This article reviews the most recent progress in the development of Nb-silicide-based in situ composites for potential applications in turbine engines with service temperatures of up to 1350°C. These composites contain high-strength Nb silicides that are toughened by a ductile Nb solid solution. Preliminary composites were derived from binary Nb-Si alloys, while more recent systems are complex and are alloyed with Ti, Hf, W, B, Ge, Cr, and Al. Alloying schemes have been developed to achieve an excellent balance of room-temperature toughness, fatigue-crack-growth behavior, high-temperature creep performance, and oxidation resistance over a broad range of temperatures. Nb-silicide-based composites are described with emphasis on processing, microstructure, and performance. Nb silicide composites have been produced using a range of processing routes, including induction skull melting, investment casting, hot extrusion, and powder metallurgy methods. Nb silicide composite properties are also compared with those of Ni-based superalloys.
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 βNb5Si3 was the primary phase and the Nbss was stable. The A15-Nb3X (X = Ge,Si,Sn) was stable only in JZ2. The Nbss+βNb5Si3 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.
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 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 βNb5Si3, 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.
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