Hydration-induced nano- to micro-scale self-recovery of the tooth enamel of the giant panda.

The tooth enamel of vertebrates comprises a hyper-mineralized bioceramic, but is distinguished by an exceptional durability to resist impact and wear throughout the lifetime of organisms; however, enamels exhibit a low resistance to the initiation of large-scale cracks comparable to that of geological minerals based on fracture mechanics. Here we reveal that the tooth enamel, specifically from the giant panda, is capable of developing durability through counteracting the early stage of damage by partially recovering its innate geometry and structure at nano- to micro- length-scales autonomously. Such an attribute results essentially from the unique architecture of tooth enamel, specifically the vertical alignment of nano-scale mineral fibers and micro-scale prisms within a water-responsive organic-rich matrix, and can lead to a decrease in the dimension of indent damage in enamel introduced by indentation. Hydration plays an effective role in promoting the recovery process and improving the indentation fracture toughness of enamel (by ∼73%), at a minor cost of micro-hardness (by ∼5%), as compared to the dehydrated state. The nano-scale mechanisms that are responsible for the recovery deformation, specifically the reorientation and rearrangement of mineral fragments and the inter- and intra-prismatic sliding between constituents that are closely related to the viscoelasticity of organic matrix, are examined and analyzed with respect to the structure of tooth enamel. Our study sheds new light on the strategies underlying Nature's design of durable ceramics which could be translated into man-made systems in developing high-performance ceramic materials. STATEMENT OF SIGNIFICANCE: Tooth enamel plays a critical role in the function of teeth by providing a hard surface layer to resist wear/impact throughout the lifetime of organisms; however, such enamel exhibits a remarkably low resistance to the initiation of large-scale cracks, of hundreds of micrometers or more, comparable to that of geological minerals. Here we reveal that tooth enamel, specifically that of the giant panda, is capable of partially recovering its geometry and structure to counteract the early stages of damage at nano- to micro-scale dimensions autonomously. Such an attribute results essentially from the architecture of enamel but is markedly enhanced by hydration. Our work discerns a series of mechanisms that lead to the deformation and recovery of enamel and identifies a unique source of durability in the enamel to accomplish this function. The ingenious design of tooth enamel may inspire the development of new durable ceramic materials in man-made systems.

Importance of oxygen in the metal-free catalytic growth of single-walled carbon nanotubes from SiO(x) by a vapor-solid-solid mechanism.

To understand in-depth the nature of the catalyst and the growth mechanism of single-walled carbon nanotubes (SWCNTs) on a newly developed silica catalyst, we performed this combined experimental and theoretical study. In situ transmission electron microscopy (TEM) observations revealed that the active catalyst for the SWCNT growth is solid and amorphous SiO(x) nanoparticles (NPs), suggesting a vapor-solid-solid growth mechanism. From in situ TEM and chemical vapor deposition growth experiments, we found that oxygen plays a crucial role in SWCNT growth in addition to the well-known catalyst size effect. Density functional theory calculations showed that oxygen atoms can enhance the capture of -CH(x) and consequently facilitate the growth of SWCNTs on oxygen-containing SiO(x) NPs.

Growth velocity and direct length-sorted growth of short single-walled carbon nanotubes by a metal-catalyst-free chemical vapor deposition process.

We report on the observation of a very low growth velocity of single-walled carbon nanotubes (SWNTs) and consequently the direct length-sorted growth and patterned growth of SWNTs by using a metal-catalyst-free chemical vapor deposition (CVD) process proposed recently by our group, in which SiO(2) serves as catalyst. We found that the growth velocity of the SWNTs from SiO(2) catalyst is only 8.3 nm/s, which is about 300 times slower than that of the commonly used iron group catalysts (Co as a counterpart catalyst in this study). Such a slow growth velocity renders direct length-sorted growth of SWNTs, especially for short SWNTs with hundreds of nanometers in length. By simply adjusting the growth duration, SWNTs with average lengths of 149, 342, and 483 nm were selectively obtained and SWNTs as short as approximately 20 nm in length can be grown directly. Moreover, comparative studies indicate that the SiO(2) catalyst possesses a much longer catalytic active time, showing sharp contrast with the commonly used Co catalyst which quickly loses its catalytic activity. Taking advantage of the very slow growth velocity of the SiO(2) catalyst, patterned growth of SWNT networks confined in a narrow region of <5 microm was also achieved. The short SWNTs may show intriguing physics owing to their finite length effect and are attractive for various practical applications.

Crystallographic tailoring of graphene by nonmetal SiO(x) nanoparticles.

In this communication, we demonstrate nonmetal SiO(x) nanoparticles (NPs) can tailor few-layer graphenes (FLGs) into graphene nanoribbons (GNRs) and regular pieces with smooth edges. The tailoring of graphene is realized by the movements of SiO(x) NPs along the graphene lattice in the atmosphere of H(2), and the tailored trenches exhibit high selectivity of the crystallographic orientation compared to the reported metal NPs. The low tailoring rate and the long lifetime provide great potential for accurate control of the trench length or the length of the tailored GNRs. As a result, smooth GNRs with a length of several micrometers and a width narrower than 10 nm are obtained. A catalytic hydrogenation mechanism is proposed for the tailoring of graphene by SiO(x) NPs. These findings open up the possibility for atomically precise graphene device fabrication without metal contamination and indicate the potential catalytic activity of nonmetal NPs for the hydrogenation of carbon materials.

Surface and interference coenhanced Raman scattering of graphene.

We propose a novel surface and interference coenhanced Raman scattering technique to dramatically enhance the Raman signal intensity of graphene by using a specifically designed substrate of Si capped with surface-active metal and oxide double layers (SMO). The total enhancement ratio can reach the order of 10(3) compared with the original Si substrate. Combining the visibility of graphene on the SMO substrate, we demonstrate that the tiny structure change and surface structure of graphene can be easily detected. This technique makes Raman spectroscopy a more powerful tool in the field of ultrasensitive characterization of graphene, isolated carbon nanotubes, and other film-like materials.

Synthesis of graphene sheets with high electrical conductivity and good thermal stability by hydrogen arc discharge exfoliation.

We developed a hydrogen arc discharge exfoliation method for the synthesis of graphene sheets (GSs) with excellent electrical conductivity and good thermal stability from graphite oxide (GO), in combination with solution-phase dispersion and centrifugation techniques. It was found that efficient exfoliation and considerable deoxygenation of GO, and defect elimination and healing of exfoliated graphite can be simultaneously achieved during the hydrogen arc discharge exfoliation process. The GSs obtained by hydrogen arc discharge exfoliation exhibit a high electrical conductivity of approximately 2 x 10(3) S/cm and high thermal stability with oxidization resistance temperature of 601 degrees C, which are much better than those prepared by argon arc discharge exfoliation (approximately 2 x 10(2) S/cm, 525 degrees C) and by conventional thermal exfoliation (approximately 80 S/cm, 507 degrees C) with the same starting GO. These results demonstrate that this hydrogen arc discharge exfoliation method is a good approach for the preparation of GSs with a good quality.

Metal-catalyst-free growth of single-walled carbon nanotubes.

We present a metal-catalyst-free CVD process for the high-efficiency growth of single-walled carbon nanotubes (SWNTs) on surface. By applying a 30-nm-thick SiO(2) sputtering deposited Si or Si/SiO(2) wafer as substrate and CH(4) as a carbon source, dense and uniform SWNT networks with high quality can be obtained without the presence of any metal species. Moreover, a simple patterned growth approach, using a scratched Si/SiO(2) wafer as substrate, is also presented for the growth of SWNTs with good position controllability. Our finding of the growth of SWNTs via a metal-catalyst-free process will provide valuable information for understanding the growth mechanism of SWNTs in-depth, which accordingly will facilitate the controllable synthesis and applications of carbon nanotubes.