NiSi–NiCr thin film thermocouples (TFTCs) have significant application value as contact temperature sensors in cutting temperature measurements owing to their fast response and negligible volume. However, due to the relatively high chemical activity of Ni-based alloys, high-temperature oxidation strongly affects the operational reliability of NiSi–NiCr TFTCs. In this respect, depositing an anti-oxidation coating onto the surface of NiSi–NiCr TFTCs is considered an effective way to protect them in high-temperature environments. In this study, NiSi and NiCr films were deposited on cemented carbides and annealed at 200 °C–600 °C in air. Scanning electron microscope, X-ray diffraction spectroscopy, X-ray photoelectron spectroscopy, and four-probe resistivity tests were used to characterize the microstructure and resistivity of NiSi and NiCr film. Then SiNxOy films were deposited onto the NiSi and NiCr films and compared with uncoated samples after annealing at 600 °C. The effect of SiNxOy films on the thermal stability and thermoelectric output of NiSi–NiCr TFTCs was investigated. The results show that the NiSi film was partially oxidized at 200 °C and entirely oxidized when the temperature exceeded 400 °C. The completely oxidized NiSi films had evident defects and cracks, and the resistivity increased by a factor of over 1000. The NiCr film could not be completely oxidized at 600 °C, which is attributed to the formation of Cr2O3 as an external oxide barrier layer. Below 600 °C, SiNxOy films could effectively protect NiSi and NiCr films from oxidation. Thus, the addition of SiNxOy film increases the maximum temperature at which NiSi–NiCr TFTCs can be used.
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