METALS AND MATERIALS International, Vol. 14, No. 6 (2008), pp. 739~743 doi: 10.3365/met.mat.2008.12.

739 Published 18 December 2008

Thermal Degradation Behavior of Inconel 617 Alloy

Tae Sun Jo , Se-Hoon Kim , Dae-Gun Kim , Ji Yeon Park , and Young Do Kim Division of Materials Science and Engineering, Hanyang University, 17, Haengdang-dong, Seongdong-gu, Seoul 133-791, Korea 2 Nuclear Materials Research Center, Korea Atomic Energy Research Institute, 150-1, Deckjin-dong, Yuseong-gu, Daejeon 305-353, Korea
Inconel 617 alloy is a candidate material for potential use as an intermediate heat exchanger (IHX) and as a hot gas duct (HGD) in high-temperature gas-cooled reactors (HTGRs) for H2 production. This alloy supports severe operating conditions of a pressure over 8 MPa and temperature that exceed 950 oC in He gas with some impurities. In this work, the oxidation behavior of Inconel 617 alloy was studied after exposure at 1050 oC for 2000 h in both air and He atmospheres. The external oxide scale was mainly composed of Cr2O3 and small amount of TiO2. The internal oxide was observed just below the external oxide scale and was distributed on the grain boundaries. The internal oxide was confirmed as Al2O3. The Cr-depleted zone and internal oxide in both environments became thicker as the exposure time increased. The Cr2O3 in air at 2000 h was thinned in terms of its scale by CrO3 evaporation and delamination. The Cr2O3 in He was constantly maintained. Keywords: Ni-base superalloys, Inconel 617, high temperature oxidation, degradation, Cr2O3
1 1 1 1 2 1,*

1. INTRODUCTION
Ni-base superalloys are well known as high-temperature materials for turbine blades, nuclear reactors and high-temperature gas-cooled reactors (HTGRs) due to their excellent overall strength, creep-rupture strength, stability and oxidation resistance at high temperatures [1-4]. Among the alloying elements in Ni-base superalloys, chromium (Cr) and aluminum (Al) can form an oxide layer that serves as a protective surface layer against degradation at high temperatures [5]. In these applications, the amount of Cr and Al in Inconel 617 should be high enough to form the oxide layer. As a wrought Ni-base superalloy, Inconel 617 alloy (Ni22.6Cr-9.53Mo-13.1Co-1.07Al-0.4Ti-0.09C, wt.%) is a candidate for use as the tube material in intermediate heat exchangers (IHX) and in the formulation of hot gas ducts (HGD) in HTGRs under severe operating conditions that o include pressures over 8 MPa and temperatures over 950 C in He gas with some impurities (e.g., H2, H2O, CO, CO2, and CH4). The oxidation behavior of Ni-base superalloys has been investigated under various conditions. There are, however, few studies regarding the effects of the atmosphere on the degradation behavior of Inconel 617 at high temperatures. In this work, the oxidation behavior of the Inconel 617 alloy was studied through exposure at 1050 oC in both an air
*Corresponding author: ydkim1@hanyang.ac.kr

and a He atmosphere for 2000 h. The behavior under high-temperature degradation is discussed in detail in terms of the microstructural changes during the surface oxidation process.

2. EXPERIMENTAL PROCEDURE
Inconel 617 alloy was annealed at 1177 C and was waterquenched. It was then formed into plates that were 20 mm thick. The composition of this material is given in Table 1. The specimens were machined to an appropriate size (12 mm 5 mm 9 mm) for an oxidation test and were exposed o to an air and a He atmosphere at 1050 C for 2000 h. Table 2 indicates the contents of the impurities in the He gas. The microstructures of each sample were observed by scanning electron microscopy (SEM) and via electron probe microanalysis (EPMA). The samples for microstructure observation were prepared by etching for 10 s to 40 s with Kallings reagent (100 ml HCl + 100 ml C2H5OH + 5 g CuCl2) [2].
o

3. RESULTS AND DISCUSSION

Figure 1 shows cross-sectional micrographs of the Inconel 617 alloy after exposure to the air and He environment at o 1050 C for 120 h and 2000 h. After exposure for 120 h, the surfaces were significantly oxidized in both atmospheres, as depicted in Figs. 1(a) and (d). The oxide layer can be distinguished

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Table 1. Chemical composition of Inconel 617 (wt.%)

Max.

C 0.09

Ni 51.99

Fe Si Mn 1.0447 0.0541 0.1279

Co 13.1

Cr 22.6

Ti 0.4

P S <0.002 <0.002

Mo 9.53

Al 1.07

B 0.002

Cu <0.01

Table 2. Contents of the impurities in the helium gas (oxygen partial pressure: 4.5 10 atm)
-7

Component He O N T.H.C. HO
2 2 2

Specification 99.9995 % 0.5 ppm below 1.5 ppm below 0.5 ppm below 3.0 ppm below

Result 99.99955 % 0.45 ppm below 1.45 ppm below 0.45 ppm below 3.00 ppm below

as two regions in both environments: the external oxide scale on the surface and internal oxide on the grain boundaries. The thickness of the external oxide scale after 120 h was approximately 15 m in air and 10 m in He. Thus, the oxide growth rate at the initial stage in air was faster than that in He, as shown in Figs. 1(a) and (d) due to the high oxygen partial pressure. After the exposure for 2000 h, the thickness of the external oxide scale in air became thin due to delamination, as shown in Figs. 1(b) and (c). On the other hand, the external oxide scale became slightly thicker during prolonged exposure in He, as presented in Figs. 1(e) and (f). The oxidation behavior is well summarized in oxide maps, in which the oxidation data are superposed on a Ni-Cr-Al ternary diagram [6-8]. Those maps are not thermodynamic diagrams but are based upon kinetic processes that take place during the scale development process. Three primary regions of oxidation are present: (I) NiO external scales + Al2O3/Cr2O3/Ni(Al,Cr)2O4 internal oxides, (II) Cr2O3 external scales + Al2O3 internal oxides, and (III) external scales of

Al2O3 only. In the Inconel 617 alloy, the oxidation occurs at the region (II); hence, the protective oxide layer mainly consists of Cr2O3 in the external oxide scales and Al2O3 in the internal oxide. Figure 2 and Figure 3 indicate the distributions of Cr, Ti, Al, Ni, Mo and Co by EPMA mapping of the cross-sectional plane. The Cr and Ti were mostly located in the external oxide scales and Al was distributed on the grain boundaries in both environments. Thus, the protective oxide layer consists mainly of Cr2O3 and small amounts of TiO2 in the external oxide scales and Al2O3 in the internal oxide. The formation of internal oxide takes place under the following conditions: (I) lower free energy of formation of the internal oxide compared to the external oxide, (II) a large negative value of the standard Gibbs free energy for the formation of oxide, and (III) a low concentration of the alloying elements [9]. The standard Gibbs free energy of Al was found to be lower than that of Cr and other alloying elements [10]. Therefore, Al2O3 should be preferentially formed as an internal oxide along the grain boundaries due to the oxygen that diffuses from the surface. Figure 4(a) shows the increasing depth of the internal oxide as the exposure time increases. The carbides on the grain boundary are dissolved, and the internal oxide is Al2O3 due to the Al that is diffused from the matrix and the oxygen that is diffused from the surface. The internal oxide formed by exposure to air was deeper than that formed by exposure to He and was preferentially distributed along the grain boundary, as shown in Fig. 1. Such internal

Fig. 1. Morphologies of Inconel 617 after aging at (a) 120 h, (b) 2000 h; (c) BSE image in air and at (d) 120 h, (e) 2000 h; (f) BSE image in He.

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Fig. 2. EPMA mapping images of Inconel 617 after aging at 2000 h for (a) Cr, (b) Ti, (c) Al, (d) Ni, (e) Mo, and (f) Co in air.

Fig. 3. EPMA mapping images of Inconel 617 after aging at 2000 h for (a) Cr, (b) Ti, (c) Al, (d) Ni, (e) Mo, and (f) Co in He.

oxide on the grain boundary strongly affects the mechanical properties. Initial cracks appear as a result of internal oxide propagation along the grain boundary [11]. In the case of the formation of the external oxide, Cr is initially oxidized on the surface due to its high concentration in the alloy and the low activation energy needed for the formation of the oxide. Subsequently, the oxidation of Cr is advanced at the surface of the Cr2O3 layer by reaction with oxygen from the gas phase coupled with Cr diffusing outward from the matrix and by carbide dissolution. Consequently, the formation of Cr2O3 creates a Cr-depleted zone just below the external oxide scale. A Cr-depleted zone with this depth depends on a number of factors, including its concentration, the rate of scale growth and the alloy inter-diffu-

sion coefficient. The Cr-depleted zone usually contains at least 18 wt.% to 20 wt.% of Cr in a Ni-Cr alloy system [10]. The amount of Cr element in the matrix of Inconel 617 is approximately 22.6 wt.%. Thus, the Cr-depleted zone expanded during the Cr2O3 growth phase due to the supply of Cr in the matrix, which itself was a result of the limited supply of Cr in the Cr-depleted zone. It is known that carbides on the grain boundary, such as M23C6 (Cr21Mo2C6) and M6C (Mo3Cr2(Ni,Co)1C), are dissolved into the matrix during the formation of a Cr-depleted zone by oxidation. Hence, the dissolved region of carbides on the grain boundary can be morphologically considered as the Cr-depleted zone [12]. Figure 4(b) presents the thickness of the Cr-depleted zone as determined by the dissolved

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Fig. 5. The concentration profiles of the Cr element after exposure for 2000 h in air and He.

Fig. 4. Change of (a) the internal oxide and (b) the Cr-depleted zone in air and He.

region of carbides on the grain boundary while increasing the exposure time in air and He. By prolonging the exposure time, the Cr-depleted zone was increased in both atmospheres, though the air environment accelerated the dissolution of carbides. Figure 5 demonstrates the concentration profile of Cr from the surface after exposure for 2000 h in the air and He environments, in which the depth of the Cr-depleted zone was in good agreement with the result for the region of dissolved carbides. The content of Cr was very high in the first region due to the Cr2O3 on the surface, after which the Cr concentration decreased rapidly. In the second region, the Cr concentration gradually increased toward the interior of the matrix. The Cr-depleted zone in the sample exposed to air was deeply expanded compared to that in the sample exposed to He. However, the external oxide scale formed in the He after 2000 h was thicker than that formed in air; this is the likely result of a scale thinning effect on the external oxide scale. There are two important types of scale thinning behaviors: delamination of the scale and evaporation of the CrO3. The delamination of the scale generally occurs in thick oxide layers on metal substrates due to compressive stress that arises

from the large differences in the thermal expansion coefficients between the scale and the matrix. Volatile CrO3 forms from the Cr2O3 by means of the following reaction: Cr2O3(s) + 3/2O2 = 2CrO3(g), depending on the temperature and the oxygen partial pressure [10,13]. The instantaneous change in the thickness of the external oxide scale is the sum of two factors: thickening due to oxidation and thinning due to delamination and volatilization. During the initial exposure, the diffusion of oxygen and Cr toward the surface of the Cr2O3 layer is rapid; hence, the oxide growth rate is accelerated and the thickening effect is dominant. As the external oxide scale thickens by oxidation, the thinning by volatilization becomes significant. When the rate of oxidation is equal to that rate of volatilization, the thickness of the oxide scale will remain constant. The vapor pressure of CrO3 increased as the oxygen partial pressure increased [10,14]. Thus, the formation of Cr2O3 took place, forming the external oxide scale simultaneously as the CrO3 evaporated. The oxygen partial pressure in He (Po2 = 4.5 10-7 atm) was considerably lower than that in air. The external oxide scale in the He was constantly maintained with the balance of the scale growth and the evaporation of CrO3 without delamination of the scale. In the air environment, strong volatilization of CrO3 will occur. Moreover, the delamination of Cr2O3 in air took place due to the increase in the compressive stress as a result of the large differences in the thermal expansion coefficient after the fast scale growth.

4. CONCLUSION
Oxidation behaviors of Inconel 617 in air and helium environments were investigated in this study. The results are given below. 1. The thickness of the external oxide scale after exposure

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for 120 h was approximately 15 m in an air and 10 m in He. The oxide growth rate in air was faster than that in He. However, the thickness of the external oxides scale became thin by extending the exposure in air to 2000 h. The external oxides scale in He was mostly maintained compared to the initial stage. 2. The Cr and Ti were mostly located in the external oxides scales and Al was distributed on the grain boundaries in both environments. The protective oxide layer mainly consisted of Cr2O3 with small amounts of TiO2 in the external oxide scale and Al2O3 in the internal oxide. 3. The formation of Cr2O3 caused a Cr-depleted zone just below the external oxide scale. The internal oxide formed preferentially in the form of Al2O3 along the grain boundaries in the Cr-depleted zone. The depths of the Cr-depleted zone and the internal oxide in the air environment were extended. 4. The external oxide scale in the air environment was thinned by CrO3 evaporation and by the delamination of the scale. On the other hand, the external oxide scale in the He environment was constantly maintained with the balance of the oxidation and the CrO3 evaporation. Moreover, delamination of the scale on the surface was not observed.

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ACKNOWLEDGMENT
This work was supported by the research fund of the Korea Atomic Energy Research Institute.