X-Ray Photoelectron Spectroscopy for Alloy Research: From Fundamental Principles to Advanced Applications

X ray photoelectron spectroscopy (XPS) is a key technique routinely employed for the chemical analysis of alloy surfaces, enabling precise nanoscale characterization of near surface elemental composition and chemical states. This review outlines the fundamental principles of XPS, typical data analysis workflows, and critical analytical considerations specific to alloy systems. Given the propensity for oxidation, multicomponent nature, and heterogeneous phase characteristics of alloys, standardized protocols are reviewed for sample preparation, binding energy calibration, peak fitting, quantitative analysis, and depth profiling. For conductive alloys, calibration using the Fermi edge or gold reference standards is specified, and the use of Auger parameters is highlighted to improve the reliability of chemical state identification. This article also systematically summarizes applications of XPS in corrosion protection, high temperature oxidation, surface modification, phase transformation, and failure analysis. It is emphasized that near surface chemical information must be validated in combination with bulk phase, microstructural, and electrochemical characterization to rationally establish relationships between surface chemistry and macroscopic performance. Finally, recent advances in near ambient pressure, in situ, high resolution, and intelligent XPS techniques are reviewed, providing a standardized reference and technical support for alloy research.