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The effect of boron, in the amounts of 0.26, 0.39, and 0.59 wt.%, on the volume fraction and structure of carbides in Cr white irons was examined. It was demonstrated that the addition of boron can change the microstructural characteristics of white iron containing about 13 wt.% Cr. With increasing boron content, the volume fractions of M3C carbide increase, but the volume fracton of M7C3 carbide remains unchanged. The addition of boron tends to produce hard borides and/or borocarbides. It also prevents the formation of pearlite, which results in alloys possessing good wear resistance.