Sikandar Ali CHANNA

178 Pages·2017·10.58 MB·French

Sikandar Ali CHANNA

Mémoire présenté en vue de l’obtention du

grade de Docteur de l'Université de Nantes
sous le sceau de l’Université Bretagne Loire

École doctorale : SPIGA

Discipline : Science pour l’ingénieur
Spécialité : Thermique et Energétique
Unité de recherche : LTEN UMR CNRS 6607

Soutenance prévue le 02/10/2017

Synthesis of Ti-based nanoparticles in continuous flow microreactors

JURY

Rapporteurs : Hasna LOUAHILA Professeur des universités LUSAC, Université de Caen-Basse Normandie
Florence RAZAN Maître de conférences SATIE, École Normale Supérieure de Rennes

Examinateurs : Graziella GOGLIO Professeur des universités ICMB, Université de Bordeaux
Hassan PEERHOSSAINI Professeur des universités Université Paris Diderot
Mireille RICHARD-PLOUET Chargée de recherche CNRS, IMN - Nantes
Bertrand GARNIER Chargé de recherche CNRS, LTEN - Nantes

Invité(s) : Ahmed OULD EL MOCTAR Maître de conférences LTEN, Université de Nantes
Hélène TERRISSE Maître de conférences IMN, Université de Nantes

Directeur de Thèse : Bertrand GARNIER Chargé de recherche CNRS, LTEN - Nantes

Co-directeur de Thèse : Mireille RICHARD-PLOUET Chargée de recherche CNRS, IMN - Nantes
Ahmed OULD EL MOCTAR Maître de conférences LTEN, Université de Nantes

Acknowledgement

I would like to express my sincere gratitude to my PhD supervisors: Bertrand GARNIER,
Mireille Richard-Plouet and Ahmed OULD EL MOCTAR for their support and
encouragement during all the time of our research and writing of this thesis. Their belief in
my abilities helped me to be more confident and successfully carry on my research.
I am very thankful to jury members and reporters for their advice and suggestions.
I am very grateful to Madame Hélène TERRISSE for her discussions which helped me to
better understand the problems encountered in the DLS and improved the quality of my work.
I also want to thank to researchers, colleagues, technical staff and supporting staff at LTEN
and IMN who helped me throughout my research time including Gwenael for fabrication of
microchannels, DJAKAOU IYA SOU, Jean Yves, Gildas, Solene for their valuable inputs
related to Raman spectroscopy, DLS and chemistry.
Furthermore I also thank research internees Andres and Antoine who helped me to achieve
the tasks of this thesis.
Special thanks to my friend and internee Delphine who helped me in chemistry part and
French.
I thank my parents for supporting me consistently during these years especially my mom and
my elder brother Asadullah.
I am especially grateful to Andrew Lytle and Heather Lytle for their love and support like a
family.
Lastly I would like to thank my girl friend Marion for motivating and encouraging me
throughout the thesis time.

Table of contents :

Résumé 5 pages en français .................................................................................................... 5
General Introduction ............................................................................................................. 15
Chapter 1 ................................................................................................................................. 21
Literature review on nanoparticles productionand mixing process. ................................. 21
1.1Introduction ......................................................................................................................... 23
1.2 Synthesis of nanoparticles .................................................................................................. 23
1.2.1 Various techniques for nanoparticles production ............................................................ 23
1.3 Nanoparticles production via a continuous process using microreactors........................... 27
1.4 Mixing enhancement in microreactors ............................................................................... 30
1.4.1 Passive mixing ................................................................................................................. 31
1.4.2 Active mixing .................................................................................................................. 33
1.5 Conclusion .......................................................................................................................... 34
Chapter 2 ................................................................................................................................. 39
Materials and methods ........................................................................................................... 39
2.1 Reactants and reactions ...................................................................................................... 41
2.2 Ti-based nanoparticles production in batch process (at IMN) ........................................... 42
2.2.1 Experimental conditions in batch process ....................................................................... 42
2.2.2 Hydrolysis and condensation of TiOCl in N,N-dimethylformamide ............................ 43
2
2.3 Microreactor Devices ......................................................................................................... 46
2.3.1 Microchannel's Material .................................................................................................. 46
2.3.2 Passive mixing experimental setup. ................................................................................ 46
2.3.2.1 Microchannel ........................................................................................................ 47
2.3.2.2 Injection system .................................................................................................... 49
2.3.2.3 IR thermography ................................................................................................... 50
2.3.3 Enthalpy measurement setup ........................................................................................... 50
2.3.4 Active electrical Micromixer .......................................................................................... 53
2.4 Nanoparticles Analysis ....................................................................................................... 55
2.4.1 Dynamic Light scattering DLS technique ....................................................................... 55
2.4.1.1 Common terms used in DLS analysis. .................................................................. 58
i. Z-Average .................................................................................................................. 58
ii. Polydispersity Index .................................................................................................. 58
1
iii. Y-Intercept or Intercept ............................................................................................ 59
iv. Intensity and Volume distribution ............................................................................ 59
2.4.1.2 Sample preparation ............................................................................................... 61
2.4.2 F.T Raman Spectroscopy ................................................................................................ 61
2.4.2.1 Principle of F.T Raman spectroscopy ................................................................... 61
2.4.2.2 Calibration of selected band area and analytical method ...................................... 63
2.5 Conclusion .......................................................................................................................... 65
Chapter 3 ................................................................................................................................. 67
Fluid flow and thermal analysis ............................................................................................ 67
3.1 Pure Solution ...................................................................................................................... 69
3.2 Diluted solution with various solvents ............................................................................... 71
3.3 Pre-diluted solution with DMF .......................................................................................... 74
3.3.1 Dilution ............................................................................................................................ 74
3.3.2 Effect of concentration .................................................................................................... 75
3.3.3 Effect of flow rate ........................................................................................................... 76
3.4 Enthalpy measurement ....................................................................................................... 78
3.4.1 Enthalpy measurement for TiOCl prediluted with 2-propanol ...................................... 78
2
3.4.2 Enthalpy measurement with DMF pre-dilution .............................................................. 79
3.5 Discussion .......................................................................................................................... 81
3.6 Conclusion .......................................................................................................................... 82
Chapter 4 ................................................................................................................................. 85
Mixing enhancement using an electric field ......................................................................... 85
4.1 Introduction ........................................................................................................................ 87
4.2 Pre-mixed solution ............................................................................................................. 88
4.2.1 Results without electric field ........................................................................................... 88
4.2.2 Effect of DC Electric field............................................................................................... 91
4.2.3 Effect of AC electric field ............................................................................................... 97
4.2.3.1 Effect of flow rate on the mixing .......................................................................... 97
4.2.3.2 Joule effect .......................................................................................................... 100
4.2.3.3 Effect of Frequency on mixing ........................................................................... 101
4.2.3.4 Effect of Voltages on the mixing ........................................................................ 103
4.3 Pure Solution .................................................................................................................... 106
4.4 Conclusion ........................................................................................................................ 109
2
Chapter 5 ............................................................................................................................... 111
Sols characterizationby DLS andRaman scattering ......................................................... 111
5.1 Size distribution by DLS .................................................................................................. 113
5.1.1 Nanoparticles produced using Y-shape short microchannel (Pre-mixed Solution) ...... 113
5.1.1.1 Sols quality and polydispersity analysis ............................................................. 113
5.1.1.2 Effect of time on NPs .......................................................................................... 114
5.1.1.3 Effect of flow rate on NPs................................................................................... 116
5.1.2 Nanoparticles produced using longer microchannel ..................................................... 118
5.1.2.1 Without electric field (Pre-mixed Solution)........................................................ 118
5.1.2.1.a Sols quality and polydispersity analysis ....................................................... 118
5.1.2.1.b Effect of filtration on the sols ....................................................................... 119
5.1.2.1.c Effect of time on NPs ................................................................................... 121
5.1.2.1.d Effect of flow rate on NPs ............................................................................ 124
5.1.2.2 With electric field................................................................................................ 126
5.1.2.2.a Pre-mixed Solution ....................................................................................... 126
i. Sols quality and polydispersity analysis ............................................................... 127
ii. Effect of Filtration on NPs .................................................................................. 128
iv. Effect of time on NPs ......................................................................................... 130
iii. Effect of flow rate on NPs .................................................................................. 132
5.1.2.2.b Pure TiOCl solution .................................................................................... 134
2
i. Sols quality and polydispersity quality. ................................................................ 134
ii. Effect of Filtration on NPs .................................................................................. 136
iii. Effect of time on NPs ......................................................................................... 137
iv. Effect of flow rate on NPs .................................................................................. 139
5.1.3 Summary ....................................................................................................................... 141
5.2 Hydrolysis advancement monitored by Raman ............................................................... 142
5.2.1 Y-shape short microchannel (Pre-mixed Solution) ....................................................... 142
5.2.2 Longer microchannel (with electric field) ..................................................................... 144
5.2.2.1 Pre-mixed Solution ............................................................................................ 144
5.3 Discussion: ....................................................................................................................... 149
5.4 Conclusion ........................................................................................................................ 151

3
Chapter 6 ............................................................................................................................... 154
Conclusion and perspectives ............................................................................................... 154
6.1 Conclusion ........................................................................................................................ 156
6.2 Perspectives ...................................................................................................................... 157
ANNEX .................................................................................................................................. 160

4
Résumé 5 pages en français

«Synthèse en microréacteur de nanoparticules d'oxydes de
titane »

5
6