JMEPEG DOI: 10.

1007/s11665-013-0531-1

ASM International 1059-9495/$19.00

Aging of a New Niobium-Modied MAR-M247 Nickel-Based Superalloy

Renato Baldan, Paulo Ricardo Soares Azevedo e Silva, Carlos Angelo Nunes, and Gilberto Carvalho Coelho (Submitted November 23, 2012; in revised form February 25, 2013) MAR-M247 is a nickel-based superalloy that contains 3 wt.% Ta (weight percent of tantalum). Considering the chemical similarity between tantalum and niobium (Nb) and the lower cost of Nb, a modied MARM247 superalloy was produced with total replacement of Ta by Nb in this work. The samples were previously solutioned at 1260C for 8 h and then aged at different times (between 5 and 80 h) and temperatures (between 780 and 980C). The microstructures of the aged samples were characterized with a scanning electron microscope (SEM and FEG-SEM, both with EDS). Simulations of the MC carbide and c fraction and the Ta and Nb content in both MC carbide and c phase were performed with Thermo-Calc software (TT_Ni8 database) and simulations of the c growth rate and c mean diameter were performed with JMatPro software. MC carbide with high Hf content was observed in all the aged samples, in agreement with thermodynamic simulation results. The equilibrium c fraction decreases from 67 mol.% at 780C to 52 mol.% at 980C. Good agreement between the calculated and experimentally determined c particle size was also found. The growth rate of c at 980C is about 8 times higher than that at 780C and 3 times higher than that at 880C. The hardness values do not change considerably after aging at 780 and 880C. However, these values decrease signicantly after aging at 980C.

Keywords

aging, JMatPro, MAR-M247, nickel-based superalloy, niobium, Thermo-Calc

1. Introduction
MAR-M247 is a polycrystalline nickel-based superalloy that has excellent mechanical and oxidation resistance at elevated temperatures (Ref 1, 2). It is possible to achieve more than 60 vol.% of c phase in the microstructure of this superalloy through correct solution and aging heat treatments (Ref 1-3). Its composition contains 3 wt.% tantalum; considering the chemical similarity between tantalum and niobium and the lower cost of niobium, a modied MAR-M247 superalloy, here called MAR-M247(Nb), was produced with total replacement of tantalum by niobium atoms. Niobium is a refractory element normally present in the composition of nickel-based superalloys, replacing aluminum atoms in c phase and contributing to the formation of carbides that
Renato Baldan, Paulo Ricardo Soares Azevedo e Silva, and Carlos Angelo Nunes, Departamento de Engenharia de Materiais (DEMAR), Escola de Engenharia de Lorena (EEL), Universidade de Sao Paulo (USP), Caixa Postal 116, 12600-970 Lorena, Sao Paulo, Brazil; and Gilberto Carvalho Coelho, Departamento de Engenharia de Materiais (DEMAR), Escola de Engenharia de Lorena (EEL), Universidade de Sa o Paulo (USP), Caixa Postal 116, 12600-970 Lorena, Sa o Paulo, Brazil; and UniFoa Centro Universita rio de Volta Redonda, Nu cleo de Pesquisa, Campus Tre s Poc os, Avenida Paulo Erlei Alves Abrantes, 1325 Bairro Tre s Poc os, 27240-560 Volta Redonda, Rio de Janeiro, Brazil. Contact e-mails: renatobaldan@gmail.com, renato@ppgem. eel.usp.br, paulori@alunos. eel.usp.br, cnunes@demar.eel.usp.br, and coelho@demar.eel.usp.br.

increase grain boundary cohesion (Ref 4, 5). Niobium also contributes to the strength of the superalloy by increasing the volume fraction and thermal stability of the c phase (Ref 5-7). For example, more than 50% of cast nickel-based superalloys have between 1 and 2.5 wt.% of niobium in their composition (Ref 7). Aging heat treatment of Ni-based superalloys generally emulates solution heat treatment and provides increased creep resistance by generating very ne secondary c particles with suitable size and distribution in the c channels (Ref 8-12). To achieve the best results, the temperature and duration of heat treatment must be determined carefully because they affect the hardening behavior of these alloys. The aim of this work is to present the results concerning the microstructural changes in this new niobium-modied MARM247 Ni-based superalloy after different aging heat treatments. The results were correlated with simulations using the ThermoCalc and JMatPro softwares.

2. Materials and Experimental Procedure

The conventional MAR-M247 superalloy was modied by total replacement of the tantalum by niobium, and the composition of the new MAR-M247(Nb) superalloy is as follow (wt.%): 10.2 Co; 10.2 W; 8.5 Cr; 5.6 Al; 1.6 Nb; 1.4 Hf; 1.1 Ti; 0.7 Mo; 0.15 C; 0.06 Zr; 0.02 B; Ni balance. The alloy was prepared in a vacuum induction melting furnace and cast into cylindrical rods (15 mm diameter x 130 mm length) by pouring the liquid alloy into a ceramic shell mold prepared using the lost wax technique at Ac ote cnica Company (Jandira, Sa o Paulo, Brazil). The samples subjected to aging heat treatments were previously solutioned at 1260C for 8 h, encapsulated in quartz tubes under an argon atmosphere, and then heat treated in a

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Fig. 1

Thermo-Calc simulation of the number of moles of phase between 600 and 1400C for MAR-M247(Nb) superalloy

tubular ceramic furnace with MoSi2 heating elements. A K-type thermocouple was placed near the quartz tubes to determine the real temperature of the samples. Aging heat treatments were performed at 780, 880, and 980C for 5, 20, and 80 h. The aged samples were air cooled to room temperature. The samples were prepared for microstructural characterization using the standard metallographic procedures of grinding, polishing, and then etching with 1% citric acid and 1% ammonium persulfate in water. Microstructural analysis was performed with a conventional scanning electron microscope (SEM; LEO model 1450VP and a FEG-SEM JEOL model JSM-7001F), equipped with an EDS detector. The hardness values of all samples were determined using a Buehler Micromet hardness tester with a load of 500 gf for 30 s. Simulations of the MC carbide fraction and c fraction, and the Ta and Nb content of the MC carbide and c phase, were performed with Thermo-Calc software (TT_Ni8 database); simulations of the c growth rate and c mean diameter were performed with JMatPro software (Nickel database). The c mean diameter of aged samples was measured direct in the micrograph (500 particles randomly in each sample) with the aid of ImageJ software. The shape of each particle was approximated to a square and the area of the particles was calculated. By utilizing the equivalence of the areas, the equivalent diameter of the particles was calculated by the relationship A = pd2/4, where A is the area of the square and d is the equivalent diameter of the particle. This procedure was necessary because the simulations in JMatPro only give the diameter of c particles. Additionally, it was necessary to set the initial diameter of the c particles in order to make the simulations of the aging conditions. It is important to note that the c simulated and measured values are an average and there are bigger and smaller particles than the presented values.
Fig. 2 (a) Micrograph of the sample heat treated at 1260C for 8 h; (b) zoomed in micrograph of the region shown in (a)

3. Results and Discussion

The main purpose of the initial solution heat treatment is to dissolve c/c eutectic pools and coarse c and to reduce segregation of the as-cast material. The solutioning temperature must be higher than the c solvus, but lower than the solidus/ incipient melting temperature. During solutioning at temperatures above the c solvus, primary c particles begin to break down and gradually form small secondary c particles until

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Fig. 3 Micrographs of the MAR-M247(Nb) aged at (a) 780C for 5 h; (b) 780C for 20 h; (c) 780C for 80 h; (d) 880C for 5 h; (e) 880C for 20 h; (f) 880C for 80 h; (g) 980C for 5 h; (h) 980C for 20 h; (i) 980C for 80 h

complete c phase dissolution. When the sample is air cooled from the solutioning temperature, the solubility of aluminum and titanium in nickel decreases and causes precipitation of ne c particles. Figure 1(a) and (b) shows a simulation performed with Thermo-Calc of the number of moles of the phase between 600 and 1400C for MAR-M247(Nb) superalloy. According to Fig. 1(a), the liquidus, solidus, and c solvus temperatures calculated with Thermo-Calc for the MAR-M247(Nb) superalloy are 1360, 1310, and 1210C, respectively. These values are close to 1360, 1320, and 1220C calculated for the

conventional MAR-M247 superalloy. Additionally, there is no transformation from MC to either M23C6 or M6C through the MC + c M23C6/M6C + c reaction at any of the aging temperatures used in this work (Fig. 1b). Figure 2(a) and (b) shows micrographs of the MARM247(Nb) superalloy solutioned at 1260C for 8 h, based on previous results reported elsewhere (Ref 13). This sample has a very homogeneous c matrix, with uniformly distributed MC carbides and cuboidal c precipitates of nanometric size (92 29 nm), which are formed during cooling from the solutioning temperature.

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Fig. 3

continued

When a solutioned sample is heated up to the aging temperature, the c precipitates tend to grow, which adjusts the volume fraction dictated by thermodynamic equilibrium. Figure 3(a)-(i) shows micrographs of the aged MARM247(Nb); the c precipitates present in all aged samples are uniformly distributed in the c matrix. In order to compare the microstructure of the conventional MAR-M247 with MARM247(Nb) superalloy, Fig. 4 shows the microstructure of the conventional MAR-M247 aged at 880 and 980C for 5 h. It is possible to observe the blocky morphology of c particles in the sample aged at 980C, while the sample aged at 880C shows an irregular morphology. These results are close to the MARM247(Nb) superalloy (Fig. 3d and g) and indicate that the c shape did not change signicantly when comparing both alloys aged at the same condition. Figure 5 shows both the simulated (JMatPro software) and minimum/maximum experimental values of the c mean diameter as a function of aging conditions (time and temperature). The initial mean diameter of c particles used in the simulations was 0.1 lm, which agrees with the measured mean diameter of c in the solutioned sample. The minimum measured values are in close agreement with the simulated values. Additionally, samples heat treated at 780 and 880C for 5, 20, and 80 h do not show signicant differences in the mean c size when compared to the solutioned sample because the kinetics of the c phase growth at these temperatures is low (Table 1). However, there is a signicant increase in the kinetics of c phase growth at 980C, which is evidenced by the

large mean size of c after 80 h of aging. Table 1 shows the growth rate of c obtained with JMatPro and the expected equilibrium fraction of c at 780, 880, and 980C obtained with Thermo-Calc. The c growth rate at 980C is about 8 times higher than that at 780C and 3 times higher than that at 880C. Additionally, the c fraction for MAR-M247(Nb) superalloy decreases from 67 mol.% at 780C to 61 mol.% at 880C and 52 mol.% at 980C, which is close to 66 mol.% at 780C, 60 mol.% at 880C, and 51 mol.% at 980C found for conventional MAR-M247 superalloy. Table 2 shows the compositions of c phase and MC carbide obtained with Thermo-Calc for the MAR-M247(Nb) superalloy and for the conventional MAR-M247 as a function of the aging temperature. In both superalloys, hafnium is the main alloying element in the MC carbide. Standardless EDS analysis of the MC carbide phase in the sample aged at 880C for 5 h identied the main metallic elements present as follows (in wt.%): 54.1 1.2 Hf and 26.9 0.7 Nb for the MARM247(Nb) superalloy and 55.4 2.3 Hf and 26.4 3.8 Ta for the conventional MAR-M247 superalloy. In spite of the main elements of MC carbide being in agreement, the contents are in disagreement with the calculated values listed in Table 2, probably due to the low time of the aging heat treatment for the MC carbides to achieve the equilibrium composition. Additionally, the simulations for MC carbide show that in MARM247(Nb), as the aging temperature is increased, the amount of niobium increases while the amount of hafnium decreases. According to the Thermo-Calc simulations in Table 2, the

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Table 1 Growth rate of c (obtained with JMatPro) and c fraction (obtained with Thermo-Calc) at 780, 880, and 980C
T (C) 980 880 780 Growth rate of c, nm/h1/3 87.5 34.2 11.6 c Fraction, mol.% 52 61 67

Table 2 Ta and Nb content for MC carbides and c phase in MAR-M247(Ta) and MAR-M247(Nb) superalloys calculated with Thermo-Calc at the aging temperatures
Aging temperature, C 780 880 980 MAR-M247(Ta), wt.% MC carbide 84 Hf 74 Hf 63 Hf 6 Ta 15 Ta 24 Ta c phase 4 Ta 4 Ta 4 Ta MAR-M247(Nb), wt.% MC carbide 85 Hf 79 Hf 71 Hf 4 Nb 9 Nb 15 Nb c phase 2 Nb 2 Nb 2 Nb

Other elements are excluded due to their low concentrations

Fig. 4 Micrographs of the conventional MAR-M247 aged at (a) 880C for 5 h; (b) 980C for 5 h

Fig. 6 Hardness for the samples aged at different time and temperature conditions

Fig. 5 Mean diameter of c (in lm) at different aging heat treatment conditions obtained from simulations with JMatPro software

Figure 6 shows the hardness values of the aged MARM247(Nb) superalloy. The mean hardness value for MARM247(Nb) solutioned at 1260C for 8 h is 415 6 HV. This value is close to 417 11 HV measured for conventional MAR-M247 superalloy solutioned at 1250C for 5 h. For the aged samples, the hardness values do not change considerably after aging at 780 and 880C, in agreement with the size distribution of c particles discussed previously. However, the hardness values decrease signicantly for the material aged at 980C, most likely because of the lower volume fraction of c phase (see Table 1) and the considerable increase in c particle size, especially when aged for 80 h.

niobium content of the c phase in MAR-M247(Nb) is near 2 wt.% (1.5 at.%), whereas the tantalum content in the same phase of the conventional MAR-M247 is near 4 wt.% (1.4 at.%); these values do not change signicantly for the aging temperatures used in this work.

4. Conclusions
The liquidus, solidus, and c solvus temperatures calculated with Thermo-Calc for the new Nb-modied MAR-M247

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superalloy are 1360, 1310, and 1210C, respectively. Simulations with Thermo-Calc have shown that the MC carbides are stable between 700 and 1300C. EDS analysis of the MC carbide phase in a sample aged at 880C for 5 h identied the main metallic elements present as follows: 54.1 1.2 wt.% Hf and 26.9 0.7 wt.% Nb for the MAR-M247(Nb) superalloy. The c fraction decreases from 67 mol.% at 780C to 52 mol.% at 980C. Good agreement was also found between the calculated and experimentally determined c particle size. The c growth rate at 980C is about 8 times higher than that at 780C and 3 times higher than that at 880C. Hardness values do not change considerably after aging at 780 and 880C. However, these values decrease signicantly when the material is aged at 980C, most likely because of the lower volume fraction of c phase and the considerable increase in c particle size.

Acknowledgments
The authors are grateful to the Program Pro -Engenharias CAPES (984/2008); FAPESP (2010/05211-1); CNPq (476005/ 2010-8); Ac ote cnica Company (Jandira, Sa o Paulo, Brazil); and the Instituto Superior Te cnico (Lisbon, Portugal) for use of its FEGSEM facilities. Scholarships from FAPESP and CAPES, 2009/ 17337-2 and 141857/2009-9, respectively, are also appreciated.

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