Graphene coating on the surface of CoCrMo alloy enhances the adhesion and proliferation of bone marrow mesenchymal stem cells.

The objective was to investigate whether a graphene coating could improve the surface bioactivity of a cobalt-chromium-molybdenum-based alloy (CoCrMo). Graphene was produced by chemical vapor deposition and transferred to the surface of the CoCrMo alloy using an improved wet transfer approach. The morphology of the samples was observed, and the adhesion force and stabilization of graphene coating were analyzed by a nanoscratch test and ultrasonication test. In an in vitro study, the adhesion and proliferation of bone marrow mesenchymal stem cells (BMSCs) cultured on the samples were quantified via an Alamar Blue assay and cell counting kit-8 (CCK-8) assay. The results showed that it is feasible to apply graphene to modify the surface of a CoCrMo alloy, and the enhancement of the adhesion and proliferation of BMSCs was also shown in the present study. In conclusion, graphene exhibits considerable potential for enhancing the surface bioactivity of CoCrMo alloy.

Investigation of cell-accelerated corrosion (CAC) on the CoCrMo alloy with segregation banding: Hip implant applications.

Metal alloy microstructure plays a crucial role in corrosion associated with total hip replacement (THR). THR is a prominent strategy that uses metal implants such as cobalt-chromium-molybdenum (CoCrMo) alloys due to their advantageous biological and mechanical properties. Despite all benefits, these implants undergo corrosion and wear processes in-vivo in a synergistic manner called tribocorrosion. Also, the implant retrieval findings reported that fretting corrosion occurred in-vivo, evidenced by the damage patterns that appeared on the THR junction interfaces. There is no scientific data on the studies reporting the fretting corrosion patterns of CoCrMo microstructures in the presence of specific biological treatments to date. In the current study, Flat-on-flat fretting corrosion set-up was customized and used to study the tribocorrosion patterns of fretting corrosion to understand the role of alloy microstructure. Alloy microstructural differences were created with the implant stock metal's longitudinal and transverse cutting orientations. As a result, the transverse created the non-banded, homogenous microstructure, whereas the longitudinal cut resulted in the banded, non-homogenous microstructure on the surface of the alloy (in this manuscript, the terms homogenous and banded were used). The induced currents were monitored using a three-electrode system. Three different types of electrolytes were utilized to study the fretting corrosion patterns with both homogeneous and banded microstructures: 1. Control media 2. Spent media (the macrophage cell cultured media) 3. Challenged media (media collected after the macrophage was treated with CoCrMo particles). From the electrochemical results, in the potentiostat conditions, the banded group exhibited a higher induced current in both challenged and spent electrolyte environments than in control due to the synergistic activity of CoCrMo particles and macrophage demonstrating more corrosion loss. Additionally, both Bode and Nyquist plots reported a clear difference between the banded and homogeneous microstructure, especially with challenged electrolytes becoming more corrosion-resistant post-fretting than pre-fretting results. The banded microstructure showed a unique shape of the fretting loop, which may be due to tribochemical reactions. Therefore, from the electrochemical, mechanical, and surface analysis data results, the transverse/homogenous/non-banded alloy microstructure groups show a higher resistance to fretting-corrosion damage.

Mechanical property, corrosion behavior and cytocompatibility of CoCrMo for dental application: A comparative study of cast and laser powder bed fusion.

In this work, by employing powders sourced directly from the original ingot for additive manufacturing, we enabled a comparative overview of the performance between CoCrMo manufactured via laser powder bed fusion (LPBF) and those in their original cast condition. Microstructural analysis revealed that the cast (CT) alloy predominantly consisted of coarse grains with distribution of sigma phase, while the LPBF process resulted in a refined grain structure devoid of the sigma phase. The tensile strength tests demonstrated that the LPBF-derived CoCrMo alloy had substantially greater tensile strength, and ductility compared to CT alloy. Corrosion tests indicated superior corrosion resistance in the LPBF alloy, albeit with a lower metal ion release. In vitro assays confirmed that LPBF CoCrMo alloys displayed favorable cytocompatibility. Consequently, it is concluded that the CoCrMo alloy processed through laser powder bed fusion exhibited enhanced mechanical performance and corrosion resistance. These improvements are primarily attributed to the transformation of the original coarse columnar grain structure through the LPBF technique.

Electrophoretic Deposition of Multi-Walled Carbon Nanotube Coatings on CoCrMo Alloy for Biomedical Applications.

Carbon nanotubes are a promising material for use in innovative biomedical solutions due to their unique chemical, mechanical, electrical, and magnetic properties. This work provides a method for the development of ultrasonically assisted electrophoretic deposition of multi-walled carbon nanotubes on a CoCrMo dental alloy. Functionalization of multi-walled carbon nanotubes was carried out by chemical oxidation in a mixture of nitric and sulfuric acids. The modified and unmodified multi-walled carbon nanotubes were anaphoretically deposited on the CoCrMo alloy in an aqueous solution. Chemical composition was studied by Fourier transform infrared spectroscopy. Surface morphology was examined by scanning electron microscopy. The mechanism and kinetics of the electrochemical corrosion of the obtained coatings in artificial saliva at 37 °C were determined using the open-circuit potential method, electrochemical impedance spectroscopy, and anodic polarization curves. The capacitive behavior and high corrosion resistance of the tested electrodes were revealed. It was found that the kinetics of electrochemical corrosion of the CoCrMo electrode significantly decreased in the presence of the functionalized multi-walled carbon nanotube coating. Electrophoretic deposition was shown to be an effective, low-cost, and fast method of producing nanotubes with controlled thickness, homogeneity, and packing density.

Study on Hardness of Heat-Treated CoCrMo Alloy Recycled by Electron Beam Melting.

The hardness of heat (thermally) treated CoCrMo ingots, recycled by electron beam melting and refining (EBMR) of a technogenic CoCrMo material (waste from the dental technology) under different process conditions (temperature and residence time) is examined. The heat treatment consists of two-step heating up to temperatures of 423 K and 1343 K and retention times of 40 and 60 min, respectively. The influence of various loads (0.98 N, 1.96 N, 2.94 N, 4.9 N, and 9.8 N) on the hardness of the CoCrMo alloy, recycled by EBMR, before and after heat treatment is studied. It has been found that regardless of the EBMR process conditions, the obtained samples after heat treatment have similar hardness values (between 494.2 HV and 505.9 HV) and they are significantly lower than the hardness of the specimens before the heat treatment. The highest hardness (600 HV) is measured in the alloy recycled at 1845 K refining temperature for 20 min. This is due to the smaller crystal structure of the resulting alloy and the higher cobalt content. The results obtained show that the heat treatment leads to considerable changes in the microstructure of the CoCrMo ingots recycled by EBMR. With the increase of the e-beam refining temperature, after the heat treatment, the grains' size increases and the grains' shape indicates an incomplete phase transition from γ-fcc to ε-hcp phase. This leads to a slight increase in the hardness of the alloy.

Nanoscale Surface Refinement of CoCrMo Alloy for Artificial Knee Joints via Chemical Mechanical Polishing.

In this study, we address the challenge of surface roughness in CoCrMo alloys, typically used in artificial knee joints, which can initiate a cascade of biological responses causing inflammation, osteolysis, joint instability, and increased susceptibility to infection. We propose the application of a chemical mechanical polishing (CMP) technique, using an ecologically responsible slurry composed of 4 wt% SiO2, 0.3 wt% H2O2, 1.0 wt% glycine, and 0.05 wt% benzotriazole. Our innovative approach demonstrated significant improvements, achieving a material removal rate of 30.9 nm/min and reducing the arithmetic mean roughness from 20.76 nm to 0.25 nm, thereby enhancing the nanoscale surface quality of the artificial knee joint alloy. The smoother surface is attributed to a decrease in corrosion potential to 0.18 V and a reduction in corrosion current density from 9.55 µA/cm2 to 4.49 µA/cm2 with the addition of BTA, evidenced by electrochemical tests. Furthermore, the preservation of the phase structure of the CoCrMo alloy, as confirmed by XRD analysis and elemental mapping, ensures the structural integrity of the treated surfaces. These outcomes and our simulation results demonstrate the effectiveness of our CMP method in engineering surface treatments for artificial knee joints to optimize friction behavior and potentially extend their lifespans.

Tribological behaviour of 3D printed materials for small joint implants: A pilot study.

Additive manufacturing is a progressive method in endoprosthetics enabling customisation of implants. However, the challenge is to design articulating surfaces that are wear resistant in a long term. To tackle this challenge, it is necessary to understand the interaction between the surfaces and the lubricant synovial fluid as well as the mechanism of lubrication film formation. In this study we observed three synovial fluid constituents (albumin, γ-globulin a hyaluronic acid) in the contact area simultaneously with the coefficient of friction (CoF). Two metal alloys, CoCrMo and Ti6Al4V covered by DLC, were selected for the experiments as they are both suitable for the additive technology and commonly used in implants manufacturing. The tests were running on a custom-made pin-on-plate tribometer equipped for optical fluorescence measurements. The test apparatus allowed reciprocating motion and observation of the contact area. Our results showed differences in the pace of the CoF increase between the alloys and differences between the samples manufactured by the conventional and the additive manufacturing method. Both the conventionally and additively manufactured CrCrMo samples showed a stable CoF values from the beginning of the experiments: 0.66 (SD 0.02) for the conventional manufacturing CrCrMo samples and 0.53 (SD 0.01) for the additive manufacturing CrCrMo samples. The Ti6Al4V/DLC samples showed a stable CoF values similar to those of the CoCrMo samples not until the 240 s of experiment. These results are related to the protein formation in the contact areas as suggested by a similar increasing trend of the individual synovial fluid constituents in the contact. Increasing protein amounts in the contact led to CoF increase. There were also differences in the ratios of the individual constituents, where both the CoCrMo and the Ti6Al4V/ DLC samples manufactured additionally showed lower concentrations of γ-globulin and hyaluronic acid. These pilot results, on the one hand, support the potential of the additive manufacturing in the implantology and, on the other hand, demonstrate the application of a method suitable for the analysis of the lubricant behaviour in the contact. The method is limited in using the intensity of the emitted light to observe the behaviour of the lubricant film. Future development of the method will require a direct quantification of film thickness.

Tribological and corrosion performance of the plasma-sprayed conformal ceramic coating on selective laser melted CoCrMo alloy.

Ceramic implants have superior performance due to the excellent wear resistance and biocompatibility. However, the poor machinability limits their applications. Plasma sprayed ceramic coating on the additively manufactured metal substrate not only provides a 3-dimensional conformal implant coating and but also forms a highly wear-resistant surface layer. In this paper, three types of ceramic coatings of Al2O3, ZrO2, and Al2O3-ZrO2 composite have been fabricated by atmosphere plasma spray on the CoCrMo alloy substrate prepared by selective laser melting (SLM). It has been found that the Al2O3-ZrO2 composite coating has better corrosion and wear resistance compared with the ceramic coating (Al2O3, ZrO2) and the CoCrMo substrate. The adhesion strength between the Al2O3-ZrO2 composite coating and the substrate reaches 238 MPa. In addition, the wear and corrosion resistance increase with wear progression for all the fabricated ceramic coatings. The highly dense microstructure, fewer microcracks, and the amorphous phases are deterministic factors responsible for the superior tribological and corrosion performance of the Al2O3-ZrO2 composite coating. The fabrication route has been proved very promising to manufacture high-performance implants with ceramic coating.

Physical Properties of Electropolished CoCrMo Alloy Coated with Biodegradable Polymeric Coatings Releasing Heparin after Prolonged Exposure to Artificial Urine.

In this study, we aimed to determine the effect of long-term exposure to artificial urine on the physical properties of CoCrMo alloy with biodegradable heparin-releasing polymeric coatings. Variants of polymer coatings of poly(L,L-lactide-ɛ-caprolactone) (P(L,L-L/CL)) and poly(D,L-lactide-ɛ-caprolactone) (P(D,L-L/CL)) constituting the base for heparin-releasing (HEP) polyvinyl alcohol (PVA) coatings were analyzed. The coatings were applied by the dip-coating method. Heparin was used to counteract the incrustation process in the artificial urine. The study included tests of wettability, resistance to pitting and crevice corrosion, determination of the mass density of metal ions penetrating into the artificial urine, and the kinetics of heparin release. In addition, microscopic observations of surface roughness and adhesion to the metal substrate were performed. Electrolytically polished CoCrMo samples (as a reference level) and samples with polymer coatings were used for the tests. The tests were conducted on samples in the initial state and after 30, 60, and 90 days of exposure to artificial urine. The analysis of the test results shows that the polymer coatings contribute by improving the resistance of the metal substrate to pitting and crevice corrosion in the initial state and reducing (as compared with the metal substrate) the mass density of metal ion release into the artificial urine. Moreover, the PVA + HEP coating, regardless of the base polymer coatings used, contributes to a reduction in the incrustation process in the first 30 days of exposure to the artificial urine.

Nontribological corrosion modes dominate wrought CoCrMo acetabular taper corrosion: A retrieval study.

Corrosion of modular metal-on-metal acetabular tapers in total hip arthroplasty (THA) systems is often attributed to mechanically driven processes. Recent findings suggest that mechanically assisted crevice corrosion (MACC) might not be the dominant cause of corrosion in shell-liner tapers. This study aims to document and present the corrosion modes observed in metal-metal acetabular liners. Twenty-one retrieved wrought CoCrMo liners were examined using digital optical microscopy (DOM), scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS). Corrosion-related damage was documented in nonengagement taper regions, outside of direct taper contact. Within engagement regions, nonmechanically driven corrosion features (pitting, intergranular corrosion) were observed adjacent to fretting and material transfer, which rely on mechanical contact; corrosion independent of MACC was observed even in contact regions. Corrosion types observed included intergranular corrosion (IGC), pitting attack, phase boundary dissolution, all both outside and inside of taper junctions, and MACC within contact regions of the taper. Typical fretting scars associated with MACC were mostly absent, and were not always associated with corrosion damage where present. Finally, hard phase particles (Mo-Si-O) released from the wrought CoCrMo microstructure had redeposited within regions with material loss. Acetabular taper corrosion modes differ significantly from those in head-neck tapers and are dominated by electrochemically driven processes, not mechanical processes, as indicated by corrosion in noncontact regions. With greater prevalence of dual mobility hip implants, acetabular taper corrosion processes must be understood in order to limit their impact on device performance.

In vivo effect of UV-photofunctionalization of CoCrMo in processes of guided bone regeneration and tissue engineering.

Photofunctionalization of implant materials with ultraviolet (UV) radiation have been subject of study in the last two decades, and previous research on CoCrMo discs have showed good results in terms of bioactivity and the findings of apatite-like crystals in vitro. In the current study, CoCrMo domes were photofunctionalized with UV radiation of 254 nm on their internal faces during 24 hr; they were implanted in rabbit tibia and remained for 3, 4, and 6 weeks. The potential to induce bone formation beneath the dome-shaped membranes was evaluated through morphometric, histologic, and density measurements; and the results were compared with those obtained under control untreated domes. Higher density values were observed for irradiated domes at 3 weeks, whereas higher volumes were obtained under photofunctionalized domes for longer periods (4 and 6 weeks). Histologically, woven bone was formed by endochondral ossification in all cases; differences in the architecture and size of the trabeculae and in the number of osteoblasts were noted between irradiated and non-irradiated samples. The UV radiation of 254 nm generated a larger bone volume fraction compared to that found in the absence of UVC radiation and induced an increase of density in the early stages of healing, leading to a better initial bone quality and improved osseointegration.

Improving fretting corrosion resistance of CoCrMo alloy with TiSiN and ZrN coatings for orthopedic applications.

Total hip replacement is the most effective treatment for late stage osteoarthritis. However, adverse local tissue reactions (ALTRs) have been observed in patients with modular total hip implants. Although the detailed mechanisms of ALTRs are still unknown, fretting corrosion and the associated metal ion release from the CoCrMo femoral head at the modular junction has been reported to be a major factor. The purpose of this study is to increase the fretting corrosion resistance of the CoCrMo alloy and the associated metal ion release by applying hard coatings to the surface. Cathodic arc evaporation technique (arc-PVD) was used to deposit TiSiN and ZrN hard coatings on CoCrMo substrates. The morphology, chemical composition, crystal structures and residual stress of the coatings were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffractometry. Hardness, elastic modulus, and adhesion of the coatings were measured by nano-indentation, nano-scratch test, and the Rockwell C test. Fretting corrosion resistance tests of coated and uncoated CoCrMo discs against Ti6Al4V spheres were conducted on a four-station fretting testing machine in simulated body fluid at 1Hz for 1 million cycles. Post-fretting samples were analyzed for morphological changes, volume loss and metal ion release. Our analyses showed better surface finish and lower residual stress for ZrN coating, but higher hardness and better scratch resistance for TiSiN coating. Fretting results demonstrated substantial improvement in fretting corrosion resistance of CoCrMo with both coatings. ZrN and TiSiN decreased fretting volume loss by more than 10 times and 1000 times, respectively. Both coatings showed close to 90% decrease of Co ion release during fretting corrosion tests. Our results suggest that hard coating deposition on CoCrMo alloy can significantly improve its fretting corrosion resistance and could thus potentially alleviate ALTRs in metal hip implants.

Effect of surface mechanical attrition treatment on the microstructure of cobalt-chromium-molybdenum biomedical alloy.

This research work describes the impact of the surface mechanical attrition treatment (SMAT) on the microstructure of cobalt-chromium-molybdenum (CoCrMo), a biomedical alloy commonly used for orthopedic applications. This surface treatment induces crystalline phases transformations characterized by X-ray diffraction (XRD) and selected area electron diffraction (SAED). The corresponding structural changes are observed from cross-section images obtained by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that the SMAT process induces the martensitic transformation of the CoCrMo alloy (from γ-fcc phase to ε-hcp phase) related to an important grain refinement due to twinning and sliding.

Cobalt Chromium Molybdenum Surface Modifications Alter the Osteogenic Differentiation Potential of Human Mesenchymal Stem Cells.

Surface roughness on orthopedic implant materials has been shown to be highly influential on the behavior of osteogenic cells. Mesenchymal stem and progenitor cells (MSPCs) migrate to the interface, adhere, proliferate, and differentiate into osteoblasts, which subsequently form bone matrix. Modifications of the implant surfaces should accelerate this process and improve biocompatibility. In this study, five surface topographies on cobalt chromium molybdenum (CoCrMo) were engineered to examine the influence on MSPCs. Scanning electron microscopy revealed significant differences in the morphology of untreated CoCrMo discs in comparison with CoCrMo with a titanium nitride (TiN) coating, polished and porous coated CoCrMo surfaces, and CoCrMo with a pure titanium (cpTi) coating. Elemental analysis was performed using energy-dispersive X-ray spectroscopy (EDX). Human primary MSPCs were expanded from tissue samples of spongiosa bone and characterized according to the criteria of the International Society for Cellular Therapy. The characteristic phenotype of MSPC was confirmed by flow cytometry and multilineage differentiation. Alcaline phosphatase and osteopontin expression increased significantly in all groups about 5-fold and 10-fold, respectively, in comparison to the undifferentiated controls. The porous coated surface showed a reduced expression of osteogenic markers. Due to the osteogenic differentiation, the expression of integrin α5ß1, which is particularly important for cell-material contact, increased 4-7-fold. In the dynamic process of bone biology, MSPCs cultured and differentiated on cpTi, showed significant upregulation of IL6 and leptin.

An assessment of biomedical CoCrMo alloy fabricated by direct metal laser sintering technique for implant applications.

CoCrMo alloys have been used for several decades in implantable devices due to their favourable mechanical properties, low wear rate in addition to good biocompatibility and high corrosion resistance. These alloys are conventionally produced via casting and/or forging route, however additive manufacturing techniques being recently employed in their fabrication. In this work, CoCrMo samples were produced by direct metal laser sintering additive manufacturing process. The microstructure and surface composition were examined employing scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy (XPS). The corrosion resistance was measured in 0.14 M sodium chloride solution and in phosphate buffered solution (PBS) both with and without addition of albumin at pH 7.4 and 37 °C. For this, potentiodynamic tests in addition to electrochemical impedance spectroscopy were employed. The studied CoCrMo alloy exhibits a good corrosion resistance in solutions tested being the highest in PBS solution without albumin addition. The XPS analysis showed that the passive film composition and its thickness are not modified by the adsorbed layer. Microstructural analysis revealed occurrence of strain-induced martensitic transformation.

Fretting corrosion of Si3 N4 vs CoCrMo femoral heads on Ti-6Al-V trunnions.

Fretting corrosion at the head-neck taper junction was compared between silicon nitride (Si3 N4 ) and commercially available cobalt chrome (CoCrMo) femoral heads on titanium (Ti-6Al-4V) trunnions. An electrochemical setup was used to capture the fretting currents (characterized by oxide abrasion and repassivation) during cyclic loading. Onset load, pull-off force (disassembly load), short term and long term (1 million cycles) fretting currents were used to compare the fretting corrosion performance between the test group (Si3 N4 /Ti-6Al-4V) and the control group (CoCrMo/Ti-6Al-4V). Incremental cyclic fretting corrosion tests showed that the Si3 N4 /Ti-6Al-4V combination had statistically lower (P < .05) average fretting current of 0.189 µA (SD = 0.114 µA) compared to 0.685 µA (SD = 0.630 µA) for CoCrMo/Ti-6Al-4V for cyclic load of 3200 N. Similarly, for the one million cycle fretting corrosion tests, the Si3 N4 /Ti-6Al-4V couples had statistically lower (P < .05) average current (0.048 µA, SD = 0.025 µA) vs CoCrMo/Ti-6Al-4V couples (0.366 µA, SD = 0.143 µA). The Si3 N4 heads also had higher onset loads (P < .05) for fretting (vs CoCrMo, 2200 N vs 1740 N) indicating a difference in surface contact mechanics between the two groups. Scanning electron microscopy with energy dispersive spectroscopy confirmed material transfer from the trunnions to the heads for both groups tested, and from head to trunnion for the CoCrMo heads. Minimal Si3 N4 transfer was noted. The electrochemical, mechanical, and microscopic inspection data supported the hypothesis that Si3 N4 /Ti-6Al-4Vcombination had better fretting corrosion performance compared to CoCrMo/Ti-6Al-4V.

Investigation of CoCrMo material loss in a novel bio-tribometer designed to study direct cell reaction to wear and corrosion products.

Wear and corrosion in total hip replacement negatively impact implant service-life and patient well-being. The aim of this study was to generate a statistical response surface of material loss using an apparatus, capable of testing the effect of wear and corrosion products in situ on cells, such as macrophages. The test chamber of a ball-on-flat tribometer operating inside a CO2 incubator was integrated with an electrochemical setup and adapted for cell culture work. A 20-test series, following a 2-level 3-factor design of experiments, was performed with a ceramic head in reciprocating rotational motion against a CoCrMo-alloy disc, under constant load. The lubricant was cell culture medium (RPMI-1640+10vol% bovine serum). Response surfaces were generated, which statistically showed the influence of motion amplitude, load, and potential on the total mass loss and wear scar volume of the metallic discs. Potential had the highest impact on the total mass loss, while motion amplitude and load significantly influenced the wear scar volume. The concentrations of the alloy elements found in the lubricants reflected the bulk-alloy stoichiometry. The total concentration of Co released into the lubricant (2.3-63 ppm by total mass loss, 1.5 to 62 ppm by ICP-MS) corresponded well with the known range to trigger cell response. Tribocorrosion tests in the presence of cells and tissues, such as macrophages, lymphocytes and/or synovium, will be carried out in the future.

Damping and mechanical behavior of metal-ceramic composites applied to novel dental restorative systems.

Conversely to natural teeth, where periodontal ligament (PDL) and pulp works as a damper reducing the effect of the stress on surrounding structures, when natural teeth is lost and replaced or restored the biting forces are directly transmitted to the bone or affect the integrity of the adjacent bottom layers. In this study, damping capacity and dynamic Young's modulus of CoCrMo-porcelain composites for dental restorations were evaluated. Dynamic Young's modulus and damping capacity of materials were assessed by dynamic mechanical analyzes (DMA) at 1 and 10 Hz frequencies, over a temperature ranging (18-60 °C). Results show that by reinforcing dental porcelain with metallic particles, producing ceramic matrix composites (CMCs) with 20 vol% and 40 vol% of metallic particles, the damping capacity and dynamic Young's modulus are improved. A decrease on both properties of the metal matrix composites (MMCs) with increasing ceramic particles content (from 20 vol% to 40 vol% of ceramic phase) was observed for all the studied frequencies and temperatures. While damping capacity is strongly dependent on frequency, no significant difference in dynamic Young's modulus was found. Results show that besides the yet reported advantages of the bio-inspired functionally graded restorations over traditional bilaminate ones, traduced by improved veneer to substrate adhesion and by the enhanced thermal and mechanical stress distribution, these restorations can also display improved behavior as regard to a damping capacity, which may have a positive impact in the long-term performance of implant - supported prosthesis.

The effect of hyaluronic acid on the corrosion of an orthopedic CoCrMo-alloy in simulated inflammatory conditions.

During joint inflammation, various reactive oxygen species (ROS) are present in the surrounding tissue and joint fluid. In the laboratory, hydrogen peroxide (H2O2) is typically used to simulate inflammatory conditions, and media containing proteins and hyaluronic acid (HA) are employed to simulate joint synovial fluid. Electrochemical interactions between H2O2 and HA in the presence of a CoCrMo surface are expected, since HA molecules contain redox-active moieties. We hypothesized that any redox reactions of these moieties with ROS will mitigate the oxidizing effect of H2O2 on the CoCrMo surface, limiting the corrosion rate of the metal. Non-destructive electrochemical measurements (open circuit potential, linear polarization resistance and electrochemical impedance spectroscopy) were used to investigate the corrosion response of CoCrMo in synovial model fluid containing physiologically relevant concentrations of albumin proteins and hyaluronic acid, with and without H2O2. Two different molarities of H2O2, 3 mM and 30 mM, were tested. While both molarities are within physiological limits, 3mM is well within the range HA could mitigate, whereas 30 mM is not. Contrary to our hypothesis, HA did not alleviate corrosion in 3 mM H2O2 and even caused a corrosion increase in the case of 30 mM H2O2. The decrease in corrosion resistance of the alloy may be attributed to the complexation of degenerated HA molecular chains with chromium ions released from the metallic surface, which are necessary to build a protective oxide film. This finding has clinical implications, suggesting that HA accelerates corrosion of CoCrMo implants in the presence of strong inflammation.

Tribocorrosion of a CoCrMo alloy sliding against articular cartilage and the impact of metal ion release on chondrocytes.

Partial knee replacement and hemiarthroplasty are some of the orthopedic procedures resulting in a metal on cartilage interface. As metal implant material, CoCrMo based alloys are commonly used. The aim of the present study is to assess the role of biotribocorrosion on the CoCrMo-cartilage interface with an emphasis on metal release during sliding contact. The biotribocorrosion experiments were performed under controlled electrochemical conditions using a floating cell with a three electrode set up coupled to a microtribometer. Throughout the experiment the coefficient of friction and the open circuit potential were monitored. Analyses of the electrolyte after the experiment show that metal release can occur during sliding contact of CoCrMo alloy against articular cartilage despite the extraordinary low coefficient of friction measured. Metal release is attributed to changes in passive layer caused at the onset of sliding. The released metal was found to be forming compounds with potential cytotoxicity. Since the presence of metal ions in the cartilage matrix can potentially lead to cell apoptosis, the metabolic activity of human osteoarthritic chondrocytes (2D-cultures) was investigated in the presence of phosphate buffered saline containing metal ions using XTT-assay. The experiments indicate that critical concentrations of Co ions lead to a significant decrease in chondrocyte metabolic activity. Therefore, biotribocorrosion is a mechanism that can occur in partial replacements and lead to chondrocyte apoptosis thus playing a role in the observed accelerated degradation of the remaining cartilage tissue after the mentioned orthopedic procedures. STATEMENT OF SIGNIFICANCE: Partial replacements provide an alternative to total joint replacements. This procedure is less invasive, allows a faster rehabilitation and provides a better function of the joint. However, the remaining native cartilage experiences accelerated degradation when in contact with metallic implant components. This work investigates the role of tribocorrosion at the metal-cartilage interface during sliding. Tribocorrosion is a degradation process that can alter significantly the wear rates experienced by metallic implants and lead to the release of metal ions and particles. The released metal can form compounds with potential cytotoxicity on cartilage tissue. The knowledge gained in this work will serve to understand the mechanisms behind the failure of partial replacements and develop future biomaterials with an enhanced lifetime.