Development of nanostructured PVD coatings for total knee replacement joints using HIPIMS.

The aim of this study was to develop thin film coatings for total knee replacement joints using high power impulse magnetron sputtering (HIPIMS). An industrial size four cathode magnetron sputtering system equipped with direct current (DC) and HIPIMS power supplies was used for this purpose. Initially, Plasma diagnostics were carried out using optical emission spectroscopy (OES) while sputtering Ti target in Ar + N2 atmosphere by utilizing various HIP IMS/conventional DCMS (henceforth UBM) source combinations by varying the process parameters such as coil current and N2 flow. Then, single layer titanium nitride (TiN) coating was deposited by varying the degree of HIPIMS utilisation and the process parameters such as bias voltage and coil current to thoroughly understand the effect of degree of HIPIMS utilisation on the microstructure, residual stress, texture, mechanical, tribological and corrosion properties of such coatings. The degree of HIPIMS utilisation was altered by increasing the number of HIPIMS targets used for the deposition. Four different source combinations were used for this purpose, as follows: 4 cathodes in conventional DCMS mode to deposit pure UBM coating, 1 HIPIMS + 3UBM and 2HIPIMS + 2UBM cathodes to deposit combined HIPIMS/UBM coatings and 2HIPIMS cathodes to deposit pure HIPIMS coatings. TiN/NbN, TiCN/NbCN and CrN/NbN multilayer coatings were deposited on CoCr alloy test buttons along with other (HSS, SS and Si) substrates since our intended application is on total knee replacement joints made of CoCr alloy. The knowledge gained by investigating the TiN (Ar + N[2]) plasma and the properties of TiN was used to determine the process parameters for depositing the multilayer coatings. X- ray diffraction (XRD) technique was used for calculating the texture, residual stress and bilayer thickness of the coatings. Nanoindentation method was used to determine the nano hardness of the coatings. The adhesion strength of the coatings was estimated by scratch and Rockwell indentation tests. Pin on disc method was used for the tribological studies such as coefficient of friction and coefficient of wear. Surface roughness measurements were carried out using a surface profiler. Microstructural characterisation of the coatings was carried out using scanning electron microscope (SEM) and transmission electron microscope (TEM). Potentiodynamic polarisation method was utilised to study the corrosion performance of the coatings. Raman spectroscopy was used to study the constituents of the corrosion products and evaluate the corrosion damage. OES measurements revealed that the degree of metal ions (Ti[1+]) increased with increasing degree of HIPIMS utilisation. The hardness, tribological and corrosion properties of TiN coatings improved with increasing degree of HIPIMS utilisation. TiN and multilayer coatings deposited by HIPIMS exhibited a smooth columnar microstructure without any voided region along the column boundaries. TiN/NbN, TiCN/NbCN and CrN/NbN multilayer coatings deposited on CoCr alloy, HSS and SS test buttons exhibited superior mechanical, tribological and corrosion properties as compared to the underlying substrate

Effect of the degree of high power impulse magnetron sputtering utilisation on the structure and properties of TiN films

TiN films were deposited using high power impulse magnetron sputtering (HIPIMS) enabled four cathode industrial size coating system equipped with HIPIMS power supplies. The standard version of this system allows control over the ion bombardment during coating growth by varying the strength of the electromagnetic field of the unbalancing coils and bias voltage applied to the substrate. The coatings were produced in different coating growth conditions achieved in combined HIPIMS — direct current (dc) unbalanced magnetron sputtering (HIPIMS/UBM) processes where HIPIMS was used as an additional tool to manipulate the ionisation degree in the plasma. Four cathode combinations were explored with increasing contribution of HIPIMS namely 4UBM (pure UBM), 1HIPIMS + 3UBM, 2HIPIMS + 2UBM and 2HIPIMS (pure HIPIMS) to deposit TiN coatings. Optical emission spectroscopy (OES) measurements were carried out to examine the plasma generated by the various combinations of HIPIMS and UBM cathodes. The micro-structural study was done by scanning electron microscopy (SEM). X-ray diffraction (XRD) technique was used to calculate the residual stress and texture parameter. It has been revealed that the residual stress can be controlled in a wide range from − 0.22 GPa to − 11.67 GPa by intelligent selection of the degree of HIPIMS utilisation, strength of the electromagnetic field of the unbalancing coils and the bias voltage applied to the substrate while maintaining the stoichiometry of the coatings. The effect of the degree of HIPIMS utilisation on the microstructure, texture and residual stress is discussed. Combining HIPIMS with dc-UBM sputtering is also seen as an effective tool for improving the productivity of the deposition process

Defect growth in multilayer chromium nitride/niobium nitride coatings produced by combined high power impulse magnetron sputtering and unbalance magnetron sputtering technique

In recent years, high power impulse magnetron sputtering (HIPIMS) has caught the attention of users due to its ability to produce dense coatings. However, microscopic studies have shown that HIPIMS deposited coatings can suffer from some surface imperfections even though the overall number of defects can be significantly lower compared to, for example, arc deposited coatings of similar thicknesses. Defects can degrade the coating performance thus any kind of defect is undesirable. To better understand the nature of these imperfections and the science of their formation, a series of Chromium Nitride/Niobium Nitride (CrN/NbN) coatings were deposited using HIPIMS technique combined with unbalanced magnetron sputtering (UBM) by varying deposition times (t = 15 to 120 minutes). All other deposition parameters were kept constant in order to deposit these coatings with a consistent deposition rate and stoichiometry. In addition, coatings were deposited using pure UBM technique to compare the defects generated by these two different physical vapour deposition approaches. High-resolution scanning electron microscopy images revealed that HIPIMS/UBM and pure UBM CrN/NbN coatings have similar types of defects which could be categorised as: nodular, open void, cone-like and pinhole. Interestingly, there was no evidence of droplet formation in HIPIMS/UBM deposited coatings. The defect density calculation indicated that the defect density of HIPIMS/UBM coatings increased (from 0.48 to 3.18%) with the coating thickness. A coating produced in a relatively clean chamber had a lower defect density. Potentiodynamic polarisation experiments showed that the fluctuation in corrosion currents in HIPIMS/UBM coatings reduced with the coating thickness. This indicated that though visible on the surface, most of these defects did not penetrate thorough the whole thickness 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

Low pressure plasma nitrided CoCrMo alloy utilising HIPIMS discharge for biomedical applications

CoCrMo is a biomedical grade alloy which is widely used in the manufacturing of orthopaedic implants such as hip and knee replacement joints because of it has high hardness, high corrosion resistance, and excellent biocompatibility. However, the release of metal ions due to corrosion and wear of the alloy over time may cause allergic or other adverse reactions in some patients. To date, various surface modification techniques including nitriding, have been used to improve the performance of CoCrMo (F75) alloy. In the current work, a new low-pressure plasma nitriding process is described. Unlike conventional plasma nitriding, the process utilises High Power Impulse Magnetron Sputtering (HIPIMS) discharge, sustained on one Cr target at low power, to further enhance the ionisation of the gas in the vacuum chamber and to avoid coating deposition. The nitriding of CoCrMo alloy has been carried out in a wide range of nitriding voltages (from -500 V to -1100 V) at 400 °C for duration of 4 hours. The chemical and phase composition of the nitrided layer has been studied by various advanced surface analyses techniques. The X-ray diffraction data of all the nitrided samples revealed the formation of expanded austenite (γN) phase. Texture analyses revealed that at lower nitriding voltages (-700 V) the predominant crystallographic orientation of the compound layer is (200) whereas at higher voltages (-900 V to -1100 V) the layer develops mixed (111) and (200) texture. For samples nitrided at a lower bias voltage of - 500 V, diffraction peaks for CrN/NbN and Cr2N were also observed due to the deposition of target materials (Cr and Nb). However, no coating deposition on the substrate surface was observed at higher bias voltages (-700 V and higher) due to sufficient re-sputtering effect. The results obtained from glow discharge optical emission spectroscopy (GDOES) depth profiling showed that the depth of nitriding increased from approximately 0.7 µm at -500 V to 6 µm at -1100 V. In the pin-on-disc tribological test nitrided samples showed low coefficient of friction µ in the range of 0.6 to 0.7, compared to µ= 0.8 recorded for the untreated substrate. The wear coefficients (Kc) were found to be between 1.79 × 10-15 m3N -1m-1 (-700 V) and 4.62 × 10- 15 m3N -1m-1 (-1100 V), which were one order of magnitude lower than the untreated substrate, Kc = 6 ×10-14 m3N -1m-1 . The Knoop microhardness (HK) of nitrided samples significantly increased by a factor of 5 (HK= 2750 at -1100 V) as compared to the untreated substrate, HK=525, demonstrating the high efficiency of the process. The samples nitrided at -700 V and - 900 V exhibited enhanced corrosion resistance as compared to untreated alloy by avoiding the formation of CrN based compounds which adversely affect the corrosion performance