The investigation of 1D nanocrystals confined in carbon nanotubes Chunyang Nie To cite this version: Chunyang Nie. The investigation of 1D nanocrystals confined in carbon nanotubes. Material chem- istry. Université Paul Sabatier - Toulouse III, 2016. English. NNT : 2016TOU30214. tel-01540273 HAL Id: tel-01540273 https://tel.archives-ouvertes.fr/tel-01540273 Submitted on 16 Jun 2017 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. THÈSE En vue de l’obtention du DOCTORAT DE L’UNIVERSITÉ DE TOULOUSE Délivré par :Université Toulouse 3 Paul Sabatier (UT3 Paul Sabatier) Présentée et soutenue par Chunyang NIE Le 23/09/2016 Titre : Etude de nanocristaux unidimensionnels confinés dans des nanotubes de carbone Title : The investigation of 1D nanocrystals confined in carbon nanotubes ED SDM : Sciences et génie des matériaux - CO034 Unité de recherche : UMR 5085 CIRIMAT - Centre Interuniversitaire de Recherche et d'Ingénierie des Matériaux UPR 8011 CEMES-CNRS - Centre d'Elaboration des Matériaux et d'Etudes Structurales Directeur(s) de Thèse : Dr. Emmanuel FLAHAUT, Dr. Marc MONTHIOUX Rapporteurs : Dr. Brigitte VIGOLO Institut Jean Lamour Université de lorraine Dr. Chris EWELS Institut de Matériaux Jean ROUXEL Université de Nantes Autre(s) membre(s) du jury : Prof. Alfonso SAN MIGUEL Université Lyon 1 Président Prof. Manitra RAZAFINIMANANA Université Paul Sabatier Examinateur Acknowledgements First and foremost I would like to thank my two supervisors Dr. Emmanuel Flahaut and Dr. Marc Monthioux for their guidance, support and assistance on the research during the last three years, especially the time they gave in the preparation of this thesis during the summer holiday. I would like to thank Dr. Anne-Marie Galibert and Dr. Brigitte Soula for their help with my experimental work and the discussions with the experimental results. I wish to acknowledge Dr. Chris Ewels and Dr. Brigitte Vigolo for taking their valuable time to be the Rapporteurs of the thesis, and their comments and remarks on the thesis. I also wish to acknowledge Prof. Alfonso San Miguel and Prof. Manitra Razafinimanana for participating in the jury. I wish to acknowledge the grant of Chinese Scholoarship Council (CSC) for supporting my PhD study in France. I wish to acknowledge Dr. Christophe Laurent, Dr Claude Estournes and all Nanocomposites Nanotubes de Carbone team: Dr. Alicia Weibel, Dr. David Mesguich and Professor Alain Peigney in Centre Inter-universitaire de Recherche et d'Ingénierie des Matériaux (CIRIMAT) and Dr. Etienne Snoeck in Centre d'élaboration de matériaux et d'études structurales (CEMES) for giving me the best ambiance and conditions in the lab during my PhD. I also would like to express my big thank you to Sébastien Joulié and Florent Houdellier for their help with the training on the various kinds of transmission electron microscopes in CEMES, as well as their efforts to maintaining the good running of the microscopes (TEM). Without the microscopes, I could hardly finish my PhD study. I would like to thank Laure Noé in CEMES for her help with the preparation of TEM grid at the beginning of my thesis and her help with the operation of CM30. Then I would like to thank Lucien Datas in Centre de microcaractérisation Raimond Castaing for the help with taking beautiful TEM images of my samples with the powerful JEOL JEM-ARM200F. I would like to thank David Neumeyer in CEMES for spending time helping with the sulfurization experiments, discussing with my experiment results and giving me good advises. I would like to thank Aurélien Masseboeuf for taking time to making holograms of my sample, i processing the holograms and explaining me the results. Though nothing interesting has been found thus far, it was a good exploration and experience for me. I would like to thank Dr. Escoffier Walter and his PhD student Yang Ming in Laboratoire National des Champs Magnétiques Intenses (LNCMI) and Dr. Benjamin Lassagne in Laboratoire de Physique et Chimie des Nano-objets (LPCNO) for their help with the measurements of electrical conductivity of my samples. Though the measurements are still in processing and the full datas are not possible to be represented in this thesis, their work is valuable to my PhD project. I would like to thank all my colleagues in CIRIMAT (Pierre Lonchambon, Jean François Guillet, Thomas Lorne, …) and in CEMES (David Reyes, Juan Du, Rongrong Wang, Tian Wang, Tingting Xiao, Xiaoxiao Fu, … ) for their help and the good time we spent together. Finally, I would like to thank my family for their support and encourage during all these years. Amicalement, Chunyang Toulouse, France ii Table of contents Acknowledgements .................................................................................................................................................... i Table of Contents …………………………………………………………………………………………………..iii List of Abbreviations .................................................................................................................................................. v General Introduction ................................................................................................................................................ 1 Chapter 1 General Introduction to Filled Carbon Nanotubes ................................................................................ 3 1.1 Carbon Nanotubes ........................................................................................................................... 4 1.2 Filled Carbon Nanotubes ................................................................................................................ 6 1.2.1 A Glimpse at the History of Filling CNTs ................................................................................. 6 1.2.2 The Motivations with Filling CNTs ........................................................................................... 9 1.2.3 Filling Strategy ........................................................................................................................ 10 1.2.3.1 In Situ Filling Route ........................................................................................................ 10 1.2.3.2 Ex situ Filling Route ........................................................................................................ 13 1.2.3.2.1 Previous Opening of the Tubes ............................................................................ 13 1.2.3.2.2 Filling by Gas Phase Methods .............................................................................. 14 1.2.3.2.3 Filling by Liquid Phase Methods ......................................................................... 15 1.2.4 Species Encapsulated within CNTs ......................................................................................... 19 1.2.4.1 Atoms (Isolated, or as Chains) ........................................................................................ 20 1.2.4.2 Molecules (Isolated, or as Chains) .................................................................................. 21 1.2.4.3 Pure Elements (as Nanowires or Nanoparticles) ............................................................ 23 1.2.4.4 Compounds (as Chains, Nanowires, or Nanoparticles) .................................................. 24 1.2.5 Filling Mechanisms.................................................................................................................. 25 1.2.6 Behaviors, Properties and Applications ................................................................................... 28 1.2.6.1 Peculiar in-Tube Behavior (diffusion, coalescence, crystallization) ............................... 29 1.2.6.2 Electronic Properties (Transport, Magnetism and others) .............................................. 33 1.2.6.3 Applications ..................................................................................................................... 38 1.3 Conclusion ...................................................................................................................................... 39 References ....................................................................................................................................................... 40 Chapter 2 Investigation on the filling mechanisms of DWCNTs with foreign phases and of the resulting peculiar structures of the latter .............................................................................................................................. 59 2.1 Introduction .................................................................................................................................... 59 2.2 Preparing/gathering host CNTs and BNNTs ............................................................................... 60 2.2.1 CCVD synthesis of DWCNTs/FWCNTS ................................................................................ 60 2.2.2 Extraction of DWCNTs/FWCNTs ........................................................................................... 61 2.2.3 Nanotubes from