Investigation of nano-sized debris released from CoCrMo secondary interfaces in total hip replacements: Digestion of the flakes.

The in vivo release of wear debris and corrosion products from the metallic interfaces of total hip replacements is associated with a wide spectrum of adverse body reactions and systemic manifestations. The origin of debris and the electrochemical conditions at the sites of material loss both play a role in determining the physicochemical characteristics of the particles, and thus influence their in vivo reactivity. Debris retrieved from revised CoCrMo tapers and cement-stem interfaces consists of heterogeneous flakes that comprise mechanically mixed metal particles, corrosion products and organic material. Detailed investigation of the size and composition of the metal debris contained within these composites requires the digestion of the flakes to release the small metal particles. Here, we compare alkaline and enzymatic digestion methods that both aim to fragment the flakes and reveal their smallest building blocks. The characterization of debris cleaned with both methods revealed crystalline Cr oxide nanoparticles and clusters. Comparison between the treatments showed that the alkaline method is more efficient in fragmenting the flakes and provided cleaner and generally smaller nanoparticles than exhibited in debris released with the enzymatic treatment. The provision of cleaner nanoparticles from the alkaline method also allows the physicochemical properties of the particles to be more clearly identified. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 107B: 424-434, 2019.

Structure and corrosion resistance of Co-Cr-Mo alloy used in Birmingham Hip Resurfacing system.

PURPOSE: The endoprostheses made of cobalt-chromium-molybdenum (Co-Cr-Mo) alloys belong to the group of the most popular metallic implants used for reconstruction of hip joints. For such biomaterials, the primary goal is a correct and long-term functioning in the aggressive environment of body fluids. Therefore, the purpose of this study was to examine both the morphology and the corrosion resistance of implants made of the cobalt alloy used in Birmingham Hip Resurfacing (BHR) system (Smith & Nephew). For comparative purposes, the electrochemical studies were done for the nitrided stainless steel - Orthinox. METHODS: Observations of the microstructure of the material under investigation were performed by means of the optical metallographic microscope and the scanning electron microscope. Furthermore, Energy Dispersive X-ray Spectroscopy was used to analyse the chemical composition of the endoprosthesis. Characterisation and evaluation of electrochemical corrosion resistance of the selected alloys were performed by potentiodynamic polarisation tests. RESULTS: The structural studies confirmed that Co-Cr-Mo (BHR system) is characterised by a typical dendritic microstructure with carbide precipitates, mainly M23C6, within the interdendritic areas. The results of the polarisation measurements showed that the cobalt alloy investigated exhibits lower corrosion potential than Orthinox in the utilised environments (3% NaCl, simulated body fluid - Hank's Body Fluid). CONCLUSIONS: However, the high passivation ability of the Co-Cr-Mo alloy, as well as its resistance to the initiation and propagation of localised corrosion processes, indicate that this material is significantly more appropriate for long-term implants.

The predictive power of surface profile parameters on the amount of wear measured in vitro on metal-on-polyethylene artificial hip joints.

Various studies report a weak correlation between the average surface roughness R(a) of metallic ballheads and the observed wear rate of the polyethylene cups coupled to them. The aim of this study is to verify, with controlled in vitro experiments, whether other parameters such as the total roughness R(t), and the skewness R(sk) are better predictors of the polyethylene wear when the metallic heads present a surface conditioning that varies substantially from specimen to specimen, as is usually the case with retrieved specimens. Twelve CoCrMo (cobalt-chromium-molybdenum) ballheads were intentionally damaged in order to reproduce a wide spectrum of surface conditioning and were then subjected to the standard wear test against polyethylene cups, using a hip joint wear simulator. After 2 x 10(6) cycles the weight lost by the cups was assessed with a gravimetric procedure, and the surface roughness of the metallic ballheads was qualified in terms of R(a), R(t), and R(sk). The various parameters were correlated to the weight loss using a linear regression analysis. The skewness R(sk) showed a coefficient linear regression R2 = 0.80, while the average roughness R(a), used in most previous studies, presented an R2 = 0.56. It was concluded that when specimens with substantially different surface conditioning are compared, as in retrievals analysis, it is also important to report the skewness R(sk) so that qualify the surface roughness of the specimens can be qualified.

'Severe' wear challenge to 'as-cast' and 'double heat-treated' large-diameter metal-on-metal hip bearings.

The wear generation of double-heat-treated and as-cast large-diameter metal-on-metal (MOM) hip bearings was investigated using standard- and 'severe'-gait simulations. The test hypothesis was that double heat treatment would change MOM hip wear compared with the as-cast condition. Two groups of high-carbon MOM bearings of 40 mm diameter were manufactured and subjected to either hot isostatic pressing (HIP) and solution annealing (SA) or no heat treatment (as cast). The results showed no statistical difference between the two groups under both running-in and steady state conditions. Even under the most 'severe'-gait simulation published to date, the mean volumetric wear rates were 2.9 and 3.9 mm3 per 10(6) cycles for the HIP-SA and as-cast bearings respectively, showing a ten-fold increase in wear compared with walking. These differences were not statistically different; therefore our hypothesis was negated. Changes in alloy microstructure do not appear to influence the wear behaviour of high-carbon cast MOM articulations with similar chemical compositions. This is in sharp contrast with the published significance of bearing diameter and radial clearance on the wear of MOM hip bearings.

The effect of microstructure on the wear of cobalt-based alloys used in metal-on-metal hip implants.

The influence of microstructure on the wear of cobalt-based alloys used in metal-on-metal hip implants was investigated in a boundary lubrication regime designed to represent the conditions that occurred some of the time in vivo. These cobalt-chromium-molybdenum alloys were either wrought, with a total carbon content of 0.05 or 0.23 wt %, cast with a solution-annealing procedure or simply as-cast but not solution annealed. Bars of these different alloy grades were subjected to various heat treatments to develop different microstructures. The wear was evaluated in a linear-tracking reciprocating pin-on-plate apparatus with a 25 per cent bovine serum lubricant. The wear was found to be strongly affected by the dissolved carbon content of the alloys and mostly independent of grain size or the carbide characteristics. The increased carbon in solid solution caused reductions in volumetric wear because carbon helped to stabilize a face-centred cubic crystal structure, thus limiting the amount of strain-induced transformation to a hexagonal close-packed crystal structure. Based on the observed surface twining in and around the contact zone and the potentially detrimental effect of the hexagonal close-packed phase, it was postulated that the wear of cobalt-based alloys in the present study was controlled by a deformation mechanism.

Understanding the role of corrosion in the degradation of metal-on-metal implants.

In metal-on-metal joints the primary concerns in terms of long-term durability relate to corrosion, wear, and their joint (tribocorrosion) effects. The release of ions through corrosion processes and nanoscale debris from wear processes can seriously affect joint integrity and can lead to an adverse biological reaction by the host. In this paper an integrated study of corrosion-wear interactions in serum, Dulbecco's Modified Eagle's Medium and 0.3 per cent NaCl has demonstrated that the biological nature of the fluid affects the total degradation rate and also the level of wear-corrosion interactions. The specific action of proteins in corrosion and tribocorrosion for high-carbon Co-Cr-Mo and low-carbon Co-Cr-Mo alloys is discussed.

Wear particles from metal-on-metal total hip replacements: effects of implant design and implantation time.

Detailed characterization of wear particles is necessary to understand better the implant wear mechanisms and the periprosthetic tissue response. The purposes of the present study were to compare particle characteristics of current with older designs of metal-on-metal (MM) total hip replacements (THRs), and to determine the effect of implantation time on wear particle characteristics. Metal wear particles isolated from periprosthetic tissues from 19 patients with MM THRs of current and older designs and at different implantation times (very short, longer, and very long) were studied using transmission electron microscopy and energy dispersive X-ray analysis. The particles from the current design implants with implantation times of not more than 15 months (very short-term) were almost exclusively round to oval chromium oxide particles. In all other cases, although the predominance was still round to oval chromium oxide particles, greater proportions of cobalt-chromium-molybdenum (Co-Cr-Mo) particles, mainly needle-shaped, were detected. Very long-term THRs implanted for more than 20 years had the highest percentage of needle-shaped Co-Cr-Mo particles. Particle lengths were not markedly different between the different designs and implantation times except for the current design implants of not more than 15 months, which had a significantly smaller mean length of 39 nm. In conclusion, the implant design did not seem to have a significant influence on particle characteristics whereas the implantation time appeared to have the most effect on the particles. It should be noted that, because of the limited number of tissue retrievals available, some uncertainty remains regarding the generality of these findings.

Investigation on stick phenomena in metal-on-metal hip joints after resting periods.

Insufficient understanding of tribological behaviour in total joint arthroplasty is considered as one of the reasons for prosthesis failure. Contrary to the continuous motion input profiles of hip simulators, human locomotion contains motion interruptions. These occurring resting periods can cause stick phenomena in metal-on-metal hip joints. The aim of the present study was to investigate the tribological sensitivity of all-metal bearings to motion interruptions on in vitro test specimens and retrieved implants. Friction and wear with and without resting periods were quantified. Unlike the metal-on-polyethylene joints, the static friction of metal-on-metal joints increased up to micros = 0.3 with rest, while wear appeared to be unaffected. This effect is caused by the interlocking of firmly adhered carbon layers, which were generated from the protein-containing lubricant through tribochemical reactions. Since more than 80 per cent of the retrieved implants exhibited macroscopically visible carbon layers, the increase in friction presumably also occurs under physiological conditions, which is then transferred to the bone-implant interface. These recurrent tangential stress peaks should be considered for the design features of the cup-bone interface, in particular when larger-sized implant heads are used.

Head replacement, head rotation, and surface damage effects on metal-on-metal total hip replacements: a hip simulator study.

The possibility of replacing the femoral head alone, in either solid or articular surface replacement form, during revision operations on metal-on-metal total hip replacements remains an attractive feature of such implants. In the present investigation, laboratory simulator studies of the influence upon volumetric wear of inserting a new femoral head, of introducing some head rotation, and of damaging the femoral head by scratches have all been explored. New and rotated heads both involve an additional running-in period, but the experimental studies show that the volumetric wear associated with this process is less than the initial running-in wear. The beneficial effects upon volumetric wear of small clearances have been confirmed, while the processing of high-carbon Co-Cr-Mo materials appears to be much less influential. Scratches did not affect wear as much as head replacement or head rotation, but the ongoing wear rates were somewhat higher.

Metal-on-metal hip simulator study of increased wear particle surface area due to 'severe' patient activity.

This study investigated changes in metal-on-metal (MOM) hip wear and wear particle characteristics arising from a more aggressive patient activity level compared with normal walking. The test hypothesis was that 'severe'-gait conditions will change wear, wear particle sizes, and morphology owing to a decline in joint lubrication. Four carbon MOM hip bearings 40 mm high were subjected to normal-walking and fast-jogging simulations in an orbital hip joint simulator with 25 per cent alpha-calf serum as a lubricant. Co-Cr-Mo wear particles were extracted using an enzymatic method, and prolate ellipsoid equations were used to estimate particle volume and surface area. Fast-jogging simulations generated a sevenfold increase in volumetric wear, a 33 per cent increase in mean wear particle size, and a threefold increase in the number of larger (needle) particles compared with walking. This resulted in a twentyfold increase in total wear particle surface area per 10(6) cycles compared with walking, thereby confirming our hypothesis. The clinical significance of this result suggests that highly active MOM patients may exhibit greater ion release than less active patients.

Control of surface morphology of carbide coating on Co-Cr-Mo implant alloy.

Wear of materials used in artificial joints is a common failure mode of artificial joints. A low wear rate for implants is believed to be critical for extending implant service time. We developed a carbide-coated Co-Cr-Mo implant alloy created in plasma of methane and hydrogen mixed gas by a microwave plasma-assisted surface reaction. The carbide-coated Co-Cr-Mo has a unique "brain coral-like" surface morphology and is much harder than uncoated Co-Cr-Mo. The effect of plasma processing time and temperature on the surface morphology of the top carbide layer was studied toward optimizing the surface coating. The ratios of average roughness, Ra, core roughness, Rk, and summation of core roughness, reduced peak height (Rpk) and reduced valley depth (Rvk), Rk+Rpk+Rvk, for the 6-h/985 degrees C coating to those for the 0.5-h/985 degrees C coating were 1.9, 1.7, and 1.9, respectively. The ratios of Ra, Rk, and Rk+Rpk+Rvk for the 4-h/1000 degrees C coating to those for the 4-h/939 degrees C coating were 2.3, 2.3, and 2.0, respectively. With the proper combination of plasma processing time and temperature, it may be possible to change the thickness of the peak-valley top cluster by fourfold from approximately 0.6 microm to approximately 2.5 microm. Finally, the growth mechanism of the carbide layers on Co-Cr-Mo was discussed in the context of atomic composition analysis.

Microstructure and corrosion behaviour in biological environments of the new forged low-Ni Co-Cr-Mo alloys.

Corrosion behaviour and microstructure of developed low-Ni Co-29Cr-(6, 8)Mo (mass%) alloys and a conventional Co-29Cr-6Mo-1Ni alloy (ASTM F75-92) were investigated in saline solution (saline), Hanks' solution (Hanks), and cell culture medium (E-MEM + FBS). The forging ratios of the Co-29Cr-6Mo alloy were 50% and 88% and that of the Co-29Cr-8Mo alloy was 88%. Ni content in the air-formed surface oxide film of the low-Ni alloys was under the detection limit of XPS. The passive current densities of the low-Ni alloys were of the same order of magnitude as that of the ASTM alloy in all the solutions. The passive current densities of all the alloys did not significantly change with the inorganic ions and the biomolecules. The anodic current densities in the secondary passive region of the low-Ni alloys were lower than that of the ASTM alloy in the E-MEM + FBS. Consequently, the low-Ni alloys are expected to show as high corrosion resistance as the ASTM alloy. On the other hand, the passive current density of the Co-29Cr-6Mo alloy with a forging ratio of 50% was slightly lower than that with a forging ratio of 88% in the saline. The refining of grains by further forging causes the increase in the passive current density of the low-Ni alloy.

Electrochemical corrosion and metal ion release from Co-Cr-Mo prosthesis with titanium plasma spray coating.

The corrosion behavior of CoCrMo implants with rough titanium coatings, applied by different suppliers by either sintering or vacuum plasma spraying, has been evaluated and compared with uncoated material. The open-circuit potential, corrosion current and polarization resistance were determined by electrochemical techniques. The Co, Cr and Ti ions released from the samples into the electrolyte during a potentiostatic extraction technique were analyzed using ICP-MS. The Ti coatings from the different suppliers showed a different porous morphology, and the implants exhibited a distinct corrosion activity, underlining the importance of the coating process parameters. Among the titanium coated samples, the one with the sintered overcoat turned out to be the most resistant. Yet, on an absolute scale, they all showed a corrosion resistance inferior to that of uncoated CoCrMo or wrought titanium.

Comparison of metal release from various metallic biomaterials in vitro.

To investigate the metal release of each base and alloying elements in vitro, SUS316L stainless steel, Co-Cr-Mo casting alloy, commercially pure Ti grade 2, and Ti-6Al-4V, V-free Ti-6Al-7Nb and Ti-15Zr-4Nb-4Ta alloys were immersed in various solutions, namely, alpha-medium, PBS(-), calf serum, 0.9% NaCl, artificial saliva, 1.2 mass% L-cysteine, 1 mass% lactic acid and 0.01 mass% HCl for 7d. The difference in the quantity of Co released from the Co-Cr-Mo casting alloy was relatively small in all the solutions. The quantities of Ti released into alpha-medium, PBS(-), calf serum, 0.9% NaCl and artificial saliva were much lower than those released into 1.2% L-cysteine, 1% lactic acid and 0.01% HCl. The quantity of Fe released from SUS316L stainless steel decreased linearly with increasing pH. On the other hand, the quantity of Ti released from Ti materials increased with decreasing pH, and it markedly attenuated at pHs of approximately 4 and higher. The quantity of Ni released from stainless steel gradually decreased with increasing pH. The quantities of Al released from the Ti-6Al-4V and Ti-6Al-7Nb alloys gradually decreased with increasing pH. A small V release was observed in calf serum, PBS(-), artificial saliva, 1% lactic acid, 1.2% l-cysteine and 0.01% HCl. The quantity of Ti released from the Ti-15Zr-4Nb-4Ta alloy was smaller than those released from the Ti-6Al-4V and Ti-6Al-7Nb alloys in all the solutions. In particular, it was approximately 30% or smaller in 1% lactic acid, 1.2% L-cysteine and 0.01% HCl. The quantity of (Zr + Nb + Ta) released was also considerably lower than that of (Al + Nb) or (Al + V) released. Therefore, the Ti-15Zr-4Nb-4Ta alloy with its low metal release in vitro is considered advantageous for long-term implants.

Estudo comparativo entre as ligas DURACROM MS e "Vitálio Cirúrgico" com vistas à utilizaçäo em implantes / Comparative study between DURACOM MS and \"Chromium-Cobalt\" alloys as implant materials

O objetivo desta pesquisa foi testar comparativamente o DURACROM MS (Simonetti, 1981) e o "Vitálio Cirúrgico" (liga de Cr-Co) como possíveis materiais para prótese interna. Os corpos-de-prova foram implantados no tecido perióstico de 28 ratos Wistar, sendo 14 com cada uma das ligas. Os animais foram sacrificados nos tempos experimentais de 1, 3, 7, 14, 21, 28 e 90 dias. Ambas as ligas apresentaram resultados histológicos semelhantes, com presença de cápsula conjuntiva fibrosa aos 90 dias, näo interferindo com o mecanismo de cicatrizaçäo e com o processo de remodelaçäo do tecido ósseo da calota craniana, servindo como material para implante

The corrosion resistance of a new cobalt-chromium-molybdenum-ceramic alloy.

Cobalt-chromium alloys are extensively used for removable partial dentures and implants. Recently, this type of alloy has been introduced for porcelain-fused-to-metal crown and bridgework. The objective of this in vitro study was to evaluate the corrosion behaviour of such a ceramic alloy (Vicomp) and compare it to a cobalt-chromium alloy for removable partial dentures (Vitallium). A 0.9% saline solution and an artificial saliva were used as electrolytes. Results indicate a similar, adequate, corrosion resistance.

Organic surface film contamination of Vitallium implants.

Conventional finishing and polishing techniques used to prepare Vitallium subperiosteal dental implant castings were found to produce low energy surfaces as measured by critical surface tension. Standard metallographic preparation gave slightly higher values. Glow discharge cleaning of both types of polished surface gave much higher critical surface tension values. This suggests the presence of an organic film after surface polishing of the implant which may later affect tissue reaction, in particular attachment, as has been noticed in related animal studies.

Surface investigations of oxide layers on cobalt-chromium-alloyed orthopedic implants using ESCA technique.

The uppermost monolayers of a metal implant are far more important for the corrosion resistance than the alloy itself. Using electron spectroscopy for chemical analysis (ESCA) technique these oxide layers on Vitallium specimens were investigated regarding thickness, elemental composition, and valence state of the elements. The oxide layers on metal implants are not very strong, as they can be easily damaged mechanically. According to environmental conditions, oxide layers of different elemental composition can be grown on the same specimen.