On the Stability of Complex Concentrated (CC)/High Entropy (HE) Solid Solutions and the Contamination with Oxygen of Solid Solutions in Refractory Metal Intermetallic Composites (RM(Nb)ICs) and Refractory Complex Concentrated Alloys (RCCAs).

In as-cast (AC) or heat-treated (HT) metallic ultra-high temperature materials often "conventional" and complex-concentrated (CC) or high-entropy (HE) solid solutions (sss) are observed. Refractory metal containing bcc sss also are contaminated with oxygen. This paper studied the stability of CC/HE Nbss and the contamination with oxygen of Nbss in RM(INb)ICs, RM(Nb)ICs/RCCAs and RM(Nb)ICs/RHEAs. "Conventional" and CC/HE Nbss were compared. "Conventional" Nbss can be Ti-rich only in AC alloys. Ti-rich Nbss is not observed in HT alloys. In B containing alloys the Ti-rich Nbss is usually CC/HE. The CC/HE Nbss is stable in HT alloys with simultaneous addition of Mo, W with Hf, Ge+Sn. The implications for alloy design of correlations between the parameter δ of "conventional" and CC/HE Nbss with the B or the Ge+Sn concentration in the Nbss and of relationships of other solutes with the B or Ge+Sn content are discussed. The CC/HE Nbss has low Δχ, VEC and Ω and high ΔSmix, |ΔHmix| and δ parameters, and is formed in alloys that have high entropy of mixing. These parameters are compared with those of single-phase bcc ss HEAs and differences in ΔHmix, δ, Δχ and Ω, and similarities in ΔSmix and VEC are discussed. Relationships between the parameters of alloy and "conventional" Nbss also apply for CC/HE Nbss. The parameters δss and Ωss, and VECss and VECalloy can differentiate between types of alloying additions and their concentrations and are key regarding the formation or not of CC/HE Nbss. After isothermal oxidation at a pest temperature (800 oC/100 h) the contaminated with oxygen Nbss in the diffusion zone is CC/HE Nbss, whereas the Nbss in the bulk can be "conventional" Nbss or CC/HE Nbss. The parameters of "uncontaminated" and contaminated with oxygen sss are linked with linear relationships. There are correlations between the oxygen concentration in contaminated sss in the diffusion zone and the bulk of alloys with the parameters ΔχNbss, δNbss and VECNbss, the values of which increase with increasing oxygen concentration in the ss. The effects of contamination with oxygen of the near surface areas of a HT RM(Nb)IC with Al, Cr, Hf, Si, Sn, Ti and V additions and a high vol.% Nbss on the hardness and Young's modulus of the Nbss, and contributions to the hardness of the Nbss in B free or B containing alloys are discussed. The hardness and Young's modulus of the bcc ss increased linearly with its oxygen concentration and the change in hardness and Young's modulus due to contamination increased linearly with [O]2/3.

The Effect of Fe Addition in the RM(Nb)IC Alloy Nb-30Ti-10Si-2Al-5Cr-3Fe-5Sn-2Hf (at.%) on Its Microstructure, Complex Concentrated and High Entropy Phases, Pest Oxidation, Strength and Contamination with Oxygen, and a Comparison with Other RM(Nb)ICs, Refractory Complex Concentrated Alloys (RCCAs) and Refractory High Entropy Alloys (RHEAs).

In this work, the RM(Nb)IC alloy Nb−30Ti−10Si−5Cr−5Sn−3Fe−2Al−2Hf (NV2) was studied in the as-cast and heat-treated conditions; its isothermal oxidation at 700, 800 and 900 °C and its room temperature hardness and specific strength were compared with other Sn-containing RM(Nb)ICs­in particular, the alloy Nb−24Ti−18Si−5Cr−5Fe−5Sn (NV5)­and with RCCAs and RHEAs. The addition of Fe (a) stabilised Nbss; A15−Nb3X (X = Al, Si and Sn) and Nb3Si; metastable Nb3Si-m' and Nb5Si3 silicides; (b) supported the formation of eutectic Nbss + Nb5Si3; (c) suppressed pest oxidation at all three temperatures and (d) stabilised a Cr- and Fe-rich phase instead of a C14−Nb(Cr,Fe)2 Laves phase. Complex concentrated (or compositionally complex) and/or high entropy phases co-existed with "conventional" phases in all conditions and after oxidation at 800 °C. In NV2, the macrosegregation of Si decreased but liquation occurred at T >1200 °C. A solid solution free of Si and rich in Cr and Ti was stable after the heat treatments. The relationships between solutes in the various phases, between solutes and alloy parameters and between alloy hardness or specific strength and the alloy parameters were established (parameters δ, Δχ and VEC). The oxidation of NV2 at 700 °C was better than the other Sn-containing RM(Nb)ICs with/without Fe addition, even better than RM(Nb)IC alloys with lower vol.% Nbss. At 800 °C, the mass change of NV2 was slightly higher than that of NV5, and at 900 °C, both alloys showed scale spallation. At 800 °C, both alloys formed a more or less continuous layer of A15−Nb3X below the oxide scale, but in NV5, this compound was Sn-rich and severely oxidised. At 800 °C, in the diffusion zone (DZ) and the bulk of NV2, Nbss was more severely contaminated with oxygen than Nb5Si3, and the contamination of A15−Nb3X was in-between these phases. The contamination of all three phases was more severe in the DZ. The contamination of all three phases in the bulk of NV5 was more severe compared with NV2. The specific strength of NV2 was comparable with that of RCCAs and RHEAs, and its oxidation at all three temperatures was significantly better than RHEAs and RCCAs.

A Study of the Effects of Hf and Sn on the Microstructure, Hardness and Oxidation of Nb-18Si Silicide-Based Alloys-RM(Nb)ICs with Ti Addition and Comparison with Refractory Complex Concentrated Alloys (RCCAs).

In this paper, we present a systematic study of the as-cast and heat-treated microstructures of three refractory metal intermetallic composites based on Nb (i.e., RM(Nb)ICs), namely the alloys EZ2, EZ5, and EZ6, and one RM(Nb)IC/RCCA (refractory complex concentrated alloy), namely the alloy EZ8. We also examine the hardness and phases of these alloys. The nominal compositions (at.%) of the alloys were Nb-24Ti-18Si-5Hf-5Sn (EZ2), Nb-24Ti-18Si-5Al-5Hf-5Sn (EZ5), Nb-24Ti-18Si-5Cr-5Hf-5Sn (EZ6), and Nb-24Ti-18Si-5Al-5Cr-5Hf-5Sn (EZ8). All four alloys had density less than 7.3 g/cm3. The Nbss was stable in EZ2 and EZ6 and the C14-NbCr2 Laves phase in EZ6 and EZ8. In all four alloys, the A15-Nb3X (X = Al,Si,Sn) and the tetragonal and hexagonal Nb5Si3 were stable. Eutectics of Nbss + Nb5Si3 and Nbss + C14-NbCr2 formed in the cast alloys without and with Cr addition, respectively. In all four alloys, Nb3Si was not formed. In the heat-treated alloys EZ5 and EZ8, A15-Nb3X precipitated in the Nb5Si3 grains. The chemical compositions of Nbss + C14-NbCr2 eutectics and some Nb5Si3 silicides and lamellar microstructures corresponded to high-entropy or complex concentrated phases (compositionally complex phases). Microstructures and properties were considered from the perspective of the alloy design methodology NICE. The vol.% Nbss increased with increasing ΔχNbss. The hardness of the alloys respectively increased and decreased with increasing vol.% of A15-Nb3X and Nbss. The hardness of the A15-Nb3X increased with its parameter Δχ, and the hardness of the Nbss increased with its parameters δ and Δχ. The room-temperature-specific strength of the alloys was in the range 271.7 to 416.5 MPa cm3g-1. The effect of the synergy of Hf and Sn, or Hf and B, or Hf and Ge on the macrosegregation of solutes, microstructures, and properties of RM(Nb)ICs/RCCAs from this study and others is compared. Phase transformations involving compositionally complex phases are discussed.

Refractory Metal Intermetallic Composites, High-Entropy Alloys, and Complex Concentrated Alloys: A Route to Selecting Substrate Alloys and Bond Coat Alloys for Environmental Coatings.

This paper considers metallic ultrahigh-temperature materials (UHTMs) and the alloying behaviour and properties of alloys and their phases by using maps of the parameters δ (based on atomic size), Δχ (based on electronegativity), and valence electron concentration (VEC), and discusses what connects and what differentiates material groups in the maps. The formation of high-entropy or complex concentrated intermetallics, namely 5-3 silicides, C14 Laves and A15 compounds, and bcc solid solutions and eutectics in metallic UHTMs and their co-existence with "conventional" phases is discussed. The practicality of maps for the design/selection of substrate alloys is deliberated upon. The need for environmental coatings for metallic UHTMs was considered and the design of bond coat alloys is discussed by using relevant maps.

On the Microstructure and Properties of Nb-Ti-Cr-Al-B-Si-X (X = Hf, Sn, Ta) Refractory Complex Concentrated Alloys.

We studied the effect of the addition of Hf, Sn, or Ta on the density, macrosegregation, microstructure, hardness and oxidation of three refractory metal intermetallic composites based on Nb (RM(Nb)ICs) that were also complex concentrated alloys (i.e., RM(Nb)ICs/RCCAs), namely, the alloys TT5, TT6, and TT7, which had the nominal compositions (at.%) Nb-24Ti-18Si-5Al-5B-5Cr-6Ta, Nb-24Ti-18Si-4Al-6B-5Cr-4Sn and Nb-24Ti-17Si-5Al-6B-5Cr-5Hf, respectively. The alloys were compared with B containing and B free RM(Nb)ICs. The macrosegregation of B, Ti, and Si was reduced with the addition, respectively of Hf, Sn or Ta, Sn or Ta, and Hf or Sn. All three alloys had densities less than 7 g/cm3. The alloy TT6 had the highest specific strength in the as cast and heat-treated conditions, which was also higher than that of RCCAs and refractory metal high entropy alloys (RHEAs). The bcc solid solution Nbss and the tetragonal T2 and hexagonal D88 silicides were stable in the alloys TT5 and TT7, whereas in TT6 the stable phases were the A15-Nb3Sn and the T2 and D88 silicides. All three alloys did not pest at 800 °C, where only the scale that was formed on TT5 spalled off. At 1200 °C, the scale of TT5 spalled off, but not the scales of TT6 and TT7. Compared with the B free alloys, the synergy of B with Ta was the least effective regarding oxidation at 800 and 1200 °C. Macrosegregation of solutes, the chemical composition of phases, the hardness of the Nbss and the alloys, and the oxidation of the alloys at 800 and 1200 °C were considered from the perspective of the Niobium Intermetallic Composite Elaboration (NICE) alloy design methodology. Relationships between properties and the parameters VEC, δ, and Δχ of alloy or phase and between parameters were discussed. The trends of parameters and the location of alloys and phases in parameter maps were in agreement with NICE.

The Effect of Boron on the Microstructure and Properties of Refractory Metal Intermetallic Composites (RM(Nb)ICs) Based on Nb-24Ti-xSi (x = 16, 17 or 18 at.%) with Additions of Al, Cr or Mo.

This paper is about metallic ultra-high temperature materials, in particular, refractory metal intermetallic composites based on Nb, i.e., RM(Nb)ICs, with the addition of boron, which are compared with refractory metal high entropy alloys (RHEAs) or refractory metal complex concentrated alloys (RCCAs). We studied the effect of B addition on the density, macrosegregation, microstructure, hardness and oxidation of four RM(Nb)IC alloys, namely the alloys TT2, TT3, TT4 and TT8 with nominal compositions (at.%) Nb-24Ti-16Si-5Cr-7B, Nb-24Ti-16Si-5Al-7B, Nb-24Ti-18Si-5Al-5Cr-8B and Nb-24Ti-17Si-3.5Al-5Cr-6B-2Mo, respectively. The alloys made it possible to compare the effect of B addition on density, hardness or oxidation with that of Ge or Sn addition. The alloys were made using arc melting and their microstructures were characterised in the as cast and heat-treated conditions. The B macrosegregation was highest in TT8. The macrosegregation of Si or Ti increased with the addition of B and was lowest in TT8. The alloy TT8 had the lowest density of 6.41 g/cm3 and the highest specific strength at room temperature, which was also higher than that of RCCAs and RHEAs. The Nbss and T2 silicide were stable in the alloys TT2 and TT3, whereas in TT4 and TT8 the stable phases were the Nbss and the T2 and D88 silicides. Compared with the Ge or Sn addition in the same reference alloy, the B and Ge addition was the least and most effective at 800 °C (i.e., in the pest regime), when no other RM was present in the alloy. Like Ge or Sn, the B addition in TT2, TT3 and TT4 did not suppress scale spallation at 1200 °C. Only the alloy TT8 did not pest and its scales did not spall off at 800 and 1200 °C. The macrosegregation of Si and Ti, the chemical composition of Nbss and T2, the microhardness of Nbss and the hardness of alloys, and the oxidation of the alloys at 800 and 1200 °C were also viewed from the perspective of the alloy design methodology NICE and relationships with the alloy or phase parameters VEC, δ and Δχ. The trends of these parameters and the location of alloys and phases in parameter maps were found to be in agreement with NICE.

Refractory Metal (Nb) Intermetallic Composites, High Entropy Alloys, Complex Concentrated Alloys and the Alloy Design Methodology NICE-Mise-en-scène † Patterns of Thought and Progress.

The paper reflects on the usefulness of the alloy design methodology NICE (Niobium Intermetallic Composite Elaboration) for the development of new Nb-containing metallic ultra-high-temperature materials (UHTMs), namely refractory metal (Nb) intermetallic composites (RM(Nb)ICs), refractory high entropy alloys (RHEAs) and refractory complex concentrated alloys (RCCAs), in which the same phases can be present, specifically bcc solid solution(s), M5Si3 silicide(s) and Laves phases. The reasons why a new alloy design methodology was sought and the foundations on which NICE was built are discussed. It is shown that the alloying behavior of RM(Nb)ICs, RHEAs and RCCAs can be described by the same parameters. The practicality of parameter maps inspired by NICE for describing/understanding the alloying behavior and properties of alloys and their phases is demonstrated. It is described how NICE helps the alloy developer to understand better the alloys s/he develops and what s/he can do and predict (calculate) with NICE. The paper expands on RM(Nb)ICs, RHEAs and RCCAs with B, Ge or Sn, the addition of which and the presence of A15 compounds is recommended in RHEAs and RCCAs to achieve a balance of properties.

On the Microstructure and Properties of Nb-18Si-6Mo-5Al-5Cr-2.5W-1Hf Nb-Silicide Based Alloys with Ge, Sn and Ti Additions (at.%).

We studied the microstructures and isothermal oxidation of the Nb-silicide-based alloys Nb-11.5Ti-18Si-5Mo-2W-4.9Sn-4.6Ge-4.5Cr-4.7Al-1Hf (JZ4) and Nb-21Ti-18Si-6.7Mo-1.2W-4.4Sn-4.2Ge-4Cr-3.7Al-0.8Hf (JZ5), calculated their average creep rate for the creep goal conditions of T = 1200 °C and σ = 170 MPa, and compared properties of the two alloys with those of other refractory metal (RM) complex concentrated alloys (RCCAs). Both alloys had a density less than 7.3 g/cm3 and lower than the density of multiphase bcc solid solution + M5Si3 silicide RCCAs. There was macrosegregation of Si in both alloys, which had the same phases in their as-cast microstructures, namely ßNb5Si3, αNb5Si3, A15-Nb3X (X = Al, Ge, Si, Sn), TM5Sn2X (X = Al, Ge, Si), C14-Cr2Nb, but no solid solution. After heat treatment at 1500 °C for 100 h, a low volume fraction of a W-rich (Nb, W)ss solid solution was observed in both alloys together with ßNb5Si3, αNb5Si3 and A15-Nb3X but not the TM5Sn2X, whereas the Laves phase was observed only in JZ4. At 800 °C, both alloys did not pest, and there was no spallation of their scales at 1200 °C. At both temperatures, both alloys followed parabolic oxidation kinetics and their weight changes were lower than those of Ti-rich Nb-silicide-based alloys. The oxidation of both alloys was superior to that of other RCCAs studied to date. For each alloy the Si macrosegregation, volume fraction of solid solution, chemical composition of solid solution and Nb5Si3, and weight changes in isothermal oxidation at 800 and 1200 °C that were calculated using the alloy design methodology NICE agreed well with the experimental results.

On the Microstructure and Properties of Nb-12Ti-18Si-6Ta-5Al-5Cr-2.5W-1Hf (at.%) Silicide-Based Alloys with Ge and Sn Additions.

The microstructures and properties of the alloys JZ3 (Nb-12.4Ti-17.7Si-6Ta-2.7W-3.7Sn-4.8Ge-1Hf-4.7Al-5.2Cr) and JZ3+(Nb-12.4Ti-19.7Si-5.7Ta-2.3W-5.7Sn-4.9Ge-0.8Hf-4.6Al-5.2Cr) were studied. The densities of both alloys were lower than the densities of Ni-based superalloys and many of the refractory metal complex concentrated alloys (RCCAs) studied to date. Both alloys had Si macrosegregation and the same phases in their as cast and heat treated microstructures, namely ßNb5Si3, αNb5Si3, A15-Nb3X (X = Al, Ge, Si, Sn), C14-Cr2Nb and solid solution. W-rich solid solutions were stable in both alloys. At 800 °C only the alloy JZ3 did not show pest oxidation, and at 1200 °C a thin and well adhering scale formed only on JZ3+. The alloy JZ3+ followed parabolic oxidation with rate constant one order of magnitude higher than the single crystal Ni-superalloy CMSX-4 for the first 14 h of oxidation. The oxidation of both alloys was superior to that of RCCAs. Both alloys were predicted to have better creep at the creep goal condition compared with the superalloy CMSX-4. Calculated Si macrosegregation, solid solution volume fractions, chemical compositions of solid solution and Nb5Si3, weight changes in isothermal oxidation at 800 and 1200 °C using the alloy design methodology NICE agreed well with the experimental results.

On the Microstructure and Properties of Nb-12Ti-18Si-6Ta-2.5W-1Hf (at.%) Silicide-Based Alloys with Ge and Sn Additions.

In this paper two Nb-silicide-based alloys with nominal compositions (at.%) Nb-12Ti-18Si-6Ta-2.5W-1Hf-2Sn-2Ge (JZ1) and Nb-12Ti-18Si-6Ta-2.5W-1Hf-5Sn-5Ge (JZ2) were studied. The alloys were designed using the alloy design methodology NICE to meet specific research objectives. The cast microstructures of both alloys were sensitive to solidification conditions. There was macro-segregation of Si in JZ1 and JZ2. In both alloys the ßNb5Si3 was the primary phase and the Nbss was stable. The A15-Nb3X (X = Ge,Si,Sn) was stable only in JZ2. The Nbss+ßNb5Si3 eutectic in both alloys was not stable as was the Nb3Si silicide that formed only in JZ1. At 800 °C both alloys followed linear oxidation kinetics and were vulnerable to pesting. At 1200 °C both alloys exhibited parabolic oxidation kinetics in the early stages and linear kinetics at longer times. The adhesion of the scale that formed on JZ2 at 1200 °C and consisted of Nb and Ti-rich oxides, silica and HfO2 was better than that of JZ1. The microstructure of JZ2 was contaminated by oxygen to a depth of about 200 µm. There was no Ge or Sn present in the scale. The substrate below the scale was richer in Ge and Sn where the NbGe2, Nb5(Si1-xGex)3, W-rich Nb5(Si1-xGex)3, and A15-Nb3X compounds (X = Ge,Si,Sn) were formed in JZ2. The better oxidation behavior of JZ2 compared with JZ1 correlated well with the decrease in VEC and increase in δ parameter values, in agreement with NICE. For both alloys the experimental data for Si macrosegregation, vol.% Nbss, chemical composition of Nbss and Nb5Si3, and weight gains at 800 and 1200 °C was compared with the calculations (predictions) of NICE. The agreement was very good. The calculated creep rates of both alloys at 1200 °C and 170 MPa were lower than that of the Ni-based superalloy CMSX-4 for the same conditions but higher than 10-7 s-1.

On the Microstructure and Isothermal Oxidation at 800 and 1200 °C of the Nb-24Ti-18Si-5Al-5Cr-5Ge-5Sn (at.%) Silicide-Based Alloy.

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 ßNb5Si3, 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 , 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.

A Study of the Effect of 5 at.% Sn on the Micro-Structure and Isothermal Oxidation at 800 and 1200 °C of Nb-24Ti-18Si Based Alloys with Al and/or Cr Additions.

This paper presents the results of a systematic study of Nb-24Ti-18Si based alloys with 5 at.% Sn addition. Three alloys of nominal compositions (at.%), namely Nb-24Ti-18Si-5Cr-5Sn (ZX4), Nb-24Ti-18Si-5Al-5Sn (ZX6), and Nb-24Ti-18Si-5Al-5Cr-5Sn (ZX8), were studied to understand how the increased Sn concentration improved oxidation resistance. In all three alloys there was macrosegregation, which was most severe in ZX8 and the primary ßNb5Si3 transformed completely to αNb5Si3 after heat treatment. The Nbss was not stable in ZX6, the Nb3Sn was stable in all three alloys, and the Nbss and C14-NbCr2 Laves phase were stable in ZX4 and ZX8. The 5 at.% Sn addition suppressed pest oxidation at 800 °C but not scale spallation at 1200 °C. At both temperatures, a Sn-rich area with Nb3Sn, Nb5Sn2Si, and NbSn2 compounds developed below the scale. This area was thicker and continuous after oxidation at 1200 °C and was contaminated by oxygen at both temperatures. The contamination of the Nbss by oxygen was most severe in the bulk of all three alloys. Nb-rich, Ti-rich and Nb and Si-rich oxides formed in the scales. The adhesion of the latter on ZX6 at 1200 °C was better, compared with the alloys ZX4 and ZX8. At both temperatures, the improved oxidation 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). Comparison with similar alloys with 2 at.% Sn addition showed (a) that a higher Sn concentration is essential for the suppression of pest oxidation of Nb-24Ti-18Si based alloys with Cr and no Al additions, but not for alloys where Al and Cr are in synergy with Sn, (b) that the stability of Nb3Sn in the alloy is "assured" with 5 at.% Sn addition, which improves oxidation with/out the presence of the Laves phase and (c) that the synergy of Sn with Al presents the "best" oxidation behaviour with improved scale adhesion at high temperature.

Ab Initio Study of Ternary W5Si3 Type TM5Sn2X Compounds (TM = Nb, Ti and X = Al, Si).

The adhesion of the scale formed on Nb-silicide based alloys at 1473 K improves when Al and Sn are in synergy with Si and Ti. This improvement is observed when there is segregation of Sn in the microstructure below the alloy/scale interface and a layer rich in intermetallics that include TM5Sn2X compounds is formed at the interface. Data for the ternary compounds is scarce. In this paper elastic and thermodynamic properties of the Nb5Sn2Al, Ti5Sn2Si, Ti5Sn2Al and Nb5Sn2Si compounds were studied using the first-principles, pseudopotential plane-wave method based on density functional theory. The enthalpy of formation of the ternary intermetallics was calculated using the quasi-harmonic approximation. The calculations suggest that the Nb5Sn2Si is the stiffest; that the Nb5Sn2Al and Ti5Sn2Si are the most and less ductile phases respectively; and that Nb significantly increases the bulk, shear and elastic moduli of the ternary compound compared with Ti.

The Effect of Ge Addition on the Oxidation of Nb-24Ti-18Si Silicide Based Alloys.

In this paper, we report research about the isothermal oxidation in air at 800 and 1200 °C for 100 h of the as-cast alloys (at.%) Nb-18Si-5Ge (ZF1), Nb-18Si-10Ge (ZF2), Nb-24Ti-18Si-5Ge (ZF3), Nb-24Ti-18Si-5Cr (ZF4), Nb-24Ti-18Si-5Al (ZF5), Nb-24Ti-18Si-5Al-5Cr-5Ge (ZF6), and Nb-24Ti-18Si-5Al-5Cr-5Ge-5Hf (ZF9), the microstructures of which were reported in previous publications. Only the alloys ZF1, ZF2, and ZF3 suffered from pest oxidation at 800 °C. The Ge addition substantially improved the oxidation resistance of the other alloys both at 800 °C and 1200 °C, which followed parabolic kinetics at 800 °C and in the early stages at 1200 °C and linear kinetics at longer times, where there was spallation of the scales. The Nb2O5 and TiNb2O7 oxides were formed in the scales of the alloys ZF4, ZF5, ZF6, and ZF9 at 800 °C and 1200 °C, the GeO2 was observed in all scales and the SiO2 in the scales of the alloys ZF4 and ZF5, the CrNbO4 in the scales of the alloys ZF4, ZF6, and ZF9 and the AlNbO4 in the scales of the alloys ZF5, ZF6, and ZF9. Diffusion zones were formed below the scale/substrate interface only in the alloys ZF4 and ZF5 where the Nbss and Nb5Si3 were contaminated by oxygen. However, these phases were not contaminated by oxygen in the bulk of the alloys ZF4, ZF5, ZF6, and ZF9. The alloys ZF9 and ZF6 exhibited the best oxidation behaviour at 800 °C and 1200 °C, respectively. The alloys were compared with Nb-silicide based alloys of similar compositions without Ge and Hf additions and the alloy ZF9 with refractory metal High Entropy Alloys. Compared with the former alloys, the addition of Ge reduced the vol % of the Nbss. Compared with the latter alloys, the superior oxidation behaviour of the alloy ZF9 was attributed to its higher and lower values respectively of the parameters δ and VEC.

Phase Equilibria in the Nb-Rich Region of Al-Nb-Sn at 900 and 1200 °C.

The Al-Nb-Sn phase diagram was studied experimentally in the Nb-rich region to provide important phase equilibria information for alloy design of Nb-silicide based materials for aero engine applications. Three alloys were produced: Nb-17Al-17Sn, Nb-33Al-13Sn and Nb-16Al-20Sn (at.%). As-cast and heat-treated alloys (900 and 1200 °C) were analysed using XRD (X-ray diffraction) and SEM/EDS (scanning electron microscopy/ electron dispersive x-ray spectroscopy). Tin showed a high solubility in Nb2Al, reaching up to 21 at.% in the Sn-rich areas, substituting for Al atoms. Tin and Al also substituted for each other in the A15 phases (Nb3Al and Nb3Sn). Tin showed limited solubility in NbAl3, not exceeding 3.6 at.% as it substituted Al atoms. The solubility of Al in NbSn2 varied from 4.8 to 6.8 at.%. A ternary phase, Nb5Sn2Al with the tI32 W5Si3 crystal structure, was found to be stable. This phase was observed in the 900 °C heat-treated samples, but not in the 1200 °C heated samples.

On The Microstructures and Hardness of The Nb-24Ti-18Si-5Al-5Cr-5Ge and Nb-24Ti-18Si-5Al-5Cr-5Ge-5Hf (at.%) Silicide Based Alloys.

The microstructures and hardness of the as cast and heat treated (1400 °C/100 h) alloys Nb-24Ti-18Si-5Ge-5Cr-5Al (ZF6) and Nb-24Ti-18Si-5Ge-5Cr-5Al-5Hf (ZF9) were studied. Both alloys were compared with refractory metal bcc solid solution + intermetallic High Entropy Alloys (HEAs). There was macrosegregation of Si, Ti, Cr and Al in both alloys. The roles of Ge and Hf on macrosegregation are discussed. In both alloys the primary phase was the ßNb5Si3. In the as cast alloy ZF6 the Nbss, ßNb5Si3 and C14-NbCr2 Laves phase and Nbss + ßNb5Si3 eutectic were formed. The microstructure of the as cast alloy ZF9 consisted of Nbss, ßNb5Si3, γNb5Si3 and C14-NbCr2 Laves phase. The heat-treated microstructures of the alloys ZF6 and ZF9 consisted of Nbss, ßNb5Si3 and αNb5Si3 and Nbss, ßNb5Si3, αNb5Si3 and γNb5Si3, respectively. The surfaces of both alloys were contaminated by oxygen where TiO2 and HfO2 formed respectively in the alloys ZF6 and ZF9. Alloying with Hf increased the lattice parameter of Nbss and decreased the hardness of ZF9 and Nb5Si3. The roles of alloying additions on the hardness of the Nbss and Nb5Si3 and relationships between alloy hardness and alloy parameters VEC (valence electron concentration), δ (related to atomic size) and Δχ (related to electronegativity) were discussed.

On the Microstructure and Isothermal Oxidation at 800, 1200, and 1300 °C of the Al-25.5Nb-6Cr-0.5Hf (at %) Alloy.

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.

On the Microstructure and Isothermal Oxidation of the Si-22Fe-12Cr-12Al-10Ti-5Nb (at.%) Alloy.

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.

On the Microstructure and Isothermal Oxidation of Silica and Alumina Scale Forming Si-23Fe-15Cr-15Ti-1Nb and Si-25Nb-5Al-5Cr-5Ti (at.%) Silicide Alloys.

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.

Microstructures and Isothermal Oxidation of the Alumina Scale Forming Nb1.45Si2.7Ti2.25Al3.25Hf0.35 and Nb1.35Si2.3Ti2.3Al3.7Hf0.35 Alloys.

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.