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Nº De Arquivo Maria João Narciso Furtado de Melo Pereira Licenciada em Conservação e Restauro CHINESE COINS IN COPPER BASED ALLOYS: ELEMENTAL AND MICROSTRUCTURAL CHARACTERIZATION Dissertação para obtenção do Grau de Doutor em Conservação e Restauro, especialidade Ciências da Conservação Orientador: Maria de Fátima Araújo, Investigadora Principal, IST/ITN, Instituto Superior Técnico Universidade Técnica de Lisboa Co-orientador: Rui Jorge Cordeiro Silva, Professor Auxiliar, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa Júri: Presidente: Prof. Doutor Fernando Jorge da Silva Pina Arguentes: Prof. Doutor Luís Filipe Malheiros de Freitas Ferreira Prof. Doutor António José Estevão Grande Candeias Vogais: Profª Doutora Márcia Vilarigues Prof. Doutor António Manuel Monge Soares Março 2013 Chinese Coins In Copper Based Alloys: Elemental And Microstructural Characterization Copyright: Maria João Narciso Furtado, 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 objectivos educacionais ou de investigação, não comerciais, desde que seja dado crédito ao autor e editor. Lisboa, Setembro de 2012 ii Dedication & Acknowledgements To my family, especially my parents, who have always motivated me to work hard and pursue an education; and to my husband that also always supported and encouraged me. To my daughter, so she can one day read about the work that accompanied her mother during her first childhood and understand what was shown and discussed in the many conferences that she attended since such a young age. I would like to especially thank my supervisors, Maria de Fátima Araújo (IST/ITN, Instituto Superior Técnico, Universidade Técnica de Lisboa) and Rui Silva (Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa: FCT-UNL), for believing in me, for giving me the opportunity to develop this work and for the valuable and intense brainstorming sessions. My gratitude also goes to the Museum of the Macao Scientific and Cultural Centre, represented by its Director, Luis Filipe Sousa Barreto, that not only allowed the study of the numismatic collection held by the Centre, but also encouraged and promoted the developed work, among other things, through partial funding to attend the BUMA VII Conference in 2009; and by inviting me to perform a public lecture on the subject at the CCCM in 2011. I also would like to thank several individuals that positively contributed to the completion of the work this dissertation contains: My colleagues, Pedro Valério and Elin Figueiredo, for the initial training they patiently gave me, for the interesting work discussions and for their moral support. For their support towards the end of the work, I could not forget to mention the colleagues Filipa Pereira and Filipa Lopes. And also to the rest of my IST-ITN colleagues, that shared this academic and also personal walk with me: my marriage, pregnancy and raising of my daughter. My colleagues at the Structural Materials Group of CENIMAT/I3N (FCT-UNL), in the person of Francisco Manuel Braz Fernandes, for the dedication in preparing practical work, in paper reviewing and in results discussions. To the rest of the colleagues at CENIMAT/I3N, I am grateful for having felt welcome in spite we come from different areas of interest. My colleagues at the Conservation and Restoration Department (FCT-UNL), especially to Márcia Vilarigues and Ana Maria Martins, for the technical and logistic support given. To António Candeias, Isabel Ribeiro and Mª José Oliveira from IMC laboratories, for the use of their equipment and technical support given throughout this research. To Luís Filipe F. R. Thomaz (Instituto de Estudo Orientais, Universidade Católica Portuguesa) and to Augusto Mouta (private collector), for the interesting discussions and ideas relatively to the History of the Chinese numismatics. I also am in debt to the following persons for their support: Helen Wang (British Museum, U.K.), Quanyu Wang (British Museum, U.K.), Han Rubin (Institute of Historical Metallurgy & Materials – UST, China), Elisabetta Colla (CCCM, Portugal), R.M.Pillai (NIIST, India), Weirong Zhou (Beijing Numismatic Museum, China), Michael Wayman (Univ. Alberta, Canada) and João André Carriço. Finally, I am thankful for the following financial supports: - PhD grant (ref. SFRH/BD/29736/2006) awarded by the Portuguese Foundation for Science and Technology (FCT-MCTES) during the period of 2007-2011; - International Conference Attending grant awarded by Fundação Calouste Gulbenkian to attend the conference Eurocorr in 2010; - CENIMAT/I3N funding by FCT-MCTES to attend the conference TOFA in 2010. iii iv Sumário A colecção de moedas chinesas vazadas pertencentes ao Museu do CCCM em Lisboa (Portugal) foi disponibilizada para estudos analíticos e metalográficos. Tal investigação no Ocidente não é frequente neste tipo de artefacto, conquanto o número considerável de objectos semelhantes que integram museus e colecções privadas, na Europa e América do Norte. Primeiramente foi feita uma caracterização elementar por espectrometria FRXDE em 380 moedas em liga de cobre, que revelou diferentes tipos de ligas (cobres, bronzes e latões) com teores variáveis de elementos de liga e elementos vestigiais. Nas moedas de bronze, um dos principais constituintes foi o chumbo, que por vezes apresentava um teor consideravelmente variável entre os dois lados da mesma moeda. As moedas de latão apresentavam consideráveis teores de zinco (<63 %p), e frequentemente foi detectada a presença de chumbo, estanho, antimónio, ferro e arsénio. A observação microestrutural do interior das 109 moedas através de técnicas metalográficas permitiu confirmar a coerência da tecnologia de produção (vazamento em moldes de areia), e estabelecer um paralelo entre os teores elementares (obtidos por micro-FRX) e as fases metálicas (observadas por MO e MEV, e analisadas por EDS-MEV e micro-DRX), recorrendo ao estudo de diagramas de fases em condições de equilíbrio. A comparação entre a susceptibilidade à corrosão de fases metálicas nas moedas de bronze mostrou uma corrosão transglobular preferencial de glóbulos ricos em chumbo; e também que os produtos resultantes da corrosão do chumbo e/ou do estanho são frequentemente depositados na superfície destas moedas. Quanto às moedas em latão, verificou-se que o processo de corrosão mais comum era a deszincificação, e também que a presença de alguns elementos menores influenciava em grande medida a susceptibilidade à corrosão, prejudicando (p.e., o Fe) ou melhorando (p.e. o Sn, o Sb e o As) a resistência à corrosão das fases em que estes elementos mais se concentram. Os resultados obtidos são uma mais valia para a caracterização de ligas semelhantes, nomeadamente através da correlação entre os seus teores elementares e os micro-constituintes observados. O conhecimento das susceptibilidades à corrosão nas fases metálicas do bronze e do latão pode contribuir para um melhorado diagnóstico macroscópico de peças semelhantes ao nível da conservação dos objectos. Por último, todos os resultados obtidos durante este estudo suportam a autenticidade das peças. Termos-chave Arqueometalurgia, moedas, China, ligas de cobre, microestruturas multifásicas v vi Abstract The Chinese cast coin collection from the CCCM’s Museum in Lisbon (Portugal) was accessible for analytical and metallographic characterization. In spite of the considerable number of similar items that populate museums and private collectors in Europe and North America, studies carried out in the western world are very scarce. Firstly, elemental characterization by EDXRF spectrometry was performed on 380 copper-based coins, revealing different types of alloys (coppers, bronzes and brasses) with variable alloy elemental composition. In bronze coins one of the main constituents was lead, which sometimes presented considerable content variations between the obverse and reverse of the same coin. Brass coins were found to be rich in zinc (<63 wt.%), but often presented traces or small contents of lead, tin, antimony, iron and arsenic. Metallographic techniques used in the study of 109 coins microstructures could confirm the production process consistency (sand casting), and establish a parallel between the elemental contents (obtained by micro-EDXRF) and the present metallic phases (observed by OM and SEM, and analyzed by SEM- EDS and micro-XRD), resorting to equilibrium phase diagrams. A comparison between the corrosion susceptibility of metallic phases in bronze coins showed preferential transglobular corrosion of lead-rich globules, and also that lead and/or tin corrosion by- products are often deposited at the surface of these coins. When considering brass coins, the most common corrosion process was dezincification. Also, the presence of some minor elements was found to greatly influence the corrosion susceptibility, demoting (e.g., Fe) or promoting (e.g., Sn, Sb and As) the corrosion resistance of the phases in which these elements are in higher concentration. The obtained results are an added value to the characterization of similar alloys, namely through the co-relation between their elemental contents and the current micro-constituents.
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