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General Introduction Sustainability Issues in the Preservation of Black and White Cellulose Esters Film- Based Negatives Collections

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General Introduction Sustainability Issues in the Preservation of Black and White Cellulose Esters Film- Based Negatives Collections Élia Catarina Tavares Costa Roldão Licenciada em Conservação e Restauro A contribution for the preservation of cellulose esters black and white negatives Dissertação para obtenção do Grau de Doutor em Ciências da Conservação do Património, Especialidade em Ciências da Conservação Orientador: Doutora Ana Maria Martelo Ramos, Professora Associada, FCT NOVA Co-orientadores: Doutor Bertrand Lavédrine, CRC Doutor António Jorge D. Parola, Professor Associado com Agregação, FCT NOVA Júri: Presidente: Doutora Maria João Seixas de Melo, Professora Catedrática, FCTNOVA Arguentes: Doutor Hugh Douglas Burrows, Professor Catedrático Jubilado, FCT-UC Doutora Ana Isabel S. C. Delgado Martins, Directora do AHU-DGLAB Vogais: Doutora Ana Maria Martelo Ramos, Professora Associada, FCT NOVA Doutor João Pedro Martins de Almeida Lopes, Professor Auxiliar, FF- UL Novembro, 2018 A contribution for the preservation of cellulose esters black and white negatives Copyright © Élia Catarina Tavares Costa Roldão, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa. A Faculdade de Ciências e Tecnologia e 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 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. iii iv Dedicated to my family v vi Acknowlegments This research was developed at the Department of Conservation and Restoration, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa (FCT-UNL); Arquivo Histórico Ultramarino (AHU), Sistema de Inventário do Património Arquitectónico (SIPA); Arquivo de Documentação Fotográfica (ADF); and Arquivo Fotográfico da Biblioteca de Arte da Fundação Calouste Gulbenkian (BA-FCG) The work was financially supported by Fundação para a Ciência e Tecnologia – Ministério da Educação e Ciência (FCT/MEC) with a doctoral grant (SFRH/BD/72560/2010). First of all, I would like to thank my surpervisor, Professor Ana Maria Ramos, for her enthusiastic support, encouragement and guidance. To my co-supervisors Professor Dr. Bertrand Lavédrine and Professor Dr. António Parola, for guidance, important inputs and unconditional support. To my thesis advisory committee (Comissão de Acompanhamento da Tese), Prof. João Lopes and Prof. Rudolf Gschwind, thank you both for the discussion and inputs on the PhD Thesis Plan Evaluation. I would also like to thank all those responsible for the archives who have allowed me to access and study the collections selected for this work. I extend my most sincere thanks to Dr. Ana Martins, Dr. Alexandra Encarnação, Dr. Ana Paula Gordo and Dr. João Vieira, the vote of confidence and the support during the accomplishment of this work. I am also grateful to all the people that contributed to this study and helped me during the experimental work and data analysis: Prof. Maria João Melo (DCR, FCTUNL) for the FTIR analysis and discussion; Prof. Joana Lia Ferreira for FTIR discussion, Prof. Márcia Vilarigues and Prof. Inês Coutinho (DCR, FCTUNL), for the EDXRF analysis; dear colleagues Eva Marisole Angelin and Artur Neves for the Raman analysis, Prof. António Candeias and Dr. Gabriela Carvalho (DGPC), for the artificial ageing chamber; Daniela Gomes (CENIMAT/I3N), for the SEM-EDS analysis; Dr. José Carlos Rodrigues (IICT) for the NIR spectroscopy. To my fellow curators, photographers and archivists, Ana Coelho, Catarina Mateus, Catarina Gonçalves, Élia Marques, Lúcia Moutinho, Sónia Casquiço, Luisa Oliveira, Luís Pavão, José Paulo Ruas, Sofia Torrado, João Paulo Machado and Cátia Martins, thank you all for the encouragement and debate. To all my fellow labmates, a special thanks for your friendship, for the exchange of ideas, and for all the fun times we shared. My most sincere thanks to Ângela Ferraz, Ana Margarida Silva, Filipa Pereira, Joana Silva, Marta Félix, Sara Babo, Sílvia Sequeira, Susana Belchior, Susana Sá and Tatiana Vitorino. To Ana Maria, for her patience and support. To my friends, Catarina, Carolina, Luísa, Maria João, Ana, Rosa, Vanda, Isa and Pedro, thank you for always being there for me. vii To my parents and brother, Diana and Daniel, I express a very special and warm thanks for all the support and patience during this long journey. viii Part of the content of this Ph.D. dissertation has already been communicated in international conferences: Oral communications E. Roldão, A. J. Parola, João A. Lopes, A.M. Ramos, B. Lavédrine. Is it obvious? Not when we are dealing with cellulose nitrate. Plastics Associated with Photographic Material, Collaborative Workshop in Photograph Conservation, Foundation of the American Institute for Conservation and Center for Creative Photography, Tucson, Arizona, Estados Unidos da América, 14-18 de Março de 2016. E. Roldão, A. J. Parola, João A. Lopes, A.M. Ramos, B. Lavédrine. How far can we see? The importance of accurate film identification. SOIMA 2015 – Unlocking Sound and Image Heritage, Bruxelas, Bélgica, 3-4 Setembro. E. Roldão, A.M. Ramos. Polímeros semi-sintéticos em fotografia - o nitrato e o acetato de celulose. Encontro DigiFup – Digitalização e Tratamento da Filmoteca Ultramarina Portuguesa, Lisboa, 15 de Dezembro de 2014. J. Silva, E. Roldão, A. J. Parola, A.M. Ramos, B. Lavédrine. Conservation of cellulose acetate photographic negatives: searching for new approaches. Conference CoMa 2013 – Safeguarding Image Collections, Royal Institute for Cultural Heritage (KIK-IRPA), Bruxelas, Bélgica, 31 de Outubro de 2014. Poster J. Silva, E. Roldão, A. J. Parola, A.M. Ramos, B. Lavédrine. New Approaches to Conservation and Preservation of Cellulose Acetate Photographic Negatives. InArt'13 - 1st International Conference on Innovation in Art Research and Technology, Évora, Portugal, 10-13 Julho de 2013. Publications Artur Neves, Eva Mariasole Angelin, Élia Roldão, Maria João Melo. 2018. New insights into the degradation mechanism of cellulose nitrate in cinematographic films by Raman microscopy. Journal of Raman Spectroscopy. DOI 10.1002/jrs.5464 Silva, J., Roldão, E., Parola, A.J., Ramos, A.M., Lavédrine, B.. Conservation of cellulose acetate photographic negatives: searching for new approaches. In: H. Arijs, eds. CoMa 2013 Safeguarding Image Collection. New Castle: Cambridge Scholars Publishing, pp. 149-162. ISBN -13: 978-1-4438-6818-1. ix x Abstract Cellulose esters film-based negatives are known for their autocatalytic and irreversible decay. Over time, the ephemeral nature of these negatives became one of the most challenging issues for manufacturers, photographers, scientists, conservators, and overall caretakers that strive to foresee the decay of those composite materials and to develop preservation solutions. The aim of this study is to introduce an analytical methodology that can inform the conservator not only about the nature of the film base but also about its condition in a non-invasive way. For this purpose, three hundred and sixty-one cellulose nitrate and cellulose acetate film-based negatives (1930s-1950s) from Portuguese institutions were selected. The selection of the cases studies relied on three main criteria: historical framework of the collection, film characteristics (type of support, format, producers/brands) and preservation condition. The selected negatives are representative of European and North American producers. The objects were studied using infrared and Raman microspectroscopies (μ-FTIR and μ-Raman), pH and hardness measurements, and Near infrared spectroscopy. μ-FTIR analysis allowed to identify three types of film supports: cellulose nitrate, cellulose acetate and cellulose acetate butyrate. Based on the μ-FTIR analysis a correlation between molecular identification of the film base and notch codes was accomplished. For the set of negatives with cellulose acetate butyrate support no significant molecular changes were obtained, indicating that this type of negatives is considerably stable. Concerning cellulose nitrate and acetate-based negatives, μ-FTIR allowed to assess very different preservation conditions, ranging from Very Good to Severely degraded. A careful observation of the results obtained for cellulose nitrate-based negatives allowed concluding that negatives with spectral changes associated with severe degradation may have different degradation pathways according to thickness. Concerning cellulose acetate-based negatives, similar results were obtained. Moreover, the FTIR results enabled to identify a degradation trend associated with a film typology characterized by ‘U’ notch code and blue and brown anti-halation dyes. Different plasticizers, namely camphor, phosphates and phthalates, were also identified by μ-FTIR and μ-Raman analysis. pH and hardness measurements supported the spectral results obtained. It was confirmed that the de-esterification and chain-scission may be detected by their decrease. To confirm the chemical behaviour of cellulose nitrate-based negatives, an artificial ageing experiment (80⁰C, 90% RH) was carried out, followed by the same analytical methodology. The results obtained for samples artificially aged support the findings obtained from the study of historical films. These findings contribute for a review of the preservation strategies currently used, establishing a novel and non-invasive methodology which
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