Dry sliding wear mechanisms of HIPIMS plasma nitrided CoCrMo alloy for medical implant applications

Unlike the state-of-the-art plasma nitriding technologies where a low ionisation glow discharge is used, nitriding of CoCrMo alloy was carried out in an industrial size vacuum coater, utilising novel high ionisation, high power impulse magnetron sputtering plasma discharge mixed with unbalanced magnetron sputtering discharge. Three different nitriding voltages were used for the nitriding process. To generate more ions, two pairs of Cr and Nb targets were also operated at low power in N2:H2 gas atmosphere. Dry sliding pin on disc tests were performed at room temperature to measure the coefficient of friction and to estimate the wear coefficient. In the case of samples nitrided at lower nitriding bias voltages such as -700 V and -900 V, the oxidative mild wear mechanism was identified as the dominant wear mechanism. For higher voltage of -1100 V, despite the formation of an oxide based tribolayer severe abrasion was identified as the predominant wear mechanism due to the operation of three body contact wear involving high hardness wear particles. Among the three nitrided samples, the sample nitrided at -900 V was identified as the best with the lowest wear coefficient of Kc = 1.11×10-15 m3N-1m-1 and Knoop microhardness of 2230 HK0.010

Microstructure and load bearing capacity of TiN/NbN superlattice coatings deposited on medical grade CoCrMo Alloy by HIPIMS

In recent years significant progress has been made in the application of various ceramic, namely MeN functional coatings to engineer the surfaces of medical implants utilising metal-on-metal (MoM) articulation. This article reports on the load bearing capacity and structural response of TiN/NbN superlattice coatings deposited on medical grade CoCrMo alloy substrate under the application of localised load and the subsequent crack formation mechanism. The coatings have been deposited by mixed High Power Impulse Magnetron Sputtering-Unbalanced Magnetron Sputtering (HIPIMS-UBM) process. In the case of TiN/NbN coating deposited on CoCrMo substrate where Ecoating/Esubstrate is as high as 1.81 indicating that the substrate does not provide the necessary load bearing support for the brittle thin film, the utilisation of the Berkovich indentation technique proved to be a potent approach to study coating material as well as structural response to applied concentrated load. FIB/SEM analyses of the indented coatings revealed that in the hard-on-soft material systems cracks will initiate due to sub-coating substrate deformation and then propagate towards the coating surface. The FIB/SEM and low magnification XTEM analysis showed that an exceptionally strong TiN/NbN coating substrate adhesion bonding was achieved due to the utilisation of the HIPIMS pre-treatment. High resolution XTEM analyses revealed for the first time that during the indentation a collective rotation and alignment of the individual layers of the superlattice stack takes place without compromising coatings integrity which is clear evidence for the exeptionally high coating fracture toughness. The high toughness of the superlattice structured TiN/NbN coatings combined with their exceptionally high adhesion on madical grade CoCrMo ranks them as a strong candidate for medical implant applications

TiN/NbN nanoscale multilayer coatings deposited by High Power Impulse Magnetron Sputtering to protect medical grade CoCrMo alloys

This study describes the performance of nanoscale multilayer TiN/NbN coatings deposited on CoCrMo medical-grade alloys by utilising novel mixed high power impulse magnetron sputtering (HIPIMS) and direct current unbalanced magnetron sputtering (UBM) technique in an industrial size vacuum coater. Scanning electron microscopy analysis showed that these coatings were extremely dense without any intercolumnar voids. The coating exhibited high hardness of 28 GPa, as well as low friction and wear coefficient of 0.7 and 1.4 × 10−14 m3·N−1·m−1, respectively, as compared to the bare material. Scratch tests revealed superior coating to substrate adhesion due to the HIPIMS etching prior to coating deposition. Energy-dispersive X-ray analysis of the wear debris generated during the impact test together with focused ion beam cross-section analysis in different locations of the impact crater revealed the coating failure mechanism and further confirmed the excellent coating to substrate bonding strength. Potentiodynamic polarisation tests in NaCl and Hank’s solutions revealed the clear passivation behaviour, several orders of magnitude lower corrosion currents, and high pitting potentials of the coating, which guarantee excellent protection to the base alloy in such aggressive environments. Inductively coupled plasma mass spectrometry analysis of Hank’s solution containing corrosion debris of the coated sample revealed that the leaching of harmful metal ions from the base material was reduced to below the detection limit of the technique, thus demonstrating the high barrier properties of the coating

Development of superlattice CrNNbN coatings for joint replacements deposited by High Power Impulse Magnetron Sputtering

The demand for reliable coating on medical implants is ever growing. In this research, enhanced performance of medical implants was achieved by a CrN/NbN coating utilising nanoscale multilayer/superlattice structure. The advantages of the novel High Power Impulse Magnetron Sputtering technology, namely its unique highly ionised plasma were exploited to deposit dense and strongly adherent coatings on Co-Cr implants. TEM analyses revealed coating superlattice structure with bi-layer thickness of 3.5 nm. CrN/NbN deposited on Co-Cr samples showed exceptionally high adhesion, critical load values of LC2= 50 N in scratch adhesion tests. Nanoindentation tests showed high hardness of 34 GPa and Young's modulus of 447 GPa. Low coefficient of friction (µ) 0.49 and coating wear coefficient (KC) = 4.94 x 10-16 m3N-1m-1 were recorded in dry sliding tests. Metal ion release studies showed a reduction in Co, Cr and Mo release at physiological and elevated temperatures, (70 oC) to almost undetectable levels (<1 ppb). Rotating beam fatigue testing showed a significant increase in fatigue strength from 349±59 MPa (uncoated) to 539±59 MPa (coated). In vitro biological testing has been performed in order to assess the safety of the coating in biological environment, cytotoxicity, genotoxicity and sensitisation testing have been performed, all showing no adverse effects. Keywords: Orthopaedic implant, High Power Impulse Magnetron Sputtering, Superlattice coating, Corrosion, Biocompatibility

Real-time monitoring of plasma synthesis of functional materials by high power impulse magnetron sputtering and other PVD processes: towards a physics-constrained digital twin

Plasma synthesis of thin films by physical vapour deposition (PVD) enables the creation of materials that drive significant innovations in modern life. High value manufacturing demand for tighter quality control and better resource utilisation can be met by a digital twin capable of modelling the deposition process in real time. Optical emission spectroscopy (OES) was combined with process parameters to monitor all stages of both High Power Impulse Magnetron Sputtering (HIPIMS) and conventional magnetron sputtering processes to provide a robust method of determining process repeatability and a reliable means of process control for quality assurance purposes. Strategies and physics-based models for the in-situ real-time monitoring of coating thickness, composition, crystallographic and morphological development for a CrAlYN/CrN nanoscale multilayer film were developed. Equivalents to the ion-to-neutral ratio and metal-to-nitrogen ratios at the substrates were derived from readily available parameters including the optical emission intensities of Cr I, N2 (C-B) and Ar I lines in combination with the plasma diffusivity coefficient obtained from the ratio of substrate and cathode current densities. These optically-derived equivalent parameters identified the deposition flux conditions which trigger the switch of dominant crystallographic texture from (111) to (220) observed in XRD pole figures and the development of coating morphology from faceted to dense for a range of magnetron magnetic field configurations. OES-based strategies were developed to monitor the progress of chamber evacuation, substrate cleaning and preventative chamber wall cleaning to support process optimisation and equipment utilisation. The work paves the way to implementation of machine learning protocols for monitoring and control of these and other processing activities, including coatings development and the use of alternative deposition techniques. The work provides essential elements for the creation of a digital twin of the PVD process to both monitor and predict process outcomes such as film thickness, texture and morphology in real time