Natural composites, in particular nacre, often combine high strength and toughness thanks to highly ordered architectures and controlled geometries of the reinforcement components. However, combining strength, toughness and resorbability in synthetic materials remains a challenge in particular in the field of bone graft substitutes. In the present study, calcium phosphate-(CaP-)based materials with designed architectures inspired from natural composite materials were achieved. CaP platelets obtained by precipitation in organic medium were first aligned in chitosan matrices by solvent casting in ambient conditions. Efficient strengthening was obtained with 15 vol-% ceramic, reaching cortical bone strength (150 MPa) and preserving good ductility (5 % deformation). In a weak magnetic field, high spatial arrangement without percolation was maintained up to 20 vol-%. With directional freezing, good alignment of the platelets could be pushed up to 50 vol-%. In parallel, in situ recrystallization of CaP blocks in hydrothermal conditions led to hierarchical structures. The strength and the work-of-fracture were enhanced (300%) thanks to a change of failure mode.:Acknowledgements v
Summary vii
Background vii
Thesis outline viii
Part I: “Brick-and-mortar” structures with discrete reinforcement components ix
Part II: “Textured” structures with continuous reinforcement components x
Zusammenfassung xi
Hintergrund xi
Doktorarbeit Gliederung xii
Teil I: “Ziegelmauer-Architektur” mit diskreten Verstärkungskomponenten xiii
Teil II: “ Texturierte” Strukturen mit kontinuierlichen Verstärkungskomponenten xiv
Chapter 1: General introduction 1
Bone grafting 1
CaP ceramics 1
How to improve toughness of CaP ceramics? 2
Importance of structure design: bio-inspiration 2
What mechanical properties should be reached? 5
Specific aims 5
Two general approaches to reach the goal 6
Nacre-inspired “brick-and mortar” structures (Part I) 6
Textured ceramic monoliths (Part II) 6
References 7
Chapter 2: Theoretical calculations 11
Introduction 12
Theoretical tensile strength of β-TCP platelets and critical size for flaw tolerance 13
Optimal aspect ratio 15
Composite strength and stiffness 17
Limitations 19
References 19
PART I: NACRE-INSPIRED “BRICK-AND-MORTAR” STRUCTURES
Chapter 3: Synthesis of sub-micrometer calcium phosphate platelets 23
Introduction 24
ii
Materials and Methods 25
Precipitation method 25
Reaction parameters 25
Characterization 26
Statistical analysis of results 28
Results 28
Reproducibility of standard experiments 28
Increase of the reagent volume to increase the productivity 30
Increase of the precursors concentration to increase the productivity and modify the
particles 30
Increase of titration rate to simplify the process 32
Influence of temperature on the particles 35
Effect of the pH value on the particles 37
Effect of a longer reaction time on the particle stability 40
Study of the influence of variations of the Ca/P molar ratio 42
Discussion 43
Reproducibility 43
Productivity 44
CaP crystal shape 45
Crystal purity 47
Aspect ratio 48
Critical thickness 49
Uniformity of primary particles 50
Non agglomerated 51
General points 52
Conclusions 52
References 53
Chapter 4: Kinetics study of the calcium phosphate platelets growth 57
Introduction 58
Theory 58
Materials and methods 60
Materials and sample preparation 60
Characterization methods 61
Results 62
Visual observations during manipulations 62
SEM observations 62
XRD results 66
Size measurements 68
Kinetics calculations 70
Discussion 74
Nucleation and assembly mechanism 74
Reaction kinetics 76
Control of size and aspect ratio 76
Conclusions 77
References 78
Chapter 5: Structural design of bio-inspired composites by solvent casting 81
Foreword 82
Introduction 82
Experimental section 84
iii
Synthesis of resorbable ceramic platelets 84
Solvent casting to prove the reinforcement efficiency of DCP platelets 84
Magnetization of the platelets 85
Maintaining the orientation during drying of an hydrogel matrix 86
Results 87
Synthesis of resorbable ceramic platelets 87
Solvent casting to prove the reinforcement efficiency of CaP platelets 87
Magnetization of the platelets 91
Maintaining the orientation during drying of an hydrogel matrix 93
Discussion 95
Detrimental effect of β-TCP platelets in chitosan 95
Efficient reinforcement with DCP platelets up to a given volume fraction 96
Threshold value for strength improvement 97
Fitting the experimental results with theoretical equations 98
Conclusions 101
References 101
Chapter 6: Biodegradable, strong and tough nacre-inspired structures obtained by freezecasting
105
Introduction 106
Experimental section 108
Synthesis of resorbable ceramic platelets 108
Preliminary freeze-casting tests with β-TCP-based slurries 108
Determination of adequate freeze-casting parameters for hydrogels-CaP slurries 108
Integration of CaP platelets and local planar alignment 109
Attempts to globally align porosity in two directions 109
Densification and consolidation 110
Tensile testing 110
Results 111
Preliminary freeze-casting tests with β-TCP-based slurries 111
Determination of adequate freeze-casting parameters for hydrogels-CaP slurries 112
Integration of CaP platelets and local planar alignment 113
Attempts to globally align porosity in two directions 119
Densification and consolidation 121
Tensile testing 121
Discussion 122
Conclusions 124
References 125
PART II: TEXTURED CERAMIC MONOLITHS
Chapter 7: Micro-texturing by recrystallization of calcium phosphate blocks in hydrothermal
conditions 127
Introduction 128
Materials and Methods 130
Samples characterization 132
Results 133
Macroscopic observations 133
Microstructural changes (SEM) 133
Crystalline phase conversion (XRD) 139
iv
Mechanical properties 142
Fractured surfaces 142
Discussion 145
Conclusions 150
References 150
Chapter 8: Toughening of textured calcium phosphate blocks by polymer impregnation 155
Foreword 156
Introduction 156
Materials and Methods 157
Samples preparation 157
Characterization 158
Results 158
Porosity and microstructure 158
Composition 161
Mechanical properties 161
Discussion 162
Conclusions 164
References 164
Chapter 9: Synthesis and outlook 167
Curriculum Vitae 171
| Identifer | oai:union.ndltd.org:DRESDEN/oai:qucosa:de:qucosa:22974 |
| Date | 03 March 2015 |
| Creators | Galea, Laetitia |
| Contributors | Aneziris, Christos G., Graule, Thomas, Bohner, Marc, TU Bergakademie Freiberg |
| Source Sets | Hochschulschriftenserver (HSSS) der SLUB Dresden |
| Language | English |
| Detected Language | English |
| Type | doc-type:doctoralThesis, info:eu-repo/semantics/doctoralThesis, doc-type:Text |
| Rights | info:eu-repo/semantics/openAccess |
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