Abstract
Materials that possess the ability to self-heal cracks at room temperature, akin to living organisms, are highly sought after. However, achieving crack self-healing in inorganic materials, particularly with covalent bonds, presents a great challenge and often necessitates high temperatures and considerable atomic diffusion. Here we conducted a quantitative evaluation of the room-temperature self-healing behaviour of a fractured nanotwinned diamond composite, revealing that the self-healing properties of the composite stem from both the formation of nanoscale diamond osteoblasts comprising sp2- and sp3-hybridized carbon atoms at the fractured surfaces, and the atomic interaction transition from repulsion to attraction when the two fractured surfaces come into close proximity. The self-healing process resulted in a remarkable recovery of approximately 34% in tensile strength for the nanotwinned diamond composite. This discovery sheds light on the self-healing capability of nanostructured diamond, offering valuable insights for future research endeavours aimed at enhancing the toughness and durability of brittle ceramic materials.
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Change history
13 October 2023
In the version of the article initially published the incorrect version of the Supplementary information was included. This has now been updated in the HTML version of the article.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (52288102 to Y.T.; 51922017 and 51972009 to Y.Y.; 51532001 to L.G.; 52090020 to Y.T.; 52103322 to Y.G.) and the Natural Science Foundation of Hebei Province of China (E2022203109 to B.X.).
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Y.Y., A.N., L.G. and Y.T. proposed and supervised the project; S.C., Y.G. and T.J. synthesized the ntDC samples; K.Q., J.H., X.L., J.W. and A.N. conducted the in situ tests using SEM and TEM instruments; Q.H., L.L. and Z.Y. performed the simulations; K.Q. and X.L. prepared the sample using a FIB; and Y.Y., Y.T., L.G., B.X., A.N., K.Q., Q.H., L.L., Y.W. and Y.L. analysed the data and wrote the manuscript. All authors participated in discussions of the research.
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Extended data
Extended Data Fig. 1 A multicycle tensile fracture test of a ntDC NB (Sample 3) with a width of ~ 220 nm.
a, Sketch configuration of the dual-beam FIB system showing the preparation of the ntDC NB and PTP device on Hysitron Pi-85. The right panel is the enlarged sketch of the 3D geometry, indicating an equilateral rhombus shaped cross-section with an inner angle of 52°. The sample width observed in SEM is actually the height of the equilateral rhombus, ranging from 200 nm to 1000 nm. b−i, Initial tensile fracture test and 1st to 7th healing tests on the ntDC NB. The crack was clearly seen in b−f, as marked with the yellow arrowhead. In the last two healings (h and i), a protrusion appeared at the bottom of the fracture, as marked with the black arrowhead.
Extended Data Fig. 2 Results of multicycle tensile fracture tests of ntDC NBs with different widths.
a−d, Load versus displacement curves taken from the multicycle tensile fracture tests of ntDC NBs with different widths of ~ 300 nm, 400 nm, 500 nm and 1000 nm, respectively. The insets demonstrate the evolution of healing efficiency with multiple fracture and healing duration.
Extended Data Fig. 3 A multicycle tensile fracture test of another ntDC NB with a slightly mismatched crack (Sample 1, with width of ~ 200 nm).
a−f, Initial tensile fracture test and 1st to 5th healing tests of the ntDC NB. When the two fracture ends are in contact, an obvious misalignment is observed, as marked by the yellow arrowhead in b−f. g, The load versus displacement curves taken from the multicycle tensile fracture test. h, The healing efficiency versus healing duration curve. The maximum healing efficiency is approximately 21%.
Extended Data Fig. 4 Experimental setup and in situ tensile fracture test of a ntDC NB in TEM.
a, Photograph of the stretched chip structure based on Bestron double tilt tensile holder. In situ transmission stretching sample is fixed at the position marked by the red circle. b, Low-magnification TEM image of the sample prepared by FIB technology for in situ tensile fracture test in TEM. c to e, TEM images of the NB at moments of before fracture, after fracture, and before recovery, respectively, insets in c and e are SAED patterns taken from the corresponding white circled regions. f, High-resolution TEM image from the boxed region in e just before the recovery of the two fracture ends. Regions of diamond and DOs are labeled. g and h, Atomic-resolution high-resolution TEM images from the blue and yellow boxes in f, respectively, detailing the graphite-like layers at the fracture surfaces.
Extended Data Fig. 5 EELS analysis of the DOs region and a multicycle fracture and healing test showing the region of DOs expands.
a, EELS from the DOs region in comparison with raw glassy carbon and ntDC. The lavender and aqua regions represent 1s-π* and 1s-σ* transitions of carbon, respectively. The DOs show substantially higher fraction of sp2 (at 285 eV) and lower fraction of sp3 (at 292 eV) than those of ntDC, indicating substantial sp2 bonding in DOs. The sp3 content in DO was roughly estimated with raw glassy carbon with the two-windows method using EELS information. For two-windows method, Iπ* and Iσ* were calculated by integrating the intensity over 4 eV (283−287 eV) and 10 eV window (288−298 eV), respectively39. The sp2 ratio was calculated using the equation \({N}_{{int}\,{ratio}}=\frac{{I}_{\pi * }^{{DOs}}/{I}_{\sigma * }^{{DOs}}}{{I}_{\pi * }^{{GC}}/{I}_{\sigma * }^{{GC}}}\) and \({N}_{{int}\,{ratio}}=3x/(4-x)\), where x represents the sp2 fraction38. The estimated content of sp3 in DOs (that is, 1-x) is about 34.5% ± 3.0%. b to d, TEM images of the NB after healing duration of 10 min, 20 min and 30 min before the 1st, 2nd and 3rd healing tests, respectively. The DOs content kept increasing with fracture cycles.
Extended Data Fig. 6 The multicycle tensile fracture test result of a ntDC NB with a width of ~ 200 nm.
a, Load versus displacement curves with different healing duration timing immediately after previous fracture. b, Healing efficiency corresponding to the healing cycle in a.
Extended Data Fig. 7 Multicycle tensile fracture tests of DSC NBs in TEM and SEM.
a and b, TEM snapshots of a rectangular DSC NB along the [100] direction (~ 350 nm in width, 100 nm in thickness and 1500 nm in gauge length). SAED Patterns were taken from circled regions in a and b. c, TEM image taken from the red framed region in b, showing the typical {111} cleavage fracture. The inset is a diagram showing the geometry of two intersecting {111} cleavage surfaces. d to g, TEM images of the fractured surfaces of the DSC NB, taken after the initial tensile fracture and 1st to 3rd healing tests. h to k, HRTEM images from the surface regions in d to g, respectively (insets, corresponding fast Fourier transform images). The single-crystallinity was maintained throughout multicycle fracture and healing, with almost no DOs formed on the surface. l, SEM observations of a DSC NB ( ~ 205 nm in width, along the <100 > ) during the tensile fracture test. m, High magnification SEM image of the fractured ends, showing typical {111} cleavage fracture; n, SEM image of the fractured region after release the load. The inset shows the geometry of two intersecting {111} cleavage surfaces. o, Load versus displacement curves from the multicycle tensile fracture test. p, Healing efficiency versus healing duration of the three DSC NBs with width of ~200 nm along <100 > , <110> and <111> direction.
Extended Data Fig. 8 Total and projected density of states for DSC and diamond slab.
a, Total DOS of DSC. b, Total DOS of the diamond slab containing six (111) layers as mentioned in the method. c, Total DOS of amorphous carbon structure. d, The projected DOS (PDOS) of carbon atoms in DSC. e, PDOS of inner carbon atoms in diamond {111} slab. f, PDOS of surface carbon atoms in diamond (111) slabs.
Extended Data Fig. 9 Variations of energy and force per area with increasing distance between two fractured (001) surfaces of diamond polytypes, as well as those between two DO structures with varying sp3 content.
a and b, 2H diamond. c and d, 4H diamond. e and f, 9 R diamond. g and h, 15 R diamond. i and j, DO structures with a sp3 content of 34.7%. k and l, DO structures with a sp3 content of 63.2%. m and n, DO structures with a sp3 content of 86.1%. o, The maximum repulsive force per area versus sp3 content. The maximum repulsive force per area increases with sp3 content: 5.73 GPa for 34.7% sp3 content, 6.81 GPa for 63.2% sp3 content and 7.86 GPa for 86.1% sp3 content and eventually 12.82 GPa for cubic diamond.
Supplementary information
Supplementary Information
Supplementary Figs. 1–5 and molecular dynamics simulations.
Supplementary Video 1
The multicycle tensile fracture test on a ntDC NB with a size of 220 nm (sample 3) and the corresponding force versus displacement curve (shown in Fig. 1a–d,f); video speed is 10 times the speed of the experiment.
Supplementary Video 2
In situ observation of the amorphization of diamond and formation of DOs at the fractured surfaces (shown in Fig. 2).
Supplementary Video 3
In situ observations of the dynamic healing process between two disconnected fracture surfaces with DO protrusions (shown in Fig. 3); video speed is 10 times the speed of the experiment.
Supplementary Video 4
Molecular dynamics simulation of the self-healing process between two fractured ends of ntDC, showing that there is no diffusion during this self-healing process (shown in Supplementary Fig. 2).
Supplementary Video 5
Molecular dynamics simulation showing the formation of DO phases during the tensile fracture test (shown in Supplementary Fig. 5).
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Qiu, K., Hou, J., Chen, S. et al. Self-healing of fractured diamond. Nat. Mater. 22, 1317–1323 (2023). https://doi.org/10.1038/s41563-023-01656-4
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DOI: https://doi.org/10.1038/s41563-023-01656-4
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