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J. Mater. Sci. Technol., 2013, 29(9), 873e878

Dynamic Strain Aging in a Newly Developed NieCo-Base Superalloy with Low Stacking Fault Energy
Chenggang Tian, Chuanyong Cui*, Ling Xu, Yuefeng Gu, Xiaofeng Sun
Superalloys Division, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
[Manuscript received April 18, 2012, in revised form June 7, 2012, Available online 18 April 2013]

Characteristics of dynamic strain aging (DSA) in a NieCo-base superalloy were studied by tensile tests at temperatures ranging from 250  C to 550  C and strain rates ranging from 3 105 to 8 104 s1. Serrated flow in the tensile stress-strain curves was observed in the temperature range from 300  C to 500  C. Normal DSA behavior was found at temperatures ranging from 300  C to 350  C, while inverse DSA behavior was observed at temperatures ranging from 400  C to 500  C. The yield strength, ultimate tensile strength, elongation, work hardening index, and fracture features were not affected by temperature and strain rates in DSA regime. Negative strain-rate sensitivity of flow stress was observed in DSA regime. The analysis suggests that the ordering of the substitutional solutes around some defects like mobile dislocations and stacking faults due to the thermal activated process may cause the serrations on the tensile curves.
KEY WORDS: NiLCo base superalloy; Dynamic strain aging (DSA); Activation energy; Substitutional solute; Stacking fault

1. Introduction Ni-base superalloys are the primary materials for the blades and disks in the advanced gas turbine engines[1e3]. Many nickelbase superalloys[4e15] exhibit serrated ow related to dynamic strain aging (DSA) over a range of temperatures and strain rates. The serrated ow known as the Portevin-Le Chatelier (PLC) effect[16] and the negative strain rate sensitivity (NSRS) are the predominant characteristics in DSA regime. For example, negative strain rate sensitivity has been found in Inconel 600[4], aged Waspaloy[5,6], Inconel 718[7], CMSX-4[8], Alloy 625[9] and U720Li[12]. The critical strain (c) of serrated ow, depending on the tensile temperatures and strain rates, is a crucial factor. Based on the critical strain changing, DSA can be divided into two groups: the normal DSA and inverse DSA. The characteristic of the normal DSA is that the critical strain increases with decreasing test temperature or increasing strain rate. While the characteristic of inverse DSA is that the critical strain decreases with decreasing test temperature or increasing strain rate. Many models[5,17e20] have been proposed to explain the mechanism of DSA behaviors during tensile plastic deformation, which are based on the interactions between diffusing solute
* Corresponding author. Prof., Ph.D.; Tel.: 86 24 83978292; E-mail address: chycui@imr.ac.cn (C. Cui). 1005-0302/$ e see front matter Copyright 2013, The editorial ofce of Journal of Materials Science & Technology. Published by Elsevier Limited. All rights reserved. http://dx.doi.org/10.1016/j.jmst.2013.04.012

atoms and mobile dislocations over the range of plastic ow. The activation energies used to determine which kind of solute locking mobile dislocations are generally obtained through these models. For example, Hayes et al.[5] arrived at a conclusion in Inconel 600 and aged Waspaloy that low test temperature gave normal DSA behavior due to the carbon atmosphere aging mechanism and high test temperature gave inverse DSA behavior because of the interaction between Ni3(Al,Ti) precipitate and carbon atoms. Shankar et al.[9] noted that Mo atoms caused the normal DSA behavior at low temperature in Alloy 625. However, the activation energy cannot be used to determine where the inverse DSA behavior was observed. Nalawade et al.[10] investigated the DSA behavior of Inconel 718 and ascribed the serrated ow to the diffusion of substitutional Nb solute atoms. Hale et al.[11] suggested that the diffusion of C atoms was the reason for the serrated phenomenon at low temperature and the interaction between mobile dislocations and Cr atoms caused the serrated phenomenon at high temperature in Inconel 718SPF. Gopinath et al.[12] noted that the substitutional solutes locking the mobile dislocations are responsible for DSA behavior in U720Li, which includes the normal DSA behavior at low temperature and the inverse DSA behavior at high temperature. Recently, Cui et al.[14] found that the inverse DSA behavior may be related to the occurrence of stacking faults from TEM observation in a NieCo base superalloy. Lee et al.[21] concluded that the DSA may be caused by the breaking away of stacking faults from point defects or pointedefect complex through observing the DSA behavior of twinning-induced plasticity

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(TWIP) steel. Similarly in TWIP steel, Lee et al.[22] proposed that DSA occurs by a single diffusive jump of C atoms of the point defect complex in the stacking fault region and DSA cannot be observed until the C atom reorientation time is smaller than the residence time of the stacking faults at the point defect complex. It is assumed that the stacking faults may take effect in DSA regime in the alloy with low stacking fault energy. In this work, the newly developed NieCo-base superalloy[23] with stacking fault energy of 24.9 mJ/m2 was selected to study the role of stacking faults in DSA regime. In addition, the alloy contains substitutional (Co, Cr, Mo, Al, Ti, W) solutes and interstitial (B, C) solutes, which provides a chance to study how these solutes affect the characteristics of DSA in the alloy. 2. Experimental Table 1 lists the chemical composition of the alloy. The ingot was homogenized at 1200  C for 10 h and subsequently hot extruded to 30 mm in diameter. The alloy was treated by the following heat treatment: 1100  C for 4 h followed by air cooling and then rst aging at 650  C for 24 h followed by air cooling and then second aging at 760  C for 16 h followed by air cooling. The specimens for tensile tests were machined from the heat-treated rods. The samples with a gage section of 3 mm in diameter and 23 mm in length were used in the tensile tests. Tensile tests were carried out on a machine at temperatures ranging from 250  C to 550  C and strain rates from 3 105 to 8 104 s1. All the tensile tests were started after keeping the specimens at the test temperature for 10 min. The samples for optical microscopy (OM) observation were etched in a solution of modied Kalling reagent (100 ml HCl, 100 ml methanol and 50 g CuCl2). The samples for scanning electron microscopy (SEM) were electronically etched in an 80 ml H2O5 ml glacial acetic acid 15 ml nitric acid solution at 1.5 V, normally for 30 s. Thin foils for transmission electron microscopy (TEM) observation were prepared by means of a standard twin jet polishing technique in a solution of 10% perchloric acid and 90% ethanol at about 16 mA and 20  C. 3. Results 3.1. Microstructures Fig. 1 shows the microstructure of the alloy. The average grain size of the alloy was 33 mm (Fig. 1(a)). The inset SEM image in Fig. 1(a) reveals that the irregularly shaped particles at the grain boundary were TiC conrmed by EDS. At higher magnication (Fig. 1(b)), primary g0 (300 nm), secondary g0 (about 100 nm) and tertiary g0 precipitations (about 20 nm) were observed in the g grain. 3.2. Mechanical properties 3.2.1. Tensile stressestrain plots. Fig. 2 shows the plots of true stress vs. true strain from 250  C to 550  C at a strain rate of 3 104 s1. The serrated ow of stress was observed at the test
Table 1 Chemical composition of the NieCo based superalloy (wt%) Cr 14 Co 23 Mo 2.8 W 1.2 Ti 5.6 Al 2.3 B 0.02 C 0.02 Zr 0.03 Ce 0.01 Ni Bal. Fig. 2 True stressetrue strain curves of the alloy tested at different temperatures with a strain rate of 3 104 s1.

Fig. 1 Microstructures of the NieCo superalloy: (a) optical micrograph of the microstructure and SEM image (inset) showing TiC at the grain boundary and in the grain; (b) dark-eld TEM image showing the primary, secondary and tertiary g0 precipitations.

temperatures ranging from 300  C to 500  C. While, at the temperatures of 250  C and 550  C, the stress-strain curves were relatively smooth. The critical strain (c) of serrated ow indicated that the initial strain of serrations depended on temperature and strain rate. 3.2.2. DSA behaviors. Fig. 3 shows the variation of critical strain with strain rates and temperatures. There were two trends in Fig. 3. One is associated with the increase in c with increasing strain rate and decreasing T, which is called normal DSA; and another one is associated with the increase in c with decreasing strain rate and increasing T, which is called inverse

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Fig. 5 shows the fracture surfaces of the specimens tested in the normal DSA regime (350  C, 8 104 s1) and the inverse DSA regime (450  C, 8 104 s1). The dimples were the main characteristic of the fracture surfaces which indicated ductile fracture in both cases. These observations suggested that the characteristic of fracture in the normal DSA regime was the same as that in the inverse DSA regime. 3.2.4. Negative strain rate sensitivity (m). Strain rate sensitivity of the ow stress (s) at a given T and was estimated using the data from the stressestrain curves through following relation[5]: m log s2 =s1 _ 1 = _ 2 ;T log (2)

_) Fig. 3 Variation of critical strain (c) for serrations with strain rate ( and temperature (T).

DSA. The normal DSA behaviors occurred in the temperature range from 300  C to 350  C and the inverse DSA behaviors corresponded to the temperature range from 400  C to 500  C. 3.2.3. Tensile properties. Fig. 4 shows the variation of the yield strength, the ultimate tensile strength, the elongation and the work hardening index with temperature changing under different strain rates. The work hardening index (n) can be obtained from following relation [24,25]:

_ 1 and _ 2 , respectively. where s1 and s2 are the ow stresses at Fig. 6 shows values of m at a strain of 5% determined at different stress levels corresponding to different strain rates from the stress-strain curves. Negative strain rate sensitivity of the ow stress was observed in DSA regime and a minimum value of m at 450  C was obtained. 3.3. Microstructures after tensile test It had been known that the alloy in this experiment has a low stacking fault energy of 24.9 mJ/m2[23]. As a result, the process of super-dislocations decomposing into partial dislocations and stacking faults became easier when the plastic deformation prevailed, as shown in Fig. 7(a). When the formed stacking faults extended on the active slip planes, the partial dislocations changed their slip planes, rather than their slip directions, after their interaction with some obstacles, as shown in Fig. 7(b).

s K n

(1)

where s is the true stress, is the true strain, K is a constant and n is the work hardening index. All the factors except n can be obtained directly from the stress-strain curves. It can be seen that the four tensile properties seemed unaffected by the temperature and strain rates from Fig. 4.

Fig. 4 Variation of the tensile properties with temperature (a) yield strength; (b) ultimate tensile strength; (c) work hardening index; (d) elongation.

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Fig. 5 Fractographs of specimen tested at (a) 350  C, 8 104 s1 (normal DSA regime); (b) 450  C, 8 104 s1 (inverse DSA regime).

4. Discussion 4.1. Activation energy The evaluation of activation energy plays an important role in understanding the DSA mechanism. Based on reports in literature[5,17,2628], four different methods were employed to calculate the activation energy of serrated ow. The activation energies determined from all the methods are summarized in Table 2. It is generally accepted that when the exponent (m b) values range from 0.5 to 1, interstitial solutes are responsible for serrated ow, whereas when (m b) values range from 2 to 3, substitutional solutes are responsible[29,30]. The values of (m b) can be determined in the following relation[26]. C
mb

_ exp Q=RT K

(3)

where m is an exponent related to the vacancy concentration with plastic strain (CV fm ) and b is an exponent related to the density of mobile dislocations with plastic strain (rm fb ), _ is the strain rate, Q is the activation energy, K is a constant, R is the gas constant and T is the absolute temperature. In Table 2, the mean value of the activation energies in the normal DSA regime was calculated to be 46 kJ/mol, which is close to the activation energies for serrations reported for

Inconel 600 (58 kJ/mol)[6], Inconel 718 (42 kJ/mol)[7], and the activation energy for diffusion C in Ni (69 kJ/mol)[31]. In Inconel 600 and Inconel 718, C atoms interacting with mobile dislocations were thought to be responsible for the appearance of serrations. However, the serrated ow in NiC system was observed at a low temperature of 25  C[32], then the diffusion rates of C atoms were too high to produce an atmosphere to lock mobile dislocations at T300  C in the experiment. Additionally, the (m b) value determined to be 2.87 implies the normal DSA behavior is the result of the interaction between substitutional solutes with mobile dislocations. The mechanism for the inverse DSA behavior is also attributed to substitutional solutes pinning up mobile dislocations because the temperatures for the inverse DSA behavior are higher for interstitial solutes forming an atmosphere. The mean value of activation energy for inverse DSA behavior was estimated to be 143 kJ/mol, which is much larger than the value (46 kJ/mol) for normal DSA behavior. But the phenomenon may coincide with the trend of the stress drop indicating the height of individual serration with the increasing temperature in Fig. 8 which shows the stress drop increases with _ 3 104 s1 . the increasing temperature at 5% when Obviously, the change of stress drop and activation energy from the normal DSA region to the inverse DSA region with increasing temperature is related to the thermal activated process. It is possible that the diffusion rates of substitutional solutes are high enough to make them arrange more orderly along mobile dislocations when temperature changes from 350  C to 400  C, which produces a sharp stress drop and a sharp activation energy increase. Therefore, the ordering of substitutional solutes along mobile dislocations may cause the serrated ow in this alloy. 4.2. Stacking fault Recently, some researchers investigated the effect of stacking faults on DSA[14,21,22], as presented in the section of introduction. It is inferred from their investigations that the stacking faults may contribute to the appearance of serrations through its interaction with some solutes. As shown in Fig. 7(b), partial dislocations changed their slip planes after their interaction with some obstacles in DSA regime. As reported before, the interstitial solutes diffused too fast to form an obstacle in the temperature regime (T  300  C) where the serrated ow occurred. Therefore, the occurrence of the serrated ow can be attributed to

Fig. 6 Variation of strain rate sensitivity (m) with temperature at a strain of 5%.

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Fig. 7 TEM image showing (a) the stacking faults at 450  C, 8 105 s1; (b) stacking faults interacting with obstacles at 400  C, 3 104 s1. SF means stacking fault.

the diffusion of substitutional solutes. The substitutional solutes diffused along dislocations to the stacking faults and reoriented in the stacking fault region, which led to be an obstacle for the stacking faults moving. The interaction of this short ordered obstacle with the moving stacking faults was the reason for the serrated ow occurrence. Based on the discussion in section 4.1 and 4.2, the serrated ow in this alloy may be resulted from the interaction between the substitutional solutes and some defects such as mobile dislocations and stacking faults. The movement of the defects in the alloy is controlled by the thermal activated process. 4.3. Negative strain rate sensitivity (m) The strain rate sensitivity of the ow stress was negative in DSA regime and a minimum value of m at 450  C was obtained (Fig. 6). Mulford and Kocks[4] contended that the rate sensitivity becomes negative after a critical strain, which causes serrated ow. Sleeswyk[18] suggested that solute atmospheres form on the forest dislocations and then drain through pipe diffusion from the forest dislocations to the mobile dislocations when the mobile dislocations are waiting at the forest dislocations. Basing on this model, Mulford and Kocks[4] demonstrated that the solute atmosphere does not need pin the entire dislocation but a portion of the dislocation line at the forest dislocation which makes little diffusion produce obstacles strength with waiting

time resulting in a negative rate sensitivity. A recent model[33] favored that the strength of the forest-mobile dislocation junction increases with the size and the strength of the solute atmosphere clustering on the forest dislocation. Gopinath et al.[12] considered that the increasing resistance to the dislocation motion by the serrated ow facilitates diffusion of the solute atoms to dislocations and a resultant negative strain rate sensitivity. All the assumptions pointed out that the negative strain rate sensitivity is related to the interaction between mobile dislocations and solute atmospheres corresponding to serrated ow. From the conclusion obtained for explaining the mechanism causing serrated ow earlier, it is believed that the mechanism also inuences the trend of the value of m corresponding to the increasing temperature: the reorientation of order of the subsutitional solutes around the defects will reduce the value of m, and contrarily the destruction of order of the subsutitional solutes around the defects will increase the value of m. It can be seen that the reorientation of subsutitional solutes around defects is predominant when T  450  C and the destruction of subsutitional solutes around defects is the leading factor when T  450  C, as shown in Fig. 6. As a result, the value of m reaches minimum at 450  C.

Table 2 Summary of activation energy for the DSA behavior Calculating method _ vs. 1/T plots[23] (1) ln (2) McCormick method[14] (3) Intercept method[24] (4) Stress drop method[2,25] Average Q Q for Normal DSA (kJ/mol) Q for Inverse DSA (kJ/mol)

b 2.87)
49 50 40 46 4

46 (m

b 2.17)
138 na 149 143 5

142 (m

Fig. 8 Variation of stress drop with temperature at a stain of 5% and strain rate of 3 104 s1.

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5. Conclusions (1) The alloy exhibited normal DSA behavior at temperatures ranging from 300  C to 350  C and inverse DSA behavior at temperatures ranging from 400  C to 500  C. (2) Negative strain rate sensitivity was observed and the variation of its value with temperature related to the mechanism controlling DSA behavior. (3) The yield strength, ultimate tensile strength, elongation, work hardening index and fracture surfaces did not change noticeably in DSA regime. (4) The ordered arrangement of substitutional solutes around some defects such as mobile dislocations, stacking faults may cause the appearance of serrations in the NiCo based superalloy.

Acknowledgments This work was partly supported by Hundred of Talents Projects, the National Basic Research Program (973 Program) of China under grant No. 2010CB631206 and the National Natural Science Foundation of China (NSFC) under Grant Nos. 51171179, 51128101 and 51271174. REFERENCES
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