In vivo corrosion on retrieved hip endoprostheses and in vitro effects of corrosion products on bone mineralization.

In vivo corrosion of modular endoprostheses remains a great concern, as the release of heavy metal ions can impair the implant's service life and the wellbeing of the patient. The detailed corrosion mechanisms that occur in vivo are so far not completely understood. In this context, the effects of implant released cobalt (Co) and chromium (Cr) ions on osteoblast mineralization and gene expression have not been investigated extensively. This comprehensive study aimed at furthering the understanding of in vivo implant corrosion from the clinical signs via prosthesis retrievals and histology of the synovial membranes down to the molecular processes instigated by corrosion products and its effects on bone mineralization. A detailed in vivo failure analysis was performed investigating 22 retrieved hip endoprostheses from different manufacturers and taper material combinations. The aim was to find a correlation of taper damage and especially corrosion to susceptible biomedical alloys and its effect on periprosthetic tissue as well as the clinical implant performance with regard to revision diagnosis and presence of radiolucent lines (RLL). A second part investigated the effects of Co and Cr ions on the in vitro mineralization process of osteoblasts. Cell cultures were exposed to relevant concentrations of CoCl2 and CrCl3 (0 µM, 100 µM, 200 µM) with and without addition of phosphate. Mineralization behavior was analyzed with Alizarin Red assay and Von Kossa staining of calcium depots, alkaline phosphatase activity of osteoblasts and gene expression was analyzed with real time quantitative PCR. The retrieval study provides evidence of in vivo fretting and crevice corrosion on all metallic tapers combined with either ceramic or metal femoral heads. Within the modular taper junctions, selective dissolution of the α phase occurred in wrought TiAl6V4 alloys, and etching of the fine-grained wrought CoCr28Mo6 alloy implants was observed in formed crevices. In addition, significant amounts of wear particles and corrosion products were detected in retrieved synovial membranes. An increased risk for the occurrence of a RLL in the proximal zones was determined for patients with a corroded mixed metal taper. Whereas Co ions have hardly any effects on mineralization, Cr ions cause a significant concentration dependent decrease in mineralization rate of osteoblasts. However, this effect is alleviated by addition of a phosphate source. Our data reveal that Cr ions depleted dissolved phosphates by forming an insoluble complex (CrPO4), which inhibits the phosphate dependent mineralization process. No significant effect of the heavy metal ions on osteoblast activity by means of alkaline phosphate activity as well as on gene expression is determined. This study broadens the understanding of in vivo corrosion of metallic modular implants and its clinically relevant effects on mineralization. Based on these findings, in vivo corrosion of CoCr28Mo6 endoprostheses should be limited to avoid inhibitory effects of Cr3+ on bone mineralization which can contribute to premature implant failure.

Surface integrity modification of CoCrMo alloy by deep rolling in combination with sub-zero cooling as potential implant application.

Alloys made of CoCrMo are well established as implants materials since decades in orthopedic surgery. The good mechanical properties, biocompatibility and especially the corrosion resistance are important rationales for the use of these alloys. Nevertheless, retrieved implants from revision surgery showed the occurrence of abrasion and corrosion. The wear mechanisms and the occurring corrosion processes might be reduced with a functionalization of the surface. The hexagonal phase of the cobalt chromium matrix plays an important role in the surface functionalization. It can be specifically transformed and set during the manufacturing process. One possibility for the induction of the transformation is the use of a deep rolling process in combination with a novel "sub-zero" cooling strategy during machining. The influence of force and temperature during the deep rolling process on the formation of the hexagonal Co-phase is examined in this study. The results from the targeted setting of the hexagonal Co-phase in the subsurface are shown. For this purpose, EBSD studies have been carried out to detect and quantify the proportion of Co-hex phase in the subsurface of the modified alloys. To analyze the mechanical properties, we measured the residual stress and hardness in the near surface layer under conditions close to the application. Furthermore, we performed biological tests to show a potential influence of the modification on the biocompatibility when using the sub-zero cooling approach. We observed no negative effect on the osteoblastic cell line which attached similarly to all tested surfaces. The investigations provide first insights into the potential use of "sub-zero" cooling in modifying orthopedic implant materials, but also the respective limits with regard to the surface functionalization. Deep rolling in combination with an innovative cooling strategy has a great potential to improve the mechanical properties of CoCr28Mo6 wrought alloy, by subsurface hardening and phase transformation.

Microstructural Modification of TiAl6V4 Alloy to Avoid Detrimental Effects Due to Selective In Vivo Crevice Corrosion.

TiAl6V4 wrought alloy is a standard material used for endoprostheses due to its ideal characteristics in terms of osseointegration. However, the insufficient wear and crevice corrosion resistance of TiAl6V4 are limiting factors that can cause clinical problems. Therefore, the objective of this study was to analyze and identify suitable phases and microstructural states of TiAl6V4 alloy with advantageous implant properties by thermal treatments. By varying the temperature and cooling rate, four heat treatment strategies were derived that produced different microstructural states that differed in morphology, arrangement and proportions of phases present. All TiAl6V4 modifications were characterized regarding their microstructure, mechanical, corrosive and tribological properties, as well as cell adhesion. The acicular, martensitic microstructure achieves a significant hardness increase by up to 63% and exhibits improved corrosion and wear resistance compared to the forged condition. Whereas the modified microstructures showed similar electrochemical properties in polarization tests using different electrolytes (PBS with H2O2 and HCl additives), selective α or ß phase dissolution occurred under severe inflammatory crevice conditions after four weeks of exposure at 37 °C. The microstructurally selective corrosion processes resemble the damage patterns of retrieved Ti-based implants and provide a better understanding of clinically relevant in vivo crevice corrosion mechanisms. Furthermore, a microstructural effect on cell attachment was determined and is correlated to the size of the vanadium-rich ß phase. These key findings highlight the relevance of an adapted processing of TiAl6V4 alloy to increase the longevity of implants.

Microstructure-dependent crevice corrosion damage of implant materials CoCr28Mo6, TiAl6V4 and REX 734 under severe inflammatory conditions.

Fretting corrosion is associated with increased risk of premature implant failure. In this complex in vivo corrosion system, the contribution of static crevice corrosion of the joined metal alloys is still unknown. The aim of this study was to develop a methodology for testing crevice corrosion behavior that simulates the physiological conditions of modular taper junctions and to identify critical factors on corrosion susceptibility. Samples of medical grade CoCr28Mo6 cast and wrought alloy, TiAl6V4 wrought alloy and REX 734 stainless steel were prepared metallographically and the microstructure was investigated using scanning electron microscopy (SEM). Crevice formers that mimic typical geometries of taper junctions were developed. Crevice corrosion immersion tests were performed in different physiological fluids (bovine serum or phosphate buffered saline with additives of 30 mM H2 O2 at pH = 1) for 4 weeks at 37°C. SEM with energy dispersive X-ray spectroscopy as well as focused ion beam were used to characterize the surface morphology, investigate present damages and identify the chemical composition of residues. Macroscopic inspection showed increased crevice corrosion susceptibility of TiAl6V4 and REX 734 under severe simulated inflammatory conditions. CoCr28Mo6 cast alloy exhibited degraded areas next to Cr- and Mo-rich precipitations that were located within the opposed crevices. The results indicate that aggressive electrolyte composition and crevice heights of 50-500 µm are critical influencing factors on crevice corrosion of biomedical alloys. Furthermore, manufacturing-related microstructure of common implant alloys determines the deterioration of corrosion resistance. The developed method should be used to enhance the corrosion resistance of common implant biomaterials by an adapted microstructure.

Effect of deep rolling on subsurface conditions of CoCr28Mo6 wrought alloy to improve the wear resistance of endoprostheses.

Wear of orthopaedic endoprostheses is associated with adverse local and systemic reactions and can lead to early implant failure. Manufacturing determines the initial subsurface microstructure of an alloy that influences the implant's wear behaviour. Therefore, this study aims at generating enhanced wear resistances by a modification of the surface and subsurface microstructure of a CoCr28Mo6 wrought alloy by applying deep rolling. The state of the art was investigated by means of eleven retrieved CoCr28Mo6 hip implant components from different manufacturers with respect to their subsurface microstructure and micro hardness profiles. CoCr28Mo6 wrought alloy samples (DIN EN ISO 5832-12) were aged at 750 °C for 24 h and/or plastically deformed by deep rolling with varying axial forces (170 N, 230 N and 250 N). The samples were metallographically prepared and investigated using optical and scanning electron microscopy with EDS and EBSD, micro hardness testing, XRD and tribological testing. The retrieved implant components revealed that, independent of the manufacturer, neither the head nor the stem trunnion exhibited a defined subsurface condition. The dominant phase within the implants was face-centered cubic (fcc). Some implants exhibited single hexagonal close-packed (hcp) grains due to a stress-induced phase transformation. The initial CoCr28Mo6 wrought alloy had a fcc crystal structure. After isothermal aging, the matrix entirely transformed to a hcp structure. In the initial fcc-condition, deep rolling generated a plastically deformed surface layer within the first 100 µm and stress-induced phase transformation to hcp was observed. Micro hardness gradients were present in the subsurface of up to 600 µm depth and exhibited a maximum increase of 34% by deep rolling in comparison to the initial fcc-matrix. This trend was confirmed by a correlated increase in residual compressive stresses. In tribological tests under serum lubrication, the modified samples generated lower wear in comparison to the contemporarily used fcc-matrix samples. This study demonstrates that deep rolling is an effective processing to modify the subsurface of a biomedical CoCr28Mo6 wrought alloy in order to increase the wear resistance. The intentional transformation from the fcc to the hcp phase induced by deformation offers great potential for implant application.

Intraoperative assembly of anatomical shoulder prosthesis frequently results in malalignment of the modular taper junction.

Anatomical shoulder arthroplasties (ASA) may fail because of micromotion at the modular taper junction causing wear due to fretting. Sufficient taper strength can reduce micromotion and potential reasons for failure. However, there are no normative standards for a safe assembly process performed intraoperatively by the surgeon. The purpose of this study is to determine the effect of common intraoperative assembly strategies and to identify critical influencing factors on taper stability. ASA with standard and stemless humeral component in combination with concentric Al2 O3 heads and eccentric CoCr28Mo6 alloyed humeral heads were tested. Taper angles and surface roughness were determined. Force magnitudes and impact directions were recorded using a sensorized head impactor and a three-dimensional force measuring platform. Subsequently, the axial pull-off forces were measured and taper engagement areas were macroscopically evaluated. In comparison to standard stem tapers that were impacted with an assembly device, stemless tapers were impacted into the artificial bone with significantly lower forces. Taper strength correlates to maximum impact force and was higher for CoCr28Mo6 heads with a mean pull-off ratio of 0.56 than for Al2 O3 heads with 0.37. Interestingly, all tapers showed an asymmetric clamping behavior, due to tilting during impaction. This is caused by the variation of the resulting force vector and further promoted by humeral head eccentricity. Assembly technique markedly influences the force magnitude, impact direction, impulse, and consequently taper strength. The resulting force vector and head eccentricity were identified as potential risk factors for taper malalignment.

Retrieval study of commercially available knee implant coatings TiN, TiNbN and ZrN on TiAl6V4 and CoCr28Mo6.

BACKGROUND: Coated implant components for total knee arthroplasties are primarily used for metal-sensitive patients and are offered by different manufacturers. However, there is only little knowledge with respect to their coating design and supposed superior tribological performance. Our aim was to compare retrieved coated implants by identifying present damages, critical factors influencing the coating durability and their correlation to the clinical performance. MATERIALS AND METHODS: 28 retrieved knee endoprostheses from nine different manufacturers were analyzed for potential surface defects as well as the coating strategy for each manufacturer. The coating designs were investigated on preserved regions with regard to substrate and coating material, layer thickness and roughness using scanning electron microscopy and confocal microscopy. Furthermore, the mechanical properties and adhesive strength of the layer were evaluated by nanoindentation and scratch testing. The friction performance of the coatings against ultra-high molecular weight polyethylene (UHMWPE) was investigated in a tribological test. In addition, clinical data were collected and evaluated for all patients. RESULTS: Our cohort of 28 retrieved knee endoprostheses exhibited different damage patterns in the articulating area with an incidence of 79% for discoloration and 21% for coating delamination. All coatings presented droplets, macropores and pinholes in preserved areas, which can be attributed to the coating and post-polishing processes. Interestingly, the adhesive strength was significantly increased by 60.4% for titanium nitride coatings on TiAl6V4 alloy in comparison to CoCr28Mo6 substrates. The friction behavior of titanium nitride coatings against UHMWPE is similar to uncoated CoCr28Mo6 alloy and lowest for the ZrN multi-layer coating with a reduction of 14%. DISCUSSION: This study shows that manufacturing related coating deposition defects can cause wear due to adhesive failure and corrosion underneath the coating layers. Adhesive strength was identified as a critical factor for coating durability. Minor adhesive strength was present on CoCr28Mo6 cast alloy in comparison to good adhesion of Ti-based coatings on TiAl6V4 wrought alloy. Based on our findings, this is consistent to higher prevalence rates of CoCr28Mo6/TiNbN coatings for gross delamination and pitting damage with increasing implantation time.

In vivo corrosion and damages in modular shoulder prostheses.

Wear and corrosion at taper junctions of orthopaedic endoprostheses remain of great concern and are associated with adverse clinical reactions. Whereas tribocorrosion of hip tapers was extensively investigated, there is only little knowledge regarding the clinical performance of modular total shoulder prostheses. This retrieval study evaluated 35 modular taper junctions of anatomical shoulder explants using stereomicroscopy, confocal microscopy, as well as optical and scanning electron microscopy to determine the damage modes as well as the effects of taper topography and alloy microstructure. Among all humeral head tapers, 89% exhibited material degradation. Different overlapping wear mechanisms were identified such as plastic deformation, adhesive material transfer, microploughing, and fretting damage. Only CoCrMo cast alloy heads showed a susceptibility to electrochemically dominated fretting in comparison to CoCrMo wrought alloy. Moreover, corundum blasted stem tapers show a significantly increased incidence rate for microploughing. To date, this is the most comprehensive study on the damage types of modular taper junctions of anatomical shoulder arthroplasty proving the existence of fretting even on less weight-bearing implants. This study revealed critical fretting factors, such as the surface finish and the alloy type that are essential for the development of countermeasures that avoid any taper corrosion.