Protein-metal interactions due to fretting corrosion at the taper junction of hip implants: An in vitro investigation using Raman spectroscopy

Modular hip implants are a clinically successful and widely used treatment for patients with arthritis. Despite ongoing retrieval studies the understanding of the fundamental physico-chemical mechanisms of friction and wear within the head-taper interface is still limited. Here, we Raman-spectroscopically analyze structural features of the biotribological material which is formed within the taper joint between Ti6Al4V and low-carbon cobalt alloy or high-nitrogen steel surfaces in in vitro gross-slip fretting corrosion tests with bovine calf serum. As a function of the fretting duration, we investigate short and long aliphatic chains and their adsorption behavior on the cobalt- and steel-type surfaces. Using the intensity and frequency shifts of the amide I and III Raman bands, we furthermore identify progressive protein folding and unfolding including the secondary structures of α-helix, β-sheet, and random-coil configuration as well as the formation of proteinaceous clusters depending on the hydrophilicity of the metallic surfaces. We additionally find a mixture of chromates and iron oxides with tryptophan and tyrosine at the worn cobalt alloy and high-nitrogen steel surfaces, respectively. Also, for long fretting duration, sp² hybridized amorphous carbon is formed due to fretting-induced cleavage of proteins. STATEMENT OF SIGNIFICANCE: Despite efforts enhancing the biomedical tribology of hip implants, the impact of the organic environment on friction and wear at the femoral head-stem taper interface is limitedly understood. Using Raman spectroscopy we resolve structural changes within the biotribological material agglomerated at biomedical-grade metal alloys due to metal-organic interactions during in vitro fretting corrosion tests. Adsorption of short and long aliphatic chains, progressive protein (un)folding and proteinaceous cluster formation depend to a distinguishable extent on the fretting duration and type of alloy. Chromates and iron oxides are mixed with tryptophan and tyrosine, and amorphous carbon is formed resulting from a fretting-induced cleavage of serum proteins. Such information spectroscopically gleaned from biotribological material are vital to improve the design and performance of taper junctions.