A Study of the Effect of 2 at.% Sn on the Microstructure and Isothermal Oxidation at 800 and 1200 °C of Nb-24Ti-18Si-Based Alloys with Al and/or Cr Additions.

Alloying with Al, Cr, Sn, and Ti significantly improves the oxidation of Nb silicide-based alloys at intermediate and high temperatures. There is no agreement about what the concentration of Sn in the alloys should be. It has been suggested that with Sn ≤ 3 at.% the oxidation is improved and formation of the brittle A15-Nb₃Sn compound is suppressed. Definite improvements in oxidation behaviour have been observed with 5 at.% Sn or even higher concentrations, up to 8 at.% Sn. The research reported in this paper is about three model alloys with low Sn concentration and nominal compositions Nb-24Ti-18Si-5Cr-2Sn (ZX3), Nb-24Ti-18Si-5Al-2Sn (ZX5), and Nb-24Ti-18Si-5Al-5Cr-2Sn (ZX7) that were studied to understand the effect of the 2 at.% Sn addition on as-cast and heat-treated microstructures and isothermal oxidation in air at 800 and 1200 °C for 100 h. There was macrosegregation of Si and Ti in the alloys ZX3 and ZX5 and only of Si in the alloy ZX7. The Nb was stable in all alloys. Tin and Ti exhibited opposite partitioning behaviour in the Nb. The βNb₅Si₃ was the primary phase in all three cast alloys and had partially transformed to αNb₅Si₃ in the alloy ZX3. Aluminium in synergy with Sn increased the sluggishness of the βNb₅Si₃ to αNb₅Si₃ transformation during solidification. After the heat treatment the transformation of βNb₅Si₃ to αNb₅Si₃ had been completed in all three alloys. Fine precipitates were observed inside some αNb₅Si₃ grains in the alloys ZX5 and ZX7. In the latter alloys the A15-Nb₃X (X = Al, Si, and Sn) formed after the heat treatment, i.e., the synergy of Al and Sn promoted the stability of A15-Nb₃X intermetallic in these Nb-silicide-based alloys even at this low Sn concentration. A Nb + Nb₅Si₃ eutectic formed in all three alloys and there was evidence of anomalous eutectic in the parts of the alloys ZX3 and ZX7 that had solidified under high cooling rate and/or high melt undercooling. A very fine ternary Nb + Nb₅Si₃ + NbCr₂ eutectic was also observed in parts of the alloy ZX3 that had solidified under high cooling rate. At 800 °C none of the alloys suffered from catastrophic pest oxidation; ZX7 had a smaller oxidation rate constant. A thin Sn-rich layer formed continuously between the scale and Nb in the alloys ZX3 and ZX5. At 1200 °C the scales formed on all three alloys spalled off, the alloys exhibited parabolic oxidation in the early stages followed by linear oxidation; the alloy ZX5 gave the smallest rate constant values. A thicker continuous Sn-rich zone formed between the scale and substrate in all three alloys. This Sn-rich zone was noticeably thicker near the corners of the specimen of the alloy ZX7 and continuous around the whole specimen. The Nb₃Sn, Nb₅Sn₂Si, and NbSn₂ compounds were observed in the Sn-rich zone. At both temperatures the scales formed on all three alloys consisted of Nb-rich and Nb and Si-rich oxides, and Ti-rich oxide also was formed in the scales of the alloys ZX3 and ZX7 at 1200 °C. The formation of a Sn-rich layer/zone did not prevent the contamination of the bulk of the specimens by oxygen, as both Nb and Nb₅Si₃ were contaminated by oxygen, the former more severely than the latter.