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Warm Working Behaviour Of Alpha-iron, Fe-Si, Fe-Co And Fe-Ni Alloys : A Study Using Processing MapsAvadhani, G S 09 1900 (has links) (PDF)
No description available.
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Elipsometrie tenkých vrstev / Ellipsometry of Thin FilmsNovotný, Zbyněk January 2010 (has links)
Diploma thesis deals with ageing process of thin films of Co and Cu on Si substrate, prepared by the IBAD method. The process of film ageing, which depends on time of exposition to the atmosphere at room conditions, was investigated with spectroscopic ellipsometry (VIS+UV) and atomic force microscopy. In case of thin Co films, approximately four days long incubation period was observed. During this time period, a change in the optical parameters of the film occurs without a measurable change of the film topography. Using non-contact atomic force microscopy, a growth of the transitional film in the island growth regime was observed. During the ageing of thin Cu films, two stages of growth of the transitional layer were observed - nucleation stage and growth stage. Both of these time periods of the transitional layer growth show direct logarithmic dependence. Using non-contact atomic force microscopy, the growth of the transitional film was observed. Using atomic force microscopy in non-contact regime, time dependent measurement was done and the process of forming of one monolayer of the transitional layer was documented. Within the diploma thesis, a series of experiments on ultra high vacuum system were performed in order to investigate phase transformation of thin Fe films (22 monolayers) on Cu(100) stabilized by CO absorption. The transformation from fcc phase to bcc phase was induced by Ar+ ion beam bombardment with the ion energy in the range (0.5-4) keV. The process of phase transformation was observed by surface magneto-optic Kerr effect, Auger electron spectroscopy and low energy electron diffraction.
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Mechanistic Investigations of Metal-Metal Cooperativity in Dinickel Complexes and Iron/Cobalt Prussian Blue AnaloguesStevens, Hendrik 13 May 2021 (has links)
No description available.
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Mesure et modélisation du comportement magnéto-mécanique dissipatif des matériaux ferromagnétiques à haute limite élastique sous chargement multiaxial / Measurement and modeling of magneto-mechanical dissipative behavior of high yield stress ferromagnetic materials under multiaxial loadingRekik, Mahmoud 03 June 2014 (has links)
Les travaux de recherche discutés dans ce manuscrit concernent la conception des générateurs de puissance électrique pour l'aéronautique. L’augmentation de la puissance massique de ces équipements passe par une augmentation des vitesses de rotation, donc une augmentation des contraintes. Un premier point est de s'assurer de la bonne tenue mécanique des matériaux. Un deuxième point est de pouvoir prendre en compte les modifications du comportement magnétique (et donc in fine du couple) lorsqu'ils sont soumis à un état de contraintes multiaxial. L’étude présentée vise en particulier à illustrer l’influence d'états de contraintes biaxiaux sur le comportement magnétique des matériaux constitutifs du rotor. Le défi repose sur la mise en place de méthodes de caractérisation du comportement magnéto-mécanique dissipatif uniaxial et multiaxial des nuances développées par Aperam et utilisées par Thales Avionics pour leurs applications aéronautiques (en FeCo-2V et Fe-3%Si à grains non orientés). Des essais non conventionnels seront effectués sur des échantillons en forme de croix de manière à s'approcher des contraintes réellement subies par le rotor. Les essais sont effectués sur la machine d'essai triaxiale Astrée du LMT-Cachan. L'état de contraintes est estimé par corrélation d'images et par diffraction des rayons X. Des mesures magnétiques anhystérétiques et de pertes d'énergie sous contraintes sont reportées. D'autre part, un modèle multi-échelle multiaxial, décrivant le comportement d’un VER à partir de l'équilibre énergétique à l'échelle microscopique sera présenté. L’approche est fondée sur la comparaison des énergies libres de chaque domaine. Une comparaison probabiliste est faite pour déterminer les variables internes que sont les fractions volumiques des domaines. Différentes stratégies envisageables pour modéliser la dissipation statique seront discutées. Puis nous présentons l’approche magnéto-élastique que nous avons retenue visant à une meilleure considération de l’effet de la contrainte sur le comportement des matériaux ferromagnétiques. / The research presented in this thesis is motivated by the design of rotors for high speed rotating machines. The increased power density of these devices requires a higher rotation speed, leading to higher levels of centrifugal forces and stress in the rotor. A first point is to ensure good mechanical strength of the materials. A second point is to take into account changes in the magnetic behavior (and ultimately torque) when they are subjected to a multiaxial stress state. The present study aims at exploring the influence of biaxial stress states on the magnetic behavior of the materials of the rotor. The challenge lies in the development of methods for the characterization of the magneto-mechanical dissipative uniaxial and multiaxial behavior of metal sheets developed by Aperam Alloy and used by Thales Avionics for their aeronautical applications (in FeCo-2V and non-oriented Fe-3%Si). Non conventional experiments are performed on cross-shaped samples in order to apply biaxial stress representative of the loadings experienced by rotors of rotating machines. These experiments are performed on a multiaxial testing machine, Astrée. Stress level is estimated thanks to digital image correlation and X-ray diffraction Both anhysteretic and dissipative magnetic responses to magneto-mechanical loadings have been recorded. On the other hand, a multi-scale multiaxial model describing the behavior of a RVE from the energy balance at the microscopic scale is presented. The approach is based on a comparison of the free energy of each domain. A probabilistic comparison is made to determine the volume fraction of domains used as internal variables. Different strategies for modeling the static dissipation are discussed. Then we present the chosen magneto-elastic approach, improving the description of the effect of stress on ferromagnetic materials behavior.
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Ferrocenyl-Alkynes and Butadiynes: Reaction Behavior towards Cobalt and Iron Carbonyl CompoundsFilipczyk, Grzegorz Paweł 04 December 2017 (has links)
Die vorliegende Dissertation beschreibt die Synthese und Charakterisierung von neuartigen perferrocenylierten, cyclischen Komplexen unter Anwendung der Cobalt-vermittelten Cyclomerisierung in Kombination mit einer C-H-Bindungsaktivierung als auch die Bildung von ferrocenylierten Phosphinoalkinid-Komplexen mit Eisen- und Cobaltcarbonylen. Die elektrochemischen Eigenschaften und die Elektronentransfer-prozesse zwischen den terminalen Ferrocenyleinheiten in den unterschiedlichen cyclischen Verbindungen wurden unter Einbeziehung der Struktur/chemischen Zusammensetzung der Brückenbausteine ermittelt.
Elf perferrocenylierte, cyclische Komplexe wurden mittels [2+2] bzw. [2+2+2] Cyclomerisierung von 1,4-Diferrocenylbutadiin FcC≡C–C≡CFc (Fc = Fe(η5-C5H4)(η5-C5H5)) unter Verwendung von Dicarbonylcyclopentadienylcobalt Co(η5-C5H5)(CO)2 erhalten. Diese können in drei Gruppen unterteilt werden: (i) Produkte der Cyclodimerisierung mit zusätzlicher Kettenverlängerung, welche Cyclobutadienyl-einheiten als zentrale Brückenbausteine besitzen (3a,b und 4a,b), (ii) Produkte der Cyclodimerisierung mit gleichzeitiger CO-Insertion (6a,b,c und 7), und (iii) Produkte der Cyclotrimerisierung gefolgt von einem Ringschluss durch eine C-H-Bindungsaktivierung (5a,b,c). Die Optimierung der Reaktionsbedingungen wurde zur Ausbeutemaximierung der jeweiligen Verbindungsfamilien durchgeführt.
Ein weiterer Teil dieser Forschungsarbeit bezieht sich auf die verschiedenen Reaktionsmuster von (Ferrocenylethinyl)diphenylphosphan- mit zweikernigen Eisen- bzw. Cobaltcarbonylverbindungen in Form von Dieisennonacarbonyl und Dicobaltoctacarbonyl als Reagenzien. Dabei konnten sechs gemischte Carbonyl- und Ferrocenyl-funktionalisierte Phosphinoacetylid-Komplexe mit Eisen(0) und Cobalt(0) erhalten und charakterisiert werden.:Table of contents
Bibliografische Beschreibung und Referat iii
Abstract iv
Ort und Zeitraum der Durchführung v
Widmung vi
Präambel vii
List of Abbreviations xii
CHAPTER A Introduction 15
References 16
CHAPTER B State of Knowledge 19
1 (Spectro)electrochemical studies of mixed-valent transition metal complexes. Theoretical background 19
1.1 Mixed-valent compounds – classification 20
1.2 Spectroelectrochemistry 21
1.3 Electrochemistry 25
2 (Di)ferrocenylalkynes – synthesis and reactions 28
2.1 1,4-Diferrocenylbutadiyne 29
2.2 Other (poly)ferrocenyl substituted alkyne derivatives 35
3 Dicarbonylcyclopentadienylcobalt – [2+2] and [2+2+2] cyclo-addition reactions 37
3.1 [2+2] and [2+2+2] cycloaddition – cyclobutadiene, cyclopentadienone, benzene and pyridine based systems 38
3.2 Mechanism of [2+2] and [2+2+2] cycloaddition/cyclization and [2+2] cycloaddition/cyclization with CO insertion mediated by CoCp(CO)2 40
4 Chelation-assisted C–H bond activation mediated by cobalt species 42
5 Phosphinoalkynes and their reaction with iron and cobalt carbonyls 44
5.1 Mechanism of the P–C(sp) bond cleavage in phosphinoalkynes 48
6 Complexes setup by (ferrocenylethynyl)diphenylphosphane 50
References 56
CHAPTER C Multiferrocenyl Cobalt-Based Sandwich Compounds 64
1 Introduction 64
2 Results and Discussion 65
2.1 Synthesis and Characterization 65
2.2 Solid-State Structures 71
2.3 Electrochemistry 73
2.4 Spectroelectrochemistry 76
3 Experimental Section 79
3.1 Instrumentation 79
3.2 General Conditions 81
3.3 Reagents 81
3.4 General Procedure - Reaction of 1 with 2 81
3.4.1 Compound 3a 82
3.4.2 Compound 3b 82
3.4.3 Compound 4b 83
3.4.4 Compound 5c 83
3.4.5 Compound 6a 84
3.4.6 Compound 6b 84
3.4.7 Compound 6c 85
3.4.8 Compound 7 85
4 Supporting information 86
5 References 86
CHAPTER D Combining Cobalt-Assisted Alkyne Cyclotrimerization and Ring Formation through C–H Bond Activation: A “One-Pot” Approach to Complex Multimetallic Structures 91
1 Introduction 91
2 Results and Discussion 92
3 Experimental Section (Supporting information) 98
3.1 General Information 98
3.2 Starting Materials 98
3.3 Synthesis of 3a and 3b from 2 99
3.3.1 Complex 3a: 99
3.3.2 Complex 3b: 100
3.4 Synthesis of 9a and 9b from 1-Ferrocenylethynyl-2-Ferrocenyl Benzene (8) 101
3.4.1 Synthesis of 1-Bromo-2-Ferrocenylethynyl Benzene (7) 101
3.4.2 Synthesis of 1-Ferrocenylethynyl-2-Ferrocenyl Benzene (8) 102
3.4.3 Synthesis of 9a and 9b from 8 103
3.5 Synthesis of 3a and 3b from 1,3,5-Triethynylferrocenyl-2,4,6-Triferrocenyl Benzene (4) 105
3.5.1 Synthesis of 1,3,5-Trichloro-2,4,6-Triethynylferrocenyl Benzene (12) 105
3.5.2 Synthesis of 1,3,5-Triethynylferrocenyl-2,4,6-Triferrocenyl Benzene (4) 105
3.5.3 Synthesis of 3a and 3b from 4 106
4 Supporting information 107
4.1 Spectroelectrochemistry of 3a,b 107
4.2 Conversion of Isomer 9a to 9b – Electrochemical and Chemical oxidation 109
4.3 Chemical oxidation experiment 110
5 References 111
CHAPTER E Coordination Behavior of (Ferrocenylethynyl)diphenyl-phosphane Towards Binuclear Iron and Cobalt Carbonyls 114
1 Introduction 114
2 Results and Discussion 115
3 Experimental Section 126
3.1 Instrumentation 126
3.2 General 128
3.3 Reagents 128
3.4 Synthesis of 4 128
3.5 Synthesis of 4, 5 and 6 129
3.6 Synthesis of 6 by reacting 4 with 2 131
3.7 Synthesis of 7 and 8 131
3.8 Synthesis of 8 from 1 with 3 132
3.9 Synthesis of 9 in the reaction of 7 with 2 133
3.10 Synthesis of 9 in the reaction of 4 with 3 133
4 Electronic Supplementary Material (Supporting information) 134
5 References 134
CHAPTER F Summary 139
1 Conclusions of Chapter C (Appendix A) 139
2 Conclusions of Chapter D (Appendix B) 141
3 Conclusions of Chapter E (Appendix C) 142
Appendix 145
1 Appendix D (Chapter C) 145
2 Appendix E (Chapter D) 146
3 Appendix F (Chapter E) 147
Curriculum Vitae 150
Publications 152
Acknowledgements 154
Selbstständigkeitserklärung 155 / The present PhD study focuses on the synthesis and characterization of novel perferrocenylated cyclic complexes utilizing cobalt - mediated cyclomerization in combination with C–H bond activation as well as formation of ferrocenylated phosphino-alkyne compounds with iron and cobalt carbonyls. Electrochemical properties and electron-transfer processes between terminal ferrocenyl units in the diverse cyclic compounds are explored in relation to the chemical composition of the building blocks connecting them.
Eleven perferrocenylated cyclic compounds were obtained via [2 + 2] and [2 + 2 + 2] cyclomerization of 1,4-diferrocenylbutadiyne FcC≡C–C≡CFc (Fc = Fe(η5-C5H4)(η5-C5H5)) by the reaction with dicarbonylcyclopentadienylcobalt Co(η5-C5H5)(CO)2. They are subdivided into three groups: (i) products of cyclodimerization with additional chain extension, possessing cyclobutadienyl moieties as a central linkage unit (3a,b and 4a,b), (ii) products of cyclodimerization with consecutive CO insertion (6a,b,c and 7), and (iii) products of cyclotrimerization followed by cycle formation via C–H bond activation (5a,b,c). Optimization of the reaction conditions was made in order to maximize the amount of each group of compounds.
Furthermore, another part of this research work focuses on diverse reaction patterns of (ferrocenylethynyl)diphenylphosphane with diironnonacarbonyl and dicobaltocta-carbonyl. Six mixed carbonyl and ferrocenyl-functionalized phospinoalkynyl compounds of iron(0) and cobalt(0) were obtained and characterized.:Table of contents
Bibliografische Beschreibung und Referat iii
Abstract iv
Ort und Zeitraum der Durchführung v
Widmung vi
Präambel vii
List of Abbreviations xii
CHAPTER A Introduction 15
References 16
CHAPTER B State of Knowledge 19
1 (Spectro)electrochemical studies of mixed-valent transition metal complexes. Theoretical background 19
1.1 Mixed-valent compounds – classification 20
1.2 Spectroelectrochemistry 21
1.3 Electrochemistry 25
2 (Di)ferrocenylalkynes – synthesis and reactions 28
2.1 1,4-Diferrocenylbutadiyne 29
2.2 Other (poly)ferrocenyl substituted alkyne derivatives 35
3 Dicarbonylcyclopentadienylcobalt – [2+2] and [2+2+2] cyclo-addition reactions 37
3.1 [2+2] and [2+2+2] cycloaddition – cyclobutadiene, cyclopentadienone, benzene and pyridine based systems 38
3.2 Mechanism of [2+2] and [2+2+2] cycloaddition/cyclization and [2+2] cycloaddition/cyclization with CO insertion mediated by CoCp(CO)2 40
4 Chelation-assisted C–H bond activation mediated by cobalt species 42
5 Phosphinoalkynes and their reaction with iron and cobalt carbonyls 44
5.1 Mechanism of the P–C(sp) bond cleavage in phosphinoalkynes 48
6 Complexes setup by (ferrocenylethynyl)diphenylphosphane 50
References 56
CHAPTER C Multiferrocenyl Cobalt-Based Sandwich Compounds 64
1 Introduction 64
2 Results and Discussion 65
2.1 Synthesis and Characterization 65
2.2 Solid-State Structures 71
2.3 Electrochemistry 73
2.4 Spectroelectrochemistry 76
3 Experimental Section 79
3.1 Instrumentation 79
3.2 General Conditions 81
3.3 Reagents 81
3.4 General Procedure - Reaction of 1 with 2 81
3.4.1 Compound 3a 82
3.4.2 Compound 3b 82
3.4.3 Compound 4b 83
3.4.4 Compound 5c 83
3.4.5 Compound 6a 84
3.4.6 Compound 6b 84
3.4.7 Compound 6c 85
3.4.8 Compound 7 85
4 Supporting information 86
5 References 86
CHAPTER D Combining Cobalt-Assisted Alkyne Cyclotrimerization and Ring Formation through C–H Bond Activation: A “One-Pot” Approach to Complex Multimetallic Structures 91
1 Introduction 91
2 Results and Discussion 92
3 Experimental Section (Supporting information) 98
3.1 General Information 98
3.2 Starting Materials 98
3.3 Synthesis of 3a and 3b from 2 99
3.3.1 Complex 3a: 99
3.3.2 Complex 3b: 100
3.4 Synthesis of 9a and 9b from 1-Ferrocenylethynyl-2-Ferrocenyl Benzene (8) 101
3.4.1 Synthesis of 1-Bromo-2-Ferrocenylethynyl Benzene (7) 101
3.4.2 Synthesis of 1-Ferrocenylethynyl-2-Ferrocenyl Benzene (8) 102
3.4.3 Synthesis of 9a and 9b from 8 103
3.5 Synthesis of 3a and 3b from 1,3,5-Triethynylferrocenyl-2,4,6-Triferrocenyl Benzene (4) 105
3.5.1 Synthesis of 1,3,5-Trichloro-2,4,6-Triethynylferrocenyl Benzene (12) 105
3.5.2 Synthesis of 1,3,5-Triethynylferrocenyl-2,4,6-Triferrocenyl Benzene (4) 105
3.5.3 Synthesis of 3a and 3b from 4 106
4 Supporting information 107
4.1 Spectroelectrochemistry of 3a,b 107
4.2 Conversion of Isomer 9a to 9b – Electrochemical and Chemical oxidation 109
4.3 Chemical oxidation experiment 110
5 References 111
CHAPTER E Coordination Behavior of (Ferrocenylethynyl)diphenyl-phosphane Towards Binuclear Iron and Cobalt Carbonyls 114
1 Introduction 114
2 Results and Discussion 115
3 Experimental Section 126
3.1 Instrumentation 126
3.2 General 128
3.3 Reagents 128
3.4 Synthesis of 4 128
3.5 Synthesis of 4, 5 and 6 129
3.6 Synthesis of 6 by reacting 4 with 2 131
3.7 Synthesis of 7 and 8 131
3.8 Synthesis of 8 from 1 with 3 132
3.9 Synthesis of 9 in the reaction of 7 with 2 133
3.10 Synthesis of 9 in the reaction of 4 with 3 133
4 Electronic Supplementary Material (Supporting information) 134
5 References 134
CHAPTER F Summary 139
1 Conclusions of Chapter C (Appendix A) 139
2 Conclusions of Chapter D (Appendix B) 141
3 Conclusions of Chapter E (Appendix C) 142
Appendix 145
1 Appendix D (Chapter C) 145
2 Appendix E (Chapter D) 146
3 Appendix F (Chapter E) 147
Curriculum Vitae 150
Publications 152
Acknowledgements 154
Selbstständigkeitserklärung 155
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