RESSALVA Atendendo solicitação do(a) autor(a), o texto completo desta tese será disponibilizado somente a partir de 23/10/2025. THÈSE présentée à L’UNIVERSITÉ DE BORDEAUX École Doctorale des Sciences Chimiques et L’UNIVERSIDADE ESTADUAL PAULISTA “JÚLIO DE MESQUITA FILHO” Instituto de Química – campus Araraquara par Leonardo Vieira ALBINO pour obtenir le titre de DOCTEUR Spécialité: Chimie ET Physico-chimie de la matière condensée ********* Synthèse et étude de verres à propriétés magnéto-optiques contenant des métaux de transition et des terres rares ********* Soutenue le 23 octobre 2023 Membres du jury : de Química – Universidade Estadual Paulista « Júlio de Mesquita Filho » campus Araraquara (IQ-UNESP) M. NALIN Marcelo, Professor Instituto de Química – Universidade Estadual Paulista « Júlio de Mesquita Filho » campus Araraquara (IQ-UNESP) – Directeur de thèse M. CARDINAL Thierry, Docteur Institut de Chimie de la Matière Condensée de Bordeaux – Université de Bordeaux (ICMCB-UB) – Directeur de thèse M. DUCLERE Jean-René, Professor Institut de Recherche sur les Céramiques – Université de Limoges (IRCER-UL) – Rapporteur M. POIRIER Gael-Yves, Professor Instituto de Ciência e Tecnologia – Universidade Federal de Alfenas campus Poços de Caldas (ICT-UNIFAL-MG) – Rapporteur Mme GONÇALVES Rogéria Rocha, Professeure Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto - Universidade de São Paulo (FFCLRP-USP) – Examinateur & Président du Jury __________________________________________________________________________________ 2 Leonardo Vieira Albino Síntese e Estudo de Vidros Magneto-Ópticos contendo Metais de Transição e Terras Raras Tese em cotutela apresentada ao Instituto de Química, Universidade Estadual Paulista “Júlio de Mesquita Filho” (IQ/UNESP) e Institut de Chimie de la Matière Condensée de Bordeaux, Université de Bordeaux (ICMCB/UB) para obtenção do título de Doutor em Química, especialidade em Físico-Química da Matéria Condensada Orientador: Prof. Dr. Marcelo Nalin Coorientador: Dr. Thierry Cardinal Coorientador: Prof. Dr. Sidney José Lima Ribeiro Araraquara 2023 __________________________________________________________________________________ 3 Impacto potencial da pesquisa Vidros com aplicações magneto-ópticas vem se tornando cada vez mais procurados por pesquisadores e empresas, sendo uma promessa significativa para vários avanços tecnológicos, com impactos potenciais que abrangem diversos setores. Em primeiro lugar, a exploração destes vidros pode impulsionar as tecnologias de comunicação. Os rotadores Faraday, dispositivos que giram a polarização da luz na presença de um campo magnético, são componentes integrais em sistemas de comunicação óptica. Ao melhorar as propriedades magneto-ópticas dos vidros, os pesquisadores podem abrir caminho para redes de comunicação óptica mais eficientes e rápidas. Isto poderia levar a melhores taxas de transmissão de dados, redução de perdas de sinal e aumento de largura de banda, atendendo à crescente demanda por comunicações mais rápidas e confiáveis. Também tem implicações profundas para o desenvolvimento de tecnologias de sensoriamento. As propriedades magneto-ópticas desses vidros podem ser aproveitadas na criação de sensores magnéticos/elétricos altamente sensíveis. Esses sensores podem encontrar aplicações em diversos campos, incluindo diagnósticos médicos, monitoramento ambiental e processos industriais. Atualmente vidros magneto-ópticos apresentam-se como um possível substituto dos monocristais utilizados comercialmente, devido as características isotrópicas, o processo de produção mais simples e a possibilidade de produção de fibras ópticas. Para esse fim, várias matrizes vítreas que suportem altas concentrações de terras-raras sem induzir cristalização vem sendo sintetizadas e estudadas. Vidros borogermanato vem se mostrando uma boa alternativa, porém os reagentes e a síntese desses vidros elevam o custo. Esta tese de doutorado teve como objetivo sintetizar a caracterizar diferentes sistemas vítreos mais baratos, um borotungstato contendo terras-raras e outro fosfato contendo manganês visando obter respostas magnéticas próximas aos monocristais e vidros germanato comerciais. __________________________________________________________________________________ 4 Potential research impact Glasses with magneto-optical applications have become increasingly sought after by researchers and companies, holding significant promise for various technological advances, with potential impacts that span diverse sectors. Firstly, the exploration of these glasses can boost communication technologies. Faraday rotators, devices that rotate the polarization of light in the presence of a magnetic field, are integral components in optical communication systems. By improving the magneto-optical properties of glasses, researchers can pave the way for more efficient and faster optical communication networks. This could lead to better data transmission rates, reduced signal losses and increased bandwidth, addressing the ever-growing demand for faster and more reliable communication. Moreover, the research has profound implications for the development of advanced sensing technologies. The magneto-optical properties of these glasses can be used to create highly sensitive magnetic/electrical sensors. These sensors can find applications in a variety of fields, including medical diagnostics, environmental monitoring, and industrial processes. Currently, magneto-optical glasses are a possible replacement for commercially used monocrystals, due to their isotropic characteristics, the simpler production process and the possibility of producing optical fibers. To this end, several glass matrices that support high concentrations of rare earths without inducing crystallization have been synthesized and studied. Borogermanate glasses have proven to be a good alternative, but the reagents and synthesis of these glasses increase the cost. This doctoral thesis aimed to synthesize and characterize different cheaper glass systems, a borotungstate containing rare earths and another phosphate containing manganese, aiming to obtain magnetic responses close to commercial monocrystals and borogermanate glasses. __________________________________________________________________________________ 5 __________________________________________________________________________________ 6 Leonardo Vieira Albino; L. V. Albino; L. V. ALBINO Occupation area Major Area: Exact and Earth Sciences / Area: Chemistry / Subarea: Inorganic Chemistry. Major Area: Exact and Earth Sciences / Area: Chemistry / Subarea: Materials Chemistry. Major Area: Exact and Earth Sciences / Area: Chemistry / Subarea: Non-Crystalline Materials Chemistry. Personal information Birth date: January 21, 1994 - 29 years Nationality: Brazilian. Place of birth: Itapetininga, SP, Brazil. Affiliation: Marcos Antônio Albino and Patrícia Maria Diniz Vieira Albino. Marital status: single. Occupation: PhD student. Email: leonardoalbino63@gmail.com Curriculo Lattes (in Portuguese): http://lattes.cnpq.br/0124534306474504 ORCID iD: https://orcid.org/0000-0003-0441-2371 Professional address São Paulo State University (UNESP), Institute of Chemistry, Department of General and Inorganic Chemistry, Laboratório de Vidros Especiais (LaViE). Av. Prof. Francisco Degni, 55 Jardim Quitandinha 14800060 - Araraquara, SP, Brazil Telephone: +55 (16) 33019654 mailto:leonardoalbino63@gmail.com http://lattes.cnpq.br/0124534306474504 https://orcid.org/0000-0003-0441-2371 __________________________________________________________________________________ 7 Academic education PhD in Physico-Chimie de la Matière Condensée in progress. 2021 – in progress. Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), UMR5026, CNRS, University of Bordeaux (UB) and Bordeaux INP. Advisor: Dr. Thierry Cardinal Scholarship: FUNGlass, received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 823941. PhD in Chemistry in progress (grade CAPES 7). 2018 – in progress São Paulo State University (UNESP), Institute of Chemistry, Department of General and Inorganic Chemistry, Laboratório de Vidros Especiais (LaViE). Title of thesis: Synthesis and Study of Magneto-Optic Glasses containing Transition Metals and Rare Earths. Advisor: Prof. Dr. Marcelo Nalin. Co-advisor: Prof. Dr. Sidney José Lima Ribeiro. Scholarship: Coordenação de Apoio a Pesquisa no Ensino Superior (CAPES), Brazil. Master in Chemistry (grade CAPES 7). 2016 - 2018 São Paulo State University (UNESP), Institute of Chemistry, Department of General and Inorganic Chemistry, Laboratório de Vidros Especiais (LaViE). Title of dissertation: Study, Preparation and Application of Polymeric Optical Fibers using 3D Printing technology. Advisor: Marcelo Nalin. Scholarship: Coordination for the Improvement of Higher Education Personnel (CAPES), Brazil. Bachelor in Chemistry. 2012 - 2015 São Paulo State University (UNESP), Institute of Chemistry, Department of General and Inorganic Chemistry, Laboratório de Vidros Especiais (LaViE). __________________________________________________________________________________ 8 Title of coursework completion: Luminescent Properties of Europium and Copper Doped PbO-GeO2 Glass. Advisor: Marcelo Nalin. Scholarship: São Paulo Research Foundation (FAPESP), Brazil. Technical/Professionalizing course in Chemistry. 2010 - 2011 Salles Gomes State Technical School (Paula Souza Center). Tatuí, Brazil. Additional education Minicourse Lanthanides: Chemistry, Luminescence and Applications, by Prof. Dr. Fernando Aparecido Sigoli. (Hours: 6). 46th Annual Meeting of the Brazilian Society of Chemistry (RASBQ). Águas de Lindóia - Brazil. (2023) MOOC - Intégrité scientifique dans les métiers de la recherche. Université de Bordeaux. (2023) French language course. Niveau B2 - Evening - Département d'Etudes de Français Langue Etrangère (DEFLE). (Hours: 50). Université Bordeaux-Montaigne, France. (2022) 2nd ICG-CGCRI Tutorial 2021 on Glass Science & Technology hosted by CSIR - Central Glass & Ceramic Research Institute, Kolkata - India, in association with International Commission on Glass, from 18th to 27th January - online (2021) Pedagogical Training Workshop: Dialogues on University Teaching - PPD/FCF and Program for the Improvement and Support of Teaching in Higher Education (PAADES) - Campus (Hours: 8). São Paulo State University (UNESP), Brazil. (2019) Pedagogical Training Workshop - Program for the Improvement and Support of Teaching in Higher Education (PAADES). (Hours: 22). São Paulo State University (UNESP), Brazil. (2018) Introduction to 3D modeling of free software. (Hours: 15). Araraquara University (UNIARA), Brazil. (2016) Next generation gene arrays: fresh new tools for. (Hours: 1). AFFYMETRIX BIOTECH LTDA, AB_FORN, Brazil. (2014) __________________________________________________________________________________ 9 Web of Science, EndNote e ResearcherID. Thomson Reuters Serviços Econômicos, THOMSON REUTERS, Brazil. (2014) Forensic Medical Sciences. Courses and Events Renova, RENOVA CURSOS, Brazil. (2013) Professional Experience 1. Professor of Experimental Inorganic Chemistry for the Chemical Engineering course (2019) by the Program for the Improvement and Support of Teaching in Higher Education (PAADES). São Paulo State University (UNESP), Institute of Chemistry, Araraquara, Brazil. (2019). 64h. 2. Professor of General and Inorganic Chemistry I for the Pharmacy- Biochemistry course (evening–2019) by the Program for the Improvement and Support of Teaching in Higher Education (PAADES). São Paulo State University (UNESP), Institute of Chemistry, Araraquara, Brazil. (2019). 64h. 3. Intervention activity in the General Chemistry Laboratory discipline for 1st year students of the Chemical Engineering course by the Special Topics discipline: Chemistry Teaching Practice - Theory and experiment. São Paulo State University (UNESP), Institute of Chemistry, Araraquara, Brazil. (2017). 180h. 4. Teaching practice in Experimental Inorganic Chemistry for Licentiate in chemistry students (2013) offered by the Coordination for the Improvement of Higher Education Personnel (CAPES) and Department of General and Inorganic Chemistry, São Paulo State University (UNESP), Institute of Chemistry, Araraquara, Brazil. (2017). 60h. 5. Monitor of the General Physical Chemistry discipline for Bachelor in chemistry (2013) offered by the Department of Physical Chemistry and Tutorial Education Program in Chemistry (PET-Química). São Paulo State University (UNESP), Institute of Chemistry, Araraquara, Brazil. (2013). 60h. 6. Ministered short course Workshop: Origin, during the XLIII Chemistry Week. São Paulo State University (UNESP), Institute of Chemistry, Araraquara, Brazil. (2013). 2h. __________________________________________________________________________________ 10 Languages Portuguese Comprehends Well, Speaks Well, Reads Well, Writes Well. English Comprehends Well, Speaks Well, Reads Well, Writes Reasonably. French Comprehends Well, Speaks Well, Reads Well, Writes Well. Niveau DELF B2. Scientific production Articles published in scientific journals D. F. Franco, F. J. Caixeta, L. V. Albino, T. A. Lodi, J. R. Orives, E. O. Ghezzi, M. Nalin, Terbium-doped transparent glass-ceramics containing TbPO4 crystals: A promising material for photonic applications. Opt. Mater. X. 20 (2023) 100272 https://doi.org/10.1016/j.omx.2023.100272 Presented works 1. Albino, L. V.; Cardinal, T.; Dussauze, M.; Adamietz, F.; Toulemonde, O.; Jubera, V.; Franco, D. F.; Nalin, M. “Paramagnetic borotungstate glasses – a new magnetic-optical material”. 46 RASBQ. Águas de Lindóia - Brazil. (2023) 2. Ghezzi, E. O.; Albino, L. V.; Lodi, T. A.; Franco, D. F.; Nalin, M.; “Synthesis and characterization of glasses for ultra-sensitive magneto-optical sensors”. 46 RASBQ. Águas de Lindóia - Brazil. (2023) 3. Albino, L. V.; Cardinal, T.; Dussauze, M.; Adamietz, F.; Toulemonde, O.; Jubera, V.; Franco, D. F.; Nalin, M. “Estudos de vidros borotungstato com alta concentração de terras raras para aplicação fotônica”. Reunião Regional do Instituto Nacional de Ciência e Tecnologia de Fotônica (INFO). Ribeirão Preto - Brazil. (2023) 4. Albino, L. V.; Jubera, V.; Cardinal, T.; Toulemonde, O.; Dussauze, M.; Nalin, M. "Structural, optical and magnetic properties of high rare earths ions containing Borotungstate glasses". XX B-MRS Meeting, Foz do Iguaçu - Brazil. (2022) https://doi.org/10.1016/j.omx.2023.100272 __________________________________________________________________________________ 11 5. Albino, L. V.; Dussauze, M.; Toulemonde, O.; Jubera, V.; Cardinal, T.; Nalin, M. “Borotungstate glasses with a high concentration of rare earths for photonic application”. 26th International Congress on Glass (ICG2022). Berlin - Germany. (2022) 6. Albino, L. V.; Dussauze, M.; Danto, S.; Canioni, L.; Toulemonde, O.; Jubera, V.; Cardinal, T.; Nalin, M. “Verre borotungstate d’ions de terres rares: Matériaux magnétiques pour la photonique” 89e Congrès de l’Acfas. On-line. Oral presentation in french. 2022 7. Albino, L. V.; Dussauze, M.; Danto, S.; Canioni, L.; Toulemonde, O.; Jubera, V.; Cardinal, T.; Nalin, M. “Magnetic materials for photonic applications: Borontungstate and rare earth ions glasses”. Physical Chemistry & Chemical Physics Workshop (PCCP-2022). Université de Bordeaux. Oral presentation in English. 2022 8. Roque, N. G.; Albino, L. V.; Marcondes, L. M.; Nalin, M. “Obtenção do sistema vítreo SbPO4-ZnO-PbO-MnO e estudo das propriedades térmicas, ópticas e estruturais”. XXXII UNESP Scientific Initiation Congress (CIC-UNESP). On-line. (2020) 9. Roque, N. G.; Albino, L. V.; Marcondes, L. M.; Nalin, M. “Synthesis of the SbPO4-ZnO-PbO-MnO magneto-luminescent glasses”. #LatinXChem Twitter Conference 2020. On-line. (2020) 10. Albino, L. V.; Nalin, M. “Synthesis of transparent magneto-luminescent glass-ceramics with high concentrations of Tb3+”. II Workshop National Institute of Photonics (INFo). Araraquara, Brazil. (2020) 11. Roque, N. G.; Albino, L. V.; Nalin, M. “Synthesis of the SbPO4-ZnO-PbO- MnO magneto-luminescent glass”. II Workshop National Institute of Photonics (INFo). Araraquara, Brazil. (2020) 12. Roque, N. G.; Albino, L. V.; Nalin, M. “Estudo das propriedades térmicas, ópticas e estruturais do sistema vítreo SbPO4-ZnO-PbO em função da concentração de MnO”. XXXI UNESP Scientific Initiation Congress (CIC-UNESP). Araraquara, Brazil. (2019) __________________________________________________________________________________ 12 13. Ramos, R. G.; Albino, L. V.; Santagneli, S. H. “Estudo da estrutura e propriedades de vidros boro-fosfato modificados com AlF3”. XXXI UNESP Scientific Initiation Congress (CIC-UNESP). Araraquara, Brazil. (2019) 14. Sampaio, A. C. S.; Albino, L. V.; Nalin, M. “Estudo das propriedades térmicas, ópticas e estruturais do sistema La2O3-B2O3-WO3 dopados com Dy3+, Tb3+ e Eu3+”. XXXI UNESP Scientific Initiation Congress (CIC-UNESP). Araraquara, Brazil. (2019) 15. Sampaio, A. C. S.; Albino, L. V.; Nalin, M. “Síntese de vidros boro-tungstato com alta concentração de lantânio”. XXX UNESP Scientific Initiation Congress (CIC-UNESP). Araraquara, Brazil. (2018) 16. Albino, L. V.; Nalin, M. “Preparation of Polymeric Optical Fibers using 3D Printing technology and its application as sensors”. International Conference on Optical, Optoelectronic and Photonic Materials and Applications (ICOOPMA). Maresias, Brazil. (2018) 17. Albino, L. V.; Nalin, M. “Preparação de Fibras Ópticas Poliméricas utilizando tecnologia de Impressão 3D”. 57° Brazilian Congress of Chemistry. Gramado, Brazil. (2017) 18. de Castro, G. B.; Porsani, G. F.; Albino, L. V.; Nalin, M. “Multicore polymeric optical fiber obtained from preform with 3D printer”. XXVIII UNESP Scientific Initiation Congress (CIC-UNESP). Araraquara, Brazil. (2016) 19. Albino, L. V.; Silva, M. C. C.; Nalin, M. “Estudo das propriedades luminescentes de vidros PbO-GeO2 dopados com európio e cobre”. 38ª Annual Meeting of the Brazilian Chemical Society. Águas de Lindóia, Brazil. (2015) 20. Albino, L. V.; Silva, M. C. C.; Nalin, M. “Estudo das propriedades ópticas dos vidros e vitrocerâmicas PbO-GeO2 dopados com európio e cobre”. XXVII UNESP Scientific Initiation Congress (CIC-UNESP). Araraquara, Brazil. (2015) 21. dos Santos, I. F. M.; de Jesus, C. A. S.; Albino, L. V.; de Campos, G. P.; Faria, D. V.; Coco, J.; Teixeira, I. S.; Anhesine, N. B.; Rodrigues Júnior, J. R.; Tayar, S. P.; Lopes, M. N. “Diagnóstico PET do curso de Bacharelado em Química do IQ/UNESP/CAr”. XVIII National Meeting of PET Groups (ENAPET). Recife, Brazil. (2013) __________________________________________________________________________________ 13 Participation in Events Poster evaluation during XXXII UNESP Scientific Initiation Congress (CIC- UNESP). On-line. (2020) Presentation of “Photonic demonstration experiments: Photophone, Fiber optics and Preform; Total internal reflection; Infrared, red and green lasers” during Science at School. Araraquara, Brazil. (2019) Poster evaluation during XXXI UNESP Scientific Initiation Congress (CIC-UNESP). Araraquara, Brazil. (2019) Poster evaluation during XXX UNESP Scientific Initiation Congress (CIC-UNESP). Araraquara, Brazil. (2018) Symposium in Commemoration of the International Year of Crystallography: Impact of Crystallography in Different Areas of Science, module I, diffraction and X- ray scattering. (2014) Prizes Best works in the poster session of the Materials Division: Ghezzi, E. O.; Albino, L. V.; Lodi, T. A.; Franco, D. F.; Nalin, M.; “Synthesis and characterization of glasses for ultra-sensitive magneto-optical sensors”. 46 RASBQ. Águas de Lindóia - Brazil. (2023) __________________________________________________________________________________ 14 Dedication Dedico este trabalho ao meu querido avô José Benedito (1942–2020), homem que, mesmo sem pai, tornou-se o melhor pai e avô deste mundo, sendo uma das inúmeras vítimas da COVID-19. __________________________________________________________________________________ 15 Agradecimentos – Acknowledgment – Remerciements A jornada foi longa. Foram onze anos dedicados a viver o sonho de um jovem de 18 anos, feliz por ter passado no vestibular no curso e na cidade que queria. Não fazia ideia da proporção que me levaria no futuro. Não só conhecer e entender como a Ciência funciona e funciona, mas também contribuir para ela. Neste percurso, foram inúmeros os desafios, mas também inúmeros e agradáveis sucessos. Várias, inúmeras pessoas participaram direta ou indiretamente, para o bem ou para o mal, do meu crescimento científico, profissional e pessoal, o que me coloca numa situação difícil não só de nomeá-las todas, mas de garantir que sejam contempladas por esta simples menção. Primeiramente quero agradecer a minha família. Minha âncora. Ao meu pai Marcos, minha mãe Patrícia, minha irmã Cristiane, que me amaram desde que nasci, me incentivaram a ser uma pessoa ética, forte, alegre e humana. Aos meus avós que também nunca desistiram de pensar, orar e fazer tudo ao seu alcance por mim. Aos meus tios, primos e todos os antepassados, que apesar da minha ausência da minha cidade natal, sempre me receberam com sorrisos, gargalhadas, preocupações e acolhimento, fortalecendo-me e enchendo-me de esperança. Não posso deixar de comentar sobre a minha cidade natal, Itapetininga, a qual agradeço por ser a cidade natal de minha família e onde fiz amizades queridas que levarei comigo para toda a vida. Meu salve para vocês Bodão, Wandell, Sonoda, Tiaki, Paulinho e Bruno. Também gostaria de agradecer a meus professores do Ensino Médio, do Instituto Imaculada Conceição – Itapetininga, e do Curso Técnico em Química da Etec Sales Gomes – Tatuí, que me fizeram apaixonar pela Ciência e pela Química. A minha amada República Diretoria, que me acolheu em fevereiro de 2012. Com certeza me ajudou a vencer minha timidez, me deixando um pouco mais responsável e maduro. Obrigado por aguentarem minhas loucuras e darem-me um nome. Um abraço especial para os diretores com quem convivi: Cafundó, Ariel, Jontex, Alfi, Gargamel, Al-Jazeera, Xaveco, Nissin, Fuinha, Bombinha, Dy, Zé, Conrado, Margarida, Jan, Rooney, Féélipe, Trepadeira, Matuta, Lalau, Vlad, Bilé, Pipico, Chicabom, DuPai, Hortência, Pupunha, R7, Moiado, Carinhoso, Lírio, Ragnar, Resgate, Bife e DogRagnar. DIRETORIAA ARRUL, ARRUL, ARRUL!! Agradeço ao meu orientador Prof. Dr. Marcelo Nalin (Pre) pela oportunidade de trabalhar em seu laboratório, pelo apoio, pela inspiração, pela paciência e pelos ensinamentos em química, além da confiança depositada em mim nesses 10 anos. A todos integrantes do Laboratório de Vidros Especiais e do Laboratório de Materiais Fotônicos, em especial ao Prof. Sidney, Prof. Douglas, Dra. Silvia, Prof. Edison, Lia, Juliane, Juliana, Samira, Nicole, Antonio Eduardo, Eduardo Ghezzi, Thiago, Adriana, Bea Freitas, Fábio, Léo e Vibra, pelo conhecimento compartilhado, pelas ajudas, ombros amigos e pelas divertidas discussões. Aos funcionários e alunos do Instituto de Química, em especial os professores, por aumentar minha paixão por química no grau de querer futuramente lecionar numa __________________________________________________________________________________ 16 universidade. Também à técnica-administrativa Wennia, por todo auxílio durante a cotutela. Obrigado por essa chance que poucos no nosso país têm. This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) - Finance Code 001 (grant 88887.571031/2020-00 and 88882.330082/2019-01). I would also like to thank the FunGlass Project for funding, from the European Union's Horizon 2020 research and innovation program under the Marie Skłodowska-Curie (grant agreement 823941), to the Center for Research, Technology and Education in Vitreous Materials (FAPESP, grant 2013/07793-6) , French National Center for Scientific Research (CNRS), Bordeaux INP and National Council for Scientific and Technological Development (CNPq). Financing and support that allowed me to grow not only professionally, but also personally, socially and culturally. Um agradecimento especial as minhas professoras de línguas, Carla, et surtout Islene, pour la tâche incroyable de m'aider à apprendre la langue française en peu de temps, m'aidant toujours, avec un professionnalisme et une volonté excellents. And Lenita, my English teacher, also for all her understanding, effort and help, for bringing out my dormant "English" and helping me with my greatest difficulties with patience, professionalism and good humor. Aos meus grandes amigos que vou levar para toda a vida, Palmito, Maria, Cartola e Arroyos (Santiago) por todos os momentos alegres nessa caminhada. E ao meu querido Fernando, que conheci no início do doc durante meu café com maçã, por todo companheirismo, amizade, força, conselhos, risadas, acolhimento e amor nos momentos fáceis e terríveis por toda essa minha jornada. Você é incrível! Je n'ai pas pu m'empêcher de remercier tout particulièrement tout le monde en France. D'abord à mon directeur de thèse, M. Dr. Thierry Cardinal, pour l'opportunité de travailler dans son laboratoire, pour le soutien et pour les enseignements formidables et valables. Je ne peux pas non plus oublier de remercier Dr. Marc Dussauze et Prof. Dr. Véronique Jubera, pour son amitié et aussi pour toute sa patience et ses enseignements durant mon séjour à Bordeaux et au-delà. À l'Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB) et à l'Institut des Sciences Moléculaires (ISM) et aux personnes que j'ai rencontrées dans ces laboratoires, pour toute l'aide et la structure. Je remercie les professionnels Sylvain Danto, Olivier Toulemonde, Patrick Rosa, Mattieu Duttine et Alexandre Fargues, Fred Adamietz, Vincent Rodriguez, Christian Aupetit et, en particulier, mes amis William, Gislene, Ana, Janete, Georges, Florian, Rayan, Fouad, Alizée, Louis, Sara, Mikko, Romain, Simon, Samar, Shashank, Alice, Julia, Lara, Clara, Simon, pour la convivialité à l'intérieur et à l'extérieur du laboratoire. I hope I have reached as many people as possible. You were part of the construction of this work and of this person who speaks to you. No one can win alone! If I have seen further it is by standing on the shoulders of Giants __________________________________________________________________________________ 17 Quando a educação não é libertadora, o sonho do oprimido é ser o opressor. When education is not liberating, the dream of the oppressed is to be the oppressor. Quand l'éducation n'est pas libératrice, le rêve de l'opprimé est d'être l'oppresseur. Paulo Freire (1921–1997) Citação atribuída a Paulo Freire no livro “Começando bem, frases e pensamentos”, de Carlos H. Biagolini (2009). A frase não está presente na obra "Pedagogia do oprimido", trata-se de um resumo das ideias do autor __________________________________________________________________________________ 18 Resumo O estudo e preparação de novos materiais magneto-ópticos tem ganhado atenção significativa devido às suas potenciais aplicações em vários domínios tecnológicos. Vidros que suportam altas concentrações de íons paramagnéticos estão sendo muito procurados para esses fins, devido às propriedades inerentes que podem ser impostos aos vidros como alta janela de transmissão, altos índices de refração, fácil síntese e modelagem, todas propriedades interessantes para sistemas ópticos e inerente isotropia. Esta tese de doutorado investiga o domínio da ciência de materiais, investigando a síntese e ampla caracterização de dois sistemas vítreos, um borotungstato contendo primeiro térbio e posteriormente um estudo estendido a outros lantanídeos, e um sistema de fosfato de antimônio contendo manganês. O objetivo geral desta pesquisa é sintetizar materiais inovadores que possuam atributos magneto-ópticos elevados e interessantes, com ênfase específica em seu potencial utilidade em dispositivos que aproveitem o efeito Faraday. O estudo apresenta diferentes experimentos para determinar as características térmicas, ópticas, luminescentes, estruturais, magnéticas e magneto- ópticas dos sistemas propostos, garantindo um conhecimento aprofundado de diferentes técnicas, conceitos e métodos, importantes para aumentar o crescimento científico em química e físico-química de materiais não-cristalinos. Foram obtidos excelentes valores de constante de Curie, até 6.77 emu.Oe-1.mol-1, valores maiores que relatados na literatura, e constante de Verdet de 124 rad.T-1.m-1 632.8 nm para amostra com 27.5 %mol de Tb2O3, comparáveis a vidros e monocristais comerciais, e -55.1 rad.T-1.m-1 para a amostra 30%mol de MnO, valores inéditos para esse tipo de rotador Faraday. Ao examinar o impacto de composições variadas nas propriedades estruturais, ópticas e magnéticas dos materiais resultantes, esta tese contribui para uma compreensão mais profunda da interação entre metais de transição, terras raras e o comportamento magneto-óptico de vidros. Além disso, a tese avalia a capacidade dessas composições de vidro em exibir rotação de Faraday. Os insights obtidos com essa pesquisa não apenas avançam no conhecimento fundamental sobre a influência desses íons paramagnéticos na resposta magneto-óptica, mas também abrem caminho para o design e a realização de novos materiais magneto-ópticos. Como resultado de investigação rigorosa, esta tese de doutorado contribui significativamente para a compreensão científica e desenvolvimento prático de materiais preparados para moldar a perspectiva de aplicações magneto-ópticas. __________________________________________________________________________________ 19 Résumé L'étude et la préparation de nouveaux matériaux magnéto-optiques ont fait l'objet d'une attention particulière en raison de leurs applications potentielles dans divers domaines technologiques. Les verres qui supportent de fortes concentrations d'ions paramagnétiques sont largement recherchés à ces fins, en raison des propriétés inhérentes aux verres telles que l'isotropie, la fenêtre de transmission élevée, les indices de réfraction élevés, la synthèse et la modélisation faciles, toutes des propriétés intéressantes pour les systèmes optiques. Cette thèse de doctorat étudie le domaine de la science des matériaux avancés, en étudiant la synthèse et la caractérisation complète de deux systèmes vitreux, un borotungstate contenant d'abord du terbium et plus tard une étude étendue à d'autres lanthanides, et un système de phosphate d'antimoine contenant du manganèse. L'objectif global de cette recherche est de synthétiser des matériaux innovants qui ont des attributs magnéto-optiques élevés et intéressants, avec un accent particulier sur leur utilité potentielle dans les dispositifs qui tirent parti de l'effet Faraday. L'étude présente différentes expériences pour déterminer les caractéristiques thermiques, optiques, luminescentes, structurelles, magnétiques et magnéto-optiques des systèmes proposés, garantissant une connaissance approfondie des différentes techniques, concepts et méthodes, importants pour accroître la croissance scientifique en chimie et physique chimique des matériaux non cristallins. D'excellentes valeurs de constante de Curie ont été obtenues, jusqu'à 6,77 emu.Oe-1.mol-1, valeurs supérieures à celles rapportées dans la littérature, et une constante de Verdet de 124 rad.T-1.m-1 632,8 nm pour un échantillon de 27,5 % mol de Tb2O3, comparable aux verres et monocristaux commerciaux, et -55,1 rad.T-1.m-1 pour l'échantillon à 30%mol MnO, des valeurs sans précédent pour ce type de rotateur de Faraday. En examinant l'impact de différentes compositions sur les propriétés structurelles, optiques et magnétiques des matériaux résultants, cette thèse contribue à une compréhension plus approfondie de l'interaction entre les métaux de transition, les terres rares et le comportement magnéto-optique des verres. De plus, la thèse évalue la capacité de ces compositions de verre à présenter une rotation de Faraday. Les connaissances acquises grâce à cette recherche font non seulement progresser les connaissances fondamentales sur l’influence de ces ions paramagnétiques sur la réponse magnéto-optique, mais ouvrent également la voie à la conception et à la réalisation de nouveaux matériaux magnéto-optiques. Fruit de recherches rigoureuses, cette thèse de doctorat contribue de manière significative à la compréhension scientifique et au développement pratique de matériaux prêts à façonner les perspectives d’applications magnéto-optiques. __________________________________________________________________________________ 20 Abstract The study and preparation of new magneto-optical materials has gained significant attention due to their potential applications in various technological domains. Glasses that support high concentrations of paramagnetic ions are being widely sought after for these purposes, due to the inherent properties of glasses such as isotropy, high transmission window, high refractive indexes, easy synthesis and modelling, all interesting properties for optical systems. This doctoral thesis investigates the domain of advanced materials science, investigating the synthesis and comprehensive characterization of two glassy systems, a borotungstate containing first terbium and later an extended study to other lanthanides, and an antimony phosphate system containing manganese. The overall objective of this research is to synthesize innovative materials that have high and interesting magneto-optical attributes, with specific emphasis on their potential utility in devices that take advantage of the Faraday effect. The study presents different experiments to determine the thermal, optical, luminescent, structural, magnetic and magneto-optical characteristics of the proposed systems, guaranteeing an in-depth knowledge of different techniques, concepts and methods, important to increase the scientific growth in chemistry and chemical physics of non-crystalline materials. Excellent Curie constant values were obtained, up to 6.77 emu.Oe-1.mol-1, values higher than those reported in the literature, and Verdet constant of 124 rad.T-1.m- 1 632.8 nm for a sample with 27.5% mol of Tb2O3, comparable to commercial glasses and single crystals, and -55.1 rad.T-1.m-1 for the 30%mol MnO sample, unprecedented values for this type of Faraday rotator. By examining the impact of varying compositions on the structural, optical, and magnetic properties of the resulting materials, this thesis contributes to a deeper understanding of the interplay between transition metals, rare earths, and the magneto-optical behavior of glasses. Furthermore, the thesis evaluates the ability of these glass compositions to exhibit Faraday rotation. The insights gained from this research not only advance fundamental knowledge about the influence of these paramagnetic ions on magneto-optical response, but also pave the way for the design and realization of new magneto-optical materials. As a result of rigorous research, this doctoral thesis contributes significantly to the scientific understanding and practical development of materials poised to shape the prospect of magneto-optical applications. __________________________________________________________________________________ 21 List of Figures Figure 1. The Lycurgus Cup in reflected (a) and transmitted (b) light. Scene showing Lycurgus being enmeshed by Ambrosia, now transformed into a vine-shoot [The Trustees of the British Museum, Department of Prehistory and Europe, The British Museum. Height: 16.5 cm (with modern metal mounts), diameter: 13.2 cm][13]. ...................................................................... 37 Figure 2. Two-dimensional schematic representation illustrating the difference between: (a) the symmetrical and periodic crystalline arrangement of a crystal of composition A2O3; (b) representation of the glass network of the same compound, in which the absence of symmetry and periodicity is characterized. (Adapted from [31]) ............................................................. 40 Figure 3. Atomic-resolution images of a 2D glass. (a,b) Zachariasen’s models for a 2D crystal and a 2D amorphous glass. (c,d) Experimental TEM images of 2D crystalline and amorphous silica supported by graphene.[32] ............................................................................................. 41 Figure 4. The volume-temperature diagram for a glass-forming liquid. abc path is related to the transition from a liquid to a conventional solid, with the transformation taking place at the melting point. ade path corresponds to a decrease in temperature and increase in viscosity of the liquid, becoming a supercooled liquid, and finally, with a sudden decrease in temperature and increase in viscosity, forming a glass. afg path corresponds to the same transformation, but with faster quenching. (Adapted from [43]). ............................................................................ 46 Figure 5. Variation of molar susceptibility for each atom. For some, the diamagnetic effect is dominant, mainly due to the filling of the valence orbitals. Negative values indicate that they are repelled by the external magnetic field, B. For others, the paramagnetic effect is the most relevant, due to the number of half-filled orbitals. Positive values show that they are attracted by B. Fe, Co and Ni atoms have naturally high susceptibility, promoting ferromagnetic characteristics [Figure from Stan Zurek, Magnetic susceptibility, Encyclopedia Magnetica]. 50 Figure 6. (a) Paramagnetic (black) and diamagnetic (blue) susceptibility versus temperature under constant applied magnetic field. Inset of shown the inverse of paramagnetic susceptibility versus temperature, varying linearity. (b) Curie’s law deviation, with three different Weiss temperatures, θ < 0, θ = 0 and θ > 0. [Adapted from [47]] ....................................................... 53 Figure 7. The magnetic family tree, showing the evolution of macro-magnetic properties, the behavior of magnetic susceptibility, the organization of spins and some examples of substances that have these effects, making clear the complexity of magnetic effects[47]. ........................ 55 Figure 8. Behavior of (a) magnetic susceptibility and (b) of the inverse magnetic susceptibility for paramagnetic (red), ferromagnetic (blue) and antiferromagnetic (green) substances with temperature variation, under constant external magnetic field, showing TC and TN. (c) Representation of spin alignment for ferromagnetic (parallel alignment), antiferromagnetic (antiparallel alignment) and ferrimagnetic (antiparallel alignment with differences in intensity A and B) substances. [Adapted from [47] ................................................................................ 57 __________________________________________________________________________________ 22 Figure 9. Schematic figure of a Faraday rotator. Polarizer light λ passes through the medium with optical path l, under the external magnetic field and constant B, causing a rotation of the plane of polarization of light, measured at angle β. [Extracted from ThorLabs – Faraday Rotators page. https://www.thorlabs.com/images/TabImages/Faraday_Rotator_Diagram_D1- 780.gif] ..................................................................................................................................... 59 Figure 10. “Magneto-optical sensors” publications and citations made by Web of Science on April 14, 2023 [from Web of Science searching “Magneto-optical sensors”]. ....................... 64 Figure 11. “Magneto-optical glasses” publications and citations made by Web of Science on April 14, 2023 [from Web of Science searching “Magneto-optical glasses”]. ........................ 64 Figure 12. Magnetic signals produced by various sources[81]. .............................................. 66 Figure 13. Dependence of V on Tb3+ ion concentration and comparison to other reported data glasses at a fixed wavelength of 632.8 nm [87]. ...................................................................... 67 Figure 14. Ternary diagram of compositions in the Tb2O3-WO3-B2O3 system. Green spheres correspond to glass samples and red square to crystallized compositions. The xTb2O3-(60- x)B2O3-40WO3 (in mol %) series was chosen to study in this work. (Own authorship). ........ 85 Figure 15. Binary phase diagram for the system WO3-B2O3. [Adapted from [1]] .................. 86 Figure 16. Energy diagram representing the principle of Raman scattering compared to Rayleigh scattering, anti-Stokes scattering, and electronic and IR absorption. (Own authorship). .................................................................................................................................................. 94 Figure 17. Experimental scheme for the refraction index measurement using the Brewster angle method. The graph on the side shows an example of the angular scan for the 25Tb40W sample at 532 nm. The red fit represents the adjustment of the parameters allowing the index to be extracted in the used wavelength. (Adapted from[7]) .............................................................. 97 Figure 18. Scheme (a) and real apparatus (b) for Faraday effect measurements. Light from the 632.8 nm laser passes through the polarizer, then through the sample under the B field, which causes a rotation on the axis of polarization of the light. This deflection is measured on the second polarizer. (Own authorship).......................................................................................... 99 Figure 19. Samples xTb2O3-(60-x)B2O3-40WO3 series, after cut and polishing, with their specific names. (Own authorship). ......................................................................................... 103 Figure 20. xTb40W samples diffractograms and YBO3 analogous phase. (Own authorship). ................................................................................................................................................ 105 Figure 21. DSC curves (a), Tg and ΔT variation (b) for xTb40W samples. (Own authorship). ................................................................................................................................................ 106 __________________________________________________________________________________ 23 Figure 22. Theoretical optical basicity (Λth) and density (ρ) for the samples varying the Tb3+ ion effective concentration. (Own authorship). ...................................................................... 108 Figure 23. Raman scattering spectroscopy for the samples with different concentrations of Tb2O3, in addition to 25La40W sample, mimicking the 25Tb40W sample. (Own authorship). ................................................................................................................................................ 110 Figure 24. 11B MAS-NMR for the sample 25La40W, mimetizing sample 25Tb40W. (Own authorship). ............................................................................................................................. 112 Figure 25. Normalized infrared absorption spectra, obtained by DRIFT, for xTb40W samples and 25La40W. (Own authorship). .......................................................................................... 113 Figure 26. Absorption coefficient spectra of the xTb40W samples, with the respective absorption band. (Own authorship). ....................................................................................... 114 Figure 27. Transmittance spectra of the terbium-containing samples, with the respective absorption bands. (Own authorship). ...................................................................................... 115 Figure 29. Refractive index for samples with different contents of Tb2O3 in the ternary system and Cauchy's Law for the witch sample. (Own authorship). .................................................. 116 Figure 29. Normalized excitation spectra for the samples with different concentrations of Tb2O3, showing the 4f-4f transitions (7F6→) under λem = 543 nm. (Own authorship). .......... 118 Figure 30. Emission spectra for xTb40W samples, showing the 4f- 4f (5D4 and 5D3 →) transitions under λexc = 379 nm. ............................................................................................. 119 Figure 31. a. CIE 1931 chromaticity diagram for xTb40W samples under 379 nm excitation. b. Partial energy level diagram of Tb3+ illustrating the excitation 7F6→ 5D3+ 5G6, non-radiative decay (NR; 5D3→ 5D4), emissions 5D4→ 7FJ, and cross-relaxation process (CR) between two neighboring Tb3+ ions. ............................................................................................................ 120 Figure 32. Measured magnetic susceptibility for the 25Tb40W sample, measured by zero field- cooled (ZFC) and field-cooled (FC) methods. (Own authorship). ......................................... 121 Figure 33. Temperature dependence of the paramagnetic molar susceptibility for all samples. Inset shown the inverse of susceptibility (1/χpara) versus temperature, varying linearity and follow the Curie-Weiss law. (Own authorship). ..................................................................... 122 Figure 34. Variation of the Verdet constant by concentration of Tb3+ ions for the samples (red squares), some reference crystals (black stars) and different glass families (spheres): aluminosilicates (black), borates (red), borogermanates (orange), borogermanosilicates (yellow), borosilicates (green), fluorides (turquoise), fluorophosphates (blue) and phosphates glasses (purple). The dash line represent a fit of the data. (Own authorship). ....................... 125 __________________________________________________________________________________ 24 Figure 35. Behavior of the Verdet constant of the xTb40W samples (red squares) compared with commercially used crystals (black stars). (Own authorship). ........................................ 126 Figure 37. Samples for the 25Ln2O3-35B2O3-40WO3 system, where a. Ln = Sm, Eu, Gd, Dy, Ho, and a sample with 12.5Tb2O3-12.5Gd2O3-35B2O3-40WO3 and b. Ln = Er, Nd, Tm. (Own authorship). ............................................................................................................................. 138 Figure 38. Photo sequence of the 25Ho40W sample being attracted by a neodymium magnet at room temperature. The high concentration of paramagnetic species imparts this effect to the samples. (Own authorship). .................................................................................................... 140 Figure 39. X-ray diffractograms for the 25Ln40W, Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er or Tm samples, the ionic radius for the respective Ln3+ ion and the TmBO3 standard, hexagonal phase group P63/mmc (CIF-1511089). (Own authorship). .................................................... 141 Figure 40. DSC curves for the 25Ln40W samples. (Own authorship). ................................. 142 Figure 41. Tg and ΔT variation for each lanthanide ionic radius of 25Ln40W samples. (Own authorship). ............................................................................................................................. 144 Figure 42. a) Variation of effective ionic concentration and b) theoretical optical basicity and density for 25Ln40W samples, compared by different ionic radii of Ln3+. For the 12.5TbGd40W sample, the averages of the Tb3+ and Gd3+ radii were considered, as they represent half the concentration of each. (Own authorship). .............................................................................. 145 Figure 43. Raman spectra for each 25Ln40W sample. (Own authorship). ........................... 146 Figure 44. Normalized absorption coefficient for each sample 25Ln40W obtained Kramers- Kroning transform from infrared measurement by specular reflectance. The inset graph shows the absolute values for each sample. (Own authorship). ........................................................ 148 Figure 45. Transparency window for the 25Sm40W sample, with its main assignments starting from the ground state 6H5/2. (Own authorship). ...................................................................... 149 Figure 46. Zoom 0.2-0.8 µm transmittance spectra for the 25Sm40W sample, with its main assignments starting from the ground state 6H5/2. (Own authorship). .................................... 150 Figure 47. Zoom 0.8-1.75 µm transmittance spectra for the 25Sm40W sample, with its main assignments starting from the ground state 6H5/2. (Own authorship). .................................... 150 Figure 48. Transparency window for the 25Eu40W sample, with its main assignments starting from the ground state 7F0. (Own authorship). ......................................................................... 151 Figure 49. Transparency window for the 25Gd40W sample, with its main assignments starting from the ground state 8S7/2. (Own authorship). ....................................................................... 152 __________________________________________________________________________________ 25 Figure 50. Transparency window for the 12.5TbGd40W sample, with its main assignments starting from the ground state 7F6. 25Tb40W sample was taken as a reference. (Own authorship). ............................................................................................................................. 153 Figure 51. Transparency window for the 25Dy40W sample, with its main assignments starting from the ground state 6H15/2. (Own authorship). ..................................................................... 154 Figure 52. Zoom 0.2-0.7 µm transmittance spectra for the 25Dy40W sample, with its main assignments starting from the ground state 6H15/2. (Own authorship). ................................... 154 Figure 53. Zoom 0.7-1.6 µm transmittance spectra for the 25Dy40W sample, with its main assignments starting from the ground state 6H15/2. (Own authorship). ................................... 155 Figure 54. Transparency window for the 25Ho40W sample, with its main assignments starting from the ground state 5I8. (Own authorship)........................................................................... 156 Figure 55. Zoom 0.2-85 µm transmittance spectra for the 25Ho40W sample, with its main assignments starting from the ground state 5I8. (Own authorship). ........................................ 156 Figure 56. PL spectra for the Sm40W sample, showing the transitions from the excited level 4G5/2 corresponding to the Sm3+ ion. λexc = 404 nm. (Own authorship). ................................ 157 Figure 57. PL spectra for Eu40W sample, with the 4f-4f transitions from the excited level 5D0, corresponding to the Eu3+ ion. λexc = 394 nm. (Own authorship)........................................... 158 Figure 58. PL spectra for the 12.5TbGd40W sample, showing the transitions from the excited level 5D4 corresponding to the Tb3+ ion. λexc = 379 nm. (Own authorship). ........................... 159 Figure 59. PL spectra for the 25Dy40W sample, showing the transitions from the excited level 5F9/2 corresponding to the Dy3+ ion. λexc = 352 nm. (Own authorship). ................................. 160 Figure 60. PL spectra for the 25Ho40W sample, showing the transitions corresponding to the Ho3+ ion. λexc = 455 nm. (Own authorship). ........................................................................... 161 Figure 61. Partial energy level diagram of samples Ln3+ ions and the radiative transitions emissions [[29]]. ..................................................................................................................... 162 Figure 62. Refractive index for Ln trivalent ions glass samples. (Own authorship). ............ 163 Figure 63. Temperature dependence of the paramagnetic molar susceptibility for all 25Ln40W glass samples. Inset shown the inverse of susceptibility (1/χpara) versus temperature, varying linearity and follow the Curie-Weiss law. (Own authorship). ................................................ 165 Figure 64. Inverse of susceptibility by temperature for the samples 25Sm40W and 25Eu40W. ................................................................................................................................................ 166 __________________________________________________________________________________ 26 Figure 65. Photography of the glasses containing MnO studied in this work. (Own authorship). ................................................................................................................................................ 171 Figure 66. Sequence of photographs showing the attractive response of the glasses to the presence of a Nd-based magnet. a) and b) represent the approximation of the magnet, while the sequence after is related to the suspension of the glass piece (from c to f). (Own authorship). ................................................................................................................................................ 172 Figure 67. X-ray diffraction data for SZPxMn samples. ....................................................... 173 Figure 68. DSC curves for each SZPxMn sample, with arrow indicating the variation of Tg and Tx. (Own authorship). ............................................................................................................ 174 Figure 69. Raman scattering spectra of the samples SZPxMn with the main assignments. (Own authorship). ............................................................................................................................. 175 Figure 70. Infrared spectrum for each sample of the SZPxMn system, with the main bands marked. (Own authorship). ..................................................................................................... 176 Figure 71. Molar volume (VM) and density (ρ) variation for ion effective concentration (NMn2+) of which SZPxMn series samples. (Own authorship). ........................................................... 178 Figure 72. (a) Transmittance windows and (b) absorption coefficient spectra in SZPxMn system, with the mains transitions (Mn2+ in black and Mn3+ in blue) assigned. (Own authorship). ................................................................................................................................................ 180 Figure 73. Excitation (a), with λem = 720 nm, and emission (b), with λexc = 410 nm, spectra for samples SZPxMn system. (Own authorship). ........................................................................ 181 Figure 74. (a) Zero-field-cooled (ZFC) and field-cooled (FC) susceptibility (𝜒𝐷𝐶) as a function of the temperature (T) for the 1-x(SbPO4-ZnO-PbO)-xMnO glass with an applied magnetic field of H = 100 Oe. (b) 𝜒𝐷𝐶 − 1 vs T curve for the 30, 20, and 10 MnO containing, where the point represents the experimental data and the blue dashed line represents the fits to the Curie- Weiss law (Eq. 28). (c) Magnetization as a function of the applied magnetic field (M vs. H) loops at 5K (d) and 300 (K). The yellow continue line represents the Brillouin function fit. (Own authorship). ................................................................................................................... 182 Figure 75. μeff obtained from the analyses, where also the obtained values using Curie-Weiss law were included for comparison. (Own authorship). .......................................................... 185 Figure 76. Verdet constant (V) versus effective Mn2+ concentration (NMn2+) for SZPxMn series samples. (Own authorship). .................................................................................................... 186 __________________________________________________________________________________ 27 List of Figures in Appendix Figure A-1. Photograph of the 3D inscription attempts performed on the 25Tb40W sample, taken with a 40X objective lens. For high powers(A-1a), the formation of holes occurred and for low powers (A-1b), weak and discontinuous markings occurred. .................................... 195 Figure A-2. Preforms after trying to draw the fibers. A crystalline phase is observed in the region where preform heating occurred.................................................................................. 196 Figure A-3. Schematic illustration of the coupling between the Faraday effect (FE) and the inverse Faraday effect (IFE) in a liquid [7]. ........................................................................... 198 __________________________________________________________________________________ 28 List of Tables Table 1. Theoretical values of χdia for some ions[56]............................................................. 51 Table 2. Series of Tb-contain borotungstate glasses, showing name, nominal compositions (in mol % and cat mol %), molar mass (M) and if phase separation occurred during quenching. ................................................................................................................................................ 103 Table 3. Thermal and physical properties of the glass samples: Tg (glass transition temperature), Tx (onset of the crystallization temperature), ΔT (thermal stability parameter), ρ (density), NTb3+ (ion effective concentration), ΛTh (theoretical optical basicity) and λUV (short wavelength cut-off). ..................................................................................................... 106 Table 4. Band assignments of the main vibrational modes in Raman for the xTb40W glasses. ................................................................................................................................................ 110 Table 5. Refractive indices for xTb40W samples, at wavelengths 532, 639, 785, 935 nm with ± 0.005 error. We obtained the refractive index for 1000 nm using Cauchy's Law. .............. 117 Table 6. theoretical diamagnetic susceptibility (χdia), Weiss temperature (θ), Curie constant (C) for two units (one in Oested, Oe, e other in Tesla, T) and probed Tb2O3 % mol for each sample. ................................................................................................................................................ 122 Table 7. comparison between different Curie constant (C) values and Weiss temperature (θ) for samples from this work and examples from the literature. ............................................... 123 Table 8. Series of Ln-contain borotungstate glasses, showing name, nominal compositions (% mol and % cat mol), molar mass (M) and if phase separation occurred during quenching. .. 139 Table 9. Thermal and physical properties of the glass samples: Tg (glass transition temperature), Tx (onset of the crystallization temperature), ΔT (thermal stability parameter), ρ (density), NLn3+ (ion effective concentration), ΛTh (theoretical optical basicity) and λUV (short wavelength cut-off). ..................................................................................................... 142 Table 10. Band assignments of the main vibrational modes in Raman and Infrared for the 25Ln40W glasses. ................................................................................................................... 147 Table 11. Refractive index values for samples with different trivalent lanthanide ions for different laser wavelengths (error = ±0.005). ......................................................................... 163 Table 12. Fundamental level of Ln3+, spin angular momentum (S), orbital angular momentum (L), total angular momentum (J), diamagnetic susceptibility (χdia), Weiss temperature (θ), Curie constant (C) in two different units and Ln2O3 % mol for each 25Ln40W samples. ... 165 __________________________________________________________________________________ 29 Table 13. Chemical compositions and characteristic temperatures of the glasses studied in this work. The thermal stability parameter (ΔT) and the refractive index (λlaser = 532 nm) of the samples are also shown. ......................................................................................................... 171 Table 14. Raman scattering and infrared band assignments for SZPxMn series................... 176 Table 15. Density (ρ), ion effective concentration (NMn2+), theoretical optical basicity (ΛTh), short wavelength cut-off (λUV) and refractive index (n) at 532 nm for samples SZPxMn. .. 177 Table 16. Parameters obtained from the fits of the susceptibility (𝜒𝐷𝐶) versus temperature (T) to the Curie–Weiss law as described in the text. .................................................................... 183 __________________________________________________________________________________ 30 List of Equations Gauss’s law........................................................................................... ............................................................(Eq. 1) Gauss' s law for magnetism..................................................................................... ...........................................(Eq.2) Faraday' s law of induction................................................................................................................................(Eq.3) Ampère' s circuital law................................................................................... ....................................................(Eq.4) Magnetic suscetibility.............................................................................. .........................................................(Eq. 5) Diamagnetic susceptibility............................................................................... .................................................(Eq. 6) Spin (S), orbital (L), and total angular momentum (J)......................................................................................(Eq. 7) Curie's law................................................................................. ........................................................................(Eq.8) Curie constant............................................................................. .......................................................................(Eq.9) Landé g-factor..................................................................................... ............................................................(Eq.10) Curie–Weiss law..............................................................................................................................................(Eq.11) Faraday effect..................................................................................................................................................(Eq.12) Verdet constant, diamagnetic contribution......................................................................................................(Eq.13) Verdet constant, paramagnetic contribution....................................................................................................(Eq.14) Verdet constant, paramagnetic contribution correction...................................................................................(Eq.15) Relationship between V and α..........................................................................................................................(Eq.16) Archimedes' principle.................................................................................... ..................................................(Eq.17) Kramers-Krönig inversion technique.........................................................................................................(Eq.18-23) Ion effective concentration..............................................................................................................................(Eq.24) Theoretical optical basicity..............................................................................................................................(Eq.25) Figure of merit........................................................................................... ......................................................(Eq.26) Curie-Weiss Law for Mn.................................................................................................................................(Eq.27) Inverse of Eq.27.................................................................................... ...........................................................(Eq.28) Magnetization x Field.......................................................................... ............................................................(Eq.29) Magnetization x Field simplified.....................................................................................................................(Eq.30) __________________________________________________________________________________ 31 Summary CHAPTER I - INTRODUCTION 35 1. GLASSES 35 1.1. BRIEF HISTORY OF THE EMERGENCE OF GLASSWORKING, GLASSMAKING AND PHOTONIC GLASSES. 35 1.2. DEVELOPMENT OF THE DEFINITION OF GLASSES. 39 1.3. GLASS FORMATION FROM A MELT. 45 2. MAGNETO-OPTICAL PROPERTIES 46 2.1 BRIEF HISTORY OF MAGNETISM AND MAGNETO-OPTICAL EFFECT. 46 2.2. MAGNETISM IN ATOMS AND MACROSCOPIC MAGNETIC PROPERTIES OF MATERIALS. 48 2.3 PRINCIPLES OF THE MAGNETO-OPTICAL FARADAY EFFECT. 59 2.4 STATE OF THE ART OF FARADAY ROTATOR GLASSES. 63 REFERENCES IN THIS CHAPTER 71 OBJECTIVES OF THIS WORK 82 CHAPTER II – EXPERIMENTAL TECHNIQUES 84 1. SYNTHESIS OF THE SAMPLES 84 1.1. TB2O3-B2O3-WO3 SYSTEM 84 1.2. LN2O3-B2O3-WO3 SYSTEM 86 1.3. SBPO4 SYNTHESIS 87 1.4. SBPO4-ZNO-PBO-MNO SYSTEM 88 2. INSTRUMENTAL METHODS 88 2.1. THERMAL ANALYSIS 88 2.2. X-RAY DIFFRACTOMETRY 89 2.3. DENSITY MEASUREMENTS 90 2.4. FOURIER-TRANSFORM INFRARED SPECTROSCOPY 91 2.5. RAMAN SCATTERING SPECTROSCOPY 93 2.6. 11B-NUCLEAR MAGNETIC RESONANCE 95 2.7. UV-VISIBLE-NIR SPECTROSCOPY 95 2.8. REFRACTIVE INDEX MEASUREMENTS 96 2.9. FLUORESCENCE SPECTROSCOPY 97 2.10. MAGNETIC SUSCEPTIBILITY MEASUREMENTS 98 2.11. FARADAY EFFECT MEASUREMENTS 99 REFERENCES IN THIS CHAPTER 101 CHAPTER III - CHARACTERIZATION AND STUDY OF PROPERTIES OF THE TB2O3-B2O3-WO3 SYSTEM 103 1. SAMPLES 103 2. XRD. 104 3. THERMAL ANALYSIS 105 4. DENSITY AND OPTICAL BASICITY 106 5. STRUCTURAL ANALYSIS 109 6. UV-VIS-NIR SPECTROSCOPIES. 113 __________________________________________________________________________________ 32 7. REFRACTIVE INDEX. 116 8. FLUORESCENCE SPECTROSCOPY. 117 9. MAGNETIC SUSCEPTIBILITY 120 10. MAGNETO-OPTICAL MEASUREMENTS 124 11. PARTIAL CONCLUSIONS OF THIS CHAPTER. 126 REFERENCES IN THIS CHAPTER 128 CHAPTER IV - CHARACTERIZATION AND STUDY OF PROPERTIES OF THE LN2O3-B2O3-WO3 SYSTEM137 1. SAMPLES 137 2. XRD 140 3. THERMAL ANALYSIS AND DENSITY 142 4. DENSITY AND OPTICAL BASICITY 144 5. STRUCTURAL ANALYSIS 145 6. OPTICAL ANALYSIS 149 7. LUMINESCENCE ANALYSIS 157 8. REFRACTIVE INDEX. 162 9. MAGNETIC ANALYSIS 163 10. PARTIAL CONCLUSIONS OF THIS CHAPTER. 166 REFERENCES IN THIS CHAPTER 167 CHAPTER V - STUDY OF THE STRUCTURAL AND MAGNETIC PROPERTIES OF THE SBPO4–ZNO-PBO– MNO SYSTEM 171 1. SAMPLES 171 2. XRD 173 3. THERMAL ANALYSIS 173 4. RAMAN SCATTERING AND INFRARED SPECTROSCOPY 175 5. DENSITY. 177 6. OPTICAL ANALYSIS 179 7. LUMINESCENCE ANALYSIS 180 8. MAGNETIC ANALYSIS 181 9. MAGNETO-OPTICAL ANALYSIS. 185 10. PARTIAL CONCLUSIONS OF THIS CHAPTER. 187 REFERENCES OF THIS CHAPTER. 188 CHAPTER VI – FINAL CONCLUSION AND PERSPECTIVES 192 APPENDIX I – OTHER MEASUREMENTS AND EXPERIMENTS CARRIED OUT 194 A-I. PHOTOCHROMISM TESTS. 194 A-II. 3D INSCRIPTION. 194 A-III. OPTICAL FIBER DRAWING. 195 A-IV. MELTING-QUENCHING UNDER EXTERNAL MAGNETIC FIELD. 196 A-V. INVERSE FARADAY EFFECT MEASURES. 197 A-VI. MAGNETIC PROPERTIES UNDER IRRADIATION AT LOW TEMPERATURE. 198 __________________________________________________________________________________ 33 REFERENCES IN THIS APPENDIX 199 APPENDIX II – PERIODIC TABLE OF ELEMENTS 201 APPENDIX III – CARNALL DIAGRAM 202 APPENDIX IV – ACADEMIC TREE – LEONARDO VIEIRA ALBINO 203 Chapter I – Introduction __________________________________________________________________________________ 34 CHAPTER I – Introduction Sixth Solvay Conference, whose theme was "Le magnétisme". Paris, 1930 [47]. Seated in front: Th. de Donder, P. Zeeman, P. Weiss, A. Sommerfeld, M. Curie, P. Langevin, A. Einstein, O. Richardson, B. Cabrera, N. Bohr, W. J. De Haas; Standing: E. Herzen, E. Henriot, J. Verschaffelt, C. Manneback, A. Cotton, J. Errera, O. Stern, A. Piccard, W. Gerlach, C. Darwin, P. A. M. Dirac, H. Bauer, P. Kapitsa, L. Brillouin, H. A. Kramers, P. Debye, W. Pauli, J. Dorfman, J. H. Van Vleck, E. Fermi, W. Heisenberg. Chapter I – Introduction __________________________________________________________________________________ 35 Chapter I - Introduction 1. GLASSES 1.1. Brief history of the emergence of glassworking, glassmaking and photonic glasses. Looking at vitreous materials, from the most common and trivial to the most technological niche, it's difficult to grasp the antiquity of the crafting and production of this category of materials. Glass is one of the oldest materials to have been processed by mankind. As natural materials, found in the environment, and due to their characteristics of easy handling, being able to form excellent sharp flakes for making knives, arrowheads and spears, natural glasses, especially obsidian, were used by hominids for making tools from at least 500,000 years ago, during the Lower Paleolithic, in what is now Kenya [1]. Our species, Homo sapiens, did not appear until 315,000 years ago, so the art of manipulating glass predates humanity. With the expansion of Homo sapiens and the exit from Africa to Eurasia (90,000 years ago), and the discovery of new sites containing obsidian, this material continued to be used. During the Mesolithic (20,000 - 12,000 years ago) and Neolithic (12,000 - 7,500 years ago) periods, obsidian became increasingly important due to its ability to form more complex tools, including finer and sharper points, needles, hooks, knives, implements, jewelry, and various other items[2– 6]. Artificial glass, on the other hand, is a relatively modern development, though still surprisingly old. Archaeological evidence suggests that non-crystalline, glass-like materials called faience were used in ancient Egypt, Mesopotamia, and Syria well before the production of glass itself [7]. Egypt's favorable preservation environment means that most of the early, well-studied glassware is located there, although some may have been imported[8,9]. The earliest known glass objects, which were beads dating back 5500 years ago, were likely produced by accident during metal smelting or by the production of faience, a vitrified ceramic formed by mixing crystalline and non- crystalline phases, using a high-temperature firing process. Significantly, the emergence Chapter I – Introduction __________________________________________________________________________________ 36 of high-temperature furnaces capable of melting copper and bronze allowed for the production of faience.[10] Around 2600 BC, there is evidence of the first human-made glass, which was still quite opaque due to the technology of the time. Glass preparation techniques spread and improved with the expansion of the Bronze Age and trade between Asia Minor, Africa and Europe. As a result, increasingly complex pieces were produced, which were cheaper, more transparent, and had better results, such as in terms of shape and color.[11,12] Jumping ahead to the Roman domain of the Mediterranean, it was the Romans who became the first people to dominate the making of transparent glass. They perfected the blowing method, which involves using a metallic pipe and leaving the molten material forming a bubble while shaping it. Additionally, the Romans excelled in the production of stained glass. They were also the pioneers of the technique of producing colored stained glass for churches by adding salts during synthesis, which was highly explored in the Middle Ages to create glass of different colors. Furthermore, we must acknowledge the Lycurgus cup depicted in Figure 1 that exhibits a unique attribute of having two colors, one when viewed from the outside (reflection) and the other when viewed from the inside (transmission). Researchers were highly intrigued until a more in-depth evaluation using transmission electron microscopy revealed the presence of gold and silver nanoparticles in glass, in specific sizes and shapes. This was one of the initial demonstrations of control over crystal growth and nanotechnology. The Lycurgus cup, dating back to the 4th century, remains an enigma regarding the process used by the ancient Romans to manufacture it [13]. The glasswork produced by guilds in Venice and on the Murano islands was a notable attraction for the city-state in the Middle Ages. The addition of lead in the glass melting process alongside the development of high-temperature furnaces produced transparent glasses with a higher refractive index. This advance gave rise to the lenses in early modern telescopes and microscopes. From the 16th century onwards, handmade glass in Bavaria became famous for dominating these properties. The production was a state secret for the Bavarians. Michael Faraday was interested in synthesizing these Chapter I – Introduction __________________________________________________________________________________ 37 glasses (lead borosilicates) at the beginning of his career at the Royal Institution in London. We will discuss this in the next sections. Figure 1. The Lycurgus Cup in reflected (a) and transmitted (b) light. Scene showing Lycurgus being enmeshed by Ambrosia, now transformed into a vine-shoot [The Trustees of the British Museum, Department of Prehistory and Europe, The British Museum. Height: 16.5 cm (with modern metal mounts), diameter: 13.2 cm][13]. The glass industry was a part of the Industrial Revolution. Synthetic and refined raw materials were used for the first time in the production of windows and inert packaging. However, the unpredictability and non-homogeneity on an industrial scale were still problematic. The high, consistently accurate and reproducible optical qualities in glasses resulted from the joint efforts of Otto Schott, Carl Zeiss, and Ernst Abbe. They founded one of the pioneer glass companies, Glastechnische Laboratorium Schott & Genossen (current Schott & Associates Glass Technology Laboratory) based in Jena, capitalizing on their specialized skills. There have been significant advancements in developing new glass materials since then. For instance, the discovery of lanthanum- doped glasses in the 1930s [14], the development of no oxygen–containing chalcogenide Chapter I – Introduction __________________________________________________________________________________ 38 glasses in the 1953[15], with high transparency in the near and mid-infrared (NIR and MIR), the first metallic glass in 1960[16], the first glass laser in 1961[17], and the discovery of fluoride glasses in 1974 by Jacques Lucas, Michel and Marcel Poulain[18]. One of the most pertinent studies conducted on photonic glasses was the report by Charles K. Kao published in 1966 which concluded that the primary issue concerning the production of optical fibers for telecommunication was inadequate material purity. He predicted that fibers created from highly pure materials would exhibit a loss lower than 0.3 dB/km[19]. Consequently, Kao's accomplishment earned him the Nobel Prize in Physics in 2009. By 1970, fiber optics degradation of as low as 20 dB/km at 632.8 nm had already been achieved by Corning. In 1979, the preform and fiber production processes were further refined, decreasing the value to 0.20 dB/km at 1550 nm. Currently, the minimum attenuation in mass-produced single-mode fiber is less than 0.17 dB/km[20]. Optical fibers enabled and still enable information and knowledge to travel across the planet at the speed of light, they are the backbone of the Internet and the key to today's global communications revolution. During the COVID- 19 pandemic, we made extensive use of long-distance conferencing services powered by fiber optics, which kept us together during those difficult times. Glasses are present from the windows to cell phone screens. From beverage bottles to vaccine flasks. Composites made from bioglass have improved health care through their ability to integrate with human bone. Glass panels support solar cells and provide clean energy. The development of glass optics and optoelectronics means the James Webb Space Telescope can study the first moments after the Big Bang and expand our understanding of the universe. Glass artists around the world have introduced humanity to this wonderful material, including its remarkable fabrication methods, its inherent beauty, and its ability to capture and display nature's full spectrum of colors[21,22]. For these and many other reasons, the UN General Council declared 2022 as the International Year of Glass. Throughout history, we define ages by the materials and movements that transformed civilization, such as the Stone Age, Bronze Age, Iron Age, which provided revolutions in the civilizations that experienced them. And, as well proposed by David L. Morse and Jeffrey W. Evenson, both researchers at Corning Chapter I – Introduction __________________________________________________________________________________ 39 Incorporated, we currently live in the “Age of Glass”, due to all the social, cultural, and technological transformations associated with this class of material [23]. Welcome to the Glass Age! 1.2. Development of the definition of glasses. Although glass has been used by humans for a long time, its definition has been the subject of several debates among scholars throughout history. One of the early pioneers in the study of glasses was the renowned physicist and chemist Michael Faraday (1791-1867), who defined them as follows: “Glass may be considered rather as a solution of different substances one in another, than as a strong chemical compound.” Michael Faraday, 1830[24] In the late 19th and early 20th centuries, Gustav Tammann (1861-1938) conducted experiments that proved the possibility of creating glasses from substances besides silica. To achieve ideal and homogeneous vitrification, it was essential to prevent the creation of crystalline nuclei, which leads to the expansion of macroscopic crystals. The possible vitrification process depends on the melting temperature of the material, the temperature for liquidus pouring, and/or tempering (a heat treatment used after glass formation to reduce post-quenching stress)[25]. After conducting these studies, glass definitions were formulated based on the viscosity of solids concept. This approach was necessary because, until then, glasses had only been prepared via the melting-quenching method, which involves rapidly cooling a molten substance. The viscosity criterion defines a solid as rigid material that doesn't flow when exposed to moderate forces. As a quantitative measure, a solid can be defined as a substance with a viscosity exceeding 1014 Pa.s. “Glass is non-crystalline, strongly supercooled melt inorganic product, which reaches a rigid condition by cooling, through a progressive increase in viscosity, without crystallization occurring.” Gustav Tammann, 1925[26] Chapter I – Introduction __________________________________________________________________________________ 40 The emergence of techniques such as X-ray diffraction and the initial results from measuring glass samples[27–30] revealed that the structural organization of glasses resembles that of liquids more than crystalline solids. In 1932, William Houlder Zachariasen, a Norwegian-American researcher, published the well-known article 'The Atomic Arrangement in Glass', where he formulated his Random Network Theory (RNT) in glasses while studying their diffractograms. Zachariasen established the structural basis for the formation of glasses by melting-quenching and suggested that “the atomic arrangement in glasses was characterized by an extended three- dimensional network, which lacked symmetry and periodicity”, and that “interatomic forces were comparable to those of the corresponding crystal”. Additionally, the researcher notes that the presence or absence of periodicity and symmetry in a three- dimensional network distinguishes between a crystal and a glass.[31] Figure 2. Two-dimensional schematic representation illustrating the difference between: (a) the symmetrical and periodic crystalline arrangement of a crystal of composition A2O3; (b) representation of the glass network of the same compound, in which the absence of symmetry and periodicity is characterized. (Adapted from [31]) Chapter I – Introduction __________________________________________________________________________________ 41 Figure 2a shows the symmetric and periodic crystal arrangement of a crystal composition A2O3 in a two-dimensional format, while Figure 2b shows the glass network for the same compound, demonstrating the absence of symmetry and periodicity. This theory made the article a landmark in Glass Science. By combining Zachariasen's RNT and the contemporary concept of glass at the time of publication, we may arrive at the following definition: “Glasses are described as supercooled liquids or as solids, with absence of periodicity in the network, isotropic materials.” William H. Zachariasen, 1932[31] Figure 3. Atomic-resolution images of a 2D glass. (a,b) Zachariasen’s models for a 2D crystal and a 2D amorphous glass. (c,d) Experimental TEM images of 2D crystalline and amorphous silica supported by graphene.[32] In 2012, P. Y. Huang et al. [32] and M. Heyde et al. [33] demonstrated the atomic structure of a two-dimensional silica glass supported on graphene using Chapter I – Introduction __________________________________________________________________________________ 42 transmission electron microscopy (TEM), which emphasizes Zachariasen's accurate, insightful, and pioneering spirit. Transmission electron microscopy (TEM) experimental findings, as presented in Figure 3, closely resembled the picture proposed by Zachariasen 80 years earlier in 1932. The strong qualitative resemblance of these images to Zachariasen's model indicates that they show a 2D glass that approximately complies with the continuous random network model. In the years following Zachariasen's publication, new definitions were proposed. These were based on the non-crystalline properties of glasses, their viscosity, and the glass transition. There are several definitions for glasses found in the literature: “Glass is an X-ray amorphous material that exhibits the glass transition. This being defined as that phenomenon in which a solid amorphous phase exhibits with changing temperature (heating) a more or less sudden change in its derivative thermodynamic properties such as heat capacity and expansion coefficient, from crystal-like to liquid-like value”. J. Wong and C. Austen Angell, 1976[34] “Glasses are amorphous materials that do not have long-range translational order (periodicity), characteristic of a crystal, with glass being an amorphous solid that exhibits a glass transition.” S. R. Elliott, 1989[35] “A glass is a non-crystalline solid exhibiting the glass transition phenomenon.” J. Zarzycki, 1991[36] “Glass is an amorphous solid. A material is amorphous when it lacks long-distance order, that is, when there is no regularity in the arrangement of molecular constituents, on a scale larger than a few times the size of these groups. No distinction is made between the words vitreous and amorphous.” R. H. Doremus, 1994[37] Chapter I – Introduction __________________________________________________________________________________ 43 However, these definitions are limited in several ways. The first one does not take into account glasses obtained by sol-gel or CVD (chemical vapor deposition). The second definition would emphasize that glasses can be formed from any composition - theoretically - whether it be inorganic, organic, biological, or metallic. It is worth mentioning that until now, there has been no consensus on whether glasses are solids or supercooled liquids with such high viscosity that they appear solid but flow over time. This theory originated from the observation of ancient medieval stained glass in Europe. It was noted that the bottom of stained-glass windows were thicker than the top, implying the glass might have flowed over the centuries. The discussion culminated in an article entitled "Do cathedral glasses flow?" written by Edgar D. Zanotto [38]. Through viscosity measurements and calculations, they found that cathedrals' silica glasses would require 1032 years to flow significantly. This period is significantly longer than the current age of the Universe (13.8 x 109 years). The thicker base of stained glass was one of the challenges in producing flat glass during the medieval period. When placing the glass in the window, artisans favored positioning its thickest part downwards to prevent breakage. “Glass is an amorphous solid with complete absence of long- range order and periodicity, exhibiting a glass transition region. Any material, inorganic, organic or metal, formed by any technique, that exhibits a glass transition phenomenon is a glass.” J. E. Shelby, 1997[39] Gupta[40] proposed that a non-crystalline solid (characterized by the presence of a halo on the X-ray diffractogram without any identifiable peaks) can be divided, from a thermodynamic standpoint, into two different categories: glasses and amorphous solids. Non-crystalline solids refer to materials that possess an extended and random three-dimensional network, i.e., characterized by a lack of symmetry and translational periodicity. From a thermodynamic perspective, a non-crystalline solid is considered a glass when it undergoes the glass transition phenomenon. As a result, amorphous solids can be classified as non-crystalline solids that do not manifest the glass transition. New definitions have been suggested to support this new classification: Chapter I – Introduction __________________________________________________________________________________ 44 “A glass is a non-crystalline solid, therefore, with absence of symmetry and translational periodicity, which exhibits the phenomenon of glass transition, and can be obtained from any inorganic, organic or metallic material and formed through any preparation technique.” O. L. Alves, I. F. Gimenez and I. O. Mazali, 2001[41] “Glass is a solid having a non-crystalline structure, which continuously converts to a liquid upon heating.” Arun K. Varshneya, 2012[42] We finally arrived in 2017, when the researchers Edgar D. Zanotto and John C. Mauro published the article “The glassy state of matter: Its definition and ultimate fate”[43], in which they revised the old definitions and created a new, more comprehensive one, with a focus on both researchers in the field and the lay public: “Glass is a nonequilibrium, non-crystalline condensed state of matter that exhibits a glass transition. The structure of glasses is similar to that of their parent supercooled liquids (SCL), and they spontaneously relax toward the SCL state. Their ultimate fate, in the limit of infinite time, is to crystallize”. Edgar D. Zanotto and John C. Mauro, 2017 Theoretically, any substance can be turned into glass, as long as we can cool it from a liquid or gaseous state at such a high rate that the atoms and molecules that make it up do not have enough time to arrange themselves into organized structures that are thermodynamically more stable. As Varshneya concludes, “the kinetic theory of glass formation does not address the question as to what structural characteristics of substances encourage ready glass formation. It assumes that all substances can be brought into glassy state. The only question it addresses is what minimum cooling rate is required to avoid a perceptible degree of crystallization”[42]. Each substance has its own properties, so the cooling rate can be very different from one substance to another. For example, for liquid water to turn into glass, the cooling rate must be 107 K . s-1, Chapter I – Introduction __________________________________________________________________________________ 45 while for silica this rate is 0.9 x 10-6 K . s-1, which makes obtaining glasses of water more expensive and requires more specific techniques, in addition to limiting the size of the bulk, as there is a temperature gradient during the cooling process[44]. 1.3. Glass formation from a melt. Traditionally, conventional glasses are produced using the melting/quenching method. This method includes the melting of a mixture of initial materials, typically at high temperatures until they turn into a homogenous liquid. Then, the mixture is rapidly cooled to increase its viscosity and maintain its non-crystalline characteristic. The structures of the raw material of a glass are similar to a liquid when melted. As cooling occurs, and its viscosity increases, the molten material can follow different structural patterns based on the cooling rate used. Figure 4 shows the volume-temperature (V-T) diagram for a glass-forming liquid. According to the diagram, starting from high to low temperatures, we have the abc path, which shows the natural path for crystal formation. When we reach the melting temperature (or melting point, freezing temperature) Tf, we have an abrupt change in volume (or enthalpy) and, finally, the crystal is formed, being the lowest energy level of the compound itself. However, it is possible to cool liquids at temperatures below Tf. This metastable condition is known as super cooled liquids (SCL). It is important to point out that as the temperature decreases, the viscosity of the SCL increases proportionally. If this cooling is faster, we have the ade path. The gradual increase in viscosity occurs until the SCL does not flow, forming the glass. The transition from the SCL to the glass is instituted when the viscosity reaches the value of 1014 Pa.s. The temperature at which this transition occurs is defined as the glass transition temperature (Tg). As observed in the afg path, if the cooling rate occurs more slowly, the viscosity increases in the same proportion, forming a different glassy phase, with a different Tg, density and enthalpy, starting from the same initial liquid. The Tg represents the temperature range where structural relaxation starts (1014 Pa.s), transitioning from the glassy to the viscoelastic state. At this stage, certain properties such as viscosity, heat capacity, and thermal expansion begin to behave Chapter I – Introduction __________________________________________________________________________________ 46 differently than previously observed. Structural relaxation arises from unobstructed translational movements of chains relative to one another. It is imperative to note that the V-T diagram is solely applicable to glasses created through melting-quenching. For instance, in the sol-gel process which achieves glasses from solutions at room temperature, and is a method unsuitable for V-T diagram application. Figure 4. The volume-temperature diagram for a glass-forming liquid. abc path is related to the transition from a liquid to a conventional solid, with the transformation taking place at the melting point. ade path corresponds to a decrease in temperature and increase in viscosity of the liquid, becoming a supercooled liquid, and finally, with a sudden decrease in temperature and increase in viscosity, forming a glass. afg path corresponds to the same transformation, but with faster quenching. (Adapted from [43]). 2. MAGNETO-OPTICAL PROPERTIES 2.1 Brief history of magnetism and magneto-optical effect. Chapter I – Introduction __________________________________________________________________________________ 47 Magnetic phenomena have been present since the beginning of humanity. According to Roger Elliot: “magnetism provides a particularly good example of the way in which the exact sciences have developed”[45]. Magnetism was already known by the ancient Sumerians, Greeks, Chinese and America pre-Columbian people for millennia and interpreted it as magic. The name "magnetic" has its Greek origin, coming from the ferromagnetic stones extracted from the region of Magnesia, which became known as magnetites (from Greek μαγνῆτις [λίθος] - magnētis [lithos] - meaning "[stone] from Magnesia")[45,46]. During the Middle Ages, the Chinese developed the compass, a maritime instrument that was very relevant to the Chinese discoveries in the 15th century and the Iberian discoveries in the 16th and 17th centuries. In 1600, the Englishman William Gilbert (1544–1603) wrote De Magnete, Magneticisque Corporibus, et de Magno Magnete Tellure (On the Magnet and Magnetic Bodies, and on That Great Magnet the Earth), which is known to be the first scientific study on magnetism. In his work, Gilbert suggests that the Earth also operates as a large magnet [47]. In 1820, Hans-Christian Ørsted (1777-1851), a Danish physicist, observed that a defect occurred in a compass that was accidentally placed near his experiment while he was studying electricity and applied a current to metallic wires. This provided evidence that there was a physical relationship between electricity and magnetism. The unit of magnetic induction (Oe, oersted) in the centimeter-gram-second system (CGS) is named after Ørsted due to his contributions to the field of electromagnetism[47]. At the Royal Society in London, Humphry Davy (1778-1829) and William Hyde Wollaston (1766-1828) attempted to create an electric motor using magnets after learning of Ørsted's work, but it was Davy's student, Michael Faraday (1791-1867), who succeeded in creating the motor by using a steel magnet, a current-carrying wire, and a container of mercury as early as 1821. Faraday publicized his results in excitement without giving credit to Wollaston or Davy, causing controversy within the Royal Society. The controversy strained Faraday's relationship with his mentor Davy and possibly led to his assignment to other pursuits by the Royal Society. Faraday resumed his work on magnetism only after Davy's death years later[47,48]. Chapter I – Introduction __________________________________________________________________________________ 48 In 1845, Faraday demonstrated that it was possible to change the plane of polarization of a beam of light when this beam passed through a specific medium (in this case, a glass containing PbO with a high refractive index) under a magnetic field application, parallel to the direction of light propagation. This effect became known as the Faraday effect, the first of the discovered magneto-optical effects[49,50]. Showing the relevance of this discovery, the Faraday effect proved that light is an electromagnetic radiation, mathematically demonstrated in 1864 by James Clerk Maxwell, unifying the theories of electricity, magnetism and light, which is summarized in the four famous equations that bear his name: ∮ �⃗� . 𝑑𝐴 = 𝑞 𝜀0 𝐺𝑎𝑢𝑠𝑠′𝑠 𝐿𝑎𝑤 (𝐸𝑞. 1) ∮�⃗� . 𝑑𝐴 = 0 𝐺𝑎𝑢𝑠𝑠′𝑠 ?