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Scripta Materialia 64 (2011) 10551058

Eects of grain growth on interface diusion in nanostructured Cu

Z.B. Wang,a, K. Lu,a G. Wildeb and S.V. Divinskib,

Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang 110016, China b Institute of Materials Physics, University of Munster, Wilhelm-Klemm-Str. 10, 48149 Munster, Germany
Received 8 February 2011; accepted 15 February 2011 Available online 20 February 2011

Considerable grain growth occurred in a nanostructured Cu sample produced by surface mechanical attrition treatment during isothermal annealing at 423 K. The time-dependence of diusion of 63Ni in the nanostructured Cu was investigated by the radiotracer technique. It was shown that the apparent interfacial diusivity determined by taking into account the grain growth eects was higher by a factor of 10 than the value determined according to the model of stationary interfaces. 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Nanostructure; Surface mechanical attrition treatment; Diusion; Interface; Grain growth

Diusion in nanostructured or ultrane-grained materials produced by dierent methods of severe plastic deformation (SPD) has been investigated in numerous papers to understand the structural characteristics and properties of internal boundaries in such materials rened by the promising top-down methods [1,2]. However, conicting results have been reported. Signicantly enhanced grain boundary (GB) diusivities have been reported in some SPD materials in relation to the data in coarse-grained counterparts [35]. On the other hand, similar GB diusivities were found in materials before and after SPD processing [68]. The existence of a hierarchy of internal interfaces in SPD materials with remarkably dierent diusivities was discovered [4] and it was suggested to be responsible for this discrepancy [9]. The contribution of non-equilibrium GB (i.e. GB with higher energies and diusivities [10]), the eects of GB migration [11,12] and recrystallization [7,8], as well as the interference of other defects introduced during processing or annealing [13,14], have also been reported. These effects are often concurrent and result in a complex diusion behavior of SPD-processed materials. In our previous study [15], diusion of Ni was investigated in a nanostructured surface layer of pure Cu produced by means of surface mechanical attrition treatment (SMAT). The results showed that the GB diffusivity is increased by $4 orders of magnitude with re-


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spect to that in coarse-grained Cu of similar purity. This diusion enhancement was attributed to a larger value of the excess free energy of high-angle GBs in the nanostructured layer. The main study in Ref. [15] was carried out at temperatures below 403 K, at which the nanocrystallites are relatively stable against grain growth. At higher temperatures, signicant grain growth occurred in the topmost surface layer, which complicates the corresponding data evaluation. Such an analysis relies strongly on the underlying model of the microstructure and the grain growth characteristics, and it requires specially designed experiments for an unambiguous interpretation. In the present paper, the time-dependence of Ni diusion in nanostructured Cu produced by using SMAT is investigated at 423 K, at which a considerable grain growth of the matrix occurs. The time-dependence of the diusion rate is examined and the relationship between the microstructure evolution and the diusion kinetics is discussed. A nanostructured surface layer was produced on a Cu plate (99.995 wt.%) by means of SMAT [1618]. The thermal stability of the topmost layer of the SMAT sample was investigated by a Hitachi H-800 transmission electron microscope (TEM) operated at 200 kV. TEM foils were cut by the electro-spark discharge technique, mechanically polished, dimpled and nally ionmilled from the untreated side. Disk samples with a diameter of 11 mm and a thickness of 1.8 mm were cut from the SMAT Cu plate parallel to the treated surface. The SMAT surface was then pressed against a polished WC hard alloy plate with low

1359-6462/$ - see front matter 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.scriptamat.2011.02.018

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strain and low strain rate to produce a smooth surface, so that no further surface polishing was necessary before the diusion measurements. A 63Ni radioisotope was deposited onto the prepared surface by drying a droplet of a dilute solution of 63Ni in HCl. Diusion experiments at 423 K were performed in an oil bath furnace for dierent durations (see Table 1). After the diusion annealing treatments, samples were reduced in diameter by more than 1 mm to remove the confounding eects related to surface and lateral diusion. Diusion penetration proles were determined by parallel mechanical sectioning using a precision grinder and abrasive Mylar foils with Al2O3 particles. The mass dierence before and after each sectioning was used to determine the section thickness (and then the penetration depth, with an accuracy better than 0.1 lm). The section thickness varied from 0.3 lm to about 2 lm in the present study. The relative activity of 63Ni was measured by a TRI-CARB 2500 TR liquid-scintillation counter, and the tracer concentration (C) in each section is proportional to the relative specic activity, i.e. the ratio of the counting rate after background subtraction to the section mass. The detailed microstructure characterization of the surface layer of the as-SMAT sample was published in Ref. [18]. The grain size initially increases gradually with depth from the treated surface, from 10 3 nm at the topmost surface to $100 nm at a depth of 25 lm, then approaches the original micrometer level at a depth of $500 lm. The interface structure is sequentially dominated by twin boundaries (TBs, or TB-like interfaces), high-angle GBs, low-angle GBs and dislocation walls with increasing depth. The present work is focused on the relationship between the microstructure evolution and the diusion behavior in the top 10 lm surface layer, in which the grain sizes are initially within 1025 nm and a majority of interfaces are TBs. After an isothermal annealing at 423 K for 60 min, a typical microstructure of the topmost SMAT surface layer is shown in Figure 1. In comparison with the microstructure of the as-SMAT sample [18], the average grain size increases slightly, from 10 to 30 nm. Existing twins are still clearly visible in both the bright- and dark-eld images. The corresponding selected area electron diraction (SAED) patterns reveal an almost random crystallographic texture of the nanocrystallites. The typical microstructure of the topmost SMAT surface layer after isothermal annealing at 423 K for 1440 min is shown in Figure 2. Newly formed large grains that resulted from static recrystallization could be identied and almost no twins are observed. The grains are well dened and nearly dislocation free. An average grain size of 525 nm is determined from several TEM images of the same sample. It is generally considered that the kinetics of isothermal grain growth in polycrystalline materials ts the relationship [19] d n d n kt 0 1

size of $125 nm is calculated by this relationship after annealing at 423 K for 330 min.1 The determined grain size data of the nanostructured surface layer after annealing at 423 K for dierent durations are summarized in Table 1. Clearly, grain growth accompanies the diusion processes. A very wide grain size distribution was observed in the SMAT surface layer after the annealing treatments. This microstructure is a typical conguration of a recrystallization process in nanostructured (or ultrane grained) materials produced by means of severe plastic deformation [5,7,8,20]. However, since the section thickness of diusion measurements is considerably larger than the grain sizes, the eect of heterogeneity of the grain size on the diusion data is smeared out. For simplicity, we neglect the distribution of the grain size and grains will be considered as equiaxed with a mean size d. Figure 3 shows the measured penetration proles. The rst several points close to the surface are usually disregarded. A negligible eect of potential grinding-induced forward mixing of the radioactivity on the proles was conrmed by the zero prole measurements in our previous work [15]. It is clear that Ni has diused into the SMAT surface layer. The specic activity values decrease continuously to the background value at depths of >25 lm. The lattice diusion from the surface or short-diusion paths into the crystalline bulk is negligible in the present conditions (i.e. (Dvt)1/2 ( 1 nm; see Table 1) when using the lattice diusivity (Dv) deduced from Ref. [21]. Thus, the signicant penetration of Ni is promoted by short-circuit diusion along various interfaces in the nanostructured surface layer. Since the microstructure changes with the distance from the treated surface (y), the diusivity in the rst surface layer (y < 10 lm) is expected to be very dierent from the diusivity in the subsurface layer (10 lm < y < 25 lm). As a result, the measured concentration proles correspond to diusion in two sequential layers with dierent eective diusivities and reveal two distinct branches, i.e. a steep one and a shallow one, as shown in Figure 3. The measured tracer distribution in the rst branch (y < 10 lm) can potentially be caused by diusion from an instantaneous diusion source according to dierent models:(i) The classic Harrisons C-type regime [22]. In this case, an eective diusivity (De) is used to quantify the penetration rate along GBs and TBs according to  1 1 @ ln C Deff 2 4t @y 2 A more complicated solution for the diusion case in a two-layered material was developed in Ref. [15]. However, it was found that the dierence between the exact solution [15] and the eective solution using Eq. (2) [23] is reasonably small.(ii) The so-called CB regime, after Divinski et al. [24]. In this case, diusion along TBs proceeds in a C-type regime and diusion along

where d is the mean grain size after an annealing time t, d0 is the initial grain size, k is the temperature-dependent rate constant and n is an empirical growth exponent. Fitting the experimental data by Eq. (1), a near-linear dependence is found with n = 1 0.05, d0 % 10 nm and k % 6 103 nm s1. Accordingly, a mean grain

The present study concentrates on the reliable incorporation of the grain growth kinetics into the diusion analysis rather than on the precise examination of the growth kinetics of the nanostructured layer. The derived results are not very sensitive to the exact value of n, as shown later, supporting the validity of the present estimates.

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Z. B. Wang et al. / Scripta Materialia 64 (2011) 10551058 Table 1. Parameters of Sample T423A T423B T423C


Ni diusion in the rst surface layer (y < 10 lm) of SMAT Cu at T = 423 K. p b Time (s) Grain sizea (nm) Dv t (nm) q2 (m2)


q1.2 (m1.2) 5.04 10 7.61 106 6.01 106


q1 (m1) 5.34 105 8.12 105 6.36 105

3.63 10 1.98 104 8.64 104

30 15 125 525 256

6.5 10 1.5 10-5 3.1 10-5


4.62 10 6.94 1010 5.58 1010


The data of T423B is calculated according to Eq. (1) and the measured grain size data (by TEM) of T423A and T423C, with an initial grain size of 10 3 nm. b Calculated from the diusion equation for Cu lattice [21].

2 C gb =C 0 p


"   a2 2 # sin s Y2 d 0 1Y =s 1 2 ds 2 s Y s d

The total layer concentration of diused atoms is determined as a weighted sum, C = dCgb/d + (1 d/d)Cv. By numerical integration of the above equations, the resulting tracer concentrations can be determined using d0 and

Figure 1. Typical TEM (a) bright-eld and (b) dark-eld images of the topmost surface layer of the SMAT sample annealed at 423 K for 60 min. The inset in (b) is the corresponding SAED pattern.

high-angle GBs occurs in a B-like regime (a signicant leakage from GBs into TBs), as suggested in Ref. [15]. The penetration rate might be determined by the value of the modied triple product PGB, as  5=3 A @ ln C P GB p 6=5 3 @y t where A is the given constant determined by the TB diffusivity.(iii) Diusion controlled by migrating interfaces. The signicant accompanying grain growth aects the distribution of tracer atoms and requires a specic approach for quantifying the GB diusivity. The model of Glaeser and Evans [11] is predominantly used to analyze the diusion data in such a case, and works very well for a bicrystal in which the GB migrates with a constant rate V perpendicularly to the diusion direction. The apparent diusivity of boundaries (Db) is then determined as  2 V @ ln C Db 4 d @y where d is the boundary thickness. Hypothetically, it might _ be applied in the present case, since d k const and _ V ad. Here a is a geometrical factor ($1). However, this model fails if the diusion length exceeds the grain size, and that is the case for the nanostructured Cu studied in the present work. Recently, Klinger and Rabkin produced a more sophisticated model [12], in which grain growth is adequately taken into account via equations such as Eq. (1). The analysis of Klinger and Rabkin can generally be used straightforwardly in the case of n > 1. In the present case of near-linear grain growth, Eq. (12) in Ref. [12] is reduced to "   a2 2 # Z 2 1 sin s d 0 1Y =s 1 ds 5 C v =C v0 p 0 s d Here Cv (Cv0) is the (initial) bulk concentration of diffused atoms and Y = y(ak/dDb)1/2 is the reduced depth. The corresponding GB concentration, Cgb, is given by

Figure 2. Typical TEM bright-eld image of the topmost surface layer of the SMAT sample annealed at 423 K for 1440 min.

Relative specific activity (a.u.)

T423A T423B T423C




y (m)

Figure 3. Measured proles of 63Ni relative specic activity vs. penetration depth in SMAT Cu samples subjected to diusion treatments at 423 K for dierent durations. Relative specic activity values of samples T423B and T423C were rescaled for a convenient comparison. Table 2. Numerical parameters required for the analysis of interface diusion. d 30 125 525

fw 0.565 0.321 0.203

w 1.028 1.073 1.118

Db(EG)a (m2 s1) 2.57 10 8.34 1015 9.46 1015


Db(KR)b (m2 s1) 4.43 1014 1.85 1014 2.95 1014

Db(EG) represents the value determined by the model of Glaeser and Evans [11]. b Db(KR) represents the value determined by the model of Klinger and Rabkin [12].

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z=2 z=1.2 z=1

















t (s)

Figure 4. The diusion time dependences of the relevant prole slopes ln (qz @@y zC) with z equal to (a) 2, (b) 1.2 and (c) 1.

Although the power w is close to unity, a dierence between the predictions of the models of Glaeser and Evans and of Klinger and Rabkin is found. This dierence would be considerably larger in a common case of non-linear grain growth. This fact highlights the requirement of an adequate consideration of grain growth in nanostructured materials. Furthermore, the determined apparent diusivity is about one order of magnitude higher than those estimated without the consideration of grain growth at the same temperature (compared with the value of 1.80 1015 m2 s1 in Ref. [15]). Thus, by neglecting the eects of grain growth on tracer penetration, a much lower value of interfacial diffusivity in the nanostructured Cu was obtained at 423 K. This result is similar to what was found in ultrane-grained Cu produced by equal channel angular pressing within the temperature range of 424553 K [7]. Financial support from the Alexander von Humboldt Foundation, the Deutsche Forschungsgemeinschaft, the National Natural Science Foundation of China (50701044 and 50890171) and the MOST International S&T Cooperation project of China (2010DFB54010) is acknowledged. The authors are grateful to K. Wang for providing SMAT samples.
[1] Y.T. Zhu, T.C. Lowe, T.G. Langdon, Scripta Mater. 51 (2004) 825. [2] S.V. Divinski, H. Ro sner, G. Wilde, Functional nanostructured materialsmicrostructure, thermodynamic stability and atomic mobility, in: G. Wilde (Ed.), Nanostructured Materials, Amsterdam: Elsevier, Amsterdam Boston, 2009, p. 1. [3] Y.R. Kolobov, G.P. Grabovetskaya, M.B. Ivanov, A.P. Zhilyaev, R.Z. Valiev, Scripta Mater. 44 (2001) 873. [4] Y. Amouyal, S.V. Divinski, Y. Estrin, E. Rabkin, Acta Mater. 55 (2007) 5968. [5] Z.B. Wang, N.R. Tao, W.P. Tong, J. Lu, K. Lu, Acta Mater. 51 (2003) 4319. [6] R. Wurschum, K. Reimann, S. Gruss, et al., Phil. Mag. B 76 (1997) 407. [7] Y. Amouyal, S.V. Divinski, L. Klinger, E. Rabkin, Acta Mater. 56 (2008) 5500. [8] H.L. Wang, Z.B. Wang, K. Lu, Acta Mater. 59 (2011) 1818. [9] S.V. Divinski, G. Wilde, Mater. Sci. Forum 584586 (2008) 1012. [10] R.Z. Valiev, R.K. Islamgaliev, I.V. Alexandrov, Progr. Mat. Sci. 45 (2000) 103. [11] A.E. Glaeser, J.W. Evans, Acta Metall. 34 (1986) 1545. [12] L. Klinger, E. Rabkin, Int. J. Mater. Res. 100 (2009) 530. [13] J. Ribbe, D. Baither, G. Schmitz, S.V. Divinski, Phys. Rev. Lett. 102 (2009) 165501-1. [14] S.V. Divinski, J. Ribbe, D. Baither, et al., Acta Mater. 57 (2009) 5706. [15] Z.B. Wang, K. Lu, G. Wilde, S.V. Divinski, Acta Mater. 58 (2010) 2376. [16] K. Lu, J. Lu, J. Mater. Sci. Technol. 15 (1999) 193. [17] K. Lu, J. Lu, Mater. Sci. Eng. A 375377 (2004) 38. [18] K. Wang, N.R. Tao, G. Liu, J. Lu, K. Lu, Acta Mater. 54 (2006) 5281. [19] T.R. Malow, C.C. Koch, Acta Mater 45 (1997) 2177. [20] Y.M. Wang, M.W. Chen, F.H. Zhou, E. Ma, Nature 419 (2002) 912. [21] J. Bernardini, J. Cabane, Acta Metall. 21 (1973) 1571. [22] L.G. Harrison, Trans. Faraday Soc. 57 (1961) 597. [23] Z.B. Wang, K. Wang, K. Lu, G. Wilde, S.V. Divinski, Def. Di. Forum 58 (2010) 2376. [24] S.V. Divinski, F. Hisker, Y.S. Kang, J.S. Lee, Chr Herzig, Acta Mater 52 (2004) 631.

d. In addition, the tracer distribution can be tted by an exponential dependence on the reduced depth to a certain power of w, i.e. ln(C/C0) / Y w. Therefore, Db can be determined according to  2=w V @ ln C 7 Db fw d @y w with fw and w calculated numerically (see Table 2). The processing of diusion proles following these three models leads to a relevant slope @ ln C qz 8 @y z which denotes the linear dependence of concentration on the sectioning depth. Here z is equal to 2, 6/5 and 1 for the cases (i), (ii) and (iii), respectively. Therefore, following Eqs. (2)(4) and (7), the time dependences of the relevant slopes are expressed as 9a q2 $ t1 q6=5 $ t0:3 and 9c q1 $ t 0 respectively. The time dependences of the relevant slopes qz (z = 2, 6/5 and 1) of the rst branches of the measured diusion proles are shown in Figure 4. It is clear that the relationship Eq. (9c) is satised very well, suggesting that the diusion kinetics should be controlled by grain growth in the nanostructured surface layer at 423 K. The apparent interfacial diusivities calculated according to Eqs. (4) and (7) are listed in Table 2.2 It is found that the diusivity is almost time independent, conrming the validity of the present analysis by using the case (iii). A slight decrease in the interface diusivity with increasing grain size might be related to partial relaxation of the higher-energy state of moving interfaces. 9b

We have additionally examined the eect of the exact value of n on the derived diusivity, since in the present study the grain growth kinetics was estimated using only three data points. The numerical values of the derived diusivities changed by about 30% if n = 1.2 was tentatively used. This estimate can be used as the uncertainty of the present analysis.

qz (m )