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Abstract
The shell of pink conch is a kind of natural well-designed composite with excellent mechanical properties, which provides us
information for material design. In this paper the microstructures of pink conch shell are characterized by using SEM and TEM.
The microscopic analysis indicates that the pink conch shell is with crossed-lamellar microstructure and the angle between two
second-order lamellae is 70–90 . The cracking and fracture morphologies indicate that the crack deflection, bridge and fiber pullout
are the main toughening mechanisms. Bamboo lamellae are employed to make the simple bio-mimetic model materials. In the model
material the rotated angle between the fibers of each glued lamella varies from 0 to 90 . Three-point-bending is employed to test the
properties of models material, such as the elastic modulus, the flexural strength and the fracture strain energy density. It is found
that the fracture strain energy density of the specimens with the rotated angle between the fibers of the layers about 60 exhibits the
maximum value, which is close to the angle of the two second-order lamellae of the conch shell.
r 2003 Elsevier Ltd. All rights reserved.
0142-9612/$ - see front matter r 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0142-9612(03)00555-6
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752 D.F. Hou et al. / Biomaterials 25 (2004) 751–756
All samples are cut out from the same shell in order to
Fig. 1. Fracture surface of conch shell. minimize scatter in the tests, care is taken to prepare
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D.F. Hou et al. / Biomaterials 25 (2004) 751–756 753
(a) (b)
(c) (d)
Fig. 3. TEM micrographs of pink shell and diffraction patterns, (a) and (c) TEM micrographs of single-crystal and multicrystal; (b) and (d)
diffraction patterns of single-crystal and multicrystal.
samples. Two types of specimens (S1, S2) are prepared materials are from [8]. The comparison of the brittleness
from the middle macro-layer, i.e., the parallel and the for pink conch shell and ceramic materials is listed in
perpendicular ones with respect to the shell axis, Table 1.
respectively. Micro-hardness tester (MH-5) is employed In general the sole CaCO3 is brittle, which is the main
to perform the tests. component of conch shell, but the conch shell exhibits
rather tough (see Table 1). The resource of the high
3.2. Results and discussions toughness of conch shell might be its special micro-
structure. Therefore it is necessary to study the response
Using indentation mechanics, a simple index of of the microstructure of conch shell to its mechanical
brittleness, the ratio H=Kc ; has been derived in terms properties of the shell in details.
of basic hardness and toughness parameters [8]. Here H In order to understand the excellent toughness
is hardness (resistance to deformation) and Kc is property of the conch shell, the trace of the indentation
toughness (resistance to fracture). test is studied in detail. Fig. 5 is a typical SEM image of
Sarikaya performed four-point bend fracture tough- the indentation feature, which shows many cracks in the
ness tests for pink conch tested [9], the averaged value of middle macro-layer. The damage zones around the
the toughness is 10 MPa/m1/2. Here we employ this indentation reflect the lamellar character of the micro-
value for Kc to conduct H=Kc ; for the pink conch shell. structure. The extension of cracks is not along the
The values of brittleness H=Kc for other ceramic direction of the two diagonals, which is quite different
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754 D.F. Hou et al. / Biomaterials 25 (2004) 751–756
50 µm
from those in most monolith materials. It seems that the 4.1. Materials and methods
cracks are trying to find easy ways to extend. In fact
those weak interface (i.e. organic layer) provides the In order to study the nature of the specified angle 70–
easy way. Therefore, the binding forces between the 90 between second-order lamellas structure in the
organic phase and the aragonite layer will hinder the conch shell, mimicking materials are fabricated and
further propagation of the crack. Crack A initials from a tested.
corner of the indentation but extends in the interfaces Bamboo lamella is employed to manufacture multi-
between the first-order lamellas and then bifurcates and lamella materials. Only the middle part of the bamboo is
deflects. Many cracks stretch from crack A and extend taken to conduct the model materials so as to reduce the
through the second and the third-order lamellae. scatters of the properties of the fabricated materials. The
Apparent parallel second-order interfaces in the region bamboo lamella has fibred structures with the elastic
of cracks become visible optically, whereas they are modulus of 17.7 GPa [11]. The bamboo lamella is
invisible in the intact regions (see Fig. 5). Those main machined as a strip with the size about 60 5
cracks are clearly segmented with the segments follow- 0.4 mm3.
ing inter-lamellar boundaries. Numerous micro-cracks Gluing the bamboo lamellas with polymeric adhesive
are present parallel to these segments. These observa- whose module is about 2 GPa [11] makes the specimen.
tions identify the idea that inter-lamellar boundary is the Each specimen is composed of five lamellas glued
weak interface, and impedes the direct propagation of together. The thickness of adhesive layer is kept about
cracks. The angle between two groups of parallel cracks 0.1 mm, which indicates that the volume fraction of the
is about 70–90 . In some cases, lamella is very thin or adhesive layer is about 0.15. The lamellas in each
even disappears gradually, as shown in Fig. 5. The specimen are numbered as 1, 2, 3, 4 and 5 from upper
delocalization of damage, the abundant crack bridging layer to the lower one. The orientations of the fibers in
and the cracking branching are also very clear. It is well lamellas with the numbers 1, 3 and 5 are identical. While
known that branching crack dissipates more energy and the fibers in the lamellas with the numbers 2 and 4 rotate
enhances the toughness of materials even for the certain angle with respect to their neighbor lamellas, say
structures composing of relatively brittle constituents. lamellas 1, 3 and 5. The rotated angles between glued
On the other hand, the deflecting crack can prolong the fibers of the neighbor lamellas are selected as 0 , 20 ,
propagation path, which could absorb more energy as 45 , 60 , 75 and 90 for each group of specimens,
well, especially the propagation resistance increases respectively. Air bubbles were carefully excluded by
significantly if the crack deflects to a direction with an applying pressure regularly to the platelets. Pockets of
unfavorable stress state [10]. So such a kind of crack adhesive prevented from accumulating by allowing only
deflection results in toughening the conch shell. In the straightest edges to lie side by side. The adhesive was
addition, the multiple cracking is another effective way allowed to cure at 20 C for 48 h.
to enhance the toughness, which can even decrease the Three-point bending test is conducted to study the
orientation dependence of the toughness, since the shell mechanical response of the model materials at a span of
is a composite structure that composes many layers with 40 mm. The mechanical properties, such as the elastic
varying orientations. Fiber pullout often occurs with modulus, the flexural strength and the fracture energy
crack deflection (see Fig. 2a). Laths can be seen density, etc., are evaluated.
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D.F. Hou et al. / Biomaterials 25 (2004) 751–756 755
18
Ec ¼ Vf þ ð1 Vf ÞEm ; ð1Þ 6
4
where V ; E; f; m and c reflect the volume fraction, the 2
elastic modulus, the filler, the matrix and the composite,
0
respectively. In the Reuss model the elements are in 0 20 40 60 80 100
series [12] Rotated angle / o
1 Vf ð1 Vf Þ Fig. 7. Variations of elastic modulus vs. rotated angle of bamboo
¼ þ : ð2Þ
Ec Ef Em lamellas.
Ec
angle 70–90 of conch shell might result from the
requirement of fracture strain energy density maximum.
The higher fracture strain energy density, the higher
Em the ductility of the material. Material ductile failure is in
filler matrix fact a proper outcome of excessive internal dissipation in
Vm /(Vf +Vm)*100% the viewpoint of physicist. According to modern non-
Fig. 6. Comparative of elastic moduli of parallel and series models. equilibrium thermodynamics—dissipative structure and
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756 D.F. Hou et al. / Biomaterials 25 (2004) 751–756
0.16 Test date the fact that bio-mineralization has evolved over
0.14 Trend curve
0.12
millions of years, while materials science has only
0.10
developed over a century. In any sense, it is sure that
0.08
there is still more to be learned from our world.
0.06
0.04
0.02 Acknowledgements
0 20 40 60 80 100
Rotated angle / o The authors would like to show their thanks to
Fig. 9. Variation of strain energy density vs. rotated angle of bamboo Chinese doctoral project foundation (98069813) and the
lamellas. excellent young teacher program (20022090) for their
kind financial supports.
synergetic theories [13–15], each stable animate body has
to absorb and dissipate energy in some manners so that
a self-organized and self-constraint structure can be References
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