The research presented in this paper aspired to understand how the simultaneous addition of Ge and Sn in an Hf-free Nb-silicide-based alloy affected its oxidation resistance. Results are presented for the Nb-24Ti-18Si-5Al-5Cr-5Ge-5Sn alloy (at.%) which was studied in the as-cast and heat-treated (1400 °C/100 h) conditions and after isothermal oxidation in air at 800 and 1200 °C. There was macrosegregation in the cast alloy, in which the Nbss formed at a low volume fraction and was not stable after heat treatment at 1400 °C. The βNb5Si3, A15-Nb3Sn, and C14-NbCr2 were stable phases. The alloy did not undergo pest oxidation at 800 °C, and there was no spallation of its scale at 1200 °C. There was enrichment in Ge and Sn in the substrate below the scale/substrate interface, where the compounds Nb3Sn, Nb5Sn2Si, (Ti,Nb)6Sn5, and Nb5Ge3 were formed. After the oxidation at 1200 °C, the solid solution in the bulk of the alloy was very Ti-rich (Ti,Nb)ss. Improvement of oxidation resistance at both temperatures was accompanied by a decrease and increase, respectively, of the alloy parameters VEC (valence electron concentration) and δ, in agreement with the alloy design methodology NICE (Niobium Intermetallic Composite Elaboration). The elimination of scale spallation at 1200 °C was attributed (a) to the formation of Ti-rich (Ti,Nb)ss solid solution and (Ti,Nb)6Sn5, respectively, in the bulk and below the scale, (b) to the low concentration of Cr in the scale, (c) to the absence of GeO2 in the scale, (d) to the formation of αAl2O3 in the scale, and (e) to the presence (i) of Nb5Ge3 below the scale/substrate interface and (ii) of oxides in the scale, namely, SiO2, Al2O3, TiO2, and SnO2, and Ti2Nb10O29,TiNb2O7, and AlNbO4, respectively, with a range of intrinsic thermal shock resistances and coefficient of thermal expansion (CTE) values that reduced stresses in the scale and the substrate below it.
An Nb-silicide based alloy will require some kind of coating system. Alumina and/or SiO2 forming alloys that are chemically compatible with the substrate could be components of such systems. In this work, the microstructures, and isothermal oxidation at 800 °C and 1200 °C of the alloys (at.%) Si-23Fe-15Cr-15Ti-1Nb (OHC1) and Si-25Nb-5Al-5Cr-5Ti (OHC5) were studied. The cast microstructures consisted of the (TM)6Si5, FeSi2Ti and (Fe,Cr)Si (OHC1), and the (Nb,Ti)(Si,Al)2, (Nb,Cr,Ti)6Si5, (Cr,Ti,Nb)(Si,Al)2 (Si)ss and (Al)ss (OHC5) phases. The same compounds were present in OHC1 at 1200 °C and the (Nb,Ti)(Si,Al)2 and (Nb,Cr,Ti)6Si5 in OHC5 at 1400 °C. In OHC1 the (TM)6Si5 was the primary phase, and the FeSi and FeSi2Ti formed a binary eutectic. In OHC5 the (Nb,Ti)(Si,Al)2 was the primary phase. At 800 °C both alloys did not pest. The scale of OHC1 was composed of SiO2, TiO2 and (Cr,Fe)2O3. The OHC5 formed a very thin and adherent scale composed of Al2O3, SiO2 and (Ti(1−x−y),Crx,Nby)O2. The scale on (Cr,Ti,Nb)(Si,Al)2 had an outer layer of SiO2 and Al2O3 and an inner layer of Al2O3. The scale on the (Nb,Cr,Ti)6Si5 was thin, and consisted of (Ti(1−x−y),Crx,Nby)O2 and SiO2 and some Al2O3 near the edges. In (Nb,Ti)(Si,Al)2 the critical Al concentration for the formation of Al2O3 scale was 3 at.%. For Al < 3 at.% there was internal oxidation. At 1200 °C the scale of OHC1 was composed of a SiO2 inner layer and outer layers of Cr2O3 and TiO2, and there was internal oxidation. It is most likely that a eutectic reaction had occurred in the scale. The scale of OHC5 was α-Al2O3. Both alloys exhibited good correlations with alumina forming Nb-Ti-Si-Al-Hf alloys and with non-pesting and oxidation resistant B containing Nb-silicide based alloys in maps of the parameters δ, Δχ and VEC.
Nb-silicide based alloys are new ultra-high temperature materials that could replace Ni-based superalloys. Environmentally resistant coating system (s) with αAl2O3 or SiO2 forming bond coat alloys that are chemically compatible with the Nb-silicide based alloy substrates are needed. This paper makes a contribution to the search for non-pesting bond coat alloys. The microstructure and isothermal oxidation at 800 °C of the silicide-based alloy Si-22Fe-12Cr-12Al-10Ti-5Nb (OHC2) were studied. The cast alloy exhibited macrosegregation of all elements. The microstructures in the cast alloy and after the heat treatment at 800 °C consisted of the same phases, namely TM6Si5, TM5Si3 (TM = transition metal), FeSi2Ti, Fe3Al2Si3, (Fe,Cr)(Si,Al), and an unknown phase of dark contrast. The latter two phases were not stable at 950 °C, where the TMSi2 was formed. There was evidence of endothermic reaction(s) below 1200 °C and liquation at 1200 °C. The alloy followed parabolic oxidation kinetics after the first hour of isothermal oxidation at 800 °C, did not pest, and formed a self-healing scale, in which the dominant oxide was Al2O3. The alloy was compared with other alumina or silica scale-forming intermetallic alloys and approaches to the design of bond coat alloys were suggested.
Nb-silicide-based alloys have the potential to replace Ni-based superalloys in future aero engines to enable the latter to meet environmental and performance targets. These new alloys, like the Ni-based superalloys that are currently used, will require environmental protection with a coating system that should be chemically compatible with the substrate. A challenge for alloy development is to discover αAl2O3 scale forming coating alloys and in particular to find out whether such alloys could be “compatible” with other coating alloys for environmental coating systems for the Nb-silicide-based alloys. This paper focuses on these challenges. The alloy Al-25.5Nb-6Cr-0.5Hf (at %) was studied in the cast and heat-treated (1400 °C) conditions and after isothermal oxidation for 100 h in air at 800, 1200 and 1300 °C. The microstructure consisted of the alloyed NbAl3 and C14-NbCr2 compounds, both of which were stable at least up to 1400 °C, a eutectic of the two compounds and very small volume fractions of (Cr,Al,Nb)ss and HfO2. The prior eutectic microstructure was stable at T ≤ 1200 °C and the solid solution was not stable at T < 1200 °C. At 800 °C the alloy did not pest, but exhibited external and internal oxidation, with AlNbO4, CrNbAlO4, and αAl2O3 in the former and deeper oxidation along the NbAl3/Laves phase boundaries in the latter At 1200 and 1300 °C there was only external oxidation and the scale consisted of two layers, the outer was (Al,Cr)NbO4 intermixed with αAl2O3 and the inner was continuous αAl2O3. At all three oxidation temperatures, no Nb2Al was observed below the alloy/scale interface and Hf acted as a reactive element forming HfO2 that enhanced the adhesion of the scale. The alloy exhibited good correlations with αAl2O3 scale forming silicide and silicide + aluminide intermetallic alloys in maps of the parameters (related to atomic size), (related to electronegativity), and VEC (number of valence electrons per atom filled into the valence band) that should assist the design of bond coats that do not pest and form αAl2O3 in their scales.
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