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Solution heat-treatment of Nb-modified MAR-M247 superalloy

Paulo Ricardo Soares Azevedo e Silvaa , Renato Baldana,, Carlos Angelo Nunesa , Gilberto Carvalho Coelhoa, b , Alex Matos da Silva Costaa
Universidade de So Paulo (USP), Escola de Engenharia de Lorena (EEL), Departamento de Engenharia de Materiais (DEMAR), Plo Urbo-Industrial Gleba AI-6, Caixa Postal 116, 12600-970, Lorena, So Paulo, Brazil b UniFoa, Centro Universitrio de Volta Redonda, Ncleo de Pesquisa, Campus Trs Poos, Avenida Paulo Erlei Alves Abrantes, 1325, Bairro Trs Poos, 27240-560, Volta Redonda, Rio de Janeiro, Brazil
a

AR TIC LE D ATA
Article history: Received 5 March 2012 Received in revised form 26 August 2012 Accepted 15 November 2012 Keywords: MAR-M247 Solution heat-treatment Niobium Nickel-based superalloy Thermocalc

ABSTR ACT
MAR-M247 superalloy has excellent mechanical properties and good oxidation resistance at elevated temperatures. Niobium is an element known as phase hardener in nickel-based superalloys, besides promoting homogeneous distribution of MC carbides. This work is inserted in a project that aims to evaluate the total replacement of tantalum by niobium atoms in MAR-M247 superalloy (10.2 Co, 10.2 W, 8.5Cr, 5.6 Al, 1.6 Nb, 1.4 Hf, 1.1 Ti, 0.7 Mo, 0.15 C, 0.06 Zr, 0.015 B, Ni balancewt.%). Based on microstructural characterizations (SEM and FEG-SEM, both with EDS) of the as-cast material and heat-treated materials as well as utilizing Thermocalc simulations and experiments of differential thermal analysis (DTA), heat-treatment at 1260 C for 8 h was chosen as an ideal condition for the solution of Nb-modified MAR-M247 superalloy. The hardness of as-cast and ideally solution treated materials was 390 14 HV and 415 6 HV, respectively. 2012 Elsevier Inc. All rights reserved.

1.

Introduction

Solution heat-treatments are common in nickel-based superalloys and play a key role for the application of these materials at high temperatures [1,2]. The objectives of this heat-treatment are the complete solutioning of phase in the matrix and minimizing the segregation from non-equilibrium solidification in preparation for the aging heat-treatment [3]. Then, by aging heat-treatments, it is possible to achieve a controlled phase re-precipitation, producing a uniform and isotropic material [4]. Theoretically, the solution heat-treatment should be carried out between solvus and solidus temperatures in nickel-based superalloys, as described by Semiatin et al. [5]. However, segregation from the non-equilibrium solidification limits the real window of treatment due to incipient melting below the solidus temperature of the alloy. This window is usually between 100 and 200 C [6].

Although the primary precipitates dissolve quickly in the matrix, a substantial time is required for the dissolution of / eutectic regions and to minimize the segregation of the material, because these materials usually have several heavy alloy elements that diffuse slowly in the matrix [7]. Typical solution heat-treatments for conventional MAR-M247 superalloy are carried out at 1230 C for 2 h and 1250 C for 4 and 5 h, as published by Kattus [8], Gasko et al. [9] and Baldan [10], respectively. According to literature, niobium is a refractory element that is normally present in the composition of nickel-based superalloys, found mainly in the phase (replacing aluminum) and in the formation of different types of carbides at the grainboundaries [11,12]. Considering solution heat-treatment, niobium increases solvus temperature, avoiding the dissolution of this phase at lower temperatures. Additionally, niobium promotes the hardener effect of phase at higher temperatures by

Corresponding author. Tel.: + 55 12 3159 9912; fax: +55 12 3153 3006. E-mail addresses: paulori@alunos.eel.usp.br (P.R.S. Azevedo e Silva), renato@ppgem.eel.usp.br (R. Baldan), cnunes@demar.eel.usp.br (C.A. Nunes), coelho@demar.eel.usp.br (G.C. Coelho), alex@ppgem.eel.usp.br (A.M.S. Costa). 1044-5803/$ see front matter 2012 Elsevier Inc. All rights reserved. http://dx.doi.org/10.1016/j.matchar.2012.11.006

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increasing its volume fraction and thermal stability [13]. For this and other reasons, about 50% of casting nickel-based superalloys has between 1.0 and 2.5 wt.% of niobium in its composition, as reported by Sims [14]. In this work, an Nb-modified MAR-M247 superalloy was produced by the total replacement of tantalum atoms by niobium atoms, taking into account the chemical similarity of both elements and the lower cost of niobium. The best condition for solution heat-treatment of this superalloy was evaluated through microstructural characterizations of the as-cast and heat-treated materials, correlating and comparing the results with experiments of differential thermal analysis and simulations with Thermocalc software.

2.

Materials and Experimental Procedure

The conventional MAR-M247 superalloy was modified by the total replacement of tantalum by niobium atoms, the composition of the new Nb-modified MAR-M247 superalloy is as follows (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 130 mm length) at Aotcnica Company (Jandira, So Paulo, Brazil). After cutting the bars using electro-discharge machining (EDM), samples for solution heat-treatments were encapsulated in quartz tubes under argon atmosphere and heat-treated in a tube furnace at 1185, 1240, 1260, 1280 and 1300 C for 2, 4 and 8 h, followed by air cooling. A K-type thermocouple was placed near the sample to determine the real temperature of the sample. The temperature of the heat-treatments was chosen from simulations with Thermocalc software (TTNI8 database), based on data for the liquidus, solidus and solvus temperatures. For microstructural characterization the samples were prepared following conventional metallographic techniques and etched with a glyceregia solution (1/6 HNO3, 2/6 HCl, 3/6 glycerin, vol.%). The microstructural analyses were done with the aid of a conventional SEM LEO 1450VP model and a FEG-SEM JEOL JSM-7001F model, both with EDS detectors. The hardness values of all samples were determined using a Buehler Micromet equipment with a load of 500 gf for 30 s. Differential thermal analysis (DTA) experiments were carried out in order to determine the solvus, incipient melting and liquidus temperatures of the as-cast Nb-modified MAR-M247 superalloy. The experiments were performed in a LABSYS DTA/ DSC Setaram Instrumentation device. Cylindrical samples with 200 mg each were heated in an alumina crucible from 25 up to 1500 C with heating rate of 20 C/min in argon flux. The reference sample was an empty alumina crucible. These results were compared with those from the Thermocalc simulations.

Fig. 1 a and b Simulation of the number of mols' phase between 600 and 1400 C for Nb-modified MAR-M247 superalloy.

3.

Results and Discussion

Fig. 1a shows the simulation of number of mols of phase between 600 and 1400 C for Nb-modified MAR-M247 superalloy. The interpretation of these results was based on the work of Saunders et al. [15]. It can be seen that the volume fraction of phase decreases and that of phase increases as the

temperature increases. Additionally, the alloy has and MC carbides precipitating almost simultaneously at 1360 C. Finally, the ideal region for solution heat-treatment (between the solvus and solidus temperatures) of the alloy is a three-phase region composed by , MC carbide and MB2 boride phases and the temperature range is between 1210 and 1310 C. Fig. 1b shows the amount of minor phases from Thermocalc simulations for the same temperature range. It can be seen that MC carbide is stable and does not decompose in the whole temperature range. In addition, the M6C and M23C6 carbides may form in specific temperature ranges. Fig. 2 shows the DTA thermogram from as-cast Nb-modified MAR-M247 superalloy. The interpretation of these results was based on the work of Sponseller [16]. It is possible to observe the presence of three major regions. The one in blue refers to phase dissolution and does not show clear peak since the phase dissolves gradually in over a wide range of temperature. However, the dissolution final temperature is important because it is associated with solvus temperature (number 1).

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Fig. 2 Differential thermal analysis (DTA) of as-cast Nb-modified MAR-M247 superalloy. (For interpretation of the references to color in this figure, the reader is referred to the web version of this article.)

found in the DTA experiments of Nb-modified MAR-M247 superalloy was confirmed by microstructural characterization of samples heat-treated at 1280 C, as presented below. By comparing the results of Thermocalc simulations and DTA experiments (Table 1), it is possible to observe that the solvus, solidus and liquidus temperatures do not change significantly, but the incipient melting temperature of 1340 C for conventional as-cast MAR-M247 is higher than the temperature of 1281 C for Nb-modified MAR-M247 superalloy. Fig. 3 shows the as-cast microstructure of Nb-modified MAR-M247 superalloy. There can be seen a segregated dendritic microstructure (Fig. 3a) with primary dendrite arm spacing of about 50 m. Additionally, there are / eutectic regions and MC carbides with high aspect ratio in the interdendritic regions. The borides, predicted by Thermocalc, were not observed probably due to their very small quantity and size. Tables 2 and 3 show, respectively, EDS measurements from the dendritic/interdendritic regions and MC carbides for both conventional and Nb-modified MAR-M247 superalloys. The results have shown that Ni, Co and Cr do not have strong partition between the dendritic and interdendritic regions. However, W is found mostly in the dendritic regions. The main elements forming the carbides are Ti, Hf, W and Nb for

The region represented in green should refer to the simultaneous melting of and/or MC carbides. The temperature of the beginning of this event is associated with incipient melting (number 2) and it is lower than the solidus temperature of the material due to the segregation. Finally, the region represented in red refers either to the melting of the remaining or MC carbides. Possible thermal events associated to the formation of the minor phases indicated in Fig. 1b were not detected in the DTA thermogram. Table 1 shows the values of solvus, incipient melting, solidus, MC or melting and liquidus temperatures obtained with Thermocalc simulations and our DTA results from both as-cast Nb-modified and conventional MAR-M247 superalloys. The liquidus and solvus temperatures calculated with Thermocalc and those found in DTA experiments are in good agreement. The incipient melting temperature of 1281 C

Table 1 Thermocalc simulations and temperatures of thermal events from DTA for Nb-modified and conventional MAR-M247 superalloys, both in the as-cast condition. Event Nb-modified MAR-M247 superalloy Thermocalc (C)
Solvus Incipient melting ( or MC) Solidus MC or melting Liquidus
a

Conventional MAR-M247 superalloy Thermocalc (C)

1222 1315 1380

DTA (C)
1238 1281 a 1351 1370

DTA (C)
1225 1340 1343

1210 1310 1360

Sample heat-treated at 1280 C showed incipient melting.

Fig. 3 Micrographs of as-cast Nb-modified MAR-M247 superalloy: (a) Dendritic microstructure from solidification; and (b) / eutectic in the interdendritic region as well as phase precipitated in matrix.

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Table 2 EDS measurements from the dendritic/interdendritic regions (wt.%). Element Nb-modified MAR-M247 Dendritic regions
Ni Co W Cr 63.1 0.5 11.8 0.1 11.7 0.2 8.6 0.2

Conventional MAR-M247 Dendritic regions

59.7 0.7 9.7 0.3 14.3 0.3 8.2 0.6

Interdendritic regions
65.9 1.2 10.6 0.6 7.0 0.6 8.9 0.9

Interdendritic regions
62.9 1.0 9.3 0.2 8.6 1.8 9.1 0.4

Table 3 EDS measurements from the MC carbides (wt.%). Element

Ta Nb Hf W Ti

Conventional MAR-M247
52.5 2.7 16.7 0.6 14.0 4.8 10.5 1.9

Nb-modified MAR-M247
45.4 4.6 17.0 3.3 18.8 3.4 15.0 4.5

Nb-modified and Ti, Hf, W and Ta for conventional MAR-M247 superalloy. Heat-treatments carried out at 1185 and 1240 C have not shown any important modification of the as-cast microstructure

for treatments of reasonable duration. Fig. 4 shows the microstructure of Nb-modified MAR-M247 superalloy heat-treated at 1260 C for 2, 4 and 8 h and 1280 C for 2 h. It can be seen that increasing the time of heat-treatment reduces the segregation and the size of carbides. In the material heat-treated at 1260 C for 2 h (Fig. 4a) it is possible to note the presence of dendritic and interdendritic remaining regions, even though they are much smaller than those in the as-cast material (Fig. 3a). After 4 h of heat-treatment at 1260 C (Fig. 4b) these regions are not observed, but the chemical gradient is not eliminated. The material heat-treated at 1260 C for 8 h (Fig. 4c) has shown a very homogeneous matrix and thus, was chosen as the ideal solution heat-treatment condition for Nb-modified MAR-M247 superalloy.

Fig. 4 Micrographs of Nb-modified MAR-M247 superalloy heat-treated at: (a) 1260 C for 2 h; (b) 1260 C for 4 h; (c) 1260 C for 8 h; and (d) 1280 C for 2 h.

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At higher temperatures of treatment, such as 1280 C for 2 h, the material showed incipient melting evidences in the interdendritic regions (Fig. 4d). Fig. 5 shows in detail the region of incipient melting, which is characterized by the presence of large cluster of carbides with a film, besides a shrinkage hole caused by re-solidification. All samples heat-treated at 1280 and 1300 C have shown incipient melting regions. Fig. 6 shows micrographs obtained in a FEG-SEM of as-cast (interdendritic region) and heat-treated material after ideal solutioning condition (1260 C for 8 h). It is possible to observe the presence of cubic precipitates with approximately 0.5 m in the dendritic region of the as-cast material (Fig. 6a) and with 0.1 m in the heat-treated material (Fig. 6b). The primary particles in the as-cast material are the combination of small cubic particles. However, at the temperature of solution heattreatment, primary phase begins to break down and dissolves gradually into a small pieces known as secondary up to the complete phase dissolution, obtaining a homogeneous material composed by the matrix, MC carbides and MB2 borides (according to Thermocalc simulations). The precipitates present in the solution material are formed via solid state reaction during air cooling from the temperature of heat-treatment to room temperature, associated to a decrease of aluminum and titanium solubility in . Fig. 7 shows the hardness of Nb-modified MAR-M247 superalloy after the different solution heat-treatments. The hardness of as-cast and after ideal solution heat-treatment Nb-modified MAR-M247 superalloy (1260 C for 8 h) is 390 14 HV and 415 6 HV, respectively. It shows that the hardness did not vary significantly between the as-cast and heattreated samples.

4.

Conclusions

Fig. 6 Micrographs of Nb-modified MAR-M247 superalloy obtained in a FEG-SEM showing the -phase precipitated in matrix: (a) dendritic region of as-cast material; and (b) after solution heat-treatment (1260 C for 8 h).

The experimental results of DTA and microstructural characterizations of Nb-modified MAR-M247 superalloy showed a good agreement with Thermocalc simulations. It was possible to

determine an ideal condition for solution heat-treatment of Nb-modified MAR-M247 superalloy (1260 C for 8 h). The microstructure of the material heat-treated in this condition has shown fragmented carbides and a homogeneous matrix with

Fig. 5 Micrograph of Nb-modified MAR-M247 superalloy heat-treated at 1280 C for 2 h showing incipient melting region.

Fig. 7 Average hardness of Nb-modified MAR-M247 superalloy after solution heat-treatments.

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fine precipitates (approximately 0.1 m). It was an observed evidence of incipient melting in samples heat-treated at 1280 C. The hardness of as-cast material is 390 14HV and 4156 HV after ideal solution heat-treatment.

Acknowledgment
The authors are grateful to the Program Pr-EngenhariasCAPES (984/2008), the FAPESP (2010/05211-1), the CNPq (476005/2010-8), the Aotcnica Company (Jandira, So Paulo, Brazil) and to the Instituto Superior Tcnico, (Lisbon, Portugal) for the use of their FEG-SEM facilities. Scholarships from FAPESP and CAPES, 2009/ 17337-2 and 141857/2009-9, respectively, are also appreciated.

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