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Portuguese Silver from the 15Th to the 17Th Century, the 11 Dinheiros Silver Coins

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Portuguese Silver from the 15Th to the 17Th Century, the 11 Dinheiros Silver Coins Rui Luís Perry da Camara Borges Mestre em Conservação e Restauro pela Universidade Nova de Lisboa Portuguese silver from the 15th to the 17th century, the 11 dinheiros silver coins Dissertação para obtenção do Grau de Doutor em Ciência e Engenharia de Materiais – Especialidade em Ciência de Materiais Orientador: Rui Jorge Cordeiro da Silva, Professor Auxiliar, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa Co-orientador: Maria de Fátima Araújo, Investigadora Principal, C2TN, Instituto Superior Técnico, Universidade de Lisboa António José Estevão Grande Candeias, Professor Associado c/ Agregação, Laboratório HERCULES, Universidade de Évora Júri: Presidente: Prof. Doutor Jorge Orestes Lasbarrères Cerdeira Arguentes: Prof. Doutor Luís Filipe Malheiros de Freitas Ferreira Prof. Doutor Rui Manuel Sobral Centeno Vogais: Prof. Doutor Francisco Manuel Braz Fernandes Prof. Doutor José António Paulo Mirão Prof. Doutor Luís Manuel Cerqueira Lopes Alves Prof. Doutor Rui Jorge Cordeiro da Silva Dezembro, 2018 Portuguese Silver from the 15th to the 17th century, the 11 dinheiros coins Copyright © Rui Luís Perry da Camara Borges, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa. A Faculdade de Ciências e Tecnologia e a Universidade Nova de Lisboa têm o direito, perpétuo e sem limites geográficos, de arquivar e publicar esta dissertação através de exemplares impressos reproduzidos em papel ou de forma digital, ou por qualquer outro meio conhecido ou que venha a ser inventado, e de a divulgar através de repositórios científicos e de admitir a sua cópia e distribuição com objetivos educacionais ou de investigação, não comerciais, desde que seja dado crédito ao autor e editor. Dedicated to my family i ii Acknowledgments I shall thank to the following host institutions who have permitted me to develop my investigation: ― Instituto de Nanoestruturas, Nanomodelação e Nanofabricação (CENIMAT/I3N), Departamento de Ciências dos Materiais (DCM), Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal, ― Centro de Ciências e Tecnologias Nucleares (C2TN), Departamento de Engenharia e Ciências Nucleares (DECN), Instituto Superior Técnico, Universidade de Lisboa, Estrada Nacional, 10 (km 139.7), 2695-066 Bobadela LRS, Portugal, ― Laboratório HERCULES, Herança Cultural, Estudos e Salvaguarda, Universidade de Évora, Largo Marquês de Marialva, 8, Palácio do Vimioso, 7000-089 Évora, Portugal, ― Laboratório José de Figueiredo (LJF), Rua das Janelas Verdes 37, 1200-690 Lisboa, Portugal. ― Museu Nacional de Arte Antiga (MNAA), Rua das Janelas Verdes, 1239-017 Lisboa, Portugal, and to the following Numismatic Museums for providing access to their silver coin collections: ― Imprensa Nacional Casa da Moeda SA (INCM), Museu Numismático Português, namely to Maria João Gaiato, and ― Banco de Portugal (BdP), Museu do Dinheiro, namely to Sara Barriga and João Pedro Vieira. I would like to express my gratitude and sincere thanks to: ― My supervisors, my past university colleague and friend Rui Jorge Cordeiro da Silva (CENIMAT/I3N, DCM, FCT-UNL), Maria de Fátima Araújo (C2TN, IST-UL) and António José Estevão Grande Candeias (HERCULES, UEvora), for all the advice, guidance, patience and efforts that allowed me to accomplish this investigation, ― Luís Cerqueira Alves (C2TN, IST-UL) to whom I must make a special greatfull recognition for all his involvement and collaboration in my project, carrying out the major part of the coins and artefacts analyses, and whom I recognize as having been in practice an important supervisor as well, ― João Pedro Vieira (BdP, Museu do Dinheiro) for all the important historical and numismatical contributions and sharing of ideas that contributed to the accomplishment of this investigation, ― Gabriela Carvalho (LJF), for the assistance provided for analysing museum objects, and Luísa Penalva (MNAA) for allowing the research carried out in MNAA silverware objects, ― Pedro Aguiar-Branco and Álvaro Roquette for the disponibilization of important silverware objects for compositional analysis, ― Victoria Corregidor (C2TN, IST-UNL), Pedro Valério (C2TN, IST-UL) and Pedro Barrulas HERCULES, UEvora) for their important involment and help in the different analytical methods of coins investigation, iii ― João Cruz (DF, FCT-UNL) for having provided some coins for the invasive investigation and all his contributions to the accomplishment of this work, ― José Mirão and Luís Dias (HERCULES, UEvora), for the SEM analysis carried out at Laboratório HERCULES, ― Ernesto Figueiredo and Vitor Duarte Teodoro for their help in the indispensable statistical analysis, ― All members and collaborators of Departamento de Ciências dos Materiais (DCM, FCT- UNL) and CENIMAT/I3N, namely Elin Figueiredo and Filipa Lopes, ― and to all persons not mentioned by name, but with whom I had the privilege of sharing ideias, knowledges and comments contributing to the development of my PhD thesis. I acknowledge the financial support from Fundação para a Ciência e Tecnologia through my PhD Grant (SFRH/BD/79532/2011). Regarding the host institutions, this work was made possible by FEDER funds through the COMPETE 2020 Programme, and National Funds through Fundação para a Ciência e Tecnologia under the projects numbers UID/Multi/04349/2013 (C2TN) and POCI-01-0145-FEDER-007688, Reference UID/CTM/50025S (CENIMAT/I3N). A last final thank should be endossed by me to my family and friends, who have understood my absence for many times even in important moments, and who have always supported and encouraged me to finish this work. iv “Tudo que existe existe talvez porque outra coisa existe. Nada é, tudo coexiste: talvez assim seja certo”. Fernando Pessoa, Livro do Desassossego, 1888-1935 v vi Published work Part of the important content of this PhD thesis has been published in an international journal included in the Science Citation Index (SCI). Article published in international peer-reviewed jounal: ― Borges, R., Alves, L., Silva, R.J.C., Araújo, M.F., Candeias, A., Corregidor, V., Valério, P., Barrulas, P., 2017. Investigation of surface silver enrichment in ancient high silver alloys by PIXE, EDXRF, LA-ICP-MS and SEM-EDS, Microchemical Journal 131, 103-111, http://dx.doi.org/10.1016/j.microc.2016.12.002. vii viii Resumo Os teores de prata elevados na superfície de moedas de elevado título de prata têm sido considerados, em alguns casos, como resultantes de ligas de prata muito puras e fidedignos da composição original do seu núcleo. Até agora, tem-se desvalorizado a influência do enriquecimento superficial de prata nos resultados analíticos da superfície em moedas de prata com um título superior ao teor de prata indexado ao valor máximo da solubilidade sólida do cobre em prata (91,2% em peso). Esta investigação, direcionada para a caracterização microestrutural e química das moedas de prata portuguesas de 11 dinheiros, demonstrou a existência de importantes enriquecimentos superficiais em prata nas moedas de elevado título de prata. Nestas ligas de prata, o processo de fabrico das moedas origina uma camada subsuperficial com uma microestrutura modificada resultante de corrosão seca intergranular provocada pelas operações de recozimento e relacionada principalmente com a lixiviação preferencial da fase rica em cobre numa profundidade subsuperficial. Esta camada subsuperficial origina uma sobreestimação do teor de prata analisado por PIXE ou EDXRF, 4 a 7% maior do que aquele do núcleo das moedas, com um gradiente de composição elementar e uma profundidade desconhecida que pode estender-se até cerca de 70 μm. Este estudo mostra através da combinação de diferentes métodos de análise, EDXRF, PIXE, SEM-EDS e LA-ICP-MS, que pode perder-se informação metalúrgica relevante resultante do processo de cunhagem com base apenas numa análise superficial das ligas de elevado título de prata. Embora existam gradientes de composição de elementos menores/traço entre a superfície e o núcleo das moedas, a correlação dos seus teores à superfície permite discriminar diferentes origens da prata processada durante os séculos XV a XVII em Portugal, e nas casas da moeda de Lisboa e do Porto em diferentes períodos históricos. Os rácios de Au/Bi relacionados com a composição inicial da prata processada e os rácios de Pb/Bi relacionados com os processos metalúrgicos da prata são discriminadores importantes das ligas de elevado título de prata. O Hg é também um elemento importante para a discriminação das diferentes origens da prata. A cunhagem da moeda portuguesa processou diferentes origens de prata durante os séculos XV a XVII. A prata europeia com teores de Au e Hg elevados, e de Pb e Bi baixos, forneceu as cronologias mais antigas de Dom Afonso V e Dom João II no século XV, sendo substituída no dealbar do século XVI por um novo metal precioso que entra na capital portuguesa, com baixo teor de Au e com teor de Bi elevado, derivado provavelmente do processamento de minério de cobre argentífero. No 2º e 3º quartéis do século XVI, o teor dos elementos menores/traço de Lisboa e do Porto evolui para a homogeneização da composição observada no período Dom Sebastião I, devido provavelmente a grandes operações de reciclagem da moeda anterior realizadas em cada reinado. As cronologias Filipinas revelam a presença da nova prata americana de Potosí, introduzida em Portugal por Dom Filipe I (Felipe II da Espanha), distinguida da prata europeia em uso até 1578 no território português, pelo teor de Au < 100 ppm e de Bi muito baixo. A prata de Potosí é identificada
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