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Effect of Nanocrystalline Grain Size on the Electrochemical

Effect of Nanocrystalline Grain Size on the Electrochemical

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Effect of nanocrystalline grain sizeon the electrochemical and corrosionbehavior 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 2004Available online 6 July 2004
Abstract
Nanocrystalline nickel of different grain sizes (8–28 nm) was produced by electrodepositionusing Watt’s bath. Saccharine addition to the bath and pulsed current deposition were effectivein lowering the grain size of the deposits. The grain size and microstrain of deposits wasdetermined by X-ray diffraction analysis. The microhardness of nanocrystalline Ni rangedbetween 572 and 724 kg/mm
2
. The electrochemical behavior of nanocrystalline Ni was eval-uated in 1 mol/l H
2
SO
4
and compared with that of coarse-grained nickel. All the nickelsamples exhibited active–passive potentiodynamic polarization behavior. The zero currentpotential, passive current density and breakdown potential generally increased with decreasein grain size. The increased passive current density for nanocrystalline nickel confirmed thedefective nature of passive film that forms on nanocrystalline nickel. The tendency forlocalized corrosion was lower in case of nanocrystalline nickel as indicated by increasedbreakdown potential. Tafel and linear polarization tests revealed that the corrosion rate of freshly exposed surfaces of Ni decreased with grain size, thereby indicating greater hindranceto anodic dissolution in nanocrystalline Ni. The magnitude of compressive microstrain in theNi deposits increased with decrease in grain size.
Ó
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
Ó
2004 Elsevier Ltd. All rights reserved.doi:10.1016/j.corsci.2004.04.007www.elsevier.com/locate/corsciCorrosion Science 46 (2004) 3019–3029
 
1. Introduction
Electrodeposition is a versatile technique for producing nanocrystalline materials[1]. Only a few studies have addressed the corrosion behavior of nanocrystallinematerials [2–6]. The corrosion resistance of Fe
32
Ni
36
Cr
14
P
12
B
6
was greater for thenanocrystalline than the amorphous form [2]. The enhanced corrosion resistance of nanocrystalline Fe–8%Al in Na
2
SO
4
solution of pH 6 has been attributed to the fastdiffusion of Al through the grain boundaries to form protective passive film [3]. Thecorrosion behavior of Cu
90
Ni
10
alloy in neutral solution containing chlorides indi-cated a decrease in the protective properties of the passive layer in the nanostruc-tured alloy [4]. Nanocrystalline Zn coatings exhibited improved corrosion resistancecompared to electrogalvanized steel in deaerated 0.5 N NaOH solution [5]. Nano-crystalline nickel of grain size 32 nm displayed typical active–passive polarizationbehavior like pure coarse-grained (100
l
m) polycrystalline nickel, but nanocrystal-line Ni exhibited higher passive current density [6]. The nanocrystalline Ni wasproduced by electrodeposition without the addition of any grain refining agent to thebath [6]. It is known that smaller grain sizes can be obtained by the addition of suitable grain refining agents like saccharine or sodium citrate [7] to the electrode-position bath and by pulsing the deposition current [8]. In the present study,nanocrystalline nickel deposits of different grain sizes were produced by pulsedcurrent electrodeposition technique, using a nickel plating bath, both with saccharineand without saccharine addition. As several properties of nanocrystalline materialsare dependent on the grain size, the aim of the present study was to understand theeffect of nanograin size on the electrochemical and corrosion behavior of nano-crystalline nickel. The research also provided an opportunity to duplicate the earlierreported electrochemical data for nanocrystalline nickel [6].
2. Experimental procedure
Nanocrystalline nickel was electrodeposited on copper cathode strips using Watt’sbath (NiSO
4
Æ
6H
2
O 240 g/l, NiCl
2
Æ
6H
2
O 30 g/l and H
3
BO
3
30 g/l). Electrodepositionexperiments were performed at 45
°
C using a current density of 0.3 A/cm
2
with bothdirect and pulsed current. These parameters were arrived at after initial studies inwhich the effect of temperature and current density on the adherance, uniformity andcurrent efficiency was studied [9]. In the case of pulsed current electrodeposition,
on
was 5 ms and
off 
20 ms. The total time of deposition was 30 min, i.e., cumulative
on
.A lead–tin (Pb–7%Sn) alloy was used as anode and cold rolled copper as cathodematerial. Saccharine (10 g/l) was also added to the bath in some of the electrode-position experiments for reducing the grain size.Grain size of the deposits was calculated by the (111) X-ray diffraction (XRD)peak broadening. The diffraction patterns were obtained using CuK
a
radiation at ascan rate of 3
°
/min in a Rich Seifert diffractometer. The full width half maxima(FWHM) of the diffraction peaks were estimated by pseudo-Voigt curve fitting usinga polynomial of second degree. After subtracting the instrumental line broadening,
3020
R. Mishra, R. Balasubramaniam / Corrosion Science 46 (2004) 3019–3029
 
which was estimated using annealed Ni and silica standards, the grain size wasestimated using the (111) diffraction peak by applying the Scherrer equation [10].The microstrain in the Ni deposits was calculated by method of linear fitting of X-ray data. The slope of the plot of 
B
Ã
cos
h
vs. sin
h
provided the microstrain (
e
) asper the following relation [11]
 B
Ã
cos
h
¼
2
e
sin
h
þ
0
:
9
k
=
 D
ð
1
Þ
where
B
is the FWHM,
h
the diffraction angle,
D
the grain size and
k
(
¼
0.15405 nm)is the wavelength of the radiation used.All the deposition experiments were duplicated and good reproducibility wasobtained. The Vickers microhardness of the deposits was measured using a 100 gload. The electrodeposited samples were ultrasonically cleaned and degreased priorto electrochemical testing. Duplicate polarization (potentiodynamic, Tafel and lin-ear) experiments were conducted at ambient temperature (
$
25
°
C) in a flat polari-zation cell, using a platinum counter electrode and silver–silver chloride (SSC, +197vs. SHE) reference electrode. The pulsed current electrodeposition runs as well as theelectrochemical experiments were conducted using a computer-controlled PerkinElmer 263A potentiostat. The electrolyte used in the electrochemical experimentswas freely-aerated 1 mol/l H
2
SO
4
and all the experiments were performed with thescan rate of 0.5 mV/s, as per the procedure adopted by Rofagha et al. [6]. The freecorrosion potential was stabilized prior to each potentiodynamic polarizationexperiment. However, the Tafel and linear polarization experiments were conductedimmediately on immersion of the sample in the electrolyte in order to understand thecorrosion resistance of fresh surfaces of nanocrystalline Ni. An annealed polycrys-talline nickel sample of grain size 61
l
m was used for comparison purpose. Thesurface of the samples was observed in a JEOL JSM 840A scanning electronmicrograph, both before and after polarization experiments.
3. Results and discussions
Typical X-ray diffraction patterns of nanocrystalline Ni have been compared withthat of annealed Ni in Fig. 1. The grain sizes of the nanocrystalline nickel variedbetween 28 and 8 nm. The grain sizes and microhardness of the nickel deposits havebeen listed in Table 1. The microhardness of nanocrystalline Ni was much higherthan annealed Ni (269 kg/mm
2
) and generally increased with decreasing the grainsize. It has been reported [7,12] that the microhardness of nanocrystalline Ni in thegrain size range of 10–25 nm was 500–650 kg/mm
2
. The results of the present studyare in agreement with the reported hardness. The microhardness for deposit of grainsize 8 nm was lower than that of 10 nm grain size sample. Inverse Hall–Petchrelationship has been reported in nanocrystalline nickel in previous studies [1].Active–passive polarization behavior was observed for nanocrystalline nickel aswell as for conventional coarse-grained polycrystalline nickel (Fig. 2). The poten-tiodynamic polarization curves shown in Fig. 2 were reproducible, except for the 22nm grain size sample, based on two experiments conducted for each case. Difference
R. Mishra, R. Balasubramaniam / Corrosion Science 46 (2004) 3019–3029
3021

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