To promote the application of Fe-based amorphous coating (AMC)-protected magnesium alloys in fretting wear conditions, a Fe-based AMC with a thickness of about 164 μm was deposited on AZ31B magnesium alloy substrate by detonation spraying. The microstructure and fretting wear behaviors against GCr15 counterpart ball in different frequencies of the Fe-based AMC were studied in detail. The results show that the Fe-based AMC has a substantially complete amorphous structure, the porosity and surface hardness are ≤1.2 vol %, and 764.7 ± 37.5 Hv0.1, respectively. Therefore, the Fe-based AMC presents excellent fretting wear resistance, and its wear rate is almost 1/10 of that of AZ31B magnesium alloy, and 1/5 of that of high-velocity oxygen-fuel sprayed 316L stainless steel coating on AZ31B magnesium alloy substrate. The fretting wear behavior of Fe-based AMC was found to be sensitive to the fretting frequency: as the frequency increases from 5 to 100 Hz, the average steady-state friction coefficient increases from 0.77 to 1.07, but the wear rate exhibits an anomalous phenomenon, decreasing from 5.26 × 10−5 mm3N−1m−1 to 3.47 × 10−5 mm3N−1m−1. The improvement in wear rate is mainly attributed to the formation of an oxygen-rich river-like friction layer on the worn surface as the transient contact temperature increases with frequency, effectively suppressing delamination wear. Additionally, the occurrence of high transient frictional temperatures at high frequencies leads to evident crystallization within the coating, accompanied by the formation of nanocrystals, oxide films, and a large area river-like friction layer consisting of debris-compacted layers, which strengthens the Fe-based AMC. Consequently, the wear mechanism changes from delamination wear and abrasive wear at low frequencies to oxidative wear and adhesive wear at high frequencies, resulting in superior fretting wear resistance of the Fe-based AMC at high frequencies.
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