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.

High-Temperature Oxidation of NiAlCr–Ca and NiAlCr–Sr Alloys in Air

In this study, interrupted oxidation behavior of synthetic NiAlCr–Ca (Ca = 0.3, 1.4, 2 at.%) and NiAlCr–Sr (Sr = 0.4 at.%) alloys in the air at 1027 °C for 192 h was investigated. Parabolic rate constants (kp) showed that the Sr-containing alloy exhibited the best oxidation resistance among the alloys investigated in this study. The oxide scale formed on the Sr-containing alloy was composed of α-Al2O3 phase with Sr-rich nodules. Increasing the Ca concentration in the alloys was found to reduce the oxidation resistance due to the formation of non-protective Ca-rich complex oxides and consumption of α-Al2O3 scale by the reaction between Al2O3 and CaO. The Ca-rich complex oxides were initially formed on the Ca-rich interdendritic region and grew with time. Very little scale spallation was observed for the Sr-containing alloy, while it was notable for 0.3 at.% Ca-containing alloy. Spallation was attributed to the coefficient of thermal expansion (CTE) mismatch arisen from the formation of CaAl4O7 phase, a compound with a very low CTE.

Microstructure and Oxidation Behavior of Narrow Gap Brazing and Wide Gap Brazing Joints With Boron/Silicon-Free Nickel Base Braze Alloys

In this study, the microstructure and solidus and liquidus of several Ni-Co-Hf-Zr-Ti-Al braze alloys were first examined with the objective to develop a B- and Si-free low-melting braze alloy for narrow gap (NGB) and wide gap brazing (WGB) and turbine component repair applications. Among various alloys examined, differential scanning calorimetry (DSC) was used to measure the solidus and liquidus during heating and cooling cycles. Following the measurements of liquidus and solidus, the microstructure was evaluated using SEM. Equations for calculating solidus and liquidus based on alloy's compositions were established, and the functions of each elements on these two characteristic temperatures were discussed. One selected alloy with a liquidus of 1201 °C was further employed for NGB and WGB experiments. The results showed that it was able join Cannon Muskegon single crystal (CMSX)-4 at 1240 °C without interfacial voids, and with the use of externally applied pressure and extended homogenization treatment, the interfacial intermetallic compounds were substantially removed. Furthermore, the same braze alloy was used to fill a large artificial cavity in a WGB scheme at a reduced temperature of 1200 °C. The braze alloy was able to fully bond the filler powder alloy in addition to join the two alloys to an IN 738 substrate. Finally, oxidation test was conducted at 1050 °C (isothermal in static air) for 100 h after NGB of CMSX-4 and WGB of IN 738. The results showed that the oxide formed on the standalone braze alloy is very dense and there is no sign of spallation. It contained primarily NiO (+CoO) with no other elements measured. For the NGB joints, large amount of scale spallation was observed on base alloy CMSX-4 while the NGB joint remained spallation free. The oxide formed on the NGB was NiO with partitions of Co, Al, Ti, Cr, and W. The WGB joint region in IN 738 showed oxide scale spallation on the IN 738 substrate side, leaving behind steps and depression on the sample surface. In the WGB joint itself, there were three notable phases after oxidation test; however, no scale spallation could be found. For the majority part of the surface, a Ni-rich oxide covered the surface. There were areas of smaller oxide particles with higher Cr content. Overall, the new boron/silicon-free braze alloy was found to be able to join several superalloys in both WGB and NGB schemes without occurrence of defects and the oxidation resistance was superior to both substrate alloys examined in this study.

Microstructure and Oxidation Behaviour of NGB and WGB Joints With Boron/Silicon Free Nickel Base Braze Alloys

In this study, the microstructure and solidus and liquidus of several Ni-Co-Hf-Zr-Ti-Al braze alloys were first examined with the objective to develop a B and Si free low melting braze alloy for narrow gap (NGB) and wide gap brazing (WGB) and turbine component repair applications. Among various alloys examined, DSC was used to measure the solidus and liquidus during heating and cooling cycles. Following the measurements of liquidus and solidus, the microstructure was evaluated using SEM. Equations for calculating solidus and liquidus based on alloy’s compositions were established and the functions of each elements on these two characteristic temperatures were discussed. One selected alloy with a liquidus of 1201 °C was further employed for NGB and WGB experiments. The results showed that it was able join CMSX-4 at 1240°C without interfacial voids; and with the use of externally applied pressure and extended homogenization treatment the interfacial intermetallic compounds were substantially removed. Furthermore, the same braze alloy was used to fill a large artificial cavity in a WGB scheme at a reduced temperature of 1200°C. The braze alloy was able to fully bond the filler powder alloy in addition to join the two alloys to a IN 738 substrate. Finally, oxidation test was conducted at 1050°C (isothermal in static air) for 100 hours after NGB of CMSX-4 and WGB of IN 738. The results showed that the oxide formed on the standalone braze alloy is very dense and there is no sign of spallation. It contained primarily NiO (+CoO) with no other elements measured. For the NGB joints, large amount of scale spallation was observed on base alloy CMSX-4 while the NGB joint remained spallation free. The oxide formed on the NGB was NiO with partitions of Co, Al, Ti, Cr, and W. The WGB joint region in IN 738 showed oxide scale spallation on the IN 738 substrate side, leaving behind steps and depression on the sample surface. In the WGB joint itself, there were three notable phases after oxidation test, however, no scale spallation could be found. For the majority part of the surface, a Ni-rich oxide covered the surface. There were areas of smaller oxide particles with higher Cr content. Overall, the new boron/silicon free braze alloy was found to be able to join several superalloys in both WGB and NGB schemes without occurrence of defects and the oxidation resistance was superior to both substrate alloys examined in this study.

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 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.

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.

Increase of austenitic ductile iron type D5S durability by high temperature pre-treatment

In the present work, a performance of ASTM A439 Austenitic Ductile Iron type D5S at high temperature in the oxidizing environment was investigated. The obtained results revealed that exposure at temperatures 800?C, 850?C and 900?C resulted in relatively high mass gain and an extensive oxide scale spallation from the samples? surfaces during cooling. On the contrary, the material exposed at 950?C revealed a better oxidation resistance and no oxide scale spallation. The material exposed at 1000?C showed the best oxidation resistance among the studied samples. The surfaces and cross-sectional investigation revealed that the material exposed at 950?C formed mostly Ni/Cr/Mn-mixed protective oxide scale and local formation of Fe-rich nodules. In comparison with the sample exposed at 1000?C, a smaller amount of Fe-rich nodules per area unit was observed and most of the surface was covered by Ni/Cr/Mn-mixed protective scale. The latter was explained by the change in the calculated diffusion coefficients in the alloy for Ni and Fe, namely up to 900?C the diffusion coefficient for Fe was much higher than for Ni, while above 900?C the diffusion coefficient for Ni becomes higher than for Fe. This phenomenon was correlated with a phase transformation from ?-Fe into ?-Fe resulting in the diffusion coefficient change.

COMPARISON OF HOT CORROSION PERFORMANCE OF BARE AND NiCoCrAlY-COATED AUSTENITIC STAINLESS STEEL AISI 347 IN AGGRESSIVE WASTE HEAT INCINERATOR ENVIRONMENT AT 650∘C

The hot corrosion behavior of bare and NiCoCrAlY-coated AISI 347 steel is investigated in Na2SO4-40%K2SO4-10%NaCl-10%KCl salt atmosphere at [Formula: see text]C for 10 cycles. Each cycle contains 5[Formula: see text]h heating and 30[Formula: see text]min cooling to ambient temperature. The NiCoCrAlY coating is employed on the austenitic stainless steel AISI 347 using high-velocity oxy-fuel (HVOF) coating method. Corrosion kinetics of the hot corroded steels are determined by thermo-gravimetric technique. The surface microstructures and compositions of the coating and corrosion products of the steels are characterized using a scanning electron microscope and energy dispersive spectroscopy. The phases of the coating are analyzed using X-ray diffraction method. Higher weight gain is observed on the uncoated specimen, and more oxide scale spallation is observed due to Fe2O3 oxide layer formation. In the coated specimen, there is no spallation of any oxide scales. The coating provides the resistance to the spallation of oxide scales. The EDS point analysis and elemental mapping analysis are performed on the cross-section to analyze the distribution of corrosion products with respect to depth.