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Analysis of local deformation in indented Ensis Siliqua mollusk shells using Raman spectroscopy

Published online by Cambridge University Press:  03 March 2011

David J. Scurr  and
Stephen J. Eichhorn
David J. Scurr
Affiliation:
Materials Science Centre, School of Materials, University of Manchester, Manchester, United Kingdom M1 7HS
Stephen J. Eichhorn*
Affiliation:
Materials Science Centre, School of Materials, University of Manchester, Manchester, United Kingdom M1 7HS
*
a) Address all correspondence to this author. e-mail: [email protected]
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Abstract

The local deformation surrounding an indented area of Ensis siliqua mollusk shell is characterized using a Raman spectroscopic technique, the findings of which are related to the material’s mechanical function. Microhardness indentation of four directional planes is used to show the marked anisotropy of the structure, where the outer and inner layers of the shell are found to have a significantly higher microhardness value of 4.82 ± 0.02 GPa, compared with transverse and longitudinal cross-sectional values of 3.00 ± 0.07 GPa. This difference is related to the crossed lamellar microstructure of the shell, which is oriented to provide the maximum resistance to external attack from predators. Nanoindentation of the material shows no such anisotropy, giving mean hardness and modulus values for the four directional planes of 3.86 ± 0.10 GPa and 82.4 ± 2.7 GPa respectively, thereby clarifying the prominent role of microstructure in such materials. Scanning electron microscopy of indented samples shows that plastic deformation and delamination occur to different extents, depending on the orientation of the structure and local microstructural features such as prismatic layers. A Raman spectroscopic technique has been used to map relative deformation in the vicinity of the indents, showing that the amount of plastic or permanent deformation can be quantified, and that material delamination can be distinguished from other forms of deformation such as local cracking. These experimental methods are repeated using samples of non-biogenic aragonite, which act as an analogous material for comparison with the shell. It is proposed that the analysis of microhardness indents using Raman spectroscopy could be applied to other biomaterials exhibiting anisotropy.

Keywords

BiologicalRaman spectroscopyStress/strain relationship
Type
Articles
Information
Journal of Materials Research , Volume 21 , Issue 12 , December 2006 , pp. 3099 - 3108
Copyright
Copyright © Materials Research Society 2006

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References

REFERENCES

1.Kuhn-Spearing, L.T., Kessler, H., Chateau, E., Ballarini, R., Heuer, A.H.: Fracture mechanisms of the Strombus gigas conch shell: Implications for the design of brittle laminates. J. Mater. Sci. 31, 6583 (1996).CrossRefGoogle Scholar
2.Currey, J.D.: Mechanical-properties of mother of pearl in tension. Proc. R. Soc. London B, Biol. Sci. 196, 443 (1977).Google Scholar
3.Vincent, J.F.V.: Handbook of Elastic Properties of Solids, Liquids and Gases, Volume III: Elastic Properties of Solids: Biological and Organic Materials, Earth and Marine Sciences (Academic Press, Burlington, MA, 2001), pp. 215–219.Google Scholar
4.Kamat, S., Kessler, H., Ballarini, R., Nassirou, M., Heuer, A.H.: Fracture mechanisms of the Strombus gigas conch shell: II. Micromechanics analyses of multiple cracking and large-scale crack bridging. Acta Mater. 52, 2395 (2004).CrossRefGoogle Scholar
5.Bøggild, O.B.The shell structure of the mollusks. Kong. Dsk. Vidensk. Selsk. Skr., Natur. Math. Afd. 9, 112, 5 (1930).Google Scholar
6.Kamat, S., Su, X., Ballarini, R., Heuer, A.H.: Structural basis for the fracture toughness of the shell of the conch Strombus gigas. Nature 405, 1036 (2000).CrossRefGoogle ScholarPubMed
7.Li, X., Nardi, P.: Micro/nanomechanical characterization of a natural nanocomposite material—The shell of Pectinidae. Nanotechnology 15, 211 (2004).CrossRefGoogle Scholar
8.Dauphin, Y., Guzman, N., Denis, A., Cuif, J-P., Ortlieb, L.: Microstructure, nanostructure and composition of the shell of Concholepas concholepas (Gastropoda, Muricidae). Aquatic Living Resources 16, 95 (2003).CrossRefGoogle Scholar
9.Eichhorn, S.J., Scurr, D.J., Thompson, S.P., Golshan, M., Cernik, R.J.: The role of residual stress in the fracture properties of a natural ceramic. J. Mater. Chem. 15, 947 (2005).CrossRefGoogle Scholar
10.He, M.Y., Hutchinson, J.W.: Crack deflection at an interface between dissimilar elastic materials. Int. J. Sol. Struct. 25, 1053 (1989).Google Scholar
11.Robinson, R.F., Richardson, C.A.: The direct and indirect effects of suction dredging on a razor clam (Ensis arcuatus) population. ICES J. Marine Sci. 55, 970 (1998).CrossRefGoogle Scholar
12.Amer, M.S.: Raman spectroscopy investigations of functionally graded materials and inter-granular mechanics. Int. J. Sol. Struct. 42, 751 (2005).CrossRefGoogle Scholar
13.Steinfeld, J.I.: Molecules and Radiation: An Introduction to Molecular Spectroscopy (The MIT Press, Cambridge, MA, 1979), pp. 134–144.Google Scholar
14.Mitra, V.K., Risen, W.M., Baughman, R.H.: A laser Raman study of the stress dependence of vibrational frequencies of a monocrystalline polydiacetylene. J. Chem. Phys. 66, 2731 (1977).CrossRefGoogle Scholar
15.Lin, C., Liu, L.: Post-aragonite phase transitions in strontianite and cerussite—A high pressure Raman spectroscopic study. J. Phys. Chem. Solids 58, 977 (1997).CrossRefGoogle Scholar
16.Frech, R., Wang, E.C., Bates, J.B.: The IR spectra of CaCO3 (aragonite). Spectrochim. Acta, Part A 36, 915 (1980).CrossRefGoogle Scholar
17.Bruet, B.J.F., Qi, H.J., Boyce, M.C., Panas, R., Tai, K., Frick, L., Ortiz, C.: Nanoscale morphology and indentation of individual nacre tablets from the gastropod mollusk Trochus niloticus. J. Mater. Res. 20, 2400 (2005).CrossRefGoogle Scholar
18.Weidmann, G., Lewis, P., Reid, N.: Structural Materials, 3rd ed. (Butterworth Heinemann, Open University Press, London, UK, 1996), pp. 100–102.Google Scholar
19.Dauphin, Y., Denis, A.: Structure and composition of the aragonitic crossed lammellar layers in six species of bivalvia and gastropoda. Comp. Biochem. Physiol., A 126, 367 (2000).CrossRefGoogle Scholar
20.Taylor, J.D., Layman, M.: The mechanical properties of bivalve (Molluska) shell structures. Palaeontology 15, 256 (1972).Google Scholar
21.Hou, D.F., Zhou, G.S., Zheng, M.: Conch shell structure and its effect on mechanical behaviours. Biomaterials 25, 751 (2004).CrossRefGoogle Scholar
22.Gao, H.J., Ji, B.H., Jager, J.L., Arzt, E., Fratzl, P.: Materials become insensitive to flaws at nanoscale: Lessons from nature. Proc. Natl. Acad. Sci. U.S.A. 100, 5597 (2003).CrossRefGoogle ScholarPubMed
23.Oliver, W.C., Pharr, G.M.: An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments. J. Mater. Res. 7, 1564 (1992).CrossRefGoogle Scholar
24.Hearmon, R.F.S.: The elastic constants of anisotropic materials. Rev. Mod. Phys. 18, 409 (1946).CrossRefGoogle Scholar
25.Huggins, M.L.: The crystal structures of aragonite (CaCO3) and related minerals. Phys. Rev. 19, 354 (1922).CrossRefGoogle Scholar
26.Wainwright, S.A.: Stress and design in bivalved mollusk shell. Nature 224, 777 (1969).CrossRefGoogle Scholar