N° d’ordre : UEB/UR1 ANNÉE 2015 THÈSE / UNIVERSITÉ DE RENNES 1 sous le sceau de l’Université Européenne de Bretagne pour le grade de DOCTEUR DE L’UNIVERSITÉ DE RENNES 1 Mention : Physique Ecole doctorale (Science de la Matière) présentée par Ramona Mhanna Préparée à l’unité de recherche UMR 6251, IPR et à l’Institut Laue-Langevin, ILL Institut de Physique de Rennes UFR Sciences et Propriétés de la Matière Confinement-induced Soutenance prévue à Rennes le 29 octobre 2015 nano-segregation devant le jury composé de : of binary liquids with Natalie MALIKOVA Chargée de Recherche CNRS, Univ. Paris 6 / rapportrice amphiphilic Patrick JUDEINSTEIN interactions Directeur de Recherche CNRS, CEA Saclay / rapporteur Marianne IMPEROR-CLERC Directrice de Recherche CNRS, Univ. Paris-sud / examinatrice Renaud DENOYEL Directeur de Recherche CNRS, Univ. d'Aix-Marseille / examinateur Ronan LEFORT Maître de Conférences, Univ. Rennes 1 / examinateur Denis MORINEAU Directeur de Recherche CNRS, Univ. Rennes 1 / directeur de thèse Bernhard FRICK Chercheur, Institut Laue-Langevin, Grenoble / co- directeur de thèse ACKNOWLEDGEMENTS: I did my PhD in co-direction between the Institute of Physics of Rennes (IPR) (nanosciences and materials department) and the Institute of Laue Langevin. My utmost thanks and sincere gratitude go to my thesis directors (Dr. Denis MORINEAU and Dr. Bernhard FRICK) and my co-director (Dr. Ronan LEFORT) whose continued support and encouragement made this project possible. Denis, know that your words of wisdom and advice have always been received with highest degrees of respect. Your support, confidence and commitment to this project were instrumental to its successful completion. A wise saying that I have recently heard is: “don’t pick a job, pick a boss, as your first boss is the biggest factor in your career success. A boss who doesn’t trust you won’t give you opportunities to grow. ” I couldn’t have picked more wisely, you are my role model and you have inspired me in so many ways both at the personal and scientific levels and for that I’ll be forever grateful. I extend my thanks and gratitude to Bernhard who has shown me that there is no limit to aspiration. It was a great honor and a privilege to work with you and I’ll always be looking up to you when I think of dedication to science. I genuinely appreciate your honesty, persistence and fruitful scientific discussions which have been invaluable for the thesis. My sincere gratitude also goes to Ronan who has played a great role in this thesis and enormously attributed to its success. I am greatly thankful for your assistance, advice and support and I am quite happy that I had the opportunity to work with someone with such scientific and human qualities. I would also like to express my gratitude towards all the jury members (Renaud DENOYEL “jury president”, Marianne IMPEROR-CLERC, Patrick JUDEINSTEIN and Natalie MALIKOVA) for accepting to be a part of this long process. In your own ways, you have each added to this project and helped shape me both as a student and a researcher. Much gratitude goes to the management of the IPR (Jean-Pierre LANDESMAN) and the ILL (Helmut SCHOBER) for welcoming me in their institutes. My appreciation extends to all the IPR and ILL staff for making me feel like home over the last three years. A particular thanks goes to the members of the nanosciences department and the administrative service at the IPR as well as the student body at the ILL. A very special thought goes to my friends in France (in particular Rennes and Grenoble) and Lebanon for being there for me. I have a special place in my heart for all of you, thank you for being my big family. In addition, I would like to thank some teachers or rather mentors who inspired me to become who I am today. A huge thanks goes to you Dr. Daoud, Dr. Fares, Dr. Hala, Miss Nyola, Miss Abir, Mr. Majid, Miss Sumer and Mr. Hamad. Last but not least, I want to dedicate this thesis to my father (my hero, my supporter, my everything), my loving mother, my sisters, my brothers, my sister in law and my extended family who have always supported me. I am so lucky to have you. Your faith in me, your unconditional love and my eagerness to make you proud served as a driving force in my work. This project has been, without any doubt, the largest test of my own commitment, spanning three years away from my family and loved ones. But I have not achieved this alone. Along the way, I have received so much support from too many people to count. I definitely wouldn’t have done it if some of you weren’t in my life. Thank you for all the gracious sacrifices you have made for me while I realized this goal. Though you may not see your names here, know that your various contributions have not gone unnoticed or unappreciated. TABLE OF CONTENTS: Chapter I: Scientific Case………………………………………………………………….. 1 I.A. Introduction………………………………………………………………………………3 I.B. Confinement Effects……………………………………………………………………...5 I.B.1. Effect on Phase Transitions……………………………………………………... 5 I.B.1.1. Melting /Crystallization in Confinement………………………………...5 I.B.2.Effect on Dynamics……………………………………………………………… 7 I.B.2.1. Concept of Glass Transition…………………………………………..…7 I.B.2.2. Dynamics of Confined Super-cooled Liquids………………………….10 I.B.3.Effect on Structure………………………………………………………………13 I.B.3.1. Density Change………………………………………………………... 13 I.B.3.2. Self-assemblies in Confinement………………………………………..14 I.B.4. Phase Separation of Binary Liquids………………………………………….. ..16 I.C. Aim of the Thesis………………………………………………………………………. 20 I.D. Organization of the Thesis……………………………………………………………... 21 References…………………………………………………………………………………... 22 Chapter II: Liquids and Materials……………………………………………………….. 27 II.A. Introduction…………………………………………………………………………… 29 II.B. Liquids………………………………………………………………………………… 30 II.B.1. Tert-Butyl Alcohol……………………………………………………………. 31 II.B.2. Methanol……………………………………………………………………… 32 II.B.3.Ethanol………………………………………………………………………… 33 II.B.4. Toluene……………………………………………………………………..… 33 II.B.5. Cyclohexane…………………………………………………………………... 34 II.C. Confining Materials…………………………………………………………………… 35 II.C.1. Types of Porous Materials……………………………………………………. 35 II.C.1.1. Microporous Materials………………………………………………...35 II.C.1.2. Mesoporous Materials………………………………………………... 36 II.C.2.Synthesis………………………………………………………………………. 39 II.C.2.1. Synthesis of MCM-41………………………………………………... 39 II.C.2.2. Synthesis of SBA-15…………………………………………………. 40 II.C.2.3. Synthesis of CMK-3.……………………………………………….… 41 II.C.3. Characterization………………………………………………………………. 42 II.C.3.1. Microscopy…………………………………………………………… 42 II.C.3.2. Diffraction……………………………………………………………..44 II.C.3.3. Adsorption Isotherms………………………………………………… 47 II.C.3.4. Analysis of the Adsorption Isotherms………………………………... 49 II.C.3.5. Characterization of the Matrices………………………………………53 References …………………………………………………………………………………. 54 Chapter III: Supermolecular Order in Bulk…………………………………………….. 59 III.A. Introduction…………………………………………………………………………... 61 III.B. Methods………………………………………………………………………………. 63 III.B.1. General Background…………………………………………………………. 63 III.B.2. Experimental…………………………………………………………………. 64 III.B.3. Data Reduction………………………………………………………………. 64 III.C. Results and discussion……………………………………………………………….. 66 III.C.1. TBA-Tol/ Cyc Systems……………………………………………………… 66 III.C.1.2. Experimental Results…………………………………………………66 III.C.1.3. Ornstein-Zernike Analysis……………………………………………67 III.C.1.4 Bhatia and Thornton Analysis……………………………………...… 69 III.C.1.5. Kirkwood-Buff Analysis……………………………………..……… 72 III.C.2. Meth/Eth-Tol Systems……………………………………………………….. 74 III.D. Conclusion…………………………………………………………………………….77 References…………………………………………………………………………………... 78 Chapter IV: Local Order of Confined Binary Liquids…………………………………..81 IV.A. Introduction…………………………………………………………………………...83 IV.B. Methods and Principles………………………………………………………………. 84 V.B. 1. the Concept of Contrast variation: …………………………………………... 84 V.B.2. the Contrast Effect……………………………………………………………. 84 IV.C. SANS Measurements on Confined Mixtures………………………………………… 87 IV.C.1. Sample Preparation and Data Treatment…………………………………….. 87 IV.D. Experimental Results …………………………………………………………………89 IV.D.1. Contrast effect of the mixture of one single isotope liquid (D / H) ………….89 IV.D.2. Contrast Effect in Binary Mixtures Satisfying CM Condition ……………….90 IV.D.3. Symmetrical Mixtures with Equivalent Scattering length Densities…………91 IV.E. Structural Models ……………………………………………………………………..92 IV.E.1. Choice of Model………………………………………………………………92 IV.E.2. Theoretical Background………………………………………………………94 IV.E.2.1. Homogeneous Filling…………………………………………………94 IV.E.2.2. Core-Shell Model …………………………………………………….95 IV.E.2.3. Debye Waller Factor Model ………………………………………….96 IV.E.2.4. Microporous Corona Model ………………………………………….98 IV.F. Data Analysis………………………………………………………………………...100 IV.F.1. Data Treatment………………………………………………………………100 IV.F.1.1. Background Corrections …………………………………………….100 IV.F.1.2. Analysis of Bragg Scattering ………………………………………..100 IV.F.1.3. Model Calculations ………………………………………………….101 IV.F.2.Discussion of Data in Terms of Reliability of Models ………………………103 IV.F.2.1.Debye Waller Factor Model …………………………………………103 IV.F.2.2.Microporous Corona Model ………………………………………...115 IV.G. Conclusion …………………………………………………………………….119 References …………………………………………………………………………………121 Chapter V: Dynamics of Confined Binary Mixtures…………………………………... 123 V.A. Introduction …………………………………………………………………………..125 V.B. Glass Transition Measurements………………………………………………………126 V.B.1. Tg from Differential Scanning Calorimetry………………………………….126 V.B.1.1. Tg in Pure Compounds ………………………………………………126 V.B.1.2. Tg in Binary Mixtures ……………………………………………….128 V.B.2. Dielectric Studies of Mixtures ……………………………………………….129 V.B.2.1. Decoupling of the Different Modes………………………………….129 V.C. Quasielastic Neutron Scattering ……………………………………………………130 V.C.1. Theoretical Background ……………………………………………………130 V.C.2. Neutron Backscattering (BS) ………………………………………………132 V.C.2.1. Elastic-Inelastic Fixed Window Scans ………………………………133 V.D. Experimental Details …………………………………………………………………134 V.D.1. Sample Preparation ………………………………………………………….134 V.D.2. Experimental Conditions …………………………………………………….134 V.D.3. Data Treatment ………………………………………………………………135 V.E. Results and Discussion ……………………………………………………………….136 V.E.1 Pure components in SBA-15 ………………………………………………….136 V.E.1.1. Elastic Fixed Window Scans…………………………………………136 V.E.1.2. Mean Square Displacement (MSD) ………………………………….137 V.E.1.3. Conclusion …………………………………………………………139 V.E.2. Binary Mixtures in SBA-15 ………………………………………………….141 V.E.2.1. Contribution from Deuterated Components …………………………141 V.E.2.2 Elastic fixed Window Scans ………………………………………….144 V.E.2.3. Mean Square Displacement (MSD) ………………………………….149 V.E.3. Binary Mixtures in MCM-41 ………………………………………………150 V.E.3.1. Elastic Fixed Window Scans ………………………………………150 V.F. Conclusion ……………………………………………………………………152 References …………………………………………………………………………………153 GENERAL CONCLUSION…………………………………………………………….. 155 Annex: Q-Dependence of EFWS………………...……………………………………………i Chapter I: Scientific Case       CHAPTER I:        SCIENTIFIC CASE       1 Chapter I: Scientific case         2