The impact of Ti and temperature on the stability of Nb5Si3 phases: a first-principles study

Nb-silicide based alloys could be used at T > 1423 K in future aero-engines. Titanium is an important additive to these new alloys where it improves oxidation, fracture toughness and reduces density. The microstructures of the new alloys consist of an Nb solid solution, and silicides and other intermetallics can be present. Three Nb5Si3 polymorphs are known, namely αNb5Si3 (tI32 Cr5B3-type, D8l), βNb5Si3 (tI32 W5Si3-type, D8m) and γNb5Si3 (hP16 Mn5Si3-type, D88). In these 5–3 silicides Nb atoms can be substituted by Ti atoms. The type of stable Nb5Si3 depends on temperature and concentration of Ti addition and is important for the stability and properties of the alloys. The effect of increasing concentration of Ti on the transition temperature between the polymorphs has not been studied. In this work first-principles calculations were used to predict the stability and physical properties of the various Nb5Si3 silicides alloyed with Ti. Temperature-dependent enthalpies of formation were computed, and the transition temperature between the low (α) and high (β) temperature polymorphs of Nb5Si3 was found to decrease significantly with increasing Ti content. The γNb5Si3 was found to be stable only at high Ti concentrations, above approximately 50 at. % Ti. Calculation of physical properties and the Cauchy pressures, Pugh’s index of ductility and Poisson ratio showed that as the Ti content increased, the bulk moduli of all silicides decreased, while the shear and elastic moduli and the Debye temperature increased for the αNb5Si3 and γNb5Si3 and decreased for βNb5Si3. With the addition of Ti the αNb5Si3 and γNb5Si3 became less ductile, whereas the βNb5Si3 became more ductile. When Ti was added in the αNb5Si3 and βNb5Si3 the linear thermal expansion coefficients of the silicides decreased, but the anisotropy of coefficient of thermal expansion did not change significantly

On Nb silicide based alloys: Part II

The paper examined alloying behaviour in cast and heat treated Nb-silicide based alloys where alloying additions were transition metals (Cr, Hf, Mo, Ta, Ti, W), and simple metal or metalloid elements (Al, B, Ge, Sn). The microstructures of the alloys consisted of bcc Nbss solid solution (which could be of three types, namely normal, Ti rich and with no Si) and intermetallic(s). The study used the parameters entropy (ΔSmix) and enthalpy (ΔHmix) of mixing, atomic size difference (δ), electronegativity difference (Δχ), valence electron concentration (VEC), Ω = Tm ΔSmix/| ΔHmix | and the ratio sd/sp of sd over sp electronic configuration elements. The values of the parameters were in the ranges - 44.8 < ΔHmix < - 32.7 kJ/mol, 8.3 < ΔSmix < 14.7 J/molK, 4.4 < VEC <4.9, 8.1 < δ < 14.3, 0.12 < Δχ < 0.24, 0.57 < Ω < 0.95 and 2.12 < sd/sp < 4.03. Plots of Δχ versus δ and Δχ versus ΔHmix separated the alloys in three groups according to alloying additions. In these plots the B containing alloys formed their own group. The data for Nb solid solutions from Part I (J Alloys Compd. 708 (2017) 961–971) was used to compare the parameters of the alloys and solid solutions. Plots of Δχ versus ΔHmix and Δχ versus Ω separated the alloys and their bcc Nb solid solutions according to whether they contained B or not. The parameters ΔHmix, ΔSmix, δ and Δχ of some of the Nb-silicide based alloys were in the ranges reported for bcc solid solution + intermetallic(s) high entropy alloys. The values of the parameters ΔHmix, ΔSmix, VEC, δ and Δχ were in better agreement with those reported for amorphous alloys

A study of the effects of Hf and Sn on the microstructure, hardness and oxidation of Nb-18Si silicide based alloys without Ti addition

The paper presents the results of an experimental study of large (≈0.6 kg) arc melted buttons of four Ti free Nb-silicide based alloys with Sn addition with nominal compositions (at.%) Nb-18Si-5Hf-5Sn (EZ1), Nb-18Si-5Al-5Sn (EZ7), Nb-18Si-5Cr-5Hf-5Sn (EZ3) and Nb-18Si-5Al-5Hf-5Sn (EZ4). The alloys were studied in the as-cast and heat treated conditions. In all the alloys there was macrosegregation of Si (MACSi). Among the single element additions Hf had the weakest and Sn the strongest effect on MACSi. The simultaneous presence of Cr and Hf in the alloy EZ3 had the strongest effect on MACSi. In all the alloys the βNb5Si3 was the primary phase and was present after the heat treatment(s), the Nb3Si silicide was suppressed and the A15-Nb3Sn intermetallic was stable. The Nbss was not stable in the alloys EZ7 and EZ4 and the C14-NbCr2 Laves phase was stable in the alloy EZ3. Very Hf-rich Nb5Si3 was stable in the alloy EZ4 after prolonged heat treatments. Eutectics were observed in all the alloys. These were binary eutectics in the alloys EZ1 and EZ7, where respectively they consisted of the Nbss and βNb5Si3, and βNb5Si3 and A15-Nb3Sn phases. Most likely ternary eutectics consisting of the Nbss, C14-NbCr2 and βNb5Si3, and Nbss, βNb5Si3 and A15-Nb3Sn phases were observed, respectively in the alloys EZ3 and EZ4. The addition of Al increased the vol% of the Nb5Si3 and A15-Nb3Sn phases, particularly after the heat treatment(s). The lattice parameter of Nb respectively increased and decreased with the addition of Hf, and Al or Cr and the latter element had the stronger negative effect. Pest oxidation was not suppressed in the alloys of this study

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 βNb5Si3 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

A perspective of the design and development of metallic ultra-high temperature materials: refractory metal intermetallic composites, refractory complex concentrated alloys and refractory high entropy alloys

The paper is a personal perspective on the design of metallic ultra-high temperature materials (UHTMs). Specifically, the alloy design “landscape” of metallic UHTMs was considered from the viewpoint of the alloy design methodology NICE. The concepts of synergy, entanglement and self-regulation and their significance for alloy design/development were discussed. The risks, ecological challenges and material-environment interactions associated with the development of metallic UHTMs were highlighted. The “landscape” showed that beneath the complexities of alloy design lies an elegant and powerful unity of specific parameters that link logically and that progress can be made by recognising those interrelationships between parameters that generate interesting, diverse, and complex alloys

On the Nb5Si3 silicide in metallic ultra-high temperature materials

Refractory metal (RM) M5Si3 silicides are desirable intermetallics in metallic ultra-high temperature materials (UHTMs), owing to their creep properties and high Si content that benefits oxidation resistance. Of particular interest is the alloyed Nb5Si3 that forms in metallic UHTMs with Nb and Si addition. The choice of alloying elements and type of Nb5Si3 that is critical for achieving a balance of properties or meeting a property goal in a metallic UHTM is considered in this paper. Specifically, the different types of alloyed “normal” Nb5Si3 and Ti-rich Nb5Si3, namely “conventional”, “complex concentrated” (CC) or “high entropy” (HE) silicide, in metallic UHTMs with Nb and Si addition were studied. Advanced metallic UHTMs with additions of RMs, transition metals (TMs), Ge, Sn or Ge + Sn and with/without Al and with different Ti, Al, Cr, Si or Sn concentrations were investigated, considering that the motivation of this work was to support the design and development of metallic-UHTMs. The study of the alloyed silicides was based on the Nb/(Ti + Hf) ratio, which is key regarding creep, the parameters VEC and Δχ and relationships between them. The effect of alloying additions on the stability of “conventional”, CC or HE silicide was discussed. The creep and hardness of alloyed Nb5Si3 was considered. Relationships that link “conventional”, CC or HE bcc solid solution and Nb5Si3 in the alloy design methodology NICE (Niobium Intermetallic Composite Elaboration) were presented. For a given temperature and stress, the steady state creep rate of the alloyed silicide, in which TMs substituted Nb, and Al and B substituted Si, depended on its parameters VEC and Δχ and its Nb/(Ti + Hf) ratio, and increased with decreasing parameter and ratio value, compared with the unalloyed Nb5Si3. Types of alloyed Nb5Si3 with VEC and Δχ values closest to those of the unalloyed Nb5Si3 were identified in maps of alloyed Nb5Si3. Good agreement was shown between the calculated hardness and chemical composition of Nb5Si3 and experimental results

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 βNb5Si3, 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 βNb5Si3, 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

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

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