Crystallographic texture and microstructure of terebratulide brachiopod shell calcite: An optimized materials design with hierarchical architecture

Griesshaber, Erika; Schmahl, Wolfgang W.; Neuser, Rolf D.; Pettke, Thomas; Blüm, M.; Mutterlose, Jörg; Brand, Uwe

doi:10.2138/am.2007.2220

Cited by 101 publications

(96 citation statements)

References 65 publications

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“…Large in-plane rotation of a and b axes with respect to the shell surface normal (that is, c axis) suggests the possibility of crystallographic discontinuities through the thickness, which was confirmed by local SAED measurements. With the reasonable assumption that each building block is a single crystalline 35,36 (also supported by electron diffraction results of individual isolated fibres, Fig. 6g,h), we hypothesize that the fibres most likely do not exhibit a complete helical form.…”

Section: Articlesupporting

confidence: 59%

Hierarchical structural design for fracture resistance in the shell of the pteropod Clio pyramidata

Weaver²,

Ortiz

2015

Nat Commun

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The thecosomes are a group of planktonic pteropods with thin, 1 mm-sized aragonitic shells, which are known to possess a unique helical microstructure consisting of interlocking nanofibres. Here we investigate the detailed hierarchical structural and mechanical design of the pteropod Clio pyramidata. We quantify and elucidate the macroscopic distribution of the helical structure over the entire shell (B1 mm), the structural characteristics of the helical assembly (B10-100 mm), the anisotropic cross-sectional geometry of the fibrous building blocks (B0.5-10 mm) and the heterogeneous distribution of intracrystalline organic inclusions within individual fibres (o0.5 mm). A global fibre-like crystallographic texture is observed with local in-plane rotations. Microindentation and electron microscopy studies reveal that the helical organization of the fibrous building blocks effectively constrains mechanical damages through tortuous crack propagation. Uniaxial micropillar compression and cross-sectional transmission electron microscopy directly reveal that the interlocking fibrous building blocks further retard crack propagation at the nanometre scale.

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Section: Articlesupporting

confidence: 59%

Hierarchical structural design for fracture resistance in the shell of the pteropod Clio pyramidata

Weaver²,

Ortiz

2015

Nat Commun

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“…A "surface lamination" on the submicrometer scale is visible in SEM micrographs of fractured samples , but it is impossible to exclude that this feature is due to {104} cleavage faceting. (Schmahl et al 2004, Griesshaber et al, 2007. Both valves show a sharp uni-axial fiber texture.…”

Section: Primary Main Layer Materialsmentioning

confidence: 98%

“…The brachiopod calcite shows a pronounced and systematic pattern of crystallographic preferred orientation (Schmahl et al, 2004, Griesshaber et al, 2007, which connects the molecular scale structure with the architecture on the macroscopic scale: the [001] axes of the trigonal calcite crystals show a sharp maximum of the orientational probability density in the orientation perpendicular (or sub-perpendicular) to the shell vault (Schmahl et al, 2004, Griesshaber et al, 2007). …”

Section: Detailed Description 41 Macroscopic Morphologymentioning

confidence: 99%

Hierarchical structure of marine shell biomaterials: biomechanical functionalization of calcite by brachiopods

Schmahl¹,

Griesshaber²,

Kelm³

et al. 2012

Zeitschrift Für Kristallographie - Crystalline Materials

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Abstract. Biologic structural materials for skeletons or teeth show a hierarchical architecture, where organic macromolecules and mineral substance form a hybrid composite material with its components inter-weaved on many length scales. On the nanostructure level brachiopods form hybrid composite mesocrystals of calcite with occluded organic molecules. On the microstructure level several types of materials are produced, on which the electron back-scatter diffraction (EBSD) technique gives insight in texture and architecture. We describe the calcite single-crystal fiber composite architecture of the secondary layer involving organic matrix membranes, the competitive-growth texture of the columnar layer and the nanostructuring of the primary layer. In the overall skeleton the organic biopolymers provide flexibility and tensile strength while the mineral provides a high elastic modulus, compressive strength, hardness and resistance to abrasion. The hierarchical composite architecture, from the nanostructure to the macroscopic level provides fracture toughness. The morphogenesis of the biomaterial as a whole and of the mineral crystals is guided by the organic matrix and most probably involves amorphous calcium carbonate (ACC) precursors. In this paper we review the hierarchical architecture of rhynchonelliform brachiopod shells, which is very distinct from mollusk nacre.

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“…Major tissues of interest include the phosphatic (bone) family of materials, and the carbonatic family as found, e.g., in mollusc shells. Within the phylum Brachiopoda, both strategies of hybrid shell architecture have evolved: Calcium carbonate crystals in an organic matrix [18][19][20], and laminates of calcium phosphate nanoparticle reinforced chitin fibers [21,22]. FTIR spectroscopic microscopy is a well-established method and has been extensively used to study bone biominerals at several micrometers spatial resolution [23][24][25][26][27][28][29][30].…”

Section: Introductionmentioning

confidence: 99%

Nano-FTIR chemical mapping of minerals in biological materials

et al. 2012

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Methods for imaging of nanocomposites based on X-ray, electron, tunneling or force microscopy provide information about the shapes of nanoparticles; however, all of these methods fail on chemical recognition. Neither do they allow local identification of mineral type. We demonstrate that infrared near-field microscopy solves these requirements at 20 nm spatial resolution, highlighting, in its first application to natural nanostructures, the mineral particles in shell and bone. "Nano-FTIR" spectral images result from Fourier-transform infrared (FTIR) spectroscopy combined with scattering scanning near-field optical microscopy (s-SNOM). On polished sections of Mytilus edulis shells we observe a reproducible vibrational (phonon) resonance within all biocalcite microcrystals, and distinctly different spectra on bioaragonite. Surprisingly, we discover sparse, previously unknown, 20 nm thin nanoparticles with distinctly different spectra that are characteristic of crystalline phosphate. Multicomponent phosphate bands are observed on human tooth sections. These spectra vary characteristically near tubuli in dentin, proving a chemical or structural variation of the apatite nanocrystals. The infrared band strength correlates with the mineral density determined by electron microscopy. Since nano-FTIR sensitively responds to structural disorder it is well suited for the study of biomineral formation and aging. Generally, nano-FTIR is suitable for the analysis and identification of composite materials in any discipline, from testing during nanofabrication to even the clinical investigation of osteopathies.

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Crystallographic texture and microstructure of terebratulide brachiopod shell calcite: An optimized materials design with hierarchical architecture

Cited by 101 publications

References 65 publications

Hierarchical structural design for fracture resistance in the shell of the pteropod Clio pyramidata

Hierarchical structural design for fracture resistance in the shell of the pteropod Clio pyramidata

Hierarchical structure of marine shell biomaterials: biomechanical functionalization of calcite by brachiopods

Nano-FTIR chemical mapping of minerals in biological materials

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