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Hierarchical fibre composite structure and micromechanical properties of phosphatic and calcitic brachiopod shell biomaterials — an overview

Published online by Cambridge University Press:  05 July 2018

W. W. Schmahl ,
E. Griesshaber ,
C. Merkel ,
K. Kelm ,
J. Deuschle ,
R. D. Neuser ,
A. J. Göetz ,
A. Sehrbrock  and
W. Mader
W. W. Schmahl*
Affiliation:
GeoBioCentre and Department of Earth and Environmental Sciences, LMU Munich, Theresienstrasse 41, 80333 Munich, Germany
E. Griesshaber
Affiliation:
GeoBioCentre and Department of Earth and Environmental Sciences, LMU Munich, Theresienstrasse 41, 80333 Munich, Germany
C. Merkel
Affiliation:
GeoBioCentre and Department of Earth and Environmental Sciences, LMU Munich, Theresienstrasse 41, 80333 Munich, Germany
K. Kelm
Affiliation:
Institut für Anorganische Chemie, Römerstraβe 164, Universität Bonn, D-53117 Bonn, Germany
J. Deuschle
Affiliation:
Max Planck Institut für Metallforschung, Heisenbergstrasse 3, 70569 Stuttgart, Germany
R. D. Neuser
Affiliation:
Institut für Geologie, Mineralogie und Geophysik, Ruhr-Universität Bochum, Universitätsstrasse 150, 44801 Bochum, Germany
A. J. Göetz
Affiliation:
GeoBioCentre and Department of Earth and Environmental Sciences, LMU Munich, Theresienstrasse 41, 80333 Munich, Germany
A. Sehrbrock
Affiliation:
Forschungszentrum CAESAR, Ludwig-Erhard-Allee 2, 53175 Bonn, Germany
W. Mader
Affiliation:
Institut für Anorganische Chemie, Römerstraβe 164, Universität Bonn, D-53117 Bonn, Germany
*
*E-mail: wolfgang.schmahl@lrz.uni-muenchen.de
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Abstract

Brachiopods are a phylum of shell-forming sessile marine invertebrates which have existed since the early Cambrian. Two very different biomaterial design strategies for their shells evolved early in their history. Both strategies use hybrid fibre composites, however, one is based on mineral fibres embedded in ~2 wt.% of organic biopolymer sheaths and the inorganic fibres are calcite single crystals. In the second strategy the fibres are biopolymers and are reinforced with Ca-phosphate nanoparticles to form a fibrous nanocomposite. Here the organic component (chitin) dominates. The Ca-phosphate nanoparticle-reinforcement strategy is not unlike that in vertebrate bone, however, the microscale structure is laminated with alternating laminae which have a different degree of mineralization.

The calcitic shells feature an outer compact layer of calcite micro- and nanoparticles protecting the inner fibrous layer from the outside. Transmission electron microscopy of the fibrous layer reveals intercrystalline and intracrystalline biopolymers. The calcitic shell material is stiff with nano-indentation E-moduli of 63±8 GPa and relatively hard (Vickers microhardness up to 400 HV 0.0005/10 and nanohardness 4±0.5 GPa). Compared to inorganic calcite the microhardness is doubled and the nanohardness increases by 60%. We attribute this increased hardness to intracrystalline biopolymers. The nano-indentation E-moduli of the chitinophosphatic shells range from 3 to 55 GPa as a result of the varying degree of mineralization between their laminae, and similarly their nanohardness varies between 0.1 and 3 GPa. For brachiopods burrowing inside the sediment, the alternation of non-mineralized laminae with thin, more strongly mineralized laminae provides abrasion-resistance, hardness and longitudinal stiffness while it preserves the flexibility provided by the organic component for bending movements.

Keywords

biomineralizationhierarchical architecturenano-indentationEBSDamorphous calciumphosphateACPhydroxylapatiteHAPnacrepalaeoclimate

Information

Type
Research Article
Information
Mineralogical Magazine , Volume 72 , Issue 2 , April 2008 , pp. 541 - 562
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2008

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