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The thermal deposition of hydroxyapatite (HA) on titanium alloy substrate (Ti-6Al-4V) leads to a structure that has very good osseointegration properties. However, clinical failures have been occasionally reported at the interface between substrate and coating. Lifetime is the main parameter in such prostheses; therefore, in order to improve their quality, it is necessary to evaluate the level of stresses near the interface. The high-energy synchrotron radiation combines the advantages of a bulk analysis and reduced volume of the gauge. The objective of our study was to calculate the residual stress using a nonlinear finite-element model and to measure residual stress level near the interface, in the hydroxyapatite coating and in titanium alloy substrate with a nondestructive and high-resolution experiment. The high-energy synchrotron radiation of the BM16 beam-line at ESRF (Grenoble-France) was used with a resolution of down to 10 micrometers. The experimental measurements validate the results found by means of nonlinear finite-element analysis of the plasma spraying induced stress.