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Cited by 111Calcium Carbonate Crystallization and InhibitionMicrostructure and mechanical propertiesAdvanced Materials and Mechanics

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Origin of flaw-tolerance in nacre

Open access
Huang, Zaiwang, Li, Xiaodong·2013·Scientific Reports
DOI 10.1038/srep01693PMC PMC3631768
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Abstract

Over the past decades, our understanding of nacre's toughening origin has long stayed at the level of crack deflection along the biopolymer interface between aragonite platelets. It has been widely thought that the ceramic aragonite platelets in nacre invariably remain shielded from the propagating crack. Here we report an unexpected experimental observation that the propagating crack, surprisingly, invades the aragonite platelet following a zigzag crack propagation trajectory. The toughening origin of previously-thought brittle aragonite platelet is ascribed to its unique nanoparticle-architecture, which tunes crack propagation inside the aragonite platelet in an intergranular manner. For comparison, we also investigated the crack behavior in geologic aragonite mineral (pure monocrystal) and found that the crack propagates in a cleavage fashion, in sharp contrast with the intergranular cracking in the aragonite platelet of nacre. These two fundamentally different cracking mechanisms uncover a new toughening strategy in nacre's hierarchical flaw-tolerance design.

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Figure 1 Crack path profile and fractography within individual aragonite platelets. (a), Schematic drawing showing sample geometry and experimental scheme under three-point bending loaded along [002]. (b), Fracture path observation on nacre cross section, at a glance, indeed demonstrates crack deflection along its biopolymer interlayer in a zigzag manner. (c), A close-up view reveals at least one of two aragonite platelets (blue arrowed) has been invaded by an advancing crack considering geometrically staggered arrangement. Subsequently, however, the advancing crack is not followed by successive cleavage, but defected to biopolymer interlayer (black arrow). (d), Zigzag crack path shows the inherent extension resistance arising from the interior of individual aragonite platelets (red arrowed). (e), AFM observation confirms the zigzag crack profile within an individual aragonite platelet. (f), A closer examination (from white boxed area in Fig. 1e) reveals that crack propagation path is along the boundaries of aragonite nanoparticles.
Figure 1 Crack path profile and fractography within individual aragonite platelets. (a), Schematic drawing showing sample geometry and experimental scheme under three-point bending loaded along [002]. (b), Fracture path observation on nacre cross section, at a glance, indeed demonstrates crack deflection along its biopolymer interlayer in a zigzag manner. (c), A close-up view reveals at least one of two aragonite platelets (blue arrowed) has been invaded by an advancing crack considering geometrically staggered arrangement. Subsequently, however, the advancing crack is not followed by successive cleavage, but defected to biopolymer interlayer (black arrow). (d), Zigzag crack path shows the inherent extension resistance arising from the interior of individual aragonite platelets (red arrowed). (e), AFM observation confirms the zigzag crack profile within an individual aragonite platelet. (f), A closer examination (from white boxed area in Fig. 1e) reveals that crack propagation path is along the boundaries of aragonite nanoparticles.CC BY-NC-ND · PubMed Central
Figure 2 Zigzag crack propagation path inside an individual aragonite platelet of nacre. (a), After imposing Vickers indentation on an aragonite platelet along [002] (Section 1, Supplementary materials), a typical crack radiated from the indentation mark corner was selected from AFM observation, showing the crack propagation path in a zigzag fashion. (b), An electron-transparent TEM foil containing one crack (white arrowed) was prepared by the FIB lift-out technique. (c), Dark-field TEM image showing wavy crack propagation path, the waviness is on the order of a few nanometers, in contrast with the interface geometry between aragonite platelet and biopolymer (Section 4, Supplementary materials). (d), A typical area near the fracture edge was selected for closer examination, showing that no discernible lattice defects such as dislocation and grain boundary sliding can be detected, as confirmed by single-crystal-like diffraction pattern using fast Fourier transform (FFT) measurement (inset). (e), Schematic illustration portraits that an advancing crack prefers the boundaries of aragonite nanoparticles as the propagation path with the least resistance.
Figure 2 Zigzag crack propagation path inside an individual aragonite platelet of nacre. (a), After imposing Vickers indentation on an aragonite platelet along [002] (Section 1, Supplementary materials), a typical crack radiated from the indentation mark corner was selected from AFM observation, showing the crack propagation path in a zigzag fashion. (b), An electron-transparent TEM foil containing one crack (white arrowed) was prepared by the FIB lift-out technique. (c), Dark-field TEM image showing wavy crack propagation path, the waviness is on the order of a few nanometers, in contrast with the interface geometry between aragonite platelet and biopolymer (Section 4, Supplementary materials). (d), A typical area near the fracture edge was selected for closer examination, showing that no discernible lattice defects such as dislocation and grain boundary sliding can be detected, as confirmed by single-crystal-like diffraction pattern using fast Fourier transform (FFT) measurement (inset). (e), Schematic illustration portraits that an advancing crack prefers the boundaries of aragonite nanoparticles as the propagation path with the least resistance.CC BY-NC-ND · PubMed Central
Figure 3 Crack behavior in geologic aragonite monocrystal. (a), The growth direction of geologic aragonite monocrystal with a pseudo-hexagonal profile on the top surface is toward [002]. (b), AFM observation shows that a representative crack, radiating from the Vickers indentation mark corner on crystallographic plane (002),cleaves aragonite crystal in a straight manner, indicative of brittle fracture mode. (c), A bright-field TEM image reveals crack invasion into the geologic aragonite monocrystal in a cleavage manner, the region around the crack was determined to be single-crystal by diffraction pattern (inset). (d), At the fracture edge, a closer view of lattice fringe exhibits straight crack cleavage behavior, in stark contrast with the intergranular manner within nacre's aragonite platelet. It is worthy pointing out that the “dark” dots around the fracture edge were caused by the unavoidable contamination during the FIB fabrication, i.e. platinum implantation.
Figure 3 Crack behavior in geologic aragonite monocrystal. (a), The growth direction of geologic aragonite monocrystal with a pseudo-hexagonal profile on the top surface is toward [002]. (b), AFM observation shows that a representative crack, radiating from the Vickers indentation mark corner on crystallographic plane (002),cleaves aragonite crystal in a straight manner, indicative of brittle fracture mode. (c), A bright-field TEM image reveals crack invasion into the geologic aragonite monocrystal in a cleavage manner, the region around the crack was determined to be single-crystal by diffraction pattern (inset). (d), At the fracture edge, a closer view of lattice fringe exhibits straight crack cleavage behavior, in stark contrast with the intergranular manner within nacre's aragonite platelet. It is worthy pointing out that the “dark” dots around the fracture edge were caused by the unavoidable contamination during the FIB fabrication, i.e. platinum implantation.CC BY-NC-ND · PubMed Central
Figure 4 Nanoindentation load-displacement response from nacre's aragonite platelets and geologic aragonite monocrystal along [002]. For the geologic aragonite monocrystal, at the nanoindentation displacement of approximately 6.6 nanometers, a sudden displacement pop-in was found, which is consistent with the plasticity onset at the stress level of the theoretical strength. In comparison, no discernible pop-in event can be detected for nacre's aragonite platelets, implying the stress underneath the nanoindenter was not accumulated to the theoretical strength. Its lower loading slope and more apparent viscoelastic effect at the peak indentation holding segment jointly indicate the existence of biopolymer matrix, buffering stress concentration within individual aragonite platelets.
Figure 4 Nanoindentation load-displacement response from nacre's aragonite platelets and geologic aragonite monocrystal along [002]. For the geologic aragonite monocrystal, at the nanoindentation displacement of approximately 6.6 nanometers, a sudden displacement pop-in was found, which is consistent with the plasticity onset at the stress level of the theoretical strength. In comparison, no discernible pop-in event can be detected for nacre's aragonite platelets, implying the stress underneath the nanoindenter was not accumulated to the theoretical strength. Its lower loading slope and more apparent viscoelastic effect at the peak indentation holding segment jointly indicate the existence of biopolymer matrix, buffering stress concentration within individual aragonite platelets.CC BY-NC-ND · PubMed Central

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Metadata

Authors
Huang, Z., & Li, X.
Affiliations
University of South Carolina (US)
Corresponding author
Li, Xiaodong
Venue
Scientific Reports
Publisher
Springer Science and Business Media LLC
Published
2013-04-22
Volume
3
Issue
1
Pages
1693-1693
ISSN
2045-2322 (ISSN-L)
DOI
10.1038/srep01693
PMC
PMC3631768
OpenAlex
W2076735776
Cited by
111
References
1
Citations by year
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FWCI
3.82
Type
journal article
Language
en
Open access
Licence
Locations
  • Scientific Reports (publishedVersion, cc-by-nc-nd)
  • Europe PMC (PubMed Central) (publishedVersion, cc-by-nc-nd)
  • PubMed Central (publishedVersion, cc-by-nc-nd)
  • PubMed (publishedVersion)
Funders
  • North Carolina State University
  • University of South Carolina
  • Army Research Office
Topics
  • Physical Sciences › Materials Science › Biomaterials › Calcium Carbonate Crystallization and Inhibition
  • Physical Sciences › Materials Science › Metals and Alloys › Microstructure and mechanical properties
  • Physical Sciences › Engineering › Mechanical Engineering › Advanced Materials and Mechanics
Keywords
nacre, aragonite platelets, crack propagation, toughening mechanisms, flaw tolerance, intergranular fracture, nanoparticle structure, biominerals, hierarchical design, cleavage fracture
MeSH terms
Hardness, Materials Testing, Tensile Strength, Compressive Strength, Nacre

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