Nb–silicide based alloy will require some kind of coating system. Alumina forming alloys that are chemically compatible with the Nb–silicide based alloy substrate could be components of such systems. The intermetallic alloys Nb1.7Si2.4Ti2.4Al3Hf0.5 and Nb1.3Si2.4Ti2.4Al3.5Hf0.4 were studied in the cast, heat treated and isothermally oxidised conditions at 800 and 1200 °C to find out if they are alumina scale formers. The alloys were designed using the alloy design methodology NICE and were required (i) not to have stable solid solution phase in their microstructures; (ii) not to pest and (iii) to form alumina scale. Their microstructures consisted of silicides and aluminides. Both alloys satisfied (i) and (ii) and formed thin scales at 800 °C. At 1200 °C the former alloy suffered from internal oxidation and formed alumina intermixed with Ti rich oxide beneath a thick “layered” scale of mixed oxides that contained Ti and/or Al and/or Si. There was no internal oxidation in the latter alloy that formed a thin continuous well adhering α-Al2O3 scale that was able to repair itself during oxidation at 1200 °C. In both alloys there was severe macrosegregation of Si, which in Nb1.3Si2.4Ti2.4Al3.5Hf0.4 was almost double that in Nb1.7Si2.4Ti2.4Al3Hf0.5. The severe macrosegregation of Si contributed to the formation of a “layered” structure in the former alloy that was retained at 800 and 1200 °C. Both alloys met the “standard definition” of High Entropy Alloys (HEAs). Compared with the range of values of the parameters valence band (VEC), δ and Δχ of bcc solid solution plus intermetallic(s) HEAs, only the Δχ of the alloy Nb1.7Si2.4Ti2.4Al3Hf0.5 was within the range and the parameters VEC and δ of both alloys respectively were outside and within the corresponding ranges. The alloy Nb1.3Si2.4Ti2.4Al3.5Hf0.4 exhibited strong correlations between the parameters Δχ, δ and VEC, and the range of values of each parameter was wider compared with the alloy Nb1.7Si2.4Ti2.4Al3Hf0.5. There was a strong correlation only between the parameters Δχ and δ of the latter alloy that was similar to that of the former alloy.

In Nb-silicide based alloys Al, Cr, Hf, and Ti additions are crucial for achieving balance of properties. It is not known how the simultaneous addition of Hf with Al and Ti, or Hf with Al, Cr, and Ti affects macrosegregation, and how the alloying affects hardness, Young’s modulus and bulk alloy oxidation, and contamination of the solid solution Nbss and the Nb5Si3 compound by oxygen. Two alloys with nominal compositions (at.%) Nb-24Ti-18Si-5Al-5Hf (alloy NbSiTiHf-5Al) and Nb-24Ti-18Si-5Al-5Cr-5Hf (alloy NbSiTiHf-5Al-5Cr) were studied in the as-cast and heat-treated conditions and after isothermal oxidation at 800 and 1200 °C and were compared with similar alloys without Hf. In both alloys there was macrosegregation of Si and Ti, which was more severe in NbSiTiHf-5Al. Both alloys formed Nbss+βNb5Si3 eutectic. The Nbss was stable and its Al and Cr concentrations increased with increasing Ti concentration. In both conditions the βNb5Si3 was observed in the alloys NbSiTiHf-5Al and NbSiTiHf-5Al-5Cr, and the γNb5Si3 only in the alloy NbSiTiHf-5Al. In both heat-treated alloys, separate Hf-rich Nb5Si3 grains were formed. The Si and Al concentrations in Nb5Si3 respectively decreased and increased with increasing Ti concentration. Al and Cr had a stronger hardening effect in the Nbss than Al, Cr, and Hf. Al, Cr, and Ti had a stronger negative effect on the Young’s modulus of the Nbss compared with Al, Cr, Hf, and Ti. When Nb was substituted by Ti, Cr, and Hf, and Si by Al in the βNb5Si3, the Young’s modulus was reduced compared with the unalloyed silicide. At 800 °C both alloys did not exhibit catastrophic pest-oxidation after 100 h. The Nbss and Nb5Si3 were contaminated by oxygen in both alloys, the former more severely. At 1200 °C the scales spalled-off, more severely in the alloy NbSiTiHf-5Al, where substrate that was heavily contaminated by oxygen below the scale also spalled-off. In both alloys the contamination of Nb5Si3 and Nbss by oxygen was more severe compared with 800 °C, but the silicides were not contaminated by oxygen in their bulk. The Nbss was not contaminated by oxygen only in the bulk of the alloy NbSiTiHf-5Al-5Cr.

Coating system(s) will be required for Nb-silicide based alloys. Alumina forming alloys that are chemically compatible with the Nb-silicide based alloy substrate could be components of such systems. The intermetallic alloys Nb1.45Si2.7Ti2.25Al3.25Hf0.35 (MG5) and Nb1.35Si2.3Ti2.3Al3.7Hf0.35 (MG6) were studied in the cast, heat treated and isothermally oxidised conditions at 800 and 1200 °C to find out if they are αAl2O3 scale formers. A (Al/Si)alloy versus Nb/(Ti + Hf)alloy map, which can be considered to be a map for Multi-Principle Element or Complex Concentrated Nb-Ti-Si-Al-Hf alloys, and a [Nb/(Ti + Hf)]Nb5Si3 versus [Nb/(Ti + Hf)]alloy map were constructed making use of the alloy design methodology NICE and data from a previously studied alloy, and were used to select the alloys MG5 and MG6 that were expected (i) not to pest, (ii) to form αAl2O3 scale at 1200 °C, (iii) to have no solid solution, (iv) to form only hexagonal Nb5Si3 and (v) to have microstructures consisting of hexagonal Nb5Si3, Ti5Si3, Ti5Si4, TiSi silicides, and tri-aluminides and Al rich TiAl. Both alloys met the requirements (i) to (v). The alumina scale was able to self-heal at 1200 °C. Liquation in the alloy MG6 at 1200 °C was linked with the formation of a eutectic like structure and the TiAl aluminide in the cast alloy. Key to the oxidation of the alloys was the formation (i) of “composite” silicide grains in which the Nb5Si3 core was surrounded by the Ti5Si4 and TiSi silicides, and (ii) of tri-aluminides with high Al/Si ratio, particularly at 1200 °C and very low Nb/Ti ratio forming in-between the “composite” silicide grains. Both alloys met the “standard definition” of high entropy alloys (HEAs). Compared with HEAs with bcc solid solution and intermetallics, the VEC values of both the alloys were outside the range of reported values. The parameters VEC,  and  of Nb-Ti-Si-Al-Hf coating alloys and non-pesting Nb-silicide based alloys were compared and trends were established. Selection of coating alloys with possible “layered” structures was discussed and alloy compositions were proposed.

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