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Informations
Publié par | technischen_universitat_darmstadt |
Publié le | 01 janvier 2010 |
Nombre de lectures | 16 |
Langue | English |
Poids de l'ouvrage | 7 Mo |
Extrait
Template-assisted synthesis and
characterisation of quasi-one-
dimensional ceramic nanomaterials
Vom Fachbereich Chemie
der Technischen Universität Darmstadt
zur Erlangung des akademischen Grades eines
Doktor rerum naturalium (Dr. rer. nat.)
genehmigte
Dissertation
eingereicht von
Dipl.-Chem. Mikhail Pashchanka
aus Minsk, Belarus
Referent: Prof. Dr. J.J. Schneider
Korreferent: Prof. Dr. R. Riedel
Tag der Einreichung: 26.05.2010
Tag der mündlichen Prüfung: 12.07.2010
Darmstadt 2010
D17
Acknowledgements
First of all, I would like to express my thanks to my family and friends for the
encouragement during the last four and a half years, and especially to my mother,
who visited me from time to time during my stay in Germany.
I would like to thank my advisor Prof. Dr. J.J. Schneider for his guidance and the
opportunities that were provided both in our group and in collaboration with some
other scientific institutions.
I thank Prof. Dr. R. Riedel for valuable advices during common work on a project and
for his agreement to be a co-referee of the present thesis.
I appreciate the help, comments and suggestions from my colleagues: Dr. J. Engstler,
Dr. R.C. Hoffmann, Dr. J. Khanderi, Dr. A. Issanin, Dr. G. Cherkashinin, Dr. B.
Corzilius, Dr. O. Burghaus, Dr. P. Komissinskiy, Dr. M. Nowotny, and Dipl.-Ing. I.
Balog. I would like to say many thanks to Dr. E. Rikowski and Dr. T. Herntrich for
helping me with texts in German.
I am very grateful to Dr. A. Gurlo for the opportunity to perform experiments at ESRF
in Grenoble and for reading of some my drafts and manuscripts, as well as for other
common experiments, which not only provided useful results for the present work but
also were a great educational experience. I also would like to thank Dr. J. Grattage
for her assistance at ESRF in Grenoble.
I express my thanks to Dr. P. Kraikivskii for his help in interpretation of ESR spectra
and for the fruitful discussion of some other theoretical and practical aspects of the
work.
I am grateful to Dr. D. Dzivenko and Dr. O. Avrutina for support during my stay in
Darmstadt.
i
Results from this work already published or submitted for
publication
[1] M. Pashchanka, J. Engstler, J. J. Schneider, V. Siozios, C. Fasel, R. Hauser, I.
Kinski, R. Riedel, S. Lauterbach, H. J. Kleebe, S. Flege, W. Ensinger,
European Journal of Inorganic Chemistry 2009, 3496.
[2] M. Pashchanka, R. C. Hoffmann, J. J. Schneider, Physics, Chemistry and
Application of Nanostructures 2009, 373.
[3] M. Pashchanka, R. C. Hoffmann, J. J. Schneider, Journal of Materials
Chemistry 2010, 20, 957.
[4] M. Pashchanka, R. C. Hoffmann, A. Gurlo and J. J. Schneider, “Molecular
based chimie douce approach to 0D and 1D indium oxide nanostructures.
Evaluation of their sensing properties towards CO and H ”, submitted to 2
Journal of Materials Chemistry
Talks and conferences:
[1] Scientific Colloquium for Graduate Students. Joint Workshop of the Inorganic
Chemistry Department of TU Darmstadt and Merck KGaA, 13 March 2008,
Darmstadt, Germany
[2] TU Darmstadt – METU Ankara, Joint Graduate Workshop on Nanotechnology,
28 April 2009, Darmstadt, Germany
[3] International Conference NANOMEETING-2009, Talk № 6 in ‘Chemistry of
Nanostructures’ section, 26-29 May 2009, Minsk, Belarus
ii
Table of content
Acknowledgements ...................................................................................................... i
Results from this work already published or submitted for publication ........................ ii
Table of content .......................................................................................................... iii
Abbreviations and definitions ...................................................................................... vi
1 General introduction ............................................................................................ 1
2 Issues to be addressed in this work .................................................................... 5
3 Literature survey .................................................................................................. 7
3.1 Porous anodic aluminium oxide (PAOX) templates .................................. 7
3.1.1 Historical sketch and phenomenological theories of pores formation .... 7
3.1.2 Specific anodization conditions for size tailoring and hexagonal
arrangement of pores .......................................................................... 11
3.2 Track-etched polycarbonate templates ................................................... 13
3.3 Synthesis of Q1D nanostructures from materials, relevant to the present
work – prerequisites and previous studies .............................................. 14
3.3.1 Silicon-based carbon-containing ceramics .......................................... 14
3.3.2 Magnesium oxide ................................................................................ 16
3.3.3 Indium oxide ........................................................................................ 17
3.3.4 Undoped and Mn-doped ZnO.............................................................. 19
3.3.5 Cu-doped ZnO .................................................................................... 21
4 Results and Discussion ..................................................................................... 22
4.1 Characterisation of Porous Anodic Aluminium Oxide (PAOX) Films ....... 22
4.1.1 Variation of PAOX Geometric Parameters .......................................... 22
4.1.2 Removal of Barrier Layer from PAOX by Wet Etching Method ........... 23
4.1.3 Structural and Composition Changes in PAOX during Thermal Cure . 25
4.1.3.1 Thermogravimetric analysis of oxalic PAOX before and after wet
etching ................................................................................................. 25
4.1.3.2 XRD analysis of oxalic and sulphuric PAOX .................................... 28
4.1.4 Anodic oxidation of aluminium under pulse current conditions ............ 29
4.2 Polymer-Derived SiOC Nanotubes and Nanorods .................................. 31
4.2.1 Ceramic Nanowires Derived from 40 V PAOX Templates .................. 31
4.2.1.1 Microscopic study of polymer-derived SiOC nanowires ................... 31
4.2.1.2 FTIR study of SiOC nanowires derived from two commercial
polymers .............................................................................................. 35
4.2.1.3 Raman spectra of SiOC nanowires ................................................. 39
4.2.1.4 X-ray diffraction patterns of SiOC nanowires ................................... 40
4.2.1.5 EDX study of SP-Matrix derived SiOC composition ......................... 41
4.2.2 Ceramic Nanowires Derived from 20 V PAOX Templates .................. 42
4.2.2.1 Microscopic study ............................................................................ 42
4.2.2.2 XPS study of ceramic nanowires of a smaller diameter ................... 43
4.2.3 Results, achieved in parallel with the SiOC nanowires synthesis ........ 44
4.2.3.1 Chemical functionalization of the interior of the alumina pores ........ 44
4.2.3.2 SiC/C core-shell composite Q1D nanostructures ............................ 48
4.2.4 Brief summary of the results obtained for SiOC nanowires ................. 52
4.3 Characterisation of Track-Etched Polycarbonate Templates .................. 53
4.3.1 SEM study ........................................................................................... 53
4.3.2 TG-MS study ....................................................................................... 54
iii
4.4 Q1D MgO nanostructures from the precursor Tris(aqua)-Bis[2-
(methoxyimino)-propanoato]magnesium ................................................ 57
4.4.1 Thermal decomposition of the precursor ............................................. 57
4.4.1.1 TGA study ........................................................................................ 57
4.4.1.2 XRD study of the products, obtained from MgO precursor at different
decomposition temperatures ............................................................... 58
4.4.2 Preparation of polycrystalline MgO nanorods within track-etched
polymer template ................................................................................. 59
4.4.2.1 Microscopic study of ‘green body’ and MgO Q1D structures ........... 59
4.4.2.2 EDX Study ....................................................................................... 61
4.4.2.3 XRD study of the MgO nanorods ..................................................... 62
4.4.2.4 PL study of the MgO nanorods ........................................................ 62
4.5 Indium oxide nanotubes from oximato precursor .................................... 64
4.5.1 Properties of the precursor .................................................................. 64
4.5.2 Preparation of polycrystalline In O nanotubes from molecular Tris[2-2 3
(methoxyimino)propanoato]indi