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.

A metastable brominated nanodiamond surface enables room temperature and catalysis-free amine chemistry

Bromination of high-pressure high-temperature (HPHT) nanodiamond (ND) surfaces has not been explored and can open new avenues for increased chemical reactivity and diamond lattice covalent bond formation. The large bond dissociation energy of the diamond lattice-oxygen bond is a challenge that prevents new bonds from forming and most researchers simply use oxygen-terminated ND (alcohols and acids) as a reactive species. In this work, we transformed a tertiary alcohol-rich ND surface to an amine surface with 50% surface coverage and was limited by the initial rate of bromination. We observed that alkyl-bromide moieties are highly labile on NDs and are metastable as previously found using density functional theory. The instability of the bromine terminated ND is explained by steric hindrance and poor surface energy stabilization. The strong leaving group properties of the alkyl-bromide intermediate were found to form diamond-nitrogen bonds at room temperature and without catalysts. The chemical lability of the brominated ND surface led to efficient amination with NH3•THF at 298 K, and a catalyst-free Sonogashira-type reaction with an alkyne-amine produced an 11-fold increase in amination rate. Overlapping spectroscopies under inert, temperature-dependent and open-air conditions provided unambiguous chemical assignments. Amine-terminated NDs and folic acid were conjugated using sulfo-NHS/EDC coupling reagents to form amide bonds, confirming that standard amine chemistry remains viable. This work supports that a robust pathway exists to activate a chemically inert diamond surface at room temperature, which broadens the pathways of bond formation when a reactive alkyl-bromide surface is prepared. The unique surface properties of brominated and aminated nanodiamond reported here are impactful to researchers who wish to chemically tune diamond for quantum sensing applications or as an electron source for chemical transformations.

Nanometers-Thick Ferromagnetic Surface Produced by Laser Cutting of Diamond

In this work, we demonstrate that cutting diamond crystals with a laser (532 nm wavelength, 0.5 mJ energy, 200 ns pulse duration at 15 kHz) produces a ≲20nm thick surface layer with magnetic order at room temperature. We have measured the magnetic moment with a SQUID magnetometer of six natural and six CVD diamond crystals of different size, nitrogen content and surface orientations. A robust ferromagnetic response at 300 K is observed only for crystals that were cut with the laser along the (100) surface orientation. The magnetic signals are much weaker for the (110) and negligible for the (111) orientations. We attribute the magnetic order to the disordered graphite layer produced by the laser at the diamond surface. The ferromagnetic signal vanished after chemical etching or after moderate temperature annealing. The obtained results indicate that laser treatment of diamond may pave the way to create ferromagnetic spots at its surface.

Self-consistent modeling of microwave activated N2/CH4/H2 (and N2/H2) plasmas relevant to diamond chemical vapour deposition

The growth rate of diamond by chemical vapour deposition (CVD) from microwave (MW) plasma activated CH4/H2 gas mixtures can be significantly enhanced by adding trace quantities of N2 to the process gas mixture. Reasons for this increase remain unclear. The present article reports new, self-consistent two-dimensional modelling of MW activated N2/H2 and N2/CH4/H2 plasmas operating at pressures and powers relevant to contemporary diamond CVD, the results of which are compared and tensioned against available experimental data. The enhanced N/C/H plasma chemical modelling reveals the very limited reactivity of N2 under typical processing conditions and the dominance of N atoms amongst the dilute ‘soup’ of potentially reactive N-containing species incident on the growing diamond surface. Ways in which these various N-containing species may enhance growth rates are also discussed.

Selection of recycled water electrochemical conditioning parameters for preparation of diamond-bearing kimberlite for froth separation

The main reason of decreasing diamond recovery through froth separation is their surface hydrophilization by hypergene minerals and technogenic films, crystallized from the supersaturated aqueous phase, fixed on the surface structurally or by adhesion. Various types of physical actions, including thermal and ultrasonic treatment of the initial feed of froth separation, are recommended to increase the diamond-bearing kimberlite beneficiation process performance, providing cleaning of the surface of diamonds due to destruction of their accretions with rock minerals and removal of film hydrophilizing coatings from the surface of diamond crystals. A sample of kimberlite material with a given content of diamonds of 1.5–2 mm in size was used as a subject of research in the process of froth separation. The results of thermodynamic calculations and experimental research have substantiated the necessity of using electrochemical conditioning of recycled water for increasing the efficiency of diamond surface cleaning in froth separation operation when using the process of thermal treatment of initial ore feed. The use of diaphragmless electrochemical conditioning of recycled water increases the efficiency of thermochemical dissolution of hydrophilizing compounds on the surface of diamonds through reducing the concentration of calcium and carbonate ions as well as through shifting the medium pH to 6.1–6.5. The measurements of the limiting wetting angle showed that the maximum effect of increasing the diamond surface hydrophobicity was achieved when heat and electrochemical treatment were used together. Laboratory studies showed the possibility of increasing flotation diamond extraction from 65.7 to 91.4 % through application of electrochemical conditioning of recycled water. The optimum parameters of diaphragmless electrochemical treatment of recycled water of the froth separation cycle in conditions of application of pulp heat treatment: current density of 175–200 A/m2 and power consumption of 1.2–1.5 kWh/m3. Tests carried out at processing plant No. 3 of the Mirny GOK (Mining and Processing Complex) (Mirny, Yakutiya) showed that the application of the developed froth separation process intensification method with the use of thermal treatment of pulp and electrochemical diaphragmless treatment of recycled water allowed increasing the recovery of diamonds of +0.5–2 mm size by 4.9–5.1 %.

Mixed sp2–sp3 Nanocarbon Materials: A Status Quo Review

Carbon nanomaterials with a different character of the chemical bond—graphene (sp2) and nanodiamond (sp3)—are the building bricks for a new class of all-carbon hybrid nanomaterials, where the two different carbon networks with sp3 and sp2 hybridization coexist, interacting and even transforming into one another. The extraordinary physiochemical properties defined by the unique electronic band structure of the two border nanoallotropes ensure the immense application potential and versatility of these all-carbon nanomaterials. The review summarizes the status quo of sp2 – sp3 nanomaterials, including graphene/graphene-oxide—nanodiamond composites and hybrids, graphene/graphene-oxide—diamond heterojunctions, and other sp2–sp3 nanocarbon hybrids for sensing, electronic, and other emergent applications. Novel sp2–sp3 transitional nanocarbon phases and architectures are also discussed. Furthermore, the two-way sp2 (graphene) to sp3 (diamond surface and nanodiamond) transformations at the nanoscale, essential for innovative fabrication, and stability and chemical reactivity assessment are discussed based on extensive theoretical, computational and experimental studies.

Spectral tuning of diamond photonic crystal slabs by deposition of a thin layer with silicon vacancy centers

The controlled extraction of light from diamond optical color centers is essential for their practical prospective applications as single photon sources in quantum communications and as biomedical sensors in biosensing. Photonic crystal (PhC) structures can be employed to enhance the collection efficiency from these centers by directing the extracted light towards the detector. However, PhCs must be fabricated with nanoscale precision, which is extremely challenging to achieve for current materials and nanostructuring technologies. Imperfections inherently lead to spectral mismatch of the extraction (leaky) modes with color center emission lines. Here, we demonstrate a new and simple two-step method for fabricating diamond PhC slabs with leaky modes overlapping the emission line of the silicon vacancy (SiV) centers. In the first step, the PhC structure with leaky modes blue shifted from the SiV emission line is fabricated in a nanocrystalline diamond without SiV centers. A thin layer of SiV-rich diamond is then deposited over the PhC slab so that the spectral position of the PhC leaky modes is adjusted to the emission line of the SiV centers, thereby avoiding the need for nanoscale precision of the structuring method. An intensity enhancement of the zero-phonon line of the SiV centers by a factor of nine is achieved. The color centers in the thin surface layer are beneficial for sensing applications and their properties can also be further controlled by the diamond surface chemistry. The demonstrated PhC tuning method can also be easily adapted to other optical centers and photonic structures of different types in diamond and other materials.

Highly Conductive Nanocrystalline Diamond Films and Electronic Metallization Scheme

By using a methane and hydrogen process gas mixture in an appropriate hot-filament CVD process without further dopant, high electrical conductivity of over 100 S/cm has been achieved in nanocrystalline diamond films deposited on silicon single-crystalline substrates. Furthermore, it was found that an oxygen reactive-ion etching process (O-RIE) can improve the diamond film surface’s electron affinity, thus reducing the specific contact resistance. The reduction of the specific contact resistance by a factor of up to 16 was realized by the oxygen ion etching process, down to 6×10−6 Ωcm2 We provide a qualitative explanation for the mechanism behind the contact resistance reduction in terms of the electron affinity of the diamond surface. With the aid of XPS, AFM, and surface wetting measurements, we confirmed that a higher surface electron affinity is responsible for the lower specific contact resistance of the oxygen-terminated nanocrystalline diamond films.

Hydrogen-Terminated Diamond Surface as a Gas Sensor: A Comparative Study of Its Sensitivities

A nanocrystalline diamond (NCD) layer is used as an active (sensing) part of a conductivity gas sensor. The properties of the sensor with an NCD with H-termination (response and time characteristic of resistance change) are measured by the same equipment with a similar setup and compared with commercial sensors, a conductivity sensor with a metal oxide (MOX) active material (resistance change), and an infrared pyroelectric sensor (output voltage change) in this study. The deposited layer structure is characterized and analyzed by Scanning Electron Microscopy (SEM) and Raman spectroscopy. Electrical properties (resistance change for conductivity sensors and output voltage change for the IR pyroelectric sensor) are examined for two types of gases, oxidizing (NO2) and reducing (NH3). The parameters of the tested sensors are compared and critically evaluated. Subsequently, differences in the gas sensing principles of these conductivity sensors, namely H-terminated NCD and SnO2, are described.