Materials Science & Engineering A 577 (2013) 197 201

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Materials Science & Engineering A

journal homepage: www.elsevier.com/locate/msea

The effect of vanadium impurity on Nickel 5(012) grain boundary

EL Tayeb Bentria n, Ibn Khaldoun Lefkaier 1, Bachir Bentria 2
Laboratoire de Sciences Fondamentales, Universit Amar Telidji de Laghouat, BP 37G, Laghouat 03000, Algeria

art ic l e i nf o
Article history: Received 18 February 2013 Received in revised form 12 April 2013 Accepted 13 April 2013 Available online 21 April 2013 Keywords: Grain boundary DFT Nickel Tensile strength Segregation energy

a b s t r a c t
We report rst-principle density functional theory investigation on the effect of vanadium impurity in the nickel 5(012) symmetrical tilt grain boundary (GB) using Norm-conserving pseudopotentials. We rst calculate segregation energies for interstitial and different substitutional sites in order to determine site preference and the segregation properties of V in the Ni GB. It is found that vanadium atoms prefer to segregate in the substantial sites of the GB. Furthermore, the calculations of tensile strength for different V positions in Ni 5(012) GB show an enhancement of the maximum tensile strength sMax up to 17%, indicating that vanadium acts as a strengthening element in Ni GB, which is in agreement with experimental observations. & 2013 Elsevier B.V. All rights reserved.

1. Introduction Nickel-Based superalloys are an important class of metallic materials, they present exceptional properties of toughness, high temperature strength and resistance to degradation in corrosive or oxidizing environments. These materials are widely used in power-generation turbines, aircraft, rocket engines, and other challenging environments, including nuclear power and chemical processing plants [1]. In fact, during the past few decades, turbine airfoil temperature capability has increased on average by about 4 K/year [2]. Two major factors have made this increase possible: advanced processing techniques which improved alloy cleanliness and crystallization and superalloys development by strengthening through solid-solution and precipitation. The precipitationstrengthened alloys of our interest are used in applications requiring high-temperature strength, good corrosion and creep resistance. For example, the enhancement of turbine blades and vanes in gas turbines, is made possible through the additions of refractory elements. It was found that impurities such as B, S, P, V, Nb added in ppm concentrations can drastically change material properties [3,4]. Among refractory elements, vanadium is one of the key alloying elements contributing to the strengthening of superalloys, especially as precipitation-hardening agent [36]. In Ni-based superalloys, precipitations are formed at the grain boundaries after heat

Corresponding author. Tel.: +213 792 33 68 39; fax: +213 29 93 21 45. E-mail addresses: tayeb.bentria@gmail.com, t.bentria@lagh-univ.dz.(E. T. Bentria)lefkaier_ik@yahoo.fr.(I.K. Lefkaier)bentria_b@yahoo.co.uk.(B. Bentria) 1 Tel./fax: +213 29 92 00 66. 2 Tel.: +213 553 35 47 05. 0921-5093/$ - see front matter & 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.msea.2013.04.047

treatment or an aging process usually as carbide precipitations. This precipitation prevents grain boundary sliding and therefore the creep rupture life is improved [68]. To the best of our knowledge no quantitative work has been presented so far to determine the strengthening effect of vanadium precipitations on nickel grain boundaries. Therefore, the study of vanadium segregation and its enhancing effect on tensile strength in nickel matrix seems to be a requirement in order to further widen basic understanding of the strengthening mechanisms of nickel based superalloys. In order to carry out a theoretical investigation on the role of impurities in nickel GB, it is rst necessary to identify which GB congurations are most stable. The coincidence site lattice (CSL) concept can be used to create GB models. Using the CSL method, computer simulated samples can be generated to study GBs at an atomistic level by means of ab initio investigations. These methods are a promising and cost-effective research strategy widely used in recent years to study the role of impurities segregated atoms. Among the different possible GB congurations in BCC nickel, the 5(012) GB is wildly studied because of its simplicity and stability. Yamaguchi et al. and Kart et al. independently conducted the rstprinciples density functional theory (DFT) calculations to understand why and how Sulfur impurity atoms weaken Ni GB [9,11] and how the increasing concentration of boron impurities in Ni GB leads to its mechanical enhancement [10]. Other works were conducted in order to study the segregation of niobium in nickel 5(012) GB [13] and many sp-impurities from the 3rd, 4th and 5th period and the 1316th groups of the Periodic Table [14]. The aim of this paper is to study the segregation effects of vanadium on nickel 5(012) GB by means of DFT by calculating the tensile strength and segregation energies. Different segregation preferential sites and cut planes will be considered. This paper is

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organized as follow. After this introduction, Section 2 briey describes the structural models as well as method and parameters used in our theoretical calculations. Section 3 presents the results of our calculations and a thorough discussions on V segregation and tensile strength. Conclusions are drawn in Section 4.

c a=<110> b=<121> c=<012> a

2. Model and computational details 2.1. Electronic structure calculation Total energy calculations and geometry optimizations have been carried out using DFT pseudopotential plane wave method as implemented in Cambridge serial total energy package (CASTEP) [15]. Local density approximation LDA CA-PZ is used for the exchange-correlation potentials (CA-PZ: CeperleyAlder [16], data as parameterized by PedrewZunger [17]). Norm-conserving pseudopotentials (NCP) [18] with the following valence electronic congurations Ni:3d84S2 and V:3d34S2 were used with a plane wave cutoff energy of 720 eV. The k points sampling of Ni unit cell was carried out using 8 8 8 Monkhorst Pack mesh grid which corresponds to 3 5 1 k-points sampling of our grain boundary model. Based on conclusions of Tian et al., the spin effect is taken into consideration in all our calculations due to its effect in reducing the GB cohesive energy which has important inuence on tensile strength [19]. The calculations assure a high level convergence of the total-energy difference with respect to the number of atoms within 106 eV and maximum HellmannFeynman force within 0.1 meV/ for pure Ni 5(012) GB and energy difference of 2.105 eV for segregation and tensile test calculations. For reasonable and fast convergence of the total energy, electronic occupancies were determined according to the Gaussian scheme [20] with an energy smearing of 0.2 eV. The Pulay scheme of density mixing was used for self-consistent eld (SCF) calculations [21]. 2.2. Grain boundary modeling The FCC 5(012) 001 symmetrical tilt boundary is formed by rotating one grain 53.11 with respect to the other about a common 001 tilt axis with the boundary plane parallel to (012) [12]. This procedure produces an ideal structure. Since we study the effect of only one atom of vanadium and its concentration in GB is out of our scoop, 44-atoms supercell is used as a model of the GB, distributed on 11 layers. The inuence of the surface on our GB model is expected to be sufciently reduced so as to be negligible because it is well known that the disordering of atomic positions at the GB almost disappears over 2 or 3 atomic layers. For this reason, the unit cell used in tensile strength calculations has sufcient length (2.5 nm) in the c-axis direction with a grain size of 0.55 nm. Due to the symmetry of the grain boundary sites [12], the study of segregation effects in one grain is sufcient, so we prefer to build one side of GB with more layers than the other in order to investigate a large number of segregation possibilities. Fig. 1 shows our GB model used to study the segregation process where the atomic sites are labeled by numbers. Site 0 indicates grain boundary vacancy site used for V insertion while the other Ni sites (111) are impurity substitution sites. In order to obtain the equilibrium lattice parameters of pure ferromagnetic nickel, we performed a volume relaxation. The lattice constant is found to be equal to 3.506 (the experimental value is 3.524 ). The dimensions of the unit cell of GB model are then 3.5 4.3 24.5 3. To avoid the effect of VV interaction due to lattice periodicity, we double the lowest model parameter (Fig. 1), so we get a 7.0 4.3 24.5 3 cell. This unit cell has a vacuum region. In order to guarantee negligible interaction between the two surfaces that sandwich the vacuum region, the

Vacuum

GB

Bulk

FS

Fig. 1. Unit cell model of Ni 5(012) 001 symmetrical tilt grain boundary, model used in segregation study. Unit cell shapes are shown by solid lines. Axes directions and orientations are also presented. Atomic sites used in segregation are indicated by numbers (011).

width of this region was set to 1 nm for segregation calculations and 1.5 nm for tensile strength calculations. This vacuum region is introduced also to allow GB sliding (Fig. 1). Furthermore and order to get relevant and comparable total energies, all calculations were carried out with P1 symmetry by forcing symmetry breaking. We introduce the GB energy (GB) and free surface (FS) energy (FS) to characterize GB cohesive properties which are dened as the energies needed to create a GB and FS in the bulk. They are given by the following relations: GB
Bulk EGB tot E tot

2S

GB

and

FS

Bulk EFS tot E tot

2SFS

FS Bulk where EGB tot , E tot and Etot are total energies of the GB, FS and bulk system respectively, and SGB and SFS refer to GB and FS areas in the GB model. In order to obtain all energies on equal footing and to FS make suitable comparisons, the calculation of EBulk tot and E tot for the unperturbed FCC ferromagnetic nickel is carried out using a model with the same number of atoms and also with the same orientation of our GB model.

2.3. Segregation energy and tensile test calculations The segregation energy is dened as the difference between the total energy of a system with the impurity in the surface layer (or GB) and the energy with the impurity is in the bulk: (Eseg EFS/GBEBulk). Hence, our sign convention is that the negative segregation energy corresponds to impurities that want to segregate [22]. Here, we recall how to calculate the cohesive energy 2 and the tensile strength sMax (maximum tensile stress), as presented in [12,23]. We set a fracture plane that gives the minimum cohesive energy (Fig. 2), then the upper and lower half crystal blocks are rigidly separated by ve equal increments (from 0 nm to 0.5 nm). It should be noted that the use of larger number of increments gave always identical results. Each time in the separation process, we perform structure relaxation of the GB region, while xing atomic layers close to the free surface in order to mimic the bulk structure. Then the cohesive energy (2) of the GB is the difference between the two total energies; one is the energy of the GB without separation (point 0), and the other is the total energy for which the separating distance is so large that it does not change any more, typically after 0.5 nm separation. The maximum tensile stress is calculated as follow. A simple function f x is tted to the calculated total energy versus separation distance x.   x x f x 2 2 1 exp 2 here 2 and are tting parameters where is the ThomasFermi screening length. This function is known as the universal binding curve proposed by Rose et al. [24]. It describes well the bonding nature between atoms and constitutes the best t to metallic binding energies versus atomic distances. The tensile stress is the

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Fig. 2. Atomic congurations surrounding the fracture plane after structural relaxation. (a) For clean Ni 5(012) GB; (b) S1 case; (c) S2 case and (d) S3 case. The original environment positions corresponding these sites are presented in Fig. 1. The atomic distances are in .

Table 1 Calculated grain boundary (GB) energy and free surface (FS) energy of Ni 5(210) GB in J m2. J m2 GB energy FS energy
a

Table 2 Formation energies Ef and segregation energies Eseg for different V site occupancies in Ni 5(2 1 0) GB in eV. Site number 0 1 2 3 4 5 Ef 3.85 4.44 3.96 4.18 3.88 3.90 Eseg 0.02 0.60 0.11 0.34 0.04 0.05 Site number 6 7 8 9 10 11 Ef 3.90 3.84 4.01 3.96 4.72 5.20 Eseg 0.05 0.00 0.16 0.12 0.88 1.35

Our NCP 1.23 2.53

PP-PAW 1.23 , 1.43 , 1.33 2.34a, 2.65b, 2.29c

a b c

US-GGA 1.41 2.40e

e

Exp. (POLYCRYST) 0.93 , 1.24 2.59d, 2.02f

d f

Data taken from Ref. [14]. Data taken from Ref. [27]. c Data taken from Ref. [12]. d Data taken from Ref. [25]. e Data taken from Ref. [28]. f Data taken from Ref. [26].
b

derivative of f(x): f x 2 x 2 ex= 3

The maximum of f x is at x and corresponds to the maximum theoretical tensile stress or tensile strength sMax, therefore sMax f e1 2 4

3. Results and discussion 3.1. Grain boundary, free surface and segregation energies To verify whether the present GGA norm-conserving Pseudopotentials (NCP) basis sets are suitable to our Ni GB model, we calculated surface and grain boundary energies of nickel GB and compared them with known results of previous experimental and theoretical works, Table 1. Indeed, our results agree well with both experimental results [25,26] and previous theoretical calculations [14,12,27,28]. Thus we have a strong condence in the constructed GB conguration of this paper. The segregation energy of vanadium impurities on the Ni 5(012) symmetrical tilt grain boundary is calculated for 12 different impurity positions in order to study the segregation processes (Fig. 1). S0 is the GB vacancy insertion site and S1S11 are substitution sites. In this respect, we get 4 impurity positions in the grain boundary region (S0, S1, S2 and S3), four in the bulk (S4S8) and three sites in the surface region (S9, S10 and S11). For each conguration we perform structural relaxations of V atom and 45 close neighboring Ni atoms while xing all other atoms. Table 2 shows the calculated segregation energies of V at the 12 various sites. The surface segregation energy is negative and at least lower by 0.76 eV/atom than any GB segregation energies. This value is known as embrittling potency energy in the RiceWang model [29]. Our calculated embrittling potency of V in Ni 5(012) is smaller than that of sulfur in Ni 5(012) which is about

1.5 eV [12]. The negative values of S1, S2 and S3 V segregation energies show that vanadium has a potential to segregate to Ni GB and conrms experimental observations [8]. Furthermore, V atom prefers substitutional sites rather than possible interstitial one (S0) which presents near zero segregation energy E 0.02 eV. This value indicates a very low probability of occupation of S0 site by the V atom according to McLean's curve [30]. With 0.60 eV, S1 is the most favorable site for V atom to segregate. This situation can be deduced also from the formation energies, since the difference between the formation energy and the segregation energy is always constant and equal to 3.8 eV in our case. The later energy is the difference between bulk energies of Ni and V in the solid solution and in their energies in pure states. The values of the formation energies in the sites near the GB or the surface are affected by the displacement of atomic positions in these regions due to relaxation. sites 6 and 7 can be considered as the safe bulk sites (Fig. 1) since their formation energies are equal to 3.8 eV which is the same as the formation energy of V atom in pure bulk Ni. 3.2. Tensile strength In order to fully investigate the effect of vanadium impurity segregation on tensile strength, three typical V-segregated cases namely S1, S2 and S3 as depicted in Fig. 1, were thoroughly studied in this work. Furthermore, and for comparison purposes, the tensile strength of clean Ni GB and pure Ni single crystal were also calculated. As a result, Fig. 2(a) shows pure grain boundary region with small change in the GB tilt angle by 21 induced by structure relaxation. On the other hand, Fig. 2(b), (c) and (d) shows the optimized atomic conguration surrounding the V atom in S1, S2 and S3 sites respectively. In all Five cases, (012) is the fracture plane used in tensile strength calculations. The interlayer separation distance is parallel to the z direction of the GB model. Fig. 3(a) shows the calculated results of the evolution of the cohesive energies as a function of the separation distance between the two grains in the tensile process tted to the Rose universal binding curve. In accordance with the nding of Yamaguchi [12] for Ni 5(012) GB, we found that total energies and forces do not

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6 5

Theoretical tensile strength in GPa

40

Cohesive energy /J m-2

4 3 2 1 0 0.0 0.1 0.2 0.3 0.4 Separation distance in nm 0.5

Single crystal Clean GB S1 S2 S3

30

Single crystal Clean GB S1 S2 S3

20

10

0.0

0.1 0.2 0.3 0.4 Separation distance in nm

0.5

Fig. 3. (a) Cohesive energy in J m2 and (b) tensile stress in GPa of the Ni 5(012) 001 GB as a function of the separation distance. The interlayer distances of a perfect bulk in the c direction is taken as a reference for separations in all congurations.

converge to the required criteria for some fracture cases where the separation distance is small corresponding to 0.1 nm separation in Fig. 2. We mention here the same explanation that the total energy depends on the lateral lattice parameters (a, b) due to Poisson's ratio, and on the number of atomic layers being relaxed near the fracture plane. In addition, it is difcult to converge because strain energy is stored. For these difculties, we do not use the obtained energy value of point 0.1 nm but we take instead the mean value of the cohesive energies between 0 and 0.2 nm of separation. For large separation region (0.20.5 nm), it is considered that Poisson's ratio does not affect signicantly lattice parameters. For the clean GB, the cohesive energy increases rapidly with the increasing separation distances up to 0.3 nm, and then converges to 3.65 J m2, Table 3. As shown in Fig. 3(a) the GB systems with vanadium impurity exhibit similar trends as the clean GB, but they converge to higher cohesive energies, which are 4.08 J. m2, 3.81 J. m2, 4.36 J. m2 for S1, S2 and S3 sites respectively. For Ni single crystal case, the calculated cohesive energy 5.42 J m2 agrees well with other experimental and theoretical ndings [31,32]. Fig. 3(b) shows the tensile strength as a function of the separation distance, calculated according to Eqs. (2) and (3). As expected, for all ve systems, the stress increases with increasing separation distance to reach the maximum tensile stress sMax and then decreases to nally reaches 0. For the clean GB, the calculated sMax 27.3 GPa is in good agreement with previous theoretical calculation [12,33] see Table 3. Furthermore, the calculated tensile strength of Ni single crystal is 40 GPa, which is very close to ideal tensile strength in the 100 direction (37 GPa) estimated from experiment data [11] [34]. In the GB model with vanadium impurity, we can see from Fig. 3(b) that vanadium segregation induces an increase of the maximal tensile stress in all three sites and reaches 31.9 GPa as major value for S3 case, Table 3. Thus we can say that vanadium act as enhancing impurity in the Ni 5(012) tilt grain boundary.

Table 3 Cohesive energy (in J m2), tensile strength (GPa) and separation distance (nm) of Ni single crystal, Ni 5(210) grain boundary and for V site occupancies in substitutional sites (S1, S2, S3) in the Ni 5 GB. Single crystal Cohesive energy Our 5.42 Exp 4.44a LDA 5.98b PAW 4.52b Our 37 Exp 40c PAW 30c 0.6 Clean GB 3.65 S1 4.08 S2 3.81 S3 4.36

Tensile strength

Our 27.25 LMTO 28.9e PAW 26d 0.7

30.25

28.43

31.88

Separation distance
a

0.6

0.6

0.6

Data taken from Ref.[31]. Data taken from Ref.[32]. Data taken from Ref. [11]. d Data taken from Ref. [12]. e Data taken from Ref. [33].
b c

We found that vanadium atoms are more likely located near the grain boundary in an interstitial sites rather than inner bulk or in GB substantial site which shows a near zero segregation energy. The interstitial segregation energies of vanadium are negative and large, which means that segregation to the GB is favorable, conrming the experimental observations. Tensile theoretical calculations on different segregation positions show that vanadium acts as an enhancer to the nickel 5(012) GB tensile strength from 4% to 17% with respect to clean GB. References
[1] M. McLean, The metals society, London, 65. [2] James R. Dobbs, Jeffrey A. Graves, S. Meshkov, Superalloys (1996) 523529, TMS, 1996. [3] J.R. Davis, ASM Specialty Handbook: Nickel, Cobalt, and their Alloys, 2000, pp. 1454, ASM International. [4] A.P. Sutton, R.W. Balluf, Interfaces in Crystalline Materials, Oxford University Press, Oxford, 1995. [5] Sungho Kim, Song-Gon Kim, M.F. Horstemeyer, H. Rhee, 2011 TMS Annual Meeting and Exhibition, arXiv:1201.5915v1.cond-mat.mtrl-sci, 2012. [6] ASTM B626-03, Standard Specication for Welded Nickel and NickelCobalt Alloy Tube, vol. 02.04, 2003. [7] F. Bradley, Superalloys: A. Technical Guide, ASM International, 1988. [8] R.B. Scarlin, J.W Edington, J. Mater. Sci. 9 (1974) 15901594. [9] H.H. Kart, M Uludogan, T. Cagin, Comput. Mater. Sci. 44 (2009) 12361242. [10] H.H. Kart, T. Cagin, JAMME 30 (2008) 177181. [11] M. Yamaguchi, M. Shiga, H. Kaburaki, Science 307 (2005) 393397. [12] M. Yamaguchi, M. Shiga, H. Kaburak, Mater. Trans. 47 (2006) 26822689. [13] Damien Conntable, Benoit Ter-Ovanessian, ric Andrieu, J. Phys. Condens. Matter 24 (2012) 095010.

4. Conclusions In summary, we have calculated segregation, formation and cohesive energies together with tensile strength of vanadium impurity in the nickel 5(012) GB system using the Norm-conserving pseudopotentials as implemented in CASTEP code. The results of our calculations for sMax of pure GBs and single crystal cases are in good agreement with experimental data and previous theoretical calculations. Furthermore, the calculated GB and free surface energies agree well with experimental observations and other result based on PAW and Ultra-soft pseudopotentials.

E.T. Bentria et al. / Materials Science & Engineering A 577 (2013) 197 201 [14] M. Viansk, M. ob, Prog. Mater. Sci. 56 (2011) 817840. [15] S.J. Clark, M.D. Segall, C.J.P.J. Hasnip, M.J. Probert, K. Refson, M.C. Payne, Z. Kristallogr. 220 (2005) 567570. [16] D.M. Ceperley, B. Alder, J. Phys. Rev. Lett. 45 (1980) 566569. [17] J.P. Perdew, A. Zunger, Phys. Rev. B 23 (1981) 50485079. [18] D.R Hamann, M Schluter, C. Chiang, Phys. Rev. Lett. 43 (1979) 14941497. [19] Z.X. Tian, et al., Phys. Rev. B 79 (2009) 144114. [20] A. De Vita, I. Manassidis, J.S. Lin, Europhys. Lett. 19 (1992) 605610. [21] P. Pulay, Theory Mol. Phys. 17 (1969) 197204. [22] V.I. Razumovskiy, A.Y. Lozovoi, I.M Razumovskii, A.V. Ruban, Adv. Mater. Res. 278 (2011) 192197. [23] L. Zhang, X. Shu, S. Jin, Y. Zhang, Lu Guang-Hong, J. Phys.: Condens. Matter 22 (2010) 375401. [24] J.H. Rose, J. Ferrante, J.R. Smith, Phys. Rev. Lett. 47 (1981) 675.

201

[25] W.R. Tyson, W.R. Miller, Surf. Sci. 62 (1977) 267276. [26] T.A. Roth, Mater. Sci. Eng. 18 (1975) 183192. [27] M. Yamaguchi, M. Shiga, H. Kaburaki, J. Phys: Condens. Matter 16 (2004) 39333956. [28] Chen Lu, Peng Ping, Zhuang Hou-long, Zhou Dian-wu, Trans. Nonferrous Met. Soc. China 16 (2006) 813819. [29] R. Rice, J.S. Wang, Mater. Sci. Eng. A 107 (1989) 2340. [30] D. McLean, Grain Boundaries in Metals, Oxford University Press, London, 1957. [31] Charles Kittel, Introduction to Solid State Physics, 8th edition, John Wiley & Sons, Inc, Hoboken, NJ50. [32] P.H.T. Philipsen, E.J. Baerends, Phys. Rev. B 54 (1996) 53265333. [33] M. ern J. Pokluda, P. andera, Mater. Sci. Eng. A 387/389 (2004) 923925. [34] A. Kelly, N.H. Macmillan, Strong Solids, 3rd ed., Clarendon Press, Oxford, 1986.