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University of California, San Diego UNIVERSITY OF CALIFORNIA, SAN DIEGO STRUCTURAL AND FUNCTIONAL BIOLOGICAL MATERIALS: ABALONE NACRE, SHARP MATERIALS, AND ABALONE FOOT ADHESION A Dissertation submitted in partial satisfaction of the requirements for the degree of Doctor of Philosophy in Materials Science and Engineering by Albert Yu-Min Lin COMMITTEE IN CHARGE: Professor Marc André Meyers (Chair) Professor Michael J. Heller Professor Sungho Jin Professor Joanna McKittrick Professor Frank Eberhard Talke 2008 Copyright Albert Yu-Min Lin, 2008 All rights reserved. The dissertation of Albert Yu-Min Lin is approved and it is acceptable in quality and form for publication on microfilm: ______________________________________________________________ ______________________________________________________________ ______________________________________________________________ ______________________________________________________________ ______________________________________________________________ Chair University of California, San Diego 2008 iii Dedicated to my Grandfathers iv Oh! A bare, brown rock stood up in the sea, The waves at its feet dancing Merrily. A little bubble once came sailing by, And thus to the rock did it gaily cry, Ho! Clumsy brown stone, Quick, make way for me: I’m the fairest thing that floats on the sea. See my rainbow-robe, see my crown of light, My glittering form so airy and bright. O’er the waters blue, I’m floating away, To dance by the shore with the foam and spray. Now, make way, make way; for the waves are strong, And their rippling feet bear me fast along. But the great rock stood straight up in the sea: It looked gravely down and said pleasantly Little friend, you must go some other way; For I have not stirred this many a long day. Great billows had dashed, and angry winds blown; But my sturdy form is not overthrown. Nothing can stir me in the air or sea; Then, how can I move, little friend, for thee? Then the waves all laughed, in their voices sweet; And the sea-birds looked, from their rocky seat, At the bubble gay, who angrily cried, While its round cheek glowed with a foolish pride You shall move for me; and you shall not mock At the words I say, you ugly, rough rock. Be silent, wild birds! While stare you so? Stop laughing, rude waves, And help me to go! For I am the queen of the ocean here, And the cruel stone cannot make me fear. Dashing fiercely up, with a scornful word, Foolish bubble broke; but the Rock never stirred. Then said the sea-birds, sitting in their nests To the little ones leaning on their breasts, Be not like the bubble, headstrong, rude and vain, Seeking by violence your object to gain; But be like the rock. Steadfast, true and strong, Yet cheerful and kind and firm against wrong. Heed, little birdlings, and wiser you’ll be For the lessons learned today by the sea. - Louisa May Alcott v TABLE OF CONTENTS SIGNATURE PAGE……………………………………………………………….……iii DEDICATION…………………………………………………………………………...iv EPIGRAPH……………………………………………………………………………….v TABLE OF CONTENTS…………………………………………………………………vi LIST OF FIGURES: ........................................................................................................... x ACKNOWLEDGEMENTS............................................................................................. xxi VITA..............................................................................................................................xxiii FIELD OF STUDY........................................................................................................xxiii LIST OF PUBLICATION ............................................................................................. xxiv INTERNATIONAL CONFERENCE PRESENTATIONS............................................ xxv ABSTRACT OF THE DISSERTATION ...................................................................... xxvi CHAPTER 1 .......................................................................................................................1 CHAPTER 2 .......................................................................................................................7 2.1 Structure & Mechanical Properties............................................................................... 7 2.1.1 Biomimetics.............................................................................................................. 26 2.2 Growth: Biomineralization ......................................................................................... 29 2.3 Functional Biological Materials.................................................................................. 45 2.3.1 Sharp Materials: ...................................................................................................... 45 2.3.2 Attachment Devices: ................................................................................................ 45 CHAPTER 3 ..................................................................................................................... 59 vi EXPERIMENTAL METHODS........................................................................................ 59 3.1 Live Specimen Culturing Facilities ............................................................................ 59 3.2 Structural Characterization ......................................................................................... 61 3.2.1 Scanning Electron Microscopy Observations on the Structure of Nacre:............... 61 3.2.2 EDTA Demineralization of Nacre: .......................................................................... 62 3.2.3 Atomic Force Microscopy: ...................................................................................... 63 3.2.4 Heating: ................................................................................................................... 64 3.2.5 Deproteination:........................................................................................................ 64 3.2.6 Transmission Electron Microscopy:........................................................................ 64 3.2.7 X-ray Diffraction: .................................................................................................... 65 3.2.8 Raman Spectroscopy:............................................................................................... 66 3.2.9 Critical Point Drying:.............................................................................................. 66 3.3 Mechanical Testing of Nacre...................................................................................... 67 3.3.1 Nanoindentation: ..................................................................................................... 67 3.3.2 Quasi-static Mechanical Testing:............................................................................ 68 3.3.3 Dynamic Mechanical Testing: ................................................................................. 71 3.4 Growth Implantation: Flat Pearl and Trepanning Techniques.................................... 71 3.4.1 Flat Pearl:................................................................................................................ 71 3.4.2 Trepanning:.............................................................................................................. 72 3.4.3 Crystal Nucleation:.................................................................................................. 74 3.5 Attachment Measurements.......................................................................................... 75 3.5.1 Bulk Mechanical Testing: ........................................................................................ 75 3.5.2 Structural Characterization of Abalone Foot:......................................................... 77 vii 3.5.3 Preparation of Single Seta:...................................................................................... 78 3.5.4 Force Estimation of a Single Seta During PerpendicularPull:............................... 80 CHAPTER 4 ..................................................................................................................... 82 RESULTS AND DISCUSSION....................................................................................... 82 4.1 Structure and Mechanical Properties .......................................................................... 82 4.1.1 The Nacre of the Abalone: ....................................................................................... 82 4.1.1.1 Quasi-static Compression and Tension ................................................................ 82 4.1.1.2 Hardness and Nanoindentation ............................................................................ 89 4.1.1.3 Relationship to Structure ...................................................................................... 91 4.1.1.4 Tile-Tile Interface ................................................................................................. 95 4.1.1.5 Strength of Individual Tile .................................................................................. 118 4.1.1.6 Mesolayers .......................................................................................................... 121 4.1.2 Comparative Study: ............................................................................................... 124 4.1.2.1 Conch shell.......................................................................................................... 124 4.1.2.2 Giant Clam shell ................................................................................................
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