Polycrystalline Diamond Coating on Orthopaedic Implants: Realization, and Role of Surface Topology and Chemistry in Adsorption of Proteins and Cell Proliferation

Polycrystalline diamond has the potential to improve the osseointegration of orthopaedic implants compared to conventional osteo-implant materials such as titanium. However, despite the excellent biocompatibility and superior mechanical properties, the major challenge of using diamond for implants such as those used for hip arthroplasty is the limitations of microwave plasma chemical vapor deposition (CVD) techniques to synthesize diamond on complex-shaped objects. Here, for the first time we demonstrate diamond growth on titanium acetabular shells using surface wave plasma CVD method. Polycrystalline diamond coatings were synthesized at low temperatures (~400 °C) on three types of acetabular shells with different surface structure and porosity. We achieved diamond growth on highly porous surfaces designed to mimic the structure of the trabecular bone and improve osseointegration. Biocompatibility was investigated on nanocrystalline diamond (NCD) and ultrananocrystalline diamond (UNCD) coatings terminated either with hydrogen or oxygen. To understand the role of diamond surface topology and chemistry in attachment and proliferation of mammalian cells we investigated adsorption of extracellular matrix (ECM) proteins, and monitored metabolic activity of fibroblasts, osteoblasts, and bone marrow-derived mesenchymal stem cells (MSCs). The interaction of bovine serum albumin (BSA) and Type I collagen with diamond surface was investigated by confocal fluorescence lifetime imaging microscopy (FLIM). We found that proliferation of MSCs was better on hydrogen terminated UNCD than on oxygen terminated counterpart. These findings corelate to the behaviour of collagen on diamond substrates observed by FLIM. Hydrogen terminated UNCD provides better adhesion and proliferation for MSCs, compared to titanium, while growth of fibroblasts is poorest on hydrogen terminated NCD and osteoblasts behave similarly on all tested surfaces. These results open new opportunities for application of diamond coatings on orthopaedic implants.

Reducing Threading Dislocations of Single-Crystal Diamond via In Situ Tungsten Incorporation

A lower dislocation density substrate is essential for realizing high performance in single-crystal diamond electronic devices. The in-situ tungsten-incorporated homoepitaxial diamond by introducing tungsten hexacarbonyl has been proposed. A 3 × 3 × 0.5 mm3 high-pressure, high-temperature (001) diamond substrate was cut into four pieces with controlled experiments. The deposition of tungsten-incorporated diamond changed the atomic arrangement of the original diamond defects so that the propagation of internal dislocations could be inhibited. The SEM images showed that the etching pits density was significantly decreased from 2.8 × 105 cm−2 to 2.5 × 103 cm−2. The reduction of XRD and Raman spectroscopy FWHM proved that the double-layer tungsten-incorporated diamond has a significant effect on improving the crystal quality of diamond bulk. These results show the evident impact of in situ tungsten-incorporated growth on improving crystal quality and inhibiting the dislocations propagation of homoepitaxial diamond, which is of importance for high-quality diamond growth.

Synergistic effect of titanium, boron and oxygen on large-size single-crystal diamond growth at high pressure and high temperature

In this study, the synergistic impact of boron, oxygen and titanium on growing large single-crystal diamonds was studied using different concentrations of B2O3 in a solvent-carbon system under 5.5-5.7 GPa and 1300-1500 ℃. The study found that it was difficult for boron atoms to enter the crystal when boron and oxygen impurities were doped using B2O3 without the addition of Ti. However, a high boron content was achieved in the doped diamonds that were synthesised with the addition of Ti. Additionally, boron-oxygen complexes were found on the surface of the crystal, and oxygen-related impurities appeared in the crystal interior when Ti added in the FeNi-C system. The results showed that the introduction of Ti in the synthesis cavity could effectively control the amount of boron and oxygen in the crystal. This not only has important scientific significance for understanding the synergistic influence of boron, oxygen and titanium on the growth of diamond in the earth, but also for the preparation of high-concentration boron or oxygen containing semiconductor diamond technologies.

Experimental Modeling of Ankerite–Pyrite Interaction under Lithospheric Mantle P–T Parameters: Implications for Graphite Formation as a Result of Ankerite Sulfidation

Experimental modeling of ankerite–pyrite interaction was carried out on a multi-anvil high-pressure apparatus of a “split sphere” type (6.3 GPa, 1050–1550 °C, 20–60 h). At T ≤ 1250 °C, the formation of pyrrhotite, dolomite, magnesite, and metastable graphite was established. At higher temperatures, the generation of two immiscible melts (carbonate and sulfide ones), as well as graphite crystallization and diamond growth on seeds, occurred. It was established that the decrease in iron concentration in ankerite occurs by extraction of iron by sulfide and leads to the formation of pyrrhotite or sulfide melt, with corresponding ankerite breakdown into dolomite and magnesite. Further redox interaction of Ca,Mg,Fe carbonates with pyrrhotite (or between carbonate and sulfide melts) results in the carbonate reduction to C0 and metastable graphite formation (±diamond growth on seeds). It was established that the ankerite–pyrite interaction, which can occur in a downgoing slab, involves ankerite sulfidation that triggers further graphite-forming redox reactions and can be one of the scenarios of the elemental carbon formation under subduction settings.

Coherent interfaces with mixed hybridization govern direct transformation from graphite to diamond

Understanding the direct transformation from graphite to diamond has been a long-standing challenge with great scientific and practical importance. Previously proposed transformation mechanisms1-3, based on traditional experimental observations that lacked atomistic resolution, cannot account for the complex nanostructures occurring at graphite-diamond interfaces during the transformation4,5. Here, we report the identification of coherent graphite-diamond interfaces constituted with four structural motifs in partially transformed graphite samples recovered from static compression, using high-angle annular dark-field scanning transmission electron microscope. These observations provide vital insight into possible pathways of the transformation. Theoretical calculations confirm that transformation through these coherent interfaces is energetically favored to those through other paths previously proposed1-3. The graphite-to-diamond transformation is governed by the formation of nanoscale coherent interfaces (diamond nucleation), which, under static compression, advance to consume the remaining graphite (diamond growth). These results also shed light on transformation mechanisms of other carbon materials and boron nitride under different synthetic conditions.