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Universidade De São Paulo Faculdade De Zootecnia E Engenharia De Alimentos UNIVERSIDADE DE SÃO PAULO FACULDADE DE ZOOTECNIA E ENGENHARIA DE ALIMENTOS CHRISTIAN GAUSS Tratamento preservativo e modificação química do bambu para fins estruturais Preservative treatment and chemical modification of bamboo for structural purposes Pirassununga 2020 CHRISTIAN GAUSS Tratamento preservativo e modificação química do bambu para fins estruturais Preservative treatment and chemical modification of bamboo for structural purposes Versão Corrigida Tese apresentada à Faculdade de Zootecnia e Engenharia de Alimentos da Universidade de São Paulo, como parte dos requisitos para a obtenção do Título de Doutor em Engenharia e Ciência dos Materiais. Área de Concentração: Desenvolvimento, Caracterização, e Aplicação de Materiais voltados à Agroindústria. Orientador: Prof. Dr. Holmer Savastano Junior. Pirassununga 2020 ACKNOWLEDGEMENTS This work would not be conceived without the moral support and trust of my family. Special thanks to my mother, Fatima, my father, Rudolf, and my brother David, who always believed in my efforts to become the person who I am nowadays. Thanks for the financial support from FAPESP (Processes 2016/26022-9 and 2018/18571-8) and CAPES that provided me with all the necessary means for the development of this work. These resources were possible because of all the taxpayers from São Paulo state and Brazil. Thank you for giving me this responsibility. Special thanks to my advisor, Prof. Holmer Savastano Junior, for the guidance, support, and belief in my work even in moments of doubt and confusion. I really appreciate all the opportunities for learning and personal development available under his guidance. This thesis was made possible by his trust and advice during all my doctorate. I am also deeply thankful for Prof. Kent A. Harries, who received me with open arms during my internship at the University of Pittsburgh and guided me through important parts of this doctorate thesis. I am also grateful for his confidence in my capabilities and for driving me for the next stage of my professional path. To my beloved friends, Laura, Bruno, Leonardo, and Paulo that somehow gave me spiritual strength and perseverance to materialize this thesis and helped me seeing the world from different perspectives. To all my friends who have been part of my daily life during my journey through my doctorate (without importance order), Adriana, Gonzalo, Carlos, Carol, Leticia, G. Barbirato, Rafael, G. Carmello, Viviane, Loïc, Matheus, Erika, Valdemir, Ronaldo, Patrícia, Maria Júlia, Alda, and many others who passed through the lab. Special thanks to Marzieh Kadivar for her important help, contribution to my work, and valuable conversations about bamboo. The laboratory of Construction and Ambience and other departments of the USP-FZEA campus will be recorded in my memory for all the support provided. The help of all the technicians, Zaqueu, Diego, Mariana, Josiane, Leonardo, and Rodrigo are deeply acknowledged. Thanks to Ricardo Pereira and Sergio Brazolin for the fungi decay tests developed at IPT, São Paulo, and for the rich conversations about this important topic. I am also deeply thankful for all the help provided by students and staff from the University of Pittsburgh, Scooter, Yusuf, Chase, Chelsea and Abdullah. To Celina Llerena, Prof. Antônio L. Beraldo, and Prof. Khosrow Ghavami for introducing me to the bamboo world and for encouraging my curiosity. Lastly, I would like to thank all the engineers, researchers, enthusiasts, and readers interested in the wonderful and world-changing material: bamboo. Criamos nosso próprio caminho, com atenção no presente, ouvidos no passado e olhos no futuro. C. Gauss RESUMO GAUSS, C. Tratamento preservativo e modificação química do bambu para fins estruturais. 2020. 333 p. Tese de Doutorado – Faculdade de Zootecnia e Engenharia de Alimentos, Universidade de São Paulo, Pirassununga, 2020. Os materiais à base de bambu estão na caixa de ferramentas de práticas sustentáveis e têm um alto potencial para o desenvolvimento e a expansão de novos produtos na indústria da construção. Embora inúmeras vantagens sejam atribuídas ao bambu, existem vários problemas relacionados ao seu uso que devem ser resolvidos e mitigados. Sem tratamento adequado, os materiais de bambu não resistem a uma longa vida útil. Os procedimentos de tratamento são bem conhecidos, para os quais diversos métodos e soluções preservativas podem ser utilizados, dependendo da aplicação final, logística, condição do material e acessibilidade. No entanto, informações básicas sobre o tratamento químico do bambu em termos de tratabilidade, controle de qualidade e o efeito nas propriedades físico-mecânicas e o desenvolvimento de soluções menos perigosas são tópicos pouco explorados. Portanto, esta tese de doutorado foi dividida em duas partes/objetivos principais: avaliação de tratamentos convencionais para bambu e o uso de métodos de preservação alternativos baseados em modificação química e polimerização in-situ. Na primeira parte, preservativos convencionais foram aplicados no tratamento dos bambus Dendrocalamus. asper e Phyllostachys edulis e analisados sob o ponto de vista de aspectos de qualidade. Métodos analíticos para avaliação da tratabilidade, como penetração e retenção, foram utilizados para o bambu tratado com octaborato de sódio tetrahidratado (OST) e cromato de cobre cromatado (CCB). Testes mecânicos, físicos e químicos foram amplamente utilizados para caracterizar amostras tratadas e os efeitos dos preservativos nas propriedades mecânicas foram investigados. Adicionalmente, o bambu roliço foi objeto de caracterização mecânica detalhada por meio de análise de deformação por correlação de imagem digital. Os resultados obtidos resultaram em recomendações para futuras normas para ensaios de bambu e na observação do efeito local do nó em compressão, cisalhamento, tração e flexão. Ademais, os tratamentos investigados não mostraram efeitos prejudiciais sobre as propriedades mecânicas, especialmente o tratamento com OST, que resulta em uma melhora na resistência do bambu. Diretrizes para tratamento pelo método de imersão usando OST também foram apresentadas como uma proposta para melhorar a qualidade da produção do bambu tratado. Na segunda parte desta tese, seguindo o objetivo de melhorar as propriedades gerais do bambu, foram testados tratamentos alternativos à base de ácido cítrico e tanino em combinação com compostos de boro. Amostras quimicamente modificadas com ácido cítrico apresentaram considerável melhora na estabilidade dimensional e diminuição da absorção de água como consequência de um processo de esterificação. No entanto, a modificação aumentou a fragilidade do bambu, reduzindo especialmente a resistência à flexão. O uso de tanino/hexamina/boro polimerizado apresentou resultados positivos nas propriedades gerais do bambu, aumentando as resistências à compressão e à tração na flexão e a resistência à degradação por fungos mesmo após a lixiviação. Embora o OST tenha sido eficaz para melhorar a resistência à decomposição de fungos, a lixiviação severa diminuiu completamente sua atividade fungicida. Contudo, por meio de análises termogravimétricas, as amostras tratadas com boro exibiram melhor estabilidade térmica. Em geral, o bambu é um material fascinante. No entanto, embora seja possível obter um tratamento satisfatório, é mais difícil de ser tratado e caracterizado do que a madeira. Para superar esses problemas, são necessárias mais pesquisas em métodos de caracterização e tratamento para melhor entendimento e uso desse abundante e versátil material. Palavras chave: Ácido cítrico, Avaliação da qualidade, Boro, Caracterização mecânica, Dendrocalamus asper, Phyllostachys edulis, Tanino ABSTRACT GAUSS, C. Preservative treatment and chemical modification of bamboo for structural purposes. 2020. 333 p. Tese de Doutorado – Faculdade de Zootecnia e Engenharia de Alimentos, Universidade de São Paulo, Pirassununga, 2020. Bamboo-based materials are in the toolbox of sustainable practices and have a high potential for the development and expansion of new products in the construction industry. Although uncountable advantages are attributed to bamboo, there are several problems related to its use that must be solved and mitigated. Without proper treatment, bamboo materials cannot withstand a long service life. The treatment procedures are already well-known, in which different methods and preservative solutions can be used depending on the final application, logistics, material condition, and affordability. Yet, necessary information about the chemical treatment of bamboo in terms of treatability, quality control, and the effect on physical- mechanical properties, and the development of less hazardous solutions are topics not adequately explored. Therefore, this doctorate thesis was divided into two major parts/objectives: assessment of conventional bamboo treatments and evaluation of alternative preservation methods based on chemical modification and in-situ polymerization. In the first part, conventional preservatives were applied for Dendrocalamus. asper and Phyllostachys edulis bamboo treatment and analysed in the quality aspects point of view. Analytical methods for treatability evaluation, such as penetration and retention, were used for disodium octaborate tetrahydrate (DOT) and chromate copper borate (CCB) treated bamboo. Mechanical, physical, and chemical tests were extensively used to characterize treated samples, and the effects of the preservatives on mechanical properties were investigated. Additionally,
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