Mineralized tissues
Mineralized tissues are biological tissues that incorporate minerals into soft matrices. Typically these tissues form a protective shield or structural support. Bone, mollusc shells, deep sea sponge Euplectella species, radiolarians, diatoms, antler bone, tendon, cartilage, tooth enamel and dentin are some examples of mineralized tissues.
These tissues have been finely tuned to enhance their mechanical capabilities over millions of years of evolution. Thus, mineralized tissues have been the subject of many studies since there is a lot to learn from nature as seen from the growing field of biomimetics. The remarkable structural organization and engineering properties makes these tissues desirable candidates for duplication by artificial means. Mineralized tissues inspire miniaturization, adaptability and multifunctionality. While natural materials are made up of a limited number of components, a larger variety of material chemistries can be used to simulate the same properties in engineering applications. However, the success of biomimetics lies in fully grasping the performance and mechanics of these biological hard tissues before swapping the natural components with artificial materials for engineering design.
Mineralized tissues combine stiffness, low weight, strength and toughness due to the presence of minerals in soft protein networks and tissues. There are approximately 60 different minerals generated through biological processes, but the most common ones are calcium carbonate found in mollusk shells and hydroxyapatite present in teeth and bones. Although one might think that the mineral content of these tissues can make them fragile, studies have shown that mineralized tissues are 1,000 to 10,000 times tougher than the minerals they contain. The secret to this underlying strength is in the organized layering of the tissue. Due to this layering, loads and stresses are transferred throughout several length-scales, from macro to micro to nano, which results in the dissipation of energy within the arrangement. These scales or hierarchical structures are therefore able to distribute damage and resist cracking. Two types of biological tissues have been the target of extensive investigation, namely nacre from mollusk shells and bone, which are both high performance natural composites. Many mechanical and imaging techniques such as nanoindentation and atomic force microscopy are used to characterize these tissues. Although the degree of efficiency of biological hard tissues are yet unmatched by any man-made ceramic composites, some promising new techniques to synthesize them are currently under development. Not all mineralized tissues develop through normal physiologic processes and are beneficial to the organism. For example, kidney stones contain mineralized tissues that are developed through pathologic processes. Hence, biomineralization is an important process to understand how these diseases occur.
Evolution
The evolution of mineralized tissues has been puzzling for more than a century. It has been hypothesized that the first mechanism of animal tissue mineralization began either in the oral skeleton of conodont or the dermal skeleton of early agnathans. The dermal skeleton is just surface dentin and basal bone, which is sometimes overlaid by enameloid. It is thought that the dermal skeleton eventually became scales, which are homologous to teeth. Teeth were first seen in chondrichthyans and were made from all three components of the dermal skeleton, namely dentin, basal bone and enameloid. The mineralization mechanism of mammalian tissue was later elaborated in actinopterygians and sarcopterygians during bony fish evolution. It is expected that genetic analysis of agnathans will provide more insight into the evolution of mineralized tissues and clarify evidence from early fossil records.Hierarchical structure
Hierarchical structures are distinct features seen throughout different length scales. To understand how the hierarchical structure of mineralized tissues contributes to their remarkable properties, those for nacre and bone are described below. Hierarchical structures are characteristic of biology and are seen in all structural materials in biology such as bone and nacre from seashellsNacre
Nacre has several hierarchical structural levels.The macroscale
Some mollusc shells protect themselves from predators by using a two layered system, one of which is nacre. Nacre constitutes the inner layer while the other, outer, layer is made from calcite. The latter is hard and thus prevents any penetration through the shell, but is subject to brittle failure. On the other hand, nacre is softer and can uphold inelastic deformations, which makes it tougher than the hard outer shell. The mineral found in nacre is aragonite, CaCO3, and it occupies 95% vol. Nacre is 3000 times tougher than aragonite and this has to do with the other component in nacre, the one that takes up 5% vol., which is the softer organic biopolymers. Furthermore, the nacreous layer also contains some strands of weaker material called growth lines that can deflect cracks.The microscale
The Microscale can be imagined by a three-dimensional brick and mortar wall. The bricks would be 0.5 μm thick layers of microscopic aragonite polygonal tablets approximately 5-8 μm in diameter. What holds the bricks together are the mortars and in the case of nacre, it is the 20-30 nm organic material that plays this role. Even though these tablets are usually illustrated as flat sheets, different microscopy techniques have shown that they are wavy in nature with amplitudes as large as half of the tablet's thickness. This waviness plays an important role in the fracture of nacre as it will progressively lock the tablets when they are pulled apart and induce hardening.The nanoscale
The 30 nm thick interface between the tablets that connects them together and the aragonite grains detected by scanning electron microscopy from which the tablets themselves are made of together represent another structural level. The organic material "gluing" the tablets together is made of proteins and chitin.To summarize, on the macroscale, the shell, its two layers, and weaker strands inside nacre represent three hierarchical structures. On the microscale, the stacked tablet layers and the wavy interface between them are two other hierarchical structures. Lastly, on the nanoscale, the connecting organic material between the tablets as well as the grains from which they are made of is the final sixth hierarchical structure in nacre.