Experimental and thermodynamic assessment of the Ge-Nb-Si ternary phase diagram

2018

279

The development of Nb-silicide based alloys is frustrated by the lack of composition-process-microstructure-property data for the new alloys, and by the shortage of and/or disagreement between thermodynamic data for key binary and ternary systems that are essential for designing (selecting) alloys to meet property goals. Recent publications have discussed the importance of the parameters δ (related to atomic size), Δχ (related to electronegativity) and valence electron concentration (VEC) (number of valence electrons per atom filled into the valence band) for the alloying behavior of Nb-silicide based alloys (J Alloys Compd 748 (2018) 569), their solid solutions (J Alloys Compd 708 (2017) 961), the tetragonal Nb5Si3 (Materials 11 (2018) 69), and hexagonal C14-NbCr2 and cubic A15-Nb3X phases (Materials 11 (2018) 395) and eutectics with Nbss and Nb5Si3 (Materials 11 (2018) 592). The parameter values were calculated using actual compositions for alloys, their phases and eutectics. This paper is about the relationships that exist between the alloy parameters δ, Δχ and VEC, and creep rate and isothermal oxidation (weight gain) and the concentrations of solute elements in the alloys. Different approaches to alloy design (selection) that use property goals and these relationships for Nb-silicide based alloys are discussed and examples of selected alloy compositions and their predicted properties are given. The alloy design methodology, which has been called NICE (Niobium Intermetallic Composite Elaboration), enables one to design (select) new alloys and to predict their creep and oxidation properties and the macrosegregation of Si in cast alloys.

Section: Introductionmentioning

confidence: 99%

On Nb Silicide Based Alloys: Alloy Design and Selection

2018

279

“…Research to clarify discrepancies between existing phase diagrams [ 33 , 40 ] and to provide some of the missing data for ternary systems is underway. In the meantime, what can we learn about the alloying behaviours of the C14–NbCr 2 Laves and A15–Nb 3 X phases in Nb–silicide-based alloys from data concerning the chemical compositions of these phases in developmental alloys?…”

Section: Introductionmentioning

confidence: 99%

Alloying and Properties of C14–NbCr2 and A15–Nb3X (X = Al, Ge, Si, Sn) in Nb–Silicide-Based Alloys

2018

Self Cite

The oxidation of Nb–silicide-based alloys is improved with Al, Cr, Ge or Sn addition(s). Depending on addition(s) and its(their) concentration(s), alloyed C14-AB2 Laves and A15-A3X phases can be stable in the microstructures of the alloys. In both phases, A is the transition metal(s), and B and X respectively can be Cr, Al, Ge, Si or Sn, and Al, Ge, Si or Sn. The alloying, creep and hardness of these phases were studied using the composition weighted differences in electronegativity (∆χ), average valence electron concentrations (VEC) and atomic sizes. For the Laves phase (i) the VEC and ∆χ were in the ranges 4.976 < VEC < 5.358 and −0.503 < ∆χ < −0.107; (ii) the concentration of B (=Al + Cr + Ge + Si + Sn) varied from 50.9 to 64.5 at %; and (iii) the Cr concentration was in the range of 35.8 < Cr < 51.6 at %. Maps of ∆χ versus Cr, ∆χ versus VEC, and VEC versus atomic size separated the alloying behaviours of the elements. Compared with unalloyed NbCr2, the VEC decreased and ∆χ increased in Nb(Cr,Si)2, and the changes in both parameters increased when Nb was substituted by Ti, and Cr by Si and Al, or Si and Ge, or Si and Sn. For the A15 phase (i) the VEC and ∆χ were in the ranges 4.38 < VEC < 4.89 and 0.857 < ∆χ < 1.04, with no VEC values between 4.63 and 4.72 and (ii) the concentration of X (=Al + Ge + Si + Sn) varied from 16.3 to 22.7 at %. The VEC versus ∆χ map separated the alloying behaviours of elements. The hardness of A15-Nb3X was correlated with the parameters ∆χ and VEC. The hardness increased with increases in ∆χ and VEC. Compared with Nb3Sn, the ∆χ and hardness of Nb3(Si,Sn) increased. The substitution of Nb by Cr had the same effect on ∆χ and hardness as Hf or Ti. The ∆χ and hardness increased with Ti concentration. The addition of Al in Nb3(Si,Sn,Al) decreased the ∆χ and increased the hardness. When Ti and Hf, or Ti, Hf and Cr, were simultaneously present with Al, the ∆χ was decreased and the hardness was unchanged. The better creep of Nb(Cr,Si)2 compared with the unalloyed Laves phase was related to the decrease in the VEC and ∆χ parameters.

“…The remaining elements are all known to improve the oxidation resistance of Nb-silicide-based alloys [92]. Two more elements are known to improve the oxidation of the latter alloys, namely B and Ge, owing to their effects on phase selection and stability [59,93,94,95]. Furthermore, when the alloying behaviour of Nb-silicide-based alloys is considered, the B-containing alloys form their own group [27].…”

Section: Summary and Concluding Remarksmentioning

confidence: 99%

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

Hernández-Negrete

2019

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.