Available online at www.sciencedirect.

com

Computational Materials Science 43 (2008) 736743 www.elsevier.com/locate/commatsci

Eect of impurities on grain boundary cohesion in bcc iron

E. Wachowicz *, A. Kiejna
Institute of Experimental Physics and Interdisciplinary Center for Materials Modeling, University of Wrocaw, plac M. Borna 9, PL-50-204 Wrocaw, Poland Received 15 May 2007; received in revised form 16 January 2008; accepted 17 January 2008 Available online 10 March 2008

Abstract The eect of B, N and O impurities placed in interstitial and substitutional positions at symmetric R5(2 1 0) Fe grain boundary is studied by means of rst principles calculations. Full relaxation of supercell shape and volume is applied which results in stable asymmetric grain boundaries, depending on the impurity and its position. In all cases the big shifts (0.472.33 A) of grains with respect to each other are observed. The equilibrium distance between the grains is decreased for impurities in substitutional positions, and increased for atoms in interstitial sites, compared to the relaxed clean GB. We found that nitrogen both in interstitial and substitutional positions, and boron in substitutional position enhance cohesion while oxygen in both positions, and interstitial boron, are embrittlers. The magnetic moments of Fe atoms at clean grain boundary are remarkably increased compared to the bulk. They tend to the bulk value in the middle of the grain in an oscillatory way. 2008 Elsevier B.V. All rights reserved.
PACS: 61.72.Mm; 68.35.Dv; 71.15.Mb; 71.15.Nc; 75.50.Bb; 75.70.Cn Keywords: Density functional calculations; Grain boundary cohesion; Iron; Impurities; Embrittlement; Magnetic moments

1. Introduction The macroscopic strength of iron or steels depends mainly on the cohesion on the boundaries of grains constituting the metal. Impurities segregated at the grain boundary (GB) can drastically modify its properties. The presence of impurities at GBs can lead to embrittlement or to strengthening of the material, however, the mechanism of such a behavior is still debated. The theories explaining GB embrittlement are based on two competitive mechanisms leading to the changes in bonding at Messmer and Briant [1] suggested that electronegative impurity would draw charge away from surrounding metal atoms, thus weakening the metal bonding at grain boundary. The electropositive impurity would add charge to the metallic bonds of neighboring atoms enhancing cohesion.

Corresponding author. Tel.: +48 71 3759266; fax: +48 71 3287365. E-mail address: elwira@ifd.uni.wroc.pl (E. Wachowicz).

The explanation proposed by Haydock [2] is based on charge transfer between impurity and the host atoms and assumes that the bonding between impurities and neighboring metal atoms is covalent and highly directional. According to that theory it is the ease with which charge can ow that makes material more plastic. Therefore one should expect a large dierence in the degree of covalency in bonds between the impurity and neighboring iron atoms in case of carbon (cohesion enhancer) and phosphorus (embrittler). The controversy exists about even so widelystudied system such as Bi at Cu GB. Duscher et al. [3] claim that bismuth-induced electronic structure changes are responsible for embrittlement of Cu grain boundary. On the other hand, recent calculations by Schweinfest et al. [4] suggested that this phenomenon can be attributed to a purely atomic size eect. It is well-known from experiment that impurities such as P, S, Sn, and Sb cause intergranular embrittlement of Fe, while C and B enhance cohesion in iron and alloy steels [5]. In recent years rst-principles calculations have been

0927-0256/$ - see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.commatsci.2008.01.063

E. Wachowicz, A. Kiejna / Computational Materials Science 43 (2008) 736743

737

applied to study the role of impurities in grain boundary cohesion [611]. The extensive studies performed in the group of Freeman [610] by means of the full potential LAPW method concentrated on one of the simplest, symmetric Fe R3 (1 1 1)-oriented GB doped with dierent materials. In those calculations the atomic positions at the GB were relaxed, while the Fe atoms of inner layers were kept frozen in perfect bulk positions. In their pioneering work Wu et al. [6] calculated the strengthening properties of boron and phosphorus at Fe R3(1 1 1) GB and attributed this behavior to the number of p electrons and resulting spatial anisotropy of the bonding. The strong enhancing properties of carbon can be explained in a similar way [8]. The charge density analysis for sulfur and boron atoms inserted into Fe R31  01 1 1 GB [7] showed that B cre1 ates relatively strong bonding with neighboring Fe atoms which is in contrast to a weak bonding between S and iron. For nitrogen atoms in interstitial position at same GB of iron it was demonstrated [10] that the weakening of the GB cohesion results from a disruption of chemical bonds between neighboring Fe atoms by nitrogen. Moreover it was noticed that N atoms reduce the local magnetic energy. Calculations performed for metallic impurity atoms (Mo, Pd) at that same GB [9] showed that Mo is a strong cohesion enhancer while Pd behaves like a weak embrittler. Such a behavior is attributed to the strong/weak bonding capability of Mo/Pd compared with Fe, which makes Mo and Pd a cohesion enhancer and embrittler, respectively. The examination of dierent impurities at a Fe R3(1 1 1) GB indicated that the chemical bonding properties are mainly responsible for strengthening/embrittlement of GB. However the embrittling and strengthening eect of various impurities is still not well understood. A recent density functional theory (DFT) study by Braithwaite and Rez [11] suggests that some of the solute atoms have the embrittling properties opposite to those mentioned above. Their calculations for B, C, S, and P impurities at a Fe R5(2 1 0) GB at both interstitial and substitutional places showed that B increases cohesion while S, P, and C (in small concentration) cause embrittlement. Moreover, the interstitial impurities are favored over substitutional ones. No signicant covalent bonding between the impurity and neighboring Fe atoms was noticed. This suggests that the dependence of the GB cohesion is not related to the bonding characteristic of the impurity species but simply relates to the size of the impurity atom. The principal aim of this work is to investigate the changes in cohesive properties of the R5(2 1 0) grain boundary in a-Fe resulting from the presence of dierent solute (impurity) atoms. In this purpose we employ DFT and discuss results for three types of impurities which are known from experiment and previous calculations to have dierent inuence on GB cohesion energy. Oxygen is known to be an embrittler, nitrogen is a cohesion enhancer, and boron atom can play the either role, depending whether it is placed in interstitial or substitutional position at GB. A detailed analysis and comparison of structural and

chemical contributions to the cohesive energy due to interstitial or substitutional impurities allows us to determine their role in the embrittling or strengthening of iron GBs. Another our motivation is to study the eect of exchange and correlation energy on the cohesive properties at GBs. The local density approximation (LDA) that was applied in Ref. [11], wrongly predicts hcp structure as the ground state of Fe. Thus, besides the well-known overbinding of LDA that manifests in an underestimated lattice constant and overestimated the cohesive energy [12], also the bulk magnetic moment is underestimated. These problems are corrected by the use of the generalized gradient approximation which, at variance to [11], is applied in the calculations presented in this work. Finally, we investigate the eect of the reduced coordination and dierent impurities at the GB on the magnetic properties of the system.

2. Method of calculations The reported rst-principles total-energy calculations were performed using the Vienna ab initio simulation package (VASP) [13,14] based on density functional theory and the plane-wave basis approach. The exchange-correlation energy was described using the Perdew and Wang (PW91) [15] form of the spin-polarized generalized gradient approximation (GGSA) and the Vosko et al. [16] interpolation formula for the local part of the exchange-correlation functional. GGSA yields the correct ground-state structure of the bcc Fe crystal [12]. The lattice parameter of the bcc Fe (a = 2.844 A) was determined by us previously [17] in good agreement with measured data (aexp = 2.867 A). The electron-ionic core interactions were represented by projector-augmented-wave (PAW) potentials [18] supplied with VASP. The plane-waves basis kinetic-energy cuto of 300 eV was applied which yields well converged results. The k-space integrations were performed using a 4 8 1 MonkhorstPack k-point mesh [19] and the rst order MethfesselPaxton [20] method for Fermi surface smearing with a width of 0.2 eV. The grain boundary was modeled by two (2 1 0) oriented slabs consisting of 20 atomic layers of Fe each, reected with respect to the xy-plane, and repeated periodically throughout space (Fig. 1). Two dierent procedures for nding optimum grains placement with respect to each other, as well as optimized atomic positions within the grains, were employed. First, following the method of Ref. [11] all the atoms except for the six layers inside each of the grains were relaxed. Then, both the vertical distance between the grains (in the [2 1 0] direction) and the shift of the grains parallel to the grain boundary (in the 1  0 2 direction), were varied until the minimum of the total energy with respect to these two variables was found. The grains had a freedom to shift also in the [001] direction parallel to the GB plane, however such shifts were not favored and in that direction the original symmetry was

738

E. Wachowicz, A. Kiejna / Computational Materials Science 43 (2008) 736743

Fig. 1. Side view of the supercells representing Fe R5(2 1 0) GB applied in the calculations. (a) Ideal clean GB created by the two mirrored (2 1 0)-oriented surfaces, (b) asymmetric clean GB resulting from the supercell and atomic positions optimization, (c) the GB doped with a boron impurity atom in the interstitial position, (d) the GB with a boron impurity in the substitutional position. The darker and lighter balls represent the grain atoms lying in two dierent planes. The impurity atoms are represented by the lightest smaller balls. The dashed line indicates the grain boundary.

maintained. In the other method, which is the principal procedure applied in this work, the volume and shape of the supercell representing the GB were allowed to relax, and all atoms were allowed to optimize their positions according to the forces (i.e., until the forces on each atom converged to less than 0.05 eV/A). Each procedure applied to a symmetric GB yielded an asymmetric GB. The cohesive energy changes that result from inserting impurities are usually analyzed using the thermodynamic theory by Rice and Wang [21]. Then the grain boundary formation energy cf is dened by the following expression: cf EGB 2EFS 1

sented by its binding energy which, in the slab calculations, is dened by the following total energy dierences DEGB EI=GB EGB 2EI ; DEFS EI=FS EFS EI ; 2 3

where EI/GB, EI/FS and EI represent, respectively total energies for a GB slab with an impurity, an impurity adsorbed on the FS slab, GB slab with an impurity, and the total energy of the impurity monolayer. The dierence between DEGB and DEFS is the key quantity that determines the strengthening or embrittling eect. Using Eq. (1), the strengthening energy can be dened as DESE DEGB 2DEFS cimp ccln ; f f 4

where EGB is the total energy of the GB, and EFS is the total energy of the free surface (FS) used for the formation of the GB. The free (2 1 0) surface was modeled by a slab of 20 Fe layers separated by 12 A of vacuum and repeated periodically in space. For calculations applying a xed supercell volume the inner 8 layers were kept frozen, and the positions of all other atoms were relaxed. In the case of calculations involving full relaxation of the volume and shape of the GB supercell, in order to model the free surface, 20 Fe layers representing one grain were removed from the supercell whose size and volume remained xed at the optimized parameters resulting for the GB, and the positions of all remaining atoms were relaxed. According to [21] the strength of the interaction between an impurity and the GB or FS can be quantitatively repre-

where cimp is the formation energy of the GB with an impuf rity, and ccln is the formation energy of a clean GB. The pof sitive/negative DESE means that the impurity weakens/ strengthens the GB. To gain some more insight into the energetics of the GB formation process it is useful to discuss dierent contributions to the binding energy. For the interstitial impurity it can be decomposed into the chemical and mechanical contributions [22,23]. The chemical contribution results from a direct interaction between impurity and the host atoms and is dened as the work, DEC, needed to remove impurity while keeping all the Fe atoms frozen, DEC cimp cfrz : f f 5

Here, cfrz is the formation energy of the GB with the host f atom positions frozen in the relaxed GB conguration that

E. Wachowicz, A. Kiejna / Computational Materials Science 43 (2008) 736743

739

was calculated with the impurity, but now with the impurity removed. The mechanical contribution, DEiM , is given by the energy release during the course of Fe atoms relaxation, after the impurity is removed, and can be written as DEiM cfrz ccln : f f 6 In case of a substitutional impurity there is one more process that should be taken into account, i.e. the removal of host atom. The energy change, DER, attributed to this process can be dened as DER cf
sub=frz

ccln ; f

is the formation energy calculated for the where clean GB frozen in the relaxed conguration, and with Fe atom subsequently replaced by the impurity. Then, for a substitutional impurity the mechanical contribution, DEs , is given by M DEs cfrz cf M f
sub=frz

sub=frz cf

Thus, the analysis of various contributions to the strengthening energy requires a set of additional calculations to obsub=frz tain cfrz and cf for each impurity. In this calculations f the impurity atoms are removed from the GB while all the remaining Fe atoms are kept in unchanged positions. 3. Results 3.1. Clean grain boundary Originally, following the procedure of Ref. [11] we searched for an optimum structure of the clean Fe R5(2 1 0) GB by changing both the distance between the grains and their shift parallel to the GB in the 1  0 direc2 tion. Then, for a set of dierent pairs of distance-shift values, the optimum intergranular distance was determined from the total energy plot. Similar calculations were performed by us for several selected dr pairs. Starting from

the ideal atomic positions we increased the intergranular distance up to 0.6 A and calculated the grain boundary forcln mation energy cf as a function of the intergranular distance d (Fig. 2, left panel). The minimum in the separation energy is found for d 0.3 A. Then, for the xed optimum separation the grains were shifted in the range 01 A. The plot of the calculated formation energy vs. grain shift (Fig. 2, right panel) allows to identify r = 0.6 A as the optimum value for the grain shift. This agrees very well with the results of Ref. [11] that yielded 0.31 A for the grains distance, and 0.7 A for their shift. The relaxation of atomic positions for many dr pairs takes a lot of CPU time, therefore we decided to apply much faster way of nding optimal grain placement. It is provided by full relaxation of all atomic positions together with relaxation of the supercell volume and shape. In this type of calculations one just has to be sure that the bulk region is represented properly. The calculated interlayer distance (0.636 0.033 A) in the middle of the grain agrees very well with interplanar distance in the bulk of Fe crystal (0.636 A). The optimum grains separation (d = 0.22 A) and the grains shift (r = 0.6 0.01 A) agree very well with those determined in Ref. [11], having in mind that they were calculated using two dierent exchange-correlation functionals. The calcu lated supercell volume of 454 A3 is only about 4% less than that corresponding to the lattice parameter of the bulk Fe (472 A3). The fully relaxed supercell is both slightly compressed, in the directions 0 0  and 1  0, and slightly 1 2 tilted. The calculated formation energy of the clean GB cf, for supercell obtained by optimizing grain-distance and grain separation values, equals to 3.50 eV. For the relaxed supercell cf is only slightly smaller (3.43 eV, Table 1). This again proves that full supercell relaxation is a correct way of describing the clean GB. The above results for clean GBs give us a condence that the calculations which involve relaxation of the volume and shape of the supercell

-3.2

-3.2

=0
Formation energy, f (eV)

m = 0.3
-3.3

-3.3

-3.4

-3.4

-3.5 0 0.2 0.4 0.6

-3.5 0 0.2 0.4 0.6 0.8 1

Grain separation, ()

Grain shift, ()

Fig. 2. The formation energy of the clean GB as a function of the grain separation for r = 0 A, and as a function of the grain shift in the 1  0 direction, 2 for the optimum grain separation dm = 0.3 A.

740

E. Wachowicz, A. Kiejna / Computational Materials Science 43 (2008) 736743

Table 1 Formation energy, cf, and strengthening energy, DESE, calculated for the clean GB and for GB with impurities in interstitial or substitutional sites Impurity Interstitial cf (eV) This Clean GB B N O 3.43 3.07 3.63 2.68 Ref. [11] 5.41 5.90 DESE (eV) This 0.36 0.20 0.75 Ref. [11] 0.49 Substitutional cf (eV) This 4.01 3.64 2.62 Ref. [11] 5.07 DESE (eV) This 0.58 0.21 0.81 Ref. [11] 0.34

The negative and positive value of DESE denote strengthening and weakening of the GB cohesion, respectively.

allow to describe correctly the properties of the grain interior. Therefore, this procedure has been applied throughout this work to consider the eect of impurities on GB cohesion. However, the results of Table 1 show that the absolute values of formation energy dier by almost 2.0 eV from the cf value (5.41 eV) calculated in [11] within LSDA for the exchange-correlation functional. In order to explain the reason of this discrepancy we have performed additional calculations of the formation energy for the Fe R5(2 1 0) GB using LSDA functional. For the grains shift d = 0.3 A and the separation r = 0.7 A, corresponding to the optimum results from [11], we obtained for cf, respectively, 5.14 eV and 5.10 eV, when applying 2 4 1 and 4 8 1 k-point sets. Convergency criteria were the same as for our GGSA calculations. Having in mind that not all parameters applied in [11] were known to us, it could be stated that our LSDA results are in very good agreement with those of Ref. [11]. Thus, the results of these tests show that the major part of the discrepancy originates from the dierence between LDA and GGA functionals.

This reveals the importance of the exchange-correlation eects in the energetics of GBs. It should be also noted that the use of denser k-point mesh, that was applied in our work results in a lower binding. 3.2. Impurities at grain boundary Grain boundary impurities strongly modify not only the positions of host atoms near the impurity but also inuence the relative positions of the grains and the size of the supercell. The optimized parameters of the supercell applied for dierent impurities are summarized in Fig. 3. As it is seen, an interstitial impurity at the GB always increases the supercell volume (by some 7%). This correlates with an increased (by 0.3 A) grain separation. The changes in the average volume per atom are smaller. For an interstitial boron this volume is unaltered with respect to the clean GB supercell, whereas for N, and O, it is, respectively, decreased/increased by 0.5%. Nitrogen and oxygen impurities practically do not cause any shift of the grains with respect to the clean GB, whereas interstitial boron shifts

0.6 480 470 460 450

Grain separation, () Grain shift, ()

interstitial substitutional

Supercell volume ( )

0.4 0.2 0 -0.2 -0.4 2.5 2 1.5

Volume/atom ( )

11.4

11.3

1
0.5 0 Clean O N B

11.2

Clean

Impurity

Impurity

Fig. 3. The supercell volume, average volume per atom, grain separation, and grains shift, calculated with full optimization of volume and shape of the supercell representing clean or impurity doped GBs. The impurities are ordered with respect to the increasing covalent atomic radius: O (0.73 A), N (0.75 A), and B (0.82 A). The atomic radius of Fe atom is 1.25 A.

E. Wachowicz, A. Kiejna / Computational Materials Science 43 (2008) 736743

741

the grains by 1.19 A. A smaller atomic radius of any of the impurity atom considered here, compared with the atomic radius of Fe (1.25 A), causes that placing impurity in substitutional sites practically does not change the supercell volume. A slight decrease is observed only for N and B impurities. The changes can be more clearly seen, however, when considering the average volume per atom. For nitrogen or boron, that replaced one of the Fe atoms at the boundary, it is decreased by 0.8%. The calculated grain separations and shifts caused by dierent impurity species are displayed in the rhs panels of Fig. 3. Substitutional oxygen increases the average volume per atom by 0.6%. For substitutional impurities the grain separation is close to zero for oxygen, becomes negative for nitrogen, and is meaningfully negative for boron. (Note that d = 0 corresponds to the distance between grains in perfect bulk lattice). Interestingly, substitutional impurities cause a very large shift of the grains. For one of the iron atoms at the GB replaced by nitrogen the respective shift increases to 2.33 A. For O and for B and 1.52 A. atoms the shift amounts to 2.01 A The calculated formation energies compiled in Table 1 show that for boron substitutional sites are favored over interstitials whereas for N and O impurities the opposite is observed. The principal question that arises when studying the eect of impurities is: does the impurity strengthen or weaken the grain boundary? As can be seen from Table 1, the nitrogen in both substitutional and interstitial position is cohesion enhancer. The latter applies also to substitutional boron, whereas interstitial boron and oxygen are embrittlers. Our results for the GB doped with boron give similar size of the strengthening/embrittling energy as that in [11]. We predict, however, reversed signs for interstitial and substitutional impurities compared to [11]. It should be noted, that the cohesion strengthening/embrittling eect of boron is not very strong. For an Fe R31 1 01 1  GB 1 the eect of an interstitial B impurity is found to be neutral [6]. This gives some supporting argument for the view (see Section 3.1) that the principal reason for this discrepancy may come from dierent exchange-correlation functionals applied in this work and in [11] (GGSA vs. LSDA). Some part of the discrepancy may result from a much denser kpoint mesh that was used in our calculations: 4 8 1 compared to 2 4 1 applied in [11]. Our previous calculations [17] showed that a denser mesh is required for good description of iron surfaces. A more adequate description of the electron-ion core interaction by PAW potentials, instead of ultrasoft pseudopotentials applied in [11], may also give a minor contribution to the dierence. The strengthening eect of nitrogen impurity is rather weak (Table 1). Our result is supported by cluster calculations [24] within the framework of DFT which also indicate that N is a distinct cohesion enhancer at the Fe R3[1 1 0](1 1 1) GB. In contrast to that, FLAPW calculations performed in [10] at the GGA level reported that interstitial N is found to be a weak embrittler of same Fe R3 grain boundary. This seems to be in line with experi-

mental ndings. On the other hand, the embrittling eect of nitrogen in steels is associated [25] exclusively with nitride formation. The dierence in the strengthening potency of N impurities in Fe grains may also be related to dierent congurations of R5 GB considered in this work and R3 GB studied in [10]. Table 2 shows dierent contributions to the strengthening energy. For the interstitial impurity, in all cases, the mechanical contribution tends to weaken the GB cohesion.
Table 2 The strengthening energy and its chemical (DEC), mechanical (DEM), and host removal energy (DER) components contributing to the bonding. All values are in eV Impurity Interstitial DEC B N O 0.09 0.32 0.45 DEiM 0.28 0.12 0.30 DESE 0.36 0.20 0.75 Substitutional DEC 0.76 0.56 0.65 DEs M 1.35 2.30 1.37 DER 1.54 1.54 1.54 DESE 0.58 0.21 0.81

Negative value denotes the cohesion strengthener.

3 2.5 2 1.5 1

Clean GB

Magnetic moment (B)

3 2.5 2 1.5 1 3 2.5 2 1.5 1 0.3 0.4 0.5

B doped N doped O doped

Interstitial

Substitutional
0.6 0.7

z/z0
Fig. 4. Variation of the magnetic moment on Fe atoms of the grain in the direction perpendicular to the boundary. The positions of atoms are measured with respect to the vertical coordinate of the supercell (z0 is the height of the given supercell). The grain boundary is placed at 0.5z/z0. Horizontal dashed lines mark the magnetic moment of bulk Fe.

742

E. Wachowicz, A. Kiejna / Computational Materials Science 43 (2008) 736743

In case of boron and oxygen inserted at the GB a further weakening comes from the chemical contribution. Only in case of the interstitial N impurity the large strengthening chemical contribution dominates the bonding and cohesion at GB is increased. In case of substitutional impurities the strengthening eect of the mechanical contribution competes with the weakening resulting from the Fe atom removal. It is not surprising that the removal of a host atom for substitutional impurity signicantly weakens the grain boundary. Those two large contributions partly cancel each other, but for the N impurity the mechanical one still prevails over relatively small chemical contribution that weakens the grain, and the total GB cohesion is increased. In case of oxygen and boron the change in the chemical energy contribution, i.e. the character of the bonding in the vicinity of the impurity is responsible for the weakening/strengthening of the GB cohesion. 3.3. Magnetic properties Let us note rst that the Fe(2 1 0) surface which forms a tilted R 5 grain boundary is a relatively open surface, where coordination of atoms in the rst three layers is reduced by 4, 2, and 2 neighbors, with respect to a bulk atom that is coordinated by 8 neighbors. This results in a magnetic moment on the surface layer atom that is increased by 30% [17] in comparison to the bulk. Those calculations have also shown [17] that the magnitude of the magnetic

moment on Fe atom of the outermost surface plane depends primarily on its coordination number. The reduced saturation of bonds of the second, and the third layer atom has a minor eect on the moment [17]. In a presence of atoms of the neighboring grain the coordination of atoms at the GB is restored and therefore, in general, the magnetic moment on GB atoms is reduced compared to that at the free (2 1 0) surface. For a fully relaxed supercell representing the clean GB, the calculated magnetic moment on Fe atoms in the grain interior equals to 2.24 lB, and compares well with the value of 2.20 lB which characterizes the interior of bcc Fe crystal [17]. In the vicinity of the grain boundary the magnetic moment of iron atoms shows a meaningful variation (Fig. 4). The magnetic moments change in an oscillatory way from 2.45 lB on Fe atom placed at the GB and tend to the bulk value in the middle of the grains (Fig. 5). The magnitude of oscillations diers on two sides of the GB which reects its asymmetry and can be rationalized in terms of the improved/reduced coordination. As it seen the moment on neighboring Fe atoms on same side of GB may vary from 2.56 to 1.43 lB. While the coordination of all atoms is enhanced in comparison to a single grain surface, for some Fe atoms (as for example atoms labeled as 19 and 21 in Fig. 5) it exceeds that characteristic of a bulk Fe. In the latter cases the magnetic moments are decreased. This is reected in the calculated local density of states (LDOS) presented in Fig. 5, which displays only the population of the dominant d-states

Fig. 5. Local density of electronic d-states on the atoms closest to the clean R5(2 1 0) Fe grain boundary (left panel). For comparison the LDOS on the Fe atom of bulk layer (Fe_10) is also shown. Right panel shows LDOS for Fe atoms at the GB with substitutional boron impurity. The upper and lower halves display the majority and minority spin electron states.

E. Wachowicz, A. Kiejna / Computational Materials Science 43 (2008) 736743

743

projected onto the dierent GB atoms. Inspection of the gure shows that for a clean GB the number of occupied states for the spin down channel is increased, compared to the bulk Fe (atom 10), which results in a reduction of the magnetic moment. This also contributes to an increased metallic character of bonding at more coordinated atoms, which is manifested by an enhanced LDOS at the Fermi level, in comparison to the bulk. The eect of atomic coordination seems to be dominant also in the presence of impurities. The magnitude of the magnetic moment on Fe atoms is also aected by the magnetic moments of the impurities. The magnetic moments induced on impurity atoms in a ferromagnetic environment are rather small but can be of either sign (parallel or antiparallel) to the moments of Fe atoms. In general, they are slightly larger for interstitial than for substitutional impurity, and are respectively equal to: 0.14 lB and 0.12 lB for B; 0.09 lB and 0.08 lB for N; 0.10 lB and 0.07 lB for O. The magnetic moment on oxygen atoms is positive, and consequently, both interstitial and substitutional O increases the magnetic moment on the nearest Fe atoms up to 2.85 lB and 2.5 lB, respectively. Thus, even in the cases of the enhanced coordination due to O atoms the moments on the neighboring Fe atoms remain increased. Compared to the clean GB, oxygen impurity causes an increase in the density of minority spin d-states at the Fermi level (not shown). Substitutional nitrogen impurity preserves the asymmetry of the magnetic moments at Fe atoms nearest to the GB, giving 2.34 and 1.68 lB on the atoms nearest to substitutional impurity. Interstitial N impurity increases the magnetic moment of Fe atom placed at the GB up to 2.78 lB. The magnetic moments of Fe atoms neighboring to substitutional nitrogen are decreased to 1.78 and 1.80 lB, respectively. The magnetic moment of the Fe atom nearest to the boron impurity is reduced to 1.80 lB. Substitutional B impurity at the boundary (Fig. 5), also reduces magnetic moments on the nearestneighbor Fe atom to 1.49 lB. As it is seen, a substitutional boron impurity improves the coordination of the neighboring Fe atoms, which leads to reduced moments on Fe atoms (labeled as 18 and 20) and an antiparallel moment on boron (% 0.12 lB). 4. Summary The eects of impurities on the grain boundary cohesion was studied from rst principles. It is found that nitrogen placed in either interstitial or substitutional sites and boron in substitutional positions are cohesion enhancers. Oxygen both in interstitial and substitutional positions, and boron in interstitial position, are embrittlers. Comparison of the grain separation distance resulting from insertion of the interstitial impurity shows that it actually does not depend on the atom type. This is not the case for substitutional

impurity where the intergranular distance is smaller for B and N, which are cohesion enhancers. Analysis of the components of the strengthening energy for substitutional boron and interstitial nitrogen shows that the changes in the bonding at the grain boundary are responsible for cohesion enhancement. For substitutional nitrogen the mechanical contribution alone causes the cohesion strengthening. The boron impurity decreases the magnetic moments at nearest-neighbor Fe atoms, the oxygen impurity increases it, and for the nitrogen impurity the magnetic moments are decreased at one grain and decreased at the other. The interstitial impurities modify the magnetic moments at the Fe atoms in the vicinity of the GB, stronger than substitutional ones. Acknowledgements We appreciate useful discussions with Prof. K.J. Kurzydowski on GB properties. This work was supported by the Polish Ministry of Science in the years 20057 under Grant No. 3 T08A 030 29. We acknowledge the Interdisciplinary Centre for Mathematical and Computational Modeling (ICM), University of Warsaw for the computational Grant G28-25. References
[1] R.P. Messmer, C.L. Briant, Acta Metall. 30 (1982) 457. [2] R. Haydock, J. Phys. C 14 (1981) 3807. [3] G. Duscher, M.F. Chisholm, U. Alber, M. Ruhle, Nature Mater. 3 (2004) 621. [4] R. Schweinfest, A. Paxton, M. Finnis, Nature 432 (2004) 1008. [5] Key to steel: Steel database. URL <http://www.key-to-steel.com/>. [6] R. Wu, A.J. Freeman, G.B. Olson, Science 265 (1994) 376. [7] S. Tang, A.J. Freeman, G.B. Olson, Phys. Rev. B 50 (1994) 1. [8] R. Wu, A.J. Freeman, G.B. Olson, Phys. Rev. B 53 (1996) 7504. [9] W.T. Geng, A.J. Freeman, R. Wu, G.B. Olson, Phys. Rev. B 62 (2000) 6208. [10] M. Kim, C.B. Geller, A.J. Freeman, Scripta Mater. 50 (2004) 1341. [11] J.S. Braithwaite, P. Rez, Acta Mater. 53 (2005) 2715. [12] C. Elsasser, J. Zhu, S.G. Louie, B. Meyer, M. Fahnle, C.T. Chan, J. Phys.: Condens. Mat. 10 (1998) 5113. [13] G. Kresse, J. Hafner, Phys. Rev. B 47 (1993) 558. [14] G. Kresse, J. Hafner, Phys. Rev. B 49 (1994) 14251. [15] J. Perdew, J. Chevary, S. Vosko, K. Jackson, M. Pederson, D. Singh, C. Fiolhais, Phys. Rev. B 46 (1992) 6671. [16] S. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 58 (1980) 1200. [17] P. Bonski, A. Kiejna, Surf. Sci. 601 (2007) 123133. [18] G. Kresse, D. Joubert, Phys. Rev. B 59 (1999) 1758. [19] H. Monkhorst, J. Pack, Phys. Rev. B 13 (1976) 5188. [20] M. Methfessel, A. Paxton, Phys. Rev. B 40 (1989) 3616. [21] J.R. Rice, J.-S. Wang, Mater. Sci. Eng. A 107 (1989) 23. [22] W.T. Geng, A.J. Freeman, R. Wu, C.B. Geller, J.E. Raynolds, Phys. Rev. B 60 (1999) 7149. [23] A.Y. Lozovoi, A.T. Paxton, M.W. Finnis, Phys. Rev. B 74 (2006) 155416. [24] Y.-Q. Fen, C.-Y. Wang, Comput. Mater. Sci. 20 (2001) 48. [25] C.L. Briant, S.K. Banerji, A.M. Ritter, Metall. Trans. A 13 (1982) 1939.