X-ray diffraction and in situ pressurization of dentine apatite reveals nanocrystal modulus stiffening upon carbonate removal

Forien, Jean-Baptiste; Uzuhashi, Jun; Ohkubo, Tadakatsu; Hono, Kazuhiro; Luo, Lucy; Schwarcz, Henry P.; Deymier, Alix C.; Krywka, Christina; Fleck, Claudia; Zaslansky, Paul

doi:10.1016/j.actbio.2020.09.004

X-ray diffraction and in situ pressurization of dentine apatite reveals nanocrystal modulus stiffening upon carbonate removal

Journal Article · Thu Dec 31 23:00:00 EST 2020 · Acta Biomaterialia

DOI:https://doi.org/10.1016/j.actbio.2020.09.004· OSTI ID:1756745

Forien, Jean-Baptiste ^[1]; Uzuhashi, Jun ^[2]; ^[2]; Hono, Kazuhiro ^[2]; ^[3]; Schwarcz, Henry P. ^[3]; Deymier, Alix C. ^[4]; Krywka, Christina ^[5]; Fleck, Claudia ^[6]; Zaslansky, Paul ^[7]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
National Inst. for Materials Science, Tsukuba (Japan)
McMaster Univ., Hamilton, ON (Canada)
Univ. of Connecticut Heath Center, Farmington, CT (United States)
Helmholtz-Zentrum, Geesthacht (Germany)
Technische Univ. Berlin (Germany)
Universitätsmedizin Berlin (Germany)

Bone-like materials comprise carbonated-hydroxyapatite nanocrystals (c-Ap) embedding a fibrillar collagen matrix. The mineral particles stiffen the nanocomposite by tight attachment to the protein fibrils creating a high strength and toughness material. The nanometer dimensions of c-Ap crystals make it very challenging to measure their mechanical properties. Mineral in bony tissues such as dentine contains 2~6 wt.% carbonate with possibly different elastic properties as compared with crystalline hydroxyapatite. Here we determine strain in biogenic apatite nanocrystals by directly measuring atomic deformation in pig dentine before and after removing carbonate. Transmission electron microscopy revealed the platy 3D morphology while atom probe tomography revealed carbon inside the calcium rich domains. High-energy X-ray diffraction in combination with in situ hydrostatic pressurization quantified reversible c-Ap deformations. Additionally, crystal strains differed between annealed and ashed (decarbonated) samples, following 1 or 10 h heating at 250 °C or 550 °C respectively. Measured bulk moduli (K) and a-/c-lattice deformation ratios (η) were used to generate synthetic K_syn and ηsyn identifying the most likely elastic constants C₃₃ and C₁₃ for c-Ap. These were then used to calculate the nanoparticle elastic moduli. For ashed samples, we find an average E₁₁=107 GPa and E₃₃ =128 GPa corresponding to ~5% and ~17% stiffening of the a-/c-axes of the nanocrystals as compared with the biogenic nanocrystals in annealed samples. Ashed samples exhibit ~10% lower Poisson's ratios as compared with the 0.25~0.36 range of carbonated apatite. Carbonate in c-Ap may therefore serve for tuning local deformability within bony tissues.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1756745

Report Number(s):: LLNL-JRNL--807382; 1013076

Journal Information:: Acta Biomaterialia, Journal Name: Acta Biomaterialia Vol. 120; ISSN 1742-7061

Publisher:: Acta Materialia, Inc.Copyright Statement

Country of Publication:: United States

Language:: English

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