Corrosion Science 46 (2004) 30193029 www.elsevier.

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Eect of nanocrystalline grain size on the electrochemical and corrosion behavior of nickel
R. Mishra, R. Balasubramaniam
*
Department of Materials and Metallurgical Engineering, Indian Institute of Technology, Kanpur 208 016, India Received 8 September 2003; accepted 20 April 2004 Available online 6 July 2004

Abstract Nanocrystalline nickel of dierent grain sizes (828 nm) was produced by electrodeposition using Watts bath. Saccharine addition to the bath and pulsed current deposition were eective in lowering the grain size of the deposits. The grain size and microstrain of deposits was determined by X-ray diraction analysis. The microhardness of nanocrystalline Ni ranged between 572 and 724 kg/mm2 . The electrochemical behavior of nanocrystalline Ni was evaluated in 1 mol/l H2 SO4 and compared with that of coarse-grained nickel. All the nickel samples exhibited activepassive potentiodynamic polarization behavior. The zero current potential, passive current density and breakdown potential generally increased with decrease in grain size. The increased passive current density for nanocrystalline nickel conrmed the defective nature of passive lm that forms on nanocrystalline nickel. The tendency for localized corrosion was lower in case of nanocrystalline nickel as indicated by increased breakdown potential. Tafel and linear polarization tests revealed that the corrosion rate of freshly exposed surfaces of Ni decreased with grain size, thereby indicating greater hindrance to anodic dissolution in nanocrystalline Ni. The magnitude of compressive microstrain in the Ni deposits increased with decrease in grain size. 2004 Elsevier Ltd. All rights reserved.
Keywords: Nanocrystalline; Nickel; Polarization; Passivation; Corrosion rate; Microstrain

Corresponding author. E-mail address: bala@iitk.ac.in (R. Balasubramaniam).

0010-938X/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2004.04.007

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1. Introduction Electrodeposition is a versatile technique for producing nanocrystalline materials [1]. Only a few studies have addressed the corrosion behavior of nanocrystalline materials [26]. The corrosion resistance of Fe32 Ni36 Cr14 P12 B6 was greater for the nanocrystalline than the amorphous form [2]. The enhanced corrosion resistance of nanocrystalline Fe8%Al in Na2 SO4 solution of pH 6 has been attributed to the fast diusion of Al through the grain boundaries to form protective passive lm [3]. The corrosion behavior of Cu90 Ni10 alloy in neutral solution containing chlorides indicated a decrease in the protective properties of the passive layer in the nanostructured alloy [4]. Nanocrystalline Zn coatings exhibited improved corrosion resistance compared to electrogalvanized steel in deaerated 0.5 N NaOH solution [5]. Nanocrystalline nickel of grain size 32 nm displayed typical activepassive polarization behavior like pure coarse-grained (100 lm) polycrystalline nickel, but nanocrystalline Ni exhibited higher passive current density [6]. The nanocrystalline Ni was produced by electrodeposition without the addition of any grain rening agent to the bath [6]. It is known that smaller grain sizes can be obtained by the addition of suitable grain rening agents like saccharine or sodium citrate [7] to the electrodeposition bath and by pulsing the deposition current [8]. In the present study, nanocrystalline nickel deposits of dierent grain sizes were produced by pulsed current electrodeposition technique, using a nickel plating bath, both with saccharine and without saccharine addition. As several properties of nanocrystalline materials are dependent on the grain size, the aim of the present study was to understand the eect of nanograin size on the electrochemical and corrosion behavior of nanocrystalline nickel. The research also provided an opportunity to duplicate the earlier reported electrochemical data for nanocrystalline nickel [6].

2. Experimental procedure Nanocrystalline nickel was electrodeposited on copper cathode strips using Watts bath (NiSO4 6H2 O 240 g/l, NiCl2 6H2 O 30 g/l and H3 BO3 30 g/l). Electrodeposition experiments were performed at 45 C using a current density of 0.3 A/cm2 with both direct and pulsed current. These parameters were arrived at after initial studies in which the eect of temperature and current density on the adherance, uniformity and current eciency was studied [9]. In the case of pulsed current electrodeposition, ton was 5 ms and toff 20 ms. The total time of deposition was 30 min, i.e., cumulative ton . A leadtin (Pb7%Sn) alloy was used as anode and cold rolled copper as cathode material. Saccharine (10 g/l) was also added to the bath in some of the electrodeposition experiments for reducing the grain size. Grain size of the deposits was calculated by the (1 1 1) X-ray diraction (XRD) peak broadening. The diraction patterns were obtained using CuKa radiation at a scan rate of 3/min in a Rich Seifert diractometer. The full width half maxima (FWHM) of the diraction peaks were estimated by pseudo-Voigt curve tting using a polynomial of second degree. After subtracting the instrumental line broadening,

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which was estimated using annealed Ni and silica standards, the grain size was estimated using the (1 1 1) diraction peak by applying the Scherrer equation [10]. The microstrain in the Ni deposits was calculated by method of linear tting of X-ray data. The slope of the plot of B cos h vs. sin h provided the microstrain (e) as per the following relation [11] B cos h 2e sin h 0:9k=D 1

where B is the FWHM, h the diraction angle, D the grain size and k ( 0.15405 nm) is the wavelength of the radiation used. All the deposition experiments were duplicated and good reproducibility was obtained. The Vickers microhardness of the deposits was measured using a 100 g load. The electrodeposited samples were ultrasonically cleaned and degreased prior to electrochemical testing. Duplicate polarization (potentiodynamic, Tafel and linear) experiments were conducted at ambient temperature ($25 C) in a at polarization cell, using a platinum counter electrode and silversilver chloride (SSC, +197 vs. SHE) reference electrode. The pulsed current electrodeposition runs as well as the electrochemical experiments were conducted using a computer-controlled Perkin Elmer 263A potentiostat. The electrolyte used in the electrochemical experiments was freely-aerated 1 mol/l H2 SO4 and all the experiments were performed with the scan rate of 0.5 mV/s, as per the procedure adopted by Rofagha et al. [6]. The free corrosion potential was stabilized prior to each potentiodynamic polarization experiment. However, the Tafel and linear polarization experiments were conducted immediately on immersion of the sample in the electrolyte in order to understand the corrosion resistance of fresh surfaces of nanocrystalline Ni. An annealed polycrystalline nickel sample of grain size 61 lm was used for comparison purpose. The surface of the samples was observed in a JEOL JSM 840A scanning electron micrograph, both before and after polarization experiments.

3. Results and discussions Typical X-ray diraction patterns of nanocrystalline Ni have been compared with that of annealed Ni in Fig. 1. The grain sizes of the nanocrystalline nickel varied between 28 and 8 nm. The grain sizes and microhardness of the nickel deposits have been listed in Table 1. The microhardness of nanocrystalline Ni was much higher than annealed Ni (269 kg/mm2 ) and generally increased with decreasing the grain size. It has been reported [7,12] that the microhardness of nanocrystalline Ni in the grain size range of 1025 nm was 500650 kg/mm2 . The results of the present study are in agreement with the reported hardness. The microhardness for deposit of grain size 8 nm was lower than that of 10 nm grain size sample. Inverse HallPetch relationship has been reported in nanocrystalline nickel in previous studies [1]. Activepassive polarization behavior was observed for nanocrystalline nickel as well as for conventional coarse-grained polycrystalline nickel (Fig. 2). The potentiodynamic polarization curves shown in Fig. 2 were reproducible, except for the 22 nm grain size sample, based on two experiments conducted for each case. Dierence

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Intensity (Arb. Units)

8 nm

28 nm

Annealed

40

50

60

70

80

2 (degrees)
Fig. 1. XRD patterns of nanocrystalline Ni (8 and 28 nm) and annealed coarse-grained Ni. Table 1 Estimated grain size and microhardness of the nanocrystalline nickel deposits obtained by electrodeposition using a current density of 0.3 A/cm2 at 45 C Current Direct Direct Pulsed Pulsed Saccharine addition No Yes No Yes Grain size (nm) 28 10 22 8 Microhardness (kg/mm2 ) 572.34 18.6 724.00 17.4 626.80 28.1 689.45 16.5

2000

1500

8 nm
E (mV vs. SSC)
1000

10 nm 22 nm

500

28 nm 61 m

-500 -7 -6 -5 -4 -3 -2 -1 0 1

Log(i) (Log(A/cm2))

Fig. 2. Potentiodynamic polarization curves of nickel of dierent grain sizes in 1 mol/l H2 SO4 at scan rate of 0.5 mV/s. The experiments were conducted after stabilization of free corrosion potentials.

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in the polarization behavior was noted only in the case of 22 nm grain sized deposit. The conservative data (i.e. data showing larger passive current density and larger critical current density) has been presented in Fig. 2. Interestingly, the polarization curves for coarse-grained polycrystalline nickel and 28 nm (Fig. 2) were comparable to the polarization data reported by Rafagha et al. [6] for 100 lm grain sized coarsegrained polycrystalline nickel and 32 nm grain sized nickel (produced by electrodeposition). The passivation parameters, i.e., zero current potential (ZCP), potential for primary passivation (Epp ), potential for complete passivation (Ecp ), critical current density (icrit ), passive current density (ipass ), passive range (Eb Ecp ) and breakdown potential (Eb ), were estimated from the polarization curves and have been presented in Table 2. The critical current densities and passive current densities were determined at Epp and Ecp , respectively. There was generally a progressive shift in ZCP towards noble direction for the ner grain size deposits compared to bulk nickel. This is in agreement with the results of Rafagha et al. [6]. The hydrogen evolution reaction is predominant reduction reaction in the present case. It is known that defects like dislocation aects the kinetics of hydrogen evolution reaction. Moreover, reversible trapping of hydrogen at the dislocations, grain boundaries and voids (pores) can change the kinetics of hydrogen evolution. Therefore, catalysis of hydrogen reduction process by substantial quantity of crystalline defects (e.g., grain boundaries) at the surface of nickel deposits during electrochemical testing shifts the ZCP value in noble direction [6]. As a substantial fraction of atoms lie in the intercrystalline region of nanocrystalline nickel [13], the positive shift in the ZCP may be due to changes in hydrogen reduction processes. The critical current densities of passivation for all the nickel samples were approximately similar. This indicates that the mechanism of onset of passivity and passivation itself is similar in nature for all the Ni samples. There was a noticeable change in the passive current density for nanocrystalline nickel compared to bulk nickel. All nanograin sized deposits exhibited higher passive current density compared to coarse-grained polycrystalline nickel. This indicates the defective nature of the passive lm that forms on nanocrystalline nickel. Characterization of passive lm on nanocrystalline nickel by X-ray photoelectron spectroscopy has shown that
Table 2 Passivation parameters obtained from potentiodynamic polarization curves of nickel of dierent grain size in 1 mol/l H2 SO4 Nanocrystalline nickel Grain size ZCP (mV vs. SSC) Epp (mV vs. SSC) Ecp (mV vs. SSC) Eb (mV vs. SSC) Eb Ecp (mV) icrit (mA/cm2 ) ipass (lA/cm2 ) 28 nm )4 237 378 1330 952 16.21 301.99 22 nm 237 759 783 1470 687 145.54 354.80 10 nm 221 523 629 1500 871 30.19 323.50 8 nm 188 486 611 1540 929 23.98 501.10 Commercially pure annealed nickel 61 lm )142 148 278 1110 832 28.18 54.95

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higher number of defects were present in these passive lms [14]. It has been suggested that this should allow for easier Ni cation diusion through a more defective lm, thereby leading to higher passive current densities in the passive range for nanocrystalline Ni [14]. The imperfect passivation associated with nanocrystalline nickel may be also related to intrinsic electrochemical behavior associated with the disordered intercrystalline region in nickel [6,15]. There was a systematic increase in pitting potential (Eb ) with decrease in grain size. The lower tendency for localized grain boundary corrosion in nanocrystalline Ni has also been earlier observed [6]. This has been shown to be due to uniform distribution of S in case of nanocrystalline Ni [16]. Similarly, the lower tendency for localized corrosion in nanocrystalline Co has also been related to the uniform S distribution in the deposit [17]. The S content of and its distribution in the nanocrystalline Ni coatings were not determined in the present study. However, it is anticipated that S will be present and also that S will be uniformly distributed because similar electrodeposition conditions [16,17] were utilized to produce the nanocrystalline Ni coatings in the present study. The microstructural features of the deposited layers before and after polarization testing were recorded (Fig. 3). No signicant dierence could be observed for nanocrystalline nickel deposits. Therefore, the breakdown in passivity was not localized but spread out over the whole surface. Interestingly, the superior pitting resistance of sputter-coated nanocrystalline 304 stainless steel (grain size of 25 nm) compared to conventional 304 in HCl solution has been attributed to the defective passive lm which provides a uniform distribution of chloride ions on the specimen surface [18]. There were diculties in establishing linear Tafel regions, especially in the anodic portion of the polarization curves, presented in Fig. 2, which were determined after stabilization of free corrosion potential. These could, therefore, not be used for determining corrosion rates. However, linear Tafel regions were obtained for Tafel experiments conducted immediately after immersion of the sample in the electrolyte. The Tafel plots for bulk Ni and nanocrystalline Ni of two grain sizes (28 and 8 nm) are provided in Fig. 4. The Tafel slopes ba , bc and corrosion rates were estimated from the polarization curves and are listed in Table 3. The corrosion rates of the Ni samples were comparable, with the nanocrystalline Ni samples exhibiting marginally lower corrosion rates. The corrosion rate of Ni in 1 mol/l H2 SO4 has been reported to be between 0.254 and 1.27 mm/y [19] and, therefore, the present results for Ni of dierent grain sizes are comparable with the reported corrosion rate data for Ni. The lower corrosion rate estimated for nanocrystalline Ni could be due to the decreasing value of Tafel slopes (ba and bc ) with decreasing grain size. In a similar manner, the Tafel slopes of nanocrystalline Zn were lower than that of electrogalvanized steel of larger grain size [5]. Lower values of ba and bc lead to lower corrosion rate as per the SternGeary relation [20] icorr ba bc 2:303 Rp ba bc 2

where icorr is the corrosion current density and Rp , the polarization resistance.

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Fig. 3. SEM micrographs of 10 nm grain sized deposits (a) before and (b) after polarization study.

Fig. 5 shows the polarization resistance plots for three Ni samples. The polarization resistance was determined from the slopes of the potential vs. current plots in the range of 4 mV about the zero current potential. The corrosion rates estimated using the experimentally determined Tafel slopes (ba and bc ) and Rp are provided in Table 3. The corrosion rate data based on polarization resistance were slightly higher compared to the corrosion rates determined by the Tafel extrapolation method. However, the corrosion rates estimated using Rp data also indicated decreasing corrosion rate with decreasing grain size. Although the passive lms on nanocrystalline Ni may be poorer in corrosion resistance compared to bulk Ni, there is a general hindrance of corrosion from fresh surface of nanocrsytalline Ni. The activation barrier to dissolution from nanocrystalline Ni surfaces are higher compared to bulk Ni, thereby resulting in improved corrosion resistance for nanostructured surfaces compared to bulk surfaces. This may be related to the observation that nanocrystalline Ni showed lower tendency for localized grain boundary corrosion while in polycrystalline Ni, this can result in failures [6].

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300 200

8 nm

E (mV vs. SSC)

100 0 -100 -200 -300 -400 -7.0

28 nm 61 m

-6.5

-6.0

-5.5

-5.0

-4.5

-4.0

-3.5

-3.0

-2.5

-2.0

-1.5

Log(i) (Log(A/cm2))

Fig. 4. Tafel plots for bulk Ni, 28 and 8 nm grain sized nanocrystalline Ni conducted in 1 mol/l H2 SO4 at a scan rate of 0.5 mV/s. The experiments were conducted immediately after immersion of the samples in the electrolyte.

Table 3 Results of Tafel extrapolation and linear polarization experiments conducted in 1 mol/l H2 SO4 at a scan rate of 0.5 mV/s. The experiments were conducted immediately after immersion of the samples in the electrolyte Sample Bulk Ni 28 nm Ni 8 nm Ni bc ba icorr (Tafel extrapolation) (lA/cm ) 83.18 56.23 24.15
2

Rp (X cm2 ) 496 376 1050

icorr (Linear polarization) (lA/cm2 ) 115.40 78.61 28.94 mm/y 1.2436 0.8471 0.3118

(V/decade) )0.360 0.208 )0.234 0.120 )0.210 0.105

mm/y 0.8964 0.6059 0.2603

In this regard, it is also illuminating to note the microstrains estimated from the XRD data. The results of microstrain calculations have been listed in Table 4. The equation of the plot between B cos h and sin h is provided in this table. The nature of the plots indicated that electrodeposition synthesis technique resulted in compressive strains in the deposits, which is similar to that reported by Denis and Such [21]. In the present study, the magnitude of compressive stresses was higher in deposits with saccharine addition compared to deposits without saccharine addition. It can be also noticed from Table 4 that the magnitude of microstrain was higher with pulsing as compared to direct current deposition, both with and without saccharine addition. Interestingly, Table 4 indicates that using direct current deposition with saccharine addition produced a higher microstrain (0.00684) compared to pulsed current deposition without saccharine addition (microstrain of 0.00245). This may be associated with higher S contents with saccharine additions.

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20 15

8 nm

28 nm

Overvoltage (mV)

10 5 0 -5 -10 -15 -20 -60 -40 -20 0 20 40 60

61 m

i (A/cm2)
Fig. 5. Linear polarization plots for bulk Ni, 28 and 8 nm grain sized nanocrystalline Ni conducted in 1 mol/l H2 SO4 at a scan rate of 0.5 mV/s. The experiments were conducted immediately after immersion of the samples in the electrolyte.

Table 4 Microstrain in the deposits obtained from direct current and pulsed current experiments Sample No. 1 2 3 4 Current Direct Direct Pulsed Pulsed Saccharine addition No Yes No Yes Grain size (nm) 28 10 22 8 Equation of the line B cos h 2e sin h 0:9k=D Y Y Y Y 0:0035x 0:007 0:0097x 0:0125 0:0049x 0:0081 0:0177x 0:0287 Microstrain 0.00175 0.00485 0.00245 0.00885

It is known that compressive strains on the surface lower corrosion rate when compared to tensile stresses. The higher compressive microstrain in the 8 nm deposit could also be related to the lower corrosion rate, determined in the present study.

4. Summary The electrochemical and corrosion behavior of nanocrystalline nickel of dierent grain sizes (828 nm) in 1 mol/l H2 SO4 electrolyte has been compared with that of bulk Ni. The nanocrystalline Ni deposits were synthesized by electrodeposition. All the Ni samples exhibited activepassive polarization behavior. The shift of zero current potential in the noble direction with decreasing grain size has been related to modication in cathodic reaction (hydrogen reduction) processes. The passive current densities for nanocrystalline nickel were higher than that for bulk nickel and this has been related to the defective nature of passive lm on nanocrystalline nickel. The

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breakdown potential for ne grain sized nanocrystalline nickel was higher than coarse-grained polycrystalline nickel. The corrosion rate of freshly exposed nanocrystalline Ni was lower compared to bulk Ni, indicating a higher hindrance to anodic dissolution from the nanocrystalline Ni surfaces. XRD analysis indicated that the nanocrystalline Ni deposits were compressively strained, with microstrain increasing with decreasing grain size. Acknowledgement RB would like to acknowledge the equipment grant (potentiostat) from Alexander von Humboldt foundation.

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