Thèse Présentée pour obtention le grade de Docteur de l'Université de Strasbourg Discipline: Chimie Physique Par Zhiqiang ZHENG Spray Assembly of Polyelectrolyte and Polyelectrolyte Nanoparticle Films: Structural Characterization and Improvement of Mechanical Properties Soutenue publiquement le Octobre l'Institut Charles Sadron Membres du Jury: Directeur de Thèse: M Gero Decher Professeur Strasbourg France Président du jury: M Pierre Schaaf Professeur Strasbourg France Rapporteur Externe: M Nicholas Kotov Professeur Michigan USA Rapporteur Externe: M Lars Wagberg Professeur Stockholm Sweden Membre Invité: M Olivier Félix CR1 Strasbourg France

Charles Sadron

Description

Niveau: Supérieur, Doctorat, Bac+8
Thèse Présentée pour obtention le grade de Docteur de l'Université de Strasbourg Discipline: Chimie-Physique Par Zhiqiang ZHENG Spray-Assembly of Polyelectrolyte and Polyelectrolyte/Nanoparticle Films: Structural Characterization and Improvement of Mechanical Properties Soutenue publiquement le 26 Octobre 2009 à l'Institut Charles Sadron Membres du Jury: Directeur de Thèse: M. Gero Decher, Professeur, Strasbourg, France Président du jury: M. Pierre Schaaf, Professeur, Strasbourg, France Rapporteur Externe: M. Nicholas Kotov, Professeur, Michigan, USA Rapporteur Externe: M. Lars Wagberg, Professeur, Stockholm, Sweden Membre Invité: M. Olivier Félix, CR1, Strasbourg, France

• inorganic nanoparticle


• ministère de l'enseignement supérieur et de la recherche


• lbl films


• mechanical resistance


• centre natioanal de la recherche scientifique


• functional lbl


• nanoparticle films

Sujets

• Cousin
• Heywood
• Strasbourg
• Brinkmann
• Schaaf

Informations

• Publié par: profil-zyak-2012
• Publié le: 01 octobre 2009
• Nombre de lectures: 44
• Langue: English
• Poids de l'ouvrage: 28 Mo

Extrait

Thèse Présentée pour obtention le grade de
Docteur de l’Université de Strasbourg
Discipline: Chimie-Physique

Par
Zhiqiang ZHENG

Spray-Assembly of Polyelectrolyte and
Polyelectrolyte/Nanoparticle Films:
Structural Characterization and
Improvement of Mechanical Properties

Soutenue publiquement le 26 Octobre 2009
à l’Institut Charles Sadron

Membres du Jury:
Directeur de Thèse: M. Gero Decher, Professeur, Strasbourg, France
Président du jury: M. Pierre Schaaf, Professeur, Strasbourg, France
Rapporteur Externe: M. Nicholas Kotov, Professeur, Michigan, USA
Rapporteur Externe: M. Lars Wagberg, Professeur, Stockholm, Sweden
Membre Invité: M. Olivier Félix, CR1, Strasbourg, France

He that seeks finds
Thomas Heywood
British playwright






Learn without thinking begets ignorance
Think without learning is dangerous
The Confucian Analects, Chapter 2
Confucius


2

?????7??5|d0?7??5?Acknowledgement
First of all, I would like to express my sincere gratitude to my advisor
Professor Gero Decher for the continuous support during my doctoral
studies and research and his patience, enthusiasm, and immense passion
in science. He gave me the opportunity to get familiar with the amazing
technique: LbL and supported me in becoming a scientific researcher.

I am grateful for the abundant and invaluable help from Dr. Olivier Félix,
without whose extraordinary support my research project would not have
been possible.

I would like to thank Shahid QUERESHI, from Quaid-i-Azam University,
Pakistan. He was a visiting Ph. D student twice in our team, we worked
together in Amine based LbL films construction and the LbL films
mechanical resistance improvement. I highly appreciate the support from
Dr. Martin Brinkmann, ICS, for his help in LbL films mechanical resistance
tests by rubbing machine.

Special thanks to all my colleges, Tam, Rohama, Seb, Nicolas, FIX,
Guillaume, Jean-Louis and Eric, and also my office mates Emek and Gabi,
for all the joyful moments that we have shared in the past three years, for
your fruitful scientific discussions and inspiring ideas during my research
program.

I would like to thank all the researchers, technicians and administrative
staff at l’Institut Charles Sadron for offering me such a wonderful and
friendly working environment. I express my gratitude especially to Dr.
Fabrice Cousin in CEA, Saclay for his collaboration within our Neutron
reflectometry project., to Dr. Robert Wengeler and Dr. Sabrina Pancera as
well as BASF in Ludwigshafen, Germany for the collaborative project
“RoboSpray”. Special thanks to Dr. Karine Mougin at UHA, Mulhouse for
enlightening me the first glance of research.
3 I would like to express my gratitude to Professors Kotov, Wågberg and
Schaaf for having accepted to act as referees for my thesis work.

Thanks to French ministry of Higher Education and Research (Ministère
de l'enseignement supérieur et de la recherche), Centre Natioanal de la
Recherche Scientifique (CNRS) and BASF, Ludwigshafen, Germany for
providing me with financial support.

I dedicate my thesis to my family, my parents, and my wife nuan nuan.
Without your support and encouragement, the road could not have led so
far. To my beloved grandparents as well, I miss you and I love you all.

Last but not least, I would like to thank every scientist working in the field
of layer-by-layer assembly. Had it not been for your effort, I would never
have the opportunity to enter this amazing world.


















4
Table of Contents
List of Abbreviation ................................................................. 9

Introduction .............................................................................. 11

Chapter I. State of the Art ......................................................... 18
I.1. A brief review of 2D Self-Assembly system: From LB films to LbL films .... 18
I.2. An introduction of Polyelectrolyte Multilayer and Layer-by-Layer Self-
Assembly technique ......................................................................................... 21

I.2.1. An overview of Layer-by-Layer Self-Assembly technique .......................... 21
I.2.2. Polyelectrolyte multilayer formation, films construction and structure ........ 22
I.2.2.1. Polyelectrolyte multilayer formation: Mechanism and the three-zone
model .................................................................................................. 22
I.2.3. Key parameters in polyelectrolyte multilayer formation .............................. 27
I.2.4. Different polyelectrolyte multilayer growth regime: linear and super linear
growth ........................................................................................................ 29
I.2.5. Structure of polyelectrolyte multilayer ........................................................ 30
I.2.6. Comparison of preparation methods: dipping, spraying and spin coating .... 30
I.2.7 Beyond consecutive assembly steps: simultaneous “one-step” spraying ....... 32
I.3. Functional LbL films containing layers of inorganic nanoparticle ............... 34
I.3.1. Inorganic nanoparticle (NP) and their assembly-assembly .......................... 34
I.3.2. Gold nanoparticle (Au NP) and their assembly ........................................... 37
I.4. LbL assembly using strong interactions: covalently linked LbL films ......... 41
I.5. LbL films mechanical behavior study ............................................................ 42
I.6. Applications of LbL assembled films: toward commercial applications ...... 44
Bibliography* ............................................................................ 46

Chapter II Materials and Methods ........................................... 53
II.1. Materials ........................................................................................................ 53
II.1.1. Polymer abbreviations and structures ........................................................ 53
II.1.2. Synthesis of gold nanoparticle ................................................................... 54
II.1.3. Substrate and cleaning methods ................................................................. 55
5 II.1.4. Protocol for film preparation by spraying .................................................. 55
II.1.4.1. Manually operated sprayer cans: “Air Boy” ........................................ 56
II.1.4.2. Automated simultaneous spraying ...................................................... 56
II.1.4.3. Control parameters for manual spraying ............................................. 57
II.2. Methods .......................................................................................................... 58
II.2.1. Ellipsometry .............................................................................................. 58
II.2.1.1. Principal of ellipsometry measurement ............................................... 59
II.2.1.1.1. Polarized light ................................................................................. 59
II.2.1.1.2. Mathematical equations used in ellipsometry measurement ............. 60
II.2.1.2. Data acquisition .................................................................................. 62
II.2.1.3. Basic experimental setup for constant-angle-of-incidence ellipsometry ....
63
II.2.1.4. Limits of ellipsometric measurements ................................................. 64
II.2.1.5. Ellipsometers used in current research: PLASMOS SD2300 and
Multiskop ........................................................................................... 65
II.2.2. Ultraviolet-Visible Spectroscopy ............................................................... 67
II.2.2.1. Beer-Lambert Law ............................................................................. 67
II.2.2.2. Experimental setup of an UV-Visible spectrophotometer .................... 68
II.2.2.3. Applications of UV-Visible ................................................................ 68
II.2.3. Atomic force microscopy (AFM) .............................................................. 69
II.2.3.1. Principle and Basic set up of AFM ..................................................... 69
II.2.3.2. AFM Imaging ..................................................................................... 72
II.2.3.3. Tapping mode ..................................................................................... 73
II.2.3.4. Advantages and limits of AFM measurements .................................... 75
II.2.4. A simple mechanical wear test with rubbing machine ................................ 76
II.2.5. Neutron reflectometry ............................................................................... 76
II.2.5.1. Princ