Multiscale characterization of bone mineral: new perspectives in structural imaging using X-ray and electron diffraction contrast Mariana Verezhak To cite this version: Mariana Verezhak. Multiscale characterization of bone mineral: new perspectives in structural imag- ing using X-ray and electron diffraction contrast. Materials Science [cond-mat.mtrl-sci]. Communauté Universite Grenoble Alpes, 2016. English. tel-01576447 HAL Id: tel-01576447 https://hal.archives-ouvertes.fr/tel-01576447 Submitted on 23 Aug 2017 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. 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THESIS In order to obtain the grade of DOCTOR OF GRENOBLE ALPES UNIVERSITY Specialty: Physics/Nanophysics Ministerial order: 7 August 2006 Presented by « Mariana / VEREZHAK » Thesis supervised by « Marie/PLAZANET » and co-supervised by « Aurélien/GOURRIER » Prepared at Laboratory of Interdisciplinary Physics at Doctoral School of Physics of Grenoble Multiscale characterization of bone mineral: new perspectives in structural imaging using X-ray and electron diffraction contrast Thesis is publically defended on « 28 October 2016 », in front of the jury composed of : Prof. Franz BRUCKERT Grenoble INP UGA, President of jury Dr. Aurélien GOURRIER LIPhy, Grenoble, co-Director of thesis Prof. Thomas LAGRANGE Institute of Technology of Lausanne, Examiner Dr. Marie PLAZANET LIPhy, Grenoble, Director of thesis Prof. Sylvain RAVY Laboratory of Solid State Physics, Orsay, Referee Dr. Ina REICHE LAMS, Paris, Referee THÈSE Pour obtenir le grade de DOCTEUR DE LA COMMUNAUTÉ UNIVERSITÉ GRENOBLE ALPES Spécialité : Physique/Nanophysique Arrêté ministériel : 7 août 2006 Présentée par « Mariana / VEREZHAK » Thèse dirigée par « Marie/PLAZANET » et codirigée par « Aurélien/GOURRIER » préparée au sein du Laboratoire Interdisciplinaire de Physique dans l’Ecole Doctorale de Physique de Grenoble Caractérisation multi-échelle du minéral osseux: apport de l'imagerie structurale par contraste de diffraction des rayons X et d'électrons Thèse soutenue publiquement le « 28 octobre 2016 », devant le jury composé de : Prof. Franz BRUCKERT Grenoble INP UGA, Président du jury Dr. Aurélien GOURRIER LIPhy, Grenoble, co-Directeur de thèse Prof. Thomas LAGRANGE École Polytechnique Fédérale de Lausanne, Examinateur Dr. Marie PLAZANET LIPhy, Grenoble, Directrice de thèse Prof. Sylvain RAVY Laboratoire de Physique des Solides, Orsay, Rapporteur Dr. Ina REICHE LAMS, Paris, Rapporteur List of abbreviations and notations: ACLAR – copolymer film consisting primarily of chlorotrifluoroethylene; ACOM – automated crystal orientation mapping; CAP – collagen-apatite porosity; CL – cross link; CXDI – coherent X-ray diffraction imaging; DDSA – dodecenyl succinic anhydride; DMP-30 – tris (dimethylaminomethyl) phenol; EDX – energy dispersive X-ray analysis; FEG – field emission gun; FTIR – Fourier transform infra-red; FWHM – full width half maximum; HAP – hydroxyapatite; HPT – hyperparathyroidism; IR – infra-red; LM – light microscopy; MMA – methyl methacrylate; NMA – nadic methyl anhydride; OPT – osteopetrosis; PDF – pair distribution function; PG – proteoglycan; PMMA – poly (methyl methacrylate); PTFE – polytetrafluoroethylene; PV – Pseudo-Voigt; SAXS – small angle X-ray scattering; SEM – scanning electron microscopy; TEM – transmission electron microscopy; USAXS – ultra-small angle X-ray Scattering; UV – ultraviolet; WAXS – wide angle X-ray scattering; WSS – weighted sum of squares; XRD – X-ray diffraction. Acknowledgements I would like to express my thanks to my advisors Dr. Aurelien Gourrier and Dr. Marie Plazanet, you have been great mentors for me. I would like to thank you for allowing me to grow as a research scientist, your help and support in the moments of difficulties and many fruitful discussions during manuscript and defense preparation. Your advice on both research as well as on my career have been priceless. I would also like to thank my committee members, Dr. Sylvain Ravy, Dr. Ina Reiche, Prof. Thomas LaGrange and Prof. Franz Bruckert for accepting to be part of my PhD defense despite your dense schedules, for your brilliant comments and suggestions. I would especially like to thank our numerous collaborators, from ESRF, for help during beam-time and advice in data analysis: Dr. Manfred Burghammer and Dr. Britta Weinhausen from ID13, Dr. Yuriy Chushkin and Dr. Federico Zonton from ID10; as well as to our collaborators from SIMaP, for access to transmission electron microscope: Dr. Edgar F. Rauch and Prof. Muriel Veron; and to Dr. Pierre Bordet for the collaboration in bone tissue PDF analysis. Many thanks to Dr. Christine Lancelon-Pin (CERMAV) and Dr. Irina Snigireva (ESRF) for providing advice and instrumentation for sample preparation. Additional thanks to Dr. Delphine Farlay from INSERM (Lyon) for providing the pathological samples. Additional thanks goes to my colleagues from MOTIV group, and LIPhy in general, for many fruitful discussions and making my life in the lab dynamic and interesting. Special thanks to Rachel Genthial for every day exchange and help in getting familiar with French administration and to Brenna Hogan for help as an English native-speaker. I also acknowledge the Nanoscience Foundation in Grenoble for financial support of my thesis. A special thanks to my family. Words cannot express how grateful I am to my mother and father for raising me with a love for science and for all of the sacrifices that you’ve made Acknowledgements ___________________________________________________________________________ on my behalf. Your prayers for me have been heard. I would also like to thank all of my friends who supported me at all stages. Table of content Introduction ....................................................................................................................... 1 Chapter 1. Bone, a multiscale perspective ........................................................................ 7 1.1. Bone hierarchy ................................................................................................. 7 1.1.1. Level 1. Macrostructure: Organ ........................................................... 9 1.1.2. Level 2. Mesostructure: Tissue .......................................................... 11 1.1.3. Level 3. Microstructure: bone units (osteons and trabeculae) ........... 12 1.1.4. Level 4. Submicrostructure: lamella .................................................. 15 1.1.5. Level 5. Ultrastructure: suprafibrilar architectures ............................ 17 1.1.6. Level 6. Up-nanostructure: mineralized collagen fibril ..................... 20 1.1.7. Level 7. Nanostructure: collagen and mineral ................................... 21 1.1.8. Level 8. Molecular and crystal structure: bone crystallography ........ 22 1.2. Bone animal models ....................................................................................... 31 1.3. Heated bone .................................................................................................... 32 1.4. Pathological bone ........................................................................................... 33 Chapter 2. Materials and methods .................................................................................. 35 2.1. Sample preparation ......................................................................................... 35 2.1.1. Fixation, dehydration, impregnation and embedding choice ............. 36 2.1.2. Ultramicrotomy cutting ...................................................................... 39 2.1.3. Heat treatment .................................................................................... 40 2.2. Techniques ...................................................................................................... 41 2.2.1. Basic terminology .............................................................................. 41 2.2.1.1. Structure of the solid body .................................................... 41 2.2.1.2. Scattering vs diffraction ........................................................ 42 2.2.1.3. Diffraction vs imaging .......................................................... 48 2.2.1.4. Resolution limit, wavelength and the choice of probe .......... 49 2.2.2. X-ray radiation based techniques ....................................................... 52 2.2.2.1. Rietveld refinement ............................................................... 53 2.2.2.2. PDF analysis ......................................................................... 56 2.2.2.3. CXDI analysis ....................................................................... 59 2.2.2.4. Sources of X-ray radiation .................................................... 64 2.2.2.4.1. Powder X-ray diffraction at the laboratory source .. 64 2.2.2.4.2. Synchrotron source .................................................. 65 2.2.3. Electron radiation based techniques ................................................... 68 2.2.3.1. Electron diffraction and TEM ............................................... 68 2.2.3.2. Automated