Abstract
Introduction
Titanium and its alloys are attractive biomaterials attributable to their desirable corrosion, mechanical, biocompatibility and osseointegration properties. In particular, β – titanium alloys like the TMZF possess other advantages such as its lower modulus compared to Ti6Al4V alloy. This reduces stress shielding effect in Total Hip Arthroplasty (THA) and the replacement of V in the Ti6Al4V alloy, eliminates in-vivo V-induced toxicity. Unfortunately, implants made of TMZF were later recalled by the FDA due to higher than acceptable revision rates. The purpose of this study was to compare the fretting corrosion characteristics of Ti6Al4V and TMZF titanium alloys. It is hoped the findings will inform better design of β – titanium alloys for future applications in THA.
Method
A ball-on-flat configuration was utilised in this study to achieve a Hertzian point contact for CoCrMo – Ti6Al4V and CoCrMo – TMZF material combinations. These were assessed at a fretting displacement of ±50 µm at an initial contact pressure of 1 GPa. Each fretting test lasted 6000 cycles at a frequency of 1 Hz. A two-electrode cell set-up was used to monitor in-situ open circuit potential (OCP). The simulated physiological solution consisted of Foetal Bovine Serum (FBS) diluted to 25% with Phosphate Buffered Saline (PBS) and 0.03% Sodium Azide (SA) balance. The temperature was kept at ∼37°C. Corrosion products on the worn surfaces and subsurface transformations in both alloys were characterised using the Scanning and Transmission Electron Microscopy (SEM/TEM) to obtain high resolution micrographs. The samples were prepared using a FIB-SEM. Bright-field, dark-field and selected area electron diffraction (SAED) patterns were all captured using a scanning TEM (STEM) and Energy Dispersed X-Ray spectroscopy (EDX) mapping was carried out.
Results
The results showed that fretting regime transition from partial-slip to gross slip was delayed a few hundred cycles for TMZF relative to the Ti6Al4V (Figure 1). This indicates that the lower modulus of TMZF influences the degree of elastic deformation accommodated prior to the initiation of plastic shear at the fretting interface. The OCP directly corresponded to the fretting regime for both material combinations (Figure 2). Surface and subsurface characterisation of both alloys show differences in the structure of their mechanically mixed corrosion products and metallurgical transformations. Interestingly, an amorphous Co-rich layer was seen across the TMZF surface (Figure 3) whereas, pitting corrosion products from the CoCrMo alloy was seen on the Ti6Al4V alloy.
Conclusion
In summary, the difference in the fretting behavior of Ti6Al4V and TMZF directly corresponds to the combined differences in their elastic modulus and surface chemistry. This corresponds to the differences observed in their electrochemical behavior. However, the main differences observed were the properties of their corrosion products and subsurface metallurgical transformations. These observed characteristic differences are to be considered in further examination of the cause of higher failure rates in TMZF alloys.
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