ter aceite entrar neste barco e pelas sempre boas sugestões dadas. Ao Professor Doutor Fernando Pina que me disse "A Márcia se quer continuar a fazer investigação tem de escolher um assunto", tendo-me assim feito procurar e encontrar esta área do conhecimento que me tem dado muito prazer. À Professora Doutora Maria João Melo cuja dinâmica, motivação e procura pela excelência são sempre um exemplo a seguir. Uma palavra especial de agradecimento ao Dr. Pedro Redol pela amizade, sugestões e disponibilização das amostras dos vitrais do Mosteiro de Santa Maria da Vitória (Batalha). Ao Luís Cerqueira do ITN pela amizade, apoio, sugestões e constante disponibilidade manifestadas para as análises de microssonda iónica. Gostava também de expressar os meus agradecimentos aos meus colegas do DCR e do Centro do Vidro pela amizade, camaradagem e bom ambiente de trabalho que me foram proporcionados. À Ana Maria por estar sempre presente, tornando melhores os dias no DCR. Por fim um agradecimento especial ao Matthias e à minha família pelo apoio e incentivo constantes. Agradecimentos iv Sumário v Sumário Fragmentos de vitrais do séc. XV, provenientes do Mosteiro de Santa Maria da Vitória (Batalha), foram analisados pela primeira vez, de forma sistemática, de forma a obter-se um termo de referência para o estudo da corrosão de vidros potássicos antigos. Pare este estudo recorreu-se às espectroscopias de feixes de iões e de infravermelhos, tendo-se determinado que os vidros de base são formados por misturas de óxidos de Si, K, Ca, e de óxidos de Mn, Fe e Cu, usados como corantes, em composições que estão de acordo com o receituário da época. As grisalhas revelaram-se misturas de óxidos de Si e Pb, com elevadas concentrações de Fe e Cu, e também de Zn, cuja presença é notável uma vez que não se encontra habitualmente associado com aqueles metais. A camada de corrosão mostrou-se formada por carbonatos e oxalatos de Ca. Estabelecida a composição de referência, pretendeu-se estudar neste trabalho o efeito da introdução de elementos de coloração na deterioração de vidro potássico em presença de água, para compreender os mecanismos de corrosão dos vitrais medievais, essencial a um trabalho de conservação adequado. Assim, produziram-se vidros modelo com composições SiO 2 −CaO−K 2 O semelhantes às encontradas nos vitrais do Mosteiro da Batalha, a que foram adicionados óxidos de Cu, Fe ou Mn, isoladamente ou em combinação. Estes vidros foram sujeitos a ensaios de imersão em água de forma a simular ambientes de elevada humidade. A corrosão e a sua progressão foram caracterizadas por técnicas espectroscópicas de feixes de iões e de infravermelhos com transformada de Fourier, e por microscopia óptica, em combinação com a avaliação das alterações da solução aquosa, em particular o seu pH. As condições de testes exploradas, com e sem agitação do meio, conduziram a diferentes morfologias de superfície associadas com as diferentes taxas da corrosão. Mostra-se que se formam camadas superficiais de carbonato de Ca, e uma camada rica em Si nos períodos mais longos da imersão. Para além destas, encontram-se camadas Sumário vi enriquecidas nos elementos da transição, e uma corrosão inicial mais rápida nos vidros dopados com Cu. Este trabalho mostra que as condições experimentais escolhidas reproduzem bem a forma de corrosão encontrada nos vidros antigos de composição similar e sujeitos às condições atmosféricas ao longo de cinco séculos, e que o pH pode ser um bom parâmetro para estudar as cinéticas da corrosão em condições de humidade elevada.

Corrosion crusts, composed mainly of calcium salts, are one of the main problems that can be foun... more Corrosion crusts, composed mainly of calcium salts, are one of the main problems that can be found on the surface of stained glass. In this study, chemical characterization of corrosion products was performed on the 15th-century stained-glass panel S07c, Figura Aureolada, from the Monastery of Santa Maria da Vitória, in Batalha, Portugal, and the use of ionic liquids was assessed as an alternative to conventional cleaning methods. For better characterization and analysis of the experimental procedures, several analytical techniques were used, including optical microscopy (OM), energy dispersive X-ray fluorescence (ED-XRF), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and inductively coupled plasma atomic emission spectroscopy (ICP‑AES). The experiments revealed that some of the ionic liquids studied can be a good alternative to current cleaning methods applied to stained glass, as they reveal good properties in the removal of corrosion crusts. N...

All the glasses were found to be of soda-­‐lime-­‐silica type. The relatively high amounts of K 2... more All the glasses were found to be of soda-­‐lime-­‐silica type. The relatively high amounts of K 2 O, MgO , P 2 O 5 and the presence of chlorine suggest the use of coastal plants as the source of alkali. µ-­‐PIXE analysis also allowed to distinguish three groups regarding the alumina contents where it was possible to identify a group with low alumina contents (Al 2 O 3 < 2 wt%), a group with high alumina contents (3< Al 2 O 3 <6wt%) and a group with very high alumina contents (Al 2 O 3 > 6 wt%). This alumina content clustering suggests the use of three different silica sources which can be related to the existence of different production centers. Results will be further compared with glass compositions dating to the same period from Portugal and from several European centers , highlighting differences and similarities , and discussing the possible origin of the finds. With the aim of studying and characterizing this collection , thirty-­‐six glass fragments were sampled a...

Applied Physics A: Materials Science & Processing, 2004

Applied Physics A m. vilarigues 1,u r.c. da silva 2 Ion beam and infrared analysis of medieval st... more Applied Physics A m. vilarigues 1,u r.c. da silva 2 Ion beam and infrared analysis of medieval stained glass ABSTRACT Ion beam analysis and Fourier Transform Infrared (FTIR) spectroscopy were used to characterize 15 th century stained glass fragments from Batalha Monastery. This information is being used to help establish their origins as well as the art schools and artistic trends involved in the manufacture of these panels.

A group of late medieval and early modern glass fragments from an archaeological excavation that ... more A group of late medieval and early modern glass fragments from an archaeological excavation that took place at Avenida Miguel Fernandes in Beja, a town located in the South of Portugal, was chemically characterised by means of PIXE, micro-EDXRF and UV-Vis absorption spectroscopy. PIXE and micro-EDXRF analysis enabled the determination of the chemical composition (major, minor and trace elements) and UV-Vis absorption spectroscopy was used as a complementary technique to identify the transition metals responsible for the different colours observed in the glass objects. During the archaeological intervention, a set of 137 silos was discovered. They were used as storage containers for food during the 14th and the 15th centuries. After the end of this function, they served as rubbish pits. The glass objects were found inside these silos together with ceramics, faunal remains, coins, and metal and bone artefacts. They can be dated from the 14th to 17th century, thus providing an overview...

Organic pollutants such as formic acid , acetic acid and formaldehyde released by some materials ... more Organic pollutants such as formic acid , acetic acid and formaldehyde released by some materials (mainly wood) used for storage and display can play an important role on the alteration of the glass structure due to the alkali leaching process. It as been determined that formic acid when present inside storage or display cabinets is the one that affects most glass integrity , accelerating and deepening the alkali leaching from the silica matrix. As this situation can affect many museums on their glass collections , monitoring this compound would be of great importance for indoor preservation purposes. An optical sensor based on the layer-­‐by-­‐layer (LbL) electrostatic self-­‐assembly process is under development to identify indoor formic acid based on the immobilization of chemo-­‐responsive dyes in polymeric structures. The sensors are based on an optical response resulting from the reaction between immobilized dyes and the referred organic pollutant .

In 2008 an external ion microbeam analytical end-station became operational at the ion microprobe... more In 2008 an external ion microbeam analytical end-station became operational at the ion microprobe facility of the Laboratório de Feixe de Iões at Instituto Tecnológico e Nuclear, Portugal. Its availability adds a set of valuable analytical techniques for the community involved in the study and conservation of Cultural Heritage. With the external ion microbeam it is possible to analyze the elemental composition (in point, line or areal maps modes) and perform structural studies of different objects, large or small, using Ion Beam Analysis techniques in open air or helium atmosphere – i.e. without vacuum conditions – and without the need of sampling or any special preparation. In this article, the details concerning the external beam set-up and a selection of the results obtained from selected analyzed objects will be presented. These objects include glass fragments from a Roman villa and religious gilt objects from the XVI-XVIII centuries.

Amadeo de Souza Cardoso (1887-1918) is one of the most important Portuguese modernist artists. In... more Amadeo de Souza Cardoso (1887-1918) is one of the most important Portuguese modernist artists. In his short life he explored and combined different influences, particularly when he lived in Paris, where he was in contact with the avant-garde artists. The materials and techniques used by Amadeo are studied in the project Crossing Borders- History, materials and techniques of Portuguese painters from 1850-1918 which aims at the conservation, valorization, and access to Portuguese artists. Texture, composition and, above all, colour are the crucial features that should be explored to analyze his work. Indeed, as expressed by Gonçalves: “the impact of his [Amadeo’s] paint stems, largely, from the combination of the maximum energy of the forms with the maximum power of colours...” [1]. The goal of this work was to investigate the colorimetric properties of a representative number of paintings of Amadeo preserved at the Center of Modern Arts of the Gulbenkian Foundation, in Lisbon. Twenty...