Laser-based additive manufacturing is inherently associated with extreme, unprecedented, and rapid thermokinetics which impact the microstructural evolution in a built component. Such a unique, near to non-equilibrium microstructure/phase evolution in laser additively manufactured metallic components impact their properties in engineering application. In light of this, the present work investigates the unique microstructural traits as a result of process induced spatial and temporal variation in thermokinetic parameters in laser directed energy deposited CoCrMo biomedical alloy. The influence of such a unique microstructural evolution in laser directed energy deposited CoCrMo on electrochemical response in physiological media was elucidated and compared with a conventionally manufactured, commercially available CoCrMo component. Furthermore, while investigation of the electrochemical response, such a microstructural evolution in laser directed energy deposited CoCrMo led to in-situ surface modification of the built components in physiological media via selective, non-uniform electrochemical etching. Such in-situ surface modification resulted in enhanced biocompatibility in terms of mammalian cell growth, cell-substrate adhesion, blood compatibility, and antibacterial properties indicating improved osteointegration, compared to a conventionally manufactured, commercially available CoCrMo component.

Advanced alloys often present precipitated carbides and nitrides in their microstructure following exposure to elevated temperatures. These secondary phases are usually undesirable, because potentially deleterious for the corrosion and mechanical performances of the material. Carbides and nitrides are enriched in key alloying elements that are subtracted from their surrounding matrix areas, creating alloying element depleted zones, which might become initial sites for corrosion initiation. In this study, the influence of micro- and nano-sized precipitated carbides and nitrides on the corrosion initiation of biomedical CoCrMo alloys and duplex stainless steels has been investigated at microscopic scale, by using a combination of local probing techniques. The microstructures of the alloys were first characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and magnetic force microscopy (MFM). The Volta potential mapping of carbides and nitrides revealed their higher nobility compared to the matrix, and particularly compared to their surrounding areas, suggesting the occurrence of some alloying element depletion in the latter locations, which may lead to a higher susceptibility for corrosion initiation. In-situ electrochemical AFM studies performed at room temperature showed passive behavior for large potential ranges for both alloy families, despite the presence of the precipitated carbides or nitrides. At high anodic applied potential, at which transpassive dissolution occurs, preferential dissolution started from the areas adjacent to the precipitated carbides and nitrides, in accordance with the Volta potential results. Thus, the presence of carbides and nitrides doesn’t largely affect the corrosion resistance of the tested advanced alloys, which maintain passive behavior when exposed to highly concentrated chloride solutions at room temperature with no applied potential. The effect of nitrides on the corrosion initiation of duplex stainless steels was investigated also at temperatures above the critical pitting temperature (CPT). Depending on the type, distribution and size range of the precipitated nitrides different corrosion behaviors were observed. Intragranular (quenched-in) nano-sized nitrides (ca. 50-100 nm) finely dispersed in the ferrite grains have a minor influence on the corrosion resistance of the material at temperatures above the CPT, while larger intergranular (isothermal) nitrides (ca. 80-250 nm) precipitated along the phase boundaries cause a detrimental reduction of the corrosion resistance of the material, in particular of the austenite phase / <p>QC 20130927</p>

Total hip joint prostheses made of CoCrMo heads versus ultra high molecular weight polyethylene (UHMWPE) cups have a limited lifetime, mainly due to the wear of the UHMWPE cups as a result of high friction between the articulating surfaces leading to osteolysis and implant loosening with revision surgery becoming inevitable in more active patients. Tribology plays an important role in developing the design, minimizing wear and reducing friction of hip joint prostheses in order to improve their long-term performance, with good lubricating properties. Metal-on-metal hip resurfacing prostheses have shown significantly lower wear rates compared with conventional metal-on-polyethylene implants and thus osteolysis is potentially reduced leading to increased lifetime of the prosthesis. Nevertheless, excessive wear of metal-on-metal joints leads to metal ion release, causing pseudo-tumours and osteolysis. An alternative approach to such bearings is the use of newly developed carbon fiber-reinforced poly-ether-ether-ketone (CFR PEEK) acetabular cups articulating against ceramic femoral heads due to their better wear resistance compared to UHMWPE. In this study, therefore, friction and lubrication properties of large diameter, as cast, Co-Cr-Mo metal-on-metal hip resurfacing implants with various diameters and clearances have been investigated and compared to those of the newly developed zirconia toughened alumina (ZTA) ceramic femoral heads articulating against carbon fiber reinforced poly-ether-ether-ketone (CFR PEEK) acetabular cups with different diameters and clearances. Friction hip simulator was used to measure frictional torque and then friction factors were calculated along with Sommerfeld numbers leading to Stribeck analysis and hence the lubricating mode was also investigated. This involved using lubricants based on pure bovine serum (BS) and diluted bovine serum (25 vol. %BS+75 vol. %distilled water) with and without carboxymethyl cellulose (CMC) (as gelling agent). Standard Rheometer was used to measure lubricant viscosity ranged from 0.0014 to 0.236 Pas at a shear rate of 3000 . Pure bovine serum, diluted bovine serum without CMC and with CMC (25BS+75DW+0.5gCMC and +1gCMC) showed pseudoplastic flow behaviour up to shear rate of ~139 s⁻¹ above which a Newtonian flow with significant increase in shear stress was observed. The viscosity flow curves for the 25BS+75DW+2gCMC, +3.5gCMC and +5gCMC showed only shear thinning up to a shear rate of 3000 . The shear rate application modified the flow behaviour of bovine serum from a pseudoplastic to a Newtonian flow depending on its purity and CMC content. This will cause a different frictional behaviour depending on joint diameter and clearance, as seen in this work. The experimental data were compared with theoretical iv predictions of the lubricating regimes by calculating theoretical film thickness and lambda ratio. The metal-on-metal Biomet ReCaps showed similar trends of Stribeck curves, i.e. friction factors decreased from ~0.12 to ~0.05 as Sommerfeld numbers increased in the range of viscosities ~0.001-0.04Pas indicating mixed lubrication regimes above which the friction factor increased to ~0.13 at a viscosity of 0.236Pas. The Stribeck analyses suggested mixed lubrication as the dominant mode with the lowest friction factor in the range ~0.09 - ~0.05 at the physiological viscosities of ~0.01 to ~0.04 Pas and that such joints can be used for more active patients as compared to the conventional total hip replacement joints with 28mm diameter. The Stribeck curves for all ZTA ceramic-on-CFR PEEK components illustrated a similar trend with BS fluids showing higher friction factors (in the range 0.22-0.13) than the diluted BS+CMC fluids (in the range 0.24-0.05). The friction tests revealed boundary-mixed lubrication regimes for the ZTA ceramic-on-CFR-PEEK joints. The results, so far, are promising and suggest clearly that the newly developed ZTA ceramic femoral heads articulating against CFR PEEK cups have similar friction and lubrication behaviour at optimum clearances to those of currently used metal-onmetal hip resurfacing implants at the range of viscosities 0.00612 to 0.155Pas. These results clearly suggest that the ZTA ceramic-on-CFR-PEEK joints showed low friction at the physiological viscosities of ~0.01Pas in the range ~0.1-0.05, suggesting that these novel joints may be used as an alternative material choice for the reduction of osteolysis. The result of this investigation has suggested that the optimum clearance for the 52mm diameter MOM Biomet ReCaps could be ~170μm. However, 48 and 54mm joints showed lower friction due to clearances to be >200μm. For the 52mm ZTA ceramic-on-CFR-PEEK joints the optimum clearance seems to be ≥ 630μm radial clearance. These results suggested that increased clearance bearings have the potential to generate low friction and hence no risk of micro- or even macro-motion for the ceramic-on-CFR-PEEK joints. This study found no correlation between theoretical predictions and experimental data for all metal-onmetal and ZTA ceramic-on-CFR PEEK bearings at the physiological viscosity (0.0127Pas). However, at lubricant viscosity of 0.00157Pas, the theoretical prediction of lubrication regime correlated well with the experimental data, both illustrating boundary lubrication. As expected, a decrease in viscosity resulted decrease in the film thickness.

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Total hip joint prostheses made of CoCrMo heads versus ultra high molecular weight polyethylene (UHMWPE) cups have a limited lifetime, mainly due to the wear of the UHMWPE cups as a result of high friction between the articulating surfaces leading to osteolysis and implant loosening with revision surgery becoming inevitable in more active patients. Tribology plays an important role in developing the design, minimizing wear and reducing friction of hip joint prostheses in order to improve their long-term performance, with good lubricating properties. Metal-on-metal hip resurfacing prostheses have shown significantly lower wear rates compared with conventional metal-on-polyethylene implants and thus osteolysis is potentially reduced leading to increased lifetime of the prosthesis. Nevertheless, excessive wear of metal-on-metal joints leads to metal ion release, causing pseudo-tumours and osteolysis. An alternative approach to such bearings is the use of newly developed carbon fiber-reinforced poly-ether-ether-ketone (CFR PEEK) acetabular cups articulating against ceramic femoral heads due to their better wear resistance compared to UHMWPE. In this study, therefore, friction and lubrication properties of large diameter, as cast, Co-Cr-Mo metal-on-metal hip resurfacing implants with various diameters and clearances have been investigated and compared to those of the newly developed zirconia toughened alumina (ZTA) ceramic femoral heads articulating against carbon fiber reinforced poly-ether-ether-ketone (CFR PEEK) acetabular cups with different diameters and clearances. Friction hip simulator was used to measure frictional torque and then friction factors were calculated along with Sommerfeld numbers leading to Stribeck analysis and hence the lubricating mode was also investigated. This involved using lubricants based on pure bovine serum (BS) and diluted bovine serum (25 vol. %BS+75 vol. %distilled water) with and without carboxymethyl cellulose (CMC) (as gelling agent). Standard Rheometer was used to measure lubricant viscosity ranged from 0.0014 to 0.236 Pas at a shear rate of 3000 . Pure bovine serum, diluted bovine serum without CMC and with CMC (25BS+75DW+0.5gCMC and +1gCMC) showed pseudoplastic flow behaviour up to shear rate of ¿139 above which a Newtonian flow with significant increase in shear stress was observed. The viscosity flow curves for the 25BS+75DW+2gCMC, +3.5gCMC and +5gCMC showed only shear thinning up to a shear rate of 3000 . The shear rate application modified the flow behaviour of bovine serum from a pseudoplastic to a Newtonian flow depending on its purity and CMC content. This will cause a different frictional behaviour depending on joint diameter and clearance, as seen in this work. The experimental data were compared with theoretical iv predictions of the lubricating regimes by calculating theoretical film thickness and lambda ratio. The metal-on-metal Biomet ReCaps showed similar trends of Stribeck curves, i.e. friction factors decreased from ~0.12 to ~0.05 as Sommerfeld numbers increased in the range of viscosities ~0.001-0.04Pas indicating mixed lubrication regimes above which the friction factor increased to ~0.13 at a viscosity of 0.236Pas. The Stribeck analyses suggested mixed lubrication as the dominant mode with the lowest friction factor in the range ~0.09 - ~0.05 at the physiological viscosities of ~0.01 to ~0.04 Pas and that such joints can be used for more active patients as compared to the conventional total hip replacement joints with 28mm diameter. The Stribeck curves for all ZTA ceramic-on-CFR PEEK components illustrated a similar trend with BS fluids showing higher friction factors (in the range 0.22-0.13) than the diluted BS+CMC fluids (in the range 0.24-0.05). The friction tests revealed boundary-mixed lubrication regimes for the ZTA ceramic-on-CFR-PEEK joints. The results, so far, are promising and suggest clearly that the newly developed ZTA ceramic femoral heads articulating against CFR PEEK cups have similar friction and lubrication behaviour at optimum clearances to those of currently used metal-onmetal hip resurfacing implants at the range of viscosities 0.00612 to 0.155Pas. These results clearly suggest that the ZTA ceramic-on-CFR-PEEK joints showed low friction at the physiological viscosities of ~0.01Pas in the range ~0.1-0.05, suggesting that these novel joints may be used as an alternative material choice for the reduction of osteolysis. The result of this investigation has suggested that the optimum clearance for the 52mm diameter MOM Biomet ReCaps could be ~170¿m. However, 48 and 54mm joints showed lower friction due to clearances to be >200¿m. For the 52mm ZTA ceramic-on-CFR-PEEK joints the optimum clearance seems to be ¿ 630¿m radial clearance. These results suggested that increased clearance bearings have the potential to generate low friction and hence no risk of micro- or even macro-motion for the ceramic-on-CFR-PEEK joints. This study found no correlation between theoretical predictions and experimental data for all metal-onmetal and ZTA ceramic-on-CFR PEEK bearings at the physiological viscosity (0.0127Pas). However, at lubricant viscosity of 0.00157Pas, the theoretical prediction of lubrication regime correlated well with the experimental data, both illustrating boundary lubrication. As expected, a decrease in viscosity resulted decrease in the film thickness.