High‐Temperature Chemistry and Oxidation of ZrB ₂ Ceramics Containing SiC, Si ₃ N ₄ , Ta ₅ Si ₃ , and TaSi ₂

Abstract

The effect of Si 3 N 4 , Ta 5 Si 3 , and TaSi 2 additions on the oxidation behavior of ZrB 2 was characterized at 1200°–1500°C and compared with both ZrB 2 and ZrB 2 /SiC. Significantly improved oxidation resistance of all Si‐containing compositions relative to ZrB 2 was a result of the formation of a protective layer of borosilicate glass during exposure to the oxidizing environment. Oxidation resistance of the Si 3 N 4 ‐modified ceramics increased with increasing Si 3 N 4 content and was further improved by the addition of Cr and Ta diborides. Chromium and tantalum oxides induced phase separation in the borosilicate glass, which lead to an increase in liquidus temperature and viscosity and to a decrease in oxygen diffusivity and of boria evaporation from the glass. All tantalum silicide‐containing compositions demonstrated phase separation in the borosilicate glass and higher oxidation resistance than pure ZrB 2 , with the effect increasing with temperature. The most oxidation‐resistant ceramics contained 15 vol% Ta 5 Si 3 , 30 vol% TaSi 2 , 35 vol% Si 3 N 4 , or 20 vol% Si 3 N 4 with 10 mol% CrB 2 . These materials exceeded the oxidation resistance of the ZrB 2 /SiC ceramics below 1300°–1400°C. However, the ZrB 2 /SiC ceramics showed slightly superior oxidation resistance at 1500°C.