Int. J. Electrochem. Sci.

, 10 (2015) 4946 - 4971

International Journal of
ELECTROCHEMICAL
SCIENCE
www.electrochemsci.org

Role of Glycine as a Complexing Agent in Nickel

Electrodeposition from Acidic Sulphate Bath
Magdy A.M.Ibrahim1,2,* and Rasha M. Al Radadi1
1
Chemistry Department, Faculty of Science, Taibah University, Al Maddinah Al Mounwara, 30002
KSA
2
Chemistry Department, Faculty of Science, Ain Shams University, Abbassia, Cairo, 11566 Egypt
*
E-mail: [email protected]

Received: 12 December 2014 / Accepted: 19 March 2015 / Published: 28 April 2015

Bright nickel coatings on copper substrates were successfully produced by electrodeposition using
acidic glycine complexing baths. The investigation was conducted using electronic spectroscopy,
potentiodynamic cathodic polarization, cyclic voltammetry, in situ-anodic linear stripping voltammetry
and chronoamperometry techniques complemented with XRD analysis and SEM measurements. Such
kinetic parameters as Tafel slope, transfer coefficient and exchange current density obtained from
Tafel plots indicated that glycine had an accelerating effect on Ni2+ electroreduction. In the glycine-
containing bath, SEM analysis revealed finer grains together with the appearance of fine microcracks.
The XRD analysis showed an increase in noncrystallinity with increasing glycine concentration. The
initial nucleation and growth of nickel followed the model of 3D instantaneous nucleation. The
corrosion behaviour of the nickel coatings was studied using both anodic potentiodynamic polarization
and open circuit potential tests in 3.5% NaCl solution, and the results indicated that glycine decreased
the corrosion resistance of nickel deposits. The throwing power, as well as the throwing index, in the
presence of glycine is lower than that observed in the absence of glycine.

Keywords: glycine; potentiodynamic polarization; complexes; SEM.

1. INTRODUCTION

Electrodeposition of nickel has been investigated extensively due to its particular mechanical
properties and numerous widespread applications in industry [1–3], the majority of which require
corrosion and heat resistance ]4[. As highly resistant to tarnish and due to their high value of hardness,
they have become an alternative for electroplated chromium in hardware, automotive, electrical and
electronics accessories. Moreover, because of favourable mechanical properties, nickel electrodeposits
Int. J. Electrochem. Sci., Vol. 10, 2015 4947

are used for electroforming of printing plates, phonograph record stampers, foil, tubes, screens and
many other articles ]5[. The selection of an electroplating bath depends primarily on the required
characteristics. Electrodeposition of nickel has therefore been studied by various authors using
different baths [6-10]. Also, nickel electroplates are extensively studied from Watts type baths in the
presence of different organic brighteners [11-13]. On the other hand, glycine is used effectively in the
electrodeposition of metals and alloys due to its high buffering properties and its ability to stabilises
the pH on the electrode surface during the electrodeposition process [6,7,14-20]. Plating baths
containing glycine have better current efficiency and lead to amorphous films compared to the
crystalline films obtained using citrate [21]. Finally, glycine baths are more environment friendly than
traditional cyanide baths. Few studies have been conducted on the electrodeposition of nickel from
acidic glycine baths. Moreover, published data on the influence of glycine on the kinetics of electrode
reactions during nickel electrodeposition are scarce. The present work aims to develop new baths for
producing good quality nickel deposits. In addition, the investigation aims to elucidate the mechanism
and kinetics of nickel electrodeposition from acidic glycine baths. The corrosion resistance of the
nickel deposited as well as the throwing power and throwing index in the presence of glycine were also
investigated.

2. EXPERIMENTAL

Nickel electrodeposition onto copper substrates was achieved using an acid sulphate bath
containing NiSO4 6H2O and H3BO3 in the presence and absence of glycine as a complexing agent. All
solutions were freshly prepared with distilled water and analytical grade reagents. The pH was adjusted
using 1:1 sulphuric acid (sp.gr.1.84 g/cm3) or potassium hydroxide (10% w/v) and was measured using
a Janway 3540 pH meter. For nickel electrodeposition, a copper and a platinum sheets each of
dimensions (2.5 x 2.5 cm) were used as cathode and anode respectively. The electrodeposition cell
used was in the form of rectangular trough made of Perspex (11 x 3 cm) provided with vertical grooves
on each of the side walls to fix the electrodes. Before each run, the copper substrate was cleaned by
being dipped in a pickling solution for one minute and being rinsed in distilled water before being
dried and weighed. Direct current was supplied by a DC power supply unit (QJ3005A). The
determination of the cathodic current efficiency (F%) of nickel deposition was performed with a Cu
coulometer and the equation (F = Wexp / Wtheo), where Wexp is the weight of the deposit obtained
experimentally, and Wtheo is the weight of the deposit calculated theoretically according to Faraday’s
law [22]. All experiments were performed using unstirred solutions, 10 min plating duration, at a
temperature of 20 ± 2°C. The TP% of the solution was measured using a Haring–Blum rectangular
Perspex cell fitted with one anode between two parallel copper cathodes where the ratio of the far to
the near distance was 5:1. The TP% was calculated from Field’s formula [23]:
TP% = (L - M) / (L + M - 2) x 100 (1)
Where, L is the ratio of the cathode distance to the anode distance (far to near 5:1), and M is
the ratio of the weight of the deposited metal on the near to the weight of the deposited metal on the far
cathode. The values of M were measured as a function of L over a wide range of linear ratios varying
Int. J. Electrochem. Sci., Vol. 10, 2015 4948

between 1:1 and 5:1. The throwing index (TI) was considered to be the reciprocal of the slope of the M
against L plot.
Potentiodynamic cathodic polarization curves were recorded using copper substrates by
sweeping the potential from the rest potential toward the negative direction with a scan rate of 10 mVs -
1
. All of the electrochemical experiments were carried out using a computer assisted
potentistat/galvanostat (SI 1287 Solartron). The software packages CorrWare 2 and CorrView 2
provided by Solartron were used to measure and analyse the data. All potentials were measured
relative to a saturated calomel electrode (SCE). The classic three-electrode cell was used for the cyclic
voltammetry measurements. The working electrode was a glassy carbon electrode (GCE) (area =
0.1963 cm2) enclosed in a PVC cylinder. The GCE was polished before each experiment with a
diamond paste until a bright surface finishing was produced, then washed with distilled water. The
counter-electrode was a platinum net. In the anodic linear stripping voltammetry measurements, the
deposition of nickel from the plating bath was carried out at a constant potential at the GCE for a
constant plating time. At the end of each deposition time, stripping analysis was performed
immediately in the same plating bath (i.e., in situ) by sweeping the potential to more anodic potentials
at a sweep rate of 10 mVs-1 [5,24]. The electrochemical corrosion tests were carried out using a
classical three-electrode cell with platinum as the counter electrode, saturated calomel electrode as the
reference electrode, and the samples with an exposed area of 1 cm2 as the working electrode. The
corrosive medium used for electrochemical corrosion tests was a neutral 3.5% NaCl solution, and the
test temperature was maintained at 20°C. The surface morphologies of the nickel coatings was studied
using a scanning electron microscopy (Model Philips XL-40 FEG). The phase and the crystal structure
of the nickel coatings was analyzed by a Shimadzu XRD-6000 diffractometer (40 kV, 30 mA), Ni
filter and CuKα radiation. The drive axis is theta-2theta, scan speed 2 deg/min and preset time 0.60
sec. The absorption spectra of nickel solutions at different pH values were measured by UV-Visible
spectrometer (GBC UV-Visible Cintra 6). UV spectra were obtained using plastic cell with a light path
length of 1.0 cm.

3. RESULTS AND DISCCUSION

Although glycine is usually presented as (H2N-CH2-COOH), it is considered as a dipolar ion

(zwitterion) whose structure protonates or deprotonates, depending on the pH of solution [25]. The
equilibria between these may be depicted as shown in equation (2). Therefore, complex equilibria take
place in the solution are shown below ]7,26].

In the pH range from 3.0 to 8.0, nickel complexes of different compositions are detected in
solution depending on the concentration ratio of Ni2+ to glycine ratio in the electrolytic bath. At still
Int. J. Electrochem. Sci., Vol. 10, 2015 4949

higher pH values (8-10), Ni2+ exists preferentially as [NiGly3]- which has the higher stability constant
[7] as follows:

Therefore, ]NiGly3[ - is the most predominant complex species in the solution because it has a
much higher equilibrium constant. In addition, because there are more Ni2+ ions than glycine, there
will also be significant amounts of free Ni2+ ions present in the solution. Therefore, the following
electroreduction reactions are possible with hydrogen evolution from independent side reactions:
Ni2+ + 2e- = Ni (8)
- - -
]NiGly3[ + 2e = Ni + 3NH2CH2COO (9)

3.1 Absorption spectra

A change was observed in the colour of the nickel solutions as a function of the pH. This
finding prompted a spectroscopic investigation in the visible region. This change may be due to
transitions between the d orbitals of the transition metal in the coordination compounds.

Figure 1. The absorption spectrum of a nickel solution containing: 100 g/L NiSO4, 30 g/L H3BO3 at
different concentration of glycine.
Int. J. Electrochem. Sci., Vol. 10, 2015 4950

Fig. 1 illustrates the absorption spectra of nickel solutions at different concentrations of glycine
in the wavelength range of 300 - 1100 nm at room temperature. The spectra show the appearance of
one sharp transition at 385 nm and two transitions at 650 and 725 nm respectively due to the n-* and
d-d transitions, confirming the complex formation. It is also clear that the absorption spectra are
independent on the glycine concentration in the electrolytic solution.

Figure 2. The absorption spectrum of a nickel solution containing: 100 g/L NiSO4, 30 g/L H3BO3 and
100 g/L glycine at different pH values.

Fig. 2 shows the absorption spectra of Ni2+- g1ycine solutions at different pH values. In this
case, the two transitions at 650 and 725 nm are shifted to lower wavelengths and overlapped to one
band at 600 nm at pH 9.0. Also, the n-* transition is shifted to lower wavelengths by increasing the
pH. This could be due to the change in the ratio of the complex from 1:1 to 1:3 complexes. Significant
increase in the intensity of the absorption band can be noticed in going from low to high pH. This
indicates that the formation of the Ni2+-glycinate complex depends strongly on the pH. The formation
of Ni2+‫ ـ‬glycinate complex is easier at higher pH than at lower pH, since the intensity of the absorption
band of the Ni2+-glycinate solution is stronger at high pH values. As the acidity of solution decreases
and hence the amount of unprotonated glycine increases, the intensity of the bands grows which
confirms the formation of a complex species. This result is consistent with the results obtained by
Mizushima et al., [27[.

3.2. Voltammetric behavior

3.2.1. Potentiodynamic cathodic polarization curves

Fig. 3 shows typical cathodic polarization (i/E) curves during nickel deposition onto copper
substrate in the absence and presence of glycine (25-125 g/L). The curves were swept from the rest
Int. J. Electrochem. Sci., Vol. 10, 2015 4951

potential (-0.4 V) towards the negative direction at scan rate of 10 mVs-1. Discharge of hydrogen ions
was observed simultaneously during the deposition of Ni2+ ions. The data show that the presence of
glycine led to a significant shift in the polarization curves in the direction of more positive potentials in
addition to the increase in the current density. This effect of glycine could be related to its complex
formation with Ni2+ ions and it indicates that the complex formed activates the electroreduction of Ni 2+
ions. This implies also that glycine acts as an accelerator for nickel reduction over the copper surface
and does not block the active sites on the electrode surface for nickel deposition. This acceleration
effect of nickel ions reduction in presence of glycine was also observed by Sotskaya et al., [7].

Figure 3. Potentiodynamic cathodic polarization curves during nickel deposition at different

concentrations of glycine, scan rate = 10 mVs-1.
Int. J. Electrochem. Sci., Vol. 10, 2015 4952

Figure 4. Potentiodynamic cathodic polarization curves during nickel deposition at different pH

values, scan rate = 10 mVs-1.

Fig. 4 (A and B) display the influence of pH (pH 2.1 – 9.1) on the cathodic polarization curves
during nickel electrodeposition. The pH of each bath was adjusted by adding concentrated H 2SO4 or
KOH solution. The potentiodynamic cathodic polarization curve is shifted significantly negatively
with increasing pH. Moreover, the deposition potential of nickel is occurred at high negative potential
with increasing the pH. This trend may be related to the fact that increasing pH leads to an increase of
the hydrogen ion dissociation from the glycine molecule. Thus, the concentration of free Ni2+ ions
decreases as the pH increases. A consequent lowering of free Ni2+ ions results in a shift of the cathodic
potentials to more negative values. It is worth mentioning that the polarization curve at pH 2.1 is
mainly due to the hydrogen discharge at the cathode. With increasing pH, the slope of the i-E curves
increases as a result of a high rate of simultaneous hydrogen evolution with nickel deposition.

Figure 5. Potentiodynamic cathodic polarization curves during nickel deposition at different

temperatures, scan rate = 10 mVs-1.
Int. J. Electrochem. Sci., Vol. 10, 2015 4953

The effect of bath temperature on the potentiodynamic cathodic polarization curves during
nickel deposition is shown in Fig. 5. An increase in bath temperature decreases the cathodic
polarization due to its effect on the activation overpotential for the reducible ions. Moreover, an
increase in temperature may change the relative abundance of both complexed and uncomplexed Ni 2+
ions in the solution. These results indicate that a rise in temperature favours the complex ion
dissociation. Consequently, the concentration of the uncomplexed Co2+ ions would result in a decrease
in the reduction overpotential.

3.2.1.1.Tafel lines and electrode kinetics

To investigate the kinetics of nickel deposition in the presence of glycine, Tafel lines were used
to calculate the electrochemical parameters such as the Tafel slope bc and the transfer coefficient α.
The exchange current densities io for nickel deposition were obtained by extrapolating the Tafel lines
to zero overpotential which give relative rates of reaction at equilibrium. The data indicate that the
Tafel slopes increase in the presence of glycine and it increases with increasing the glycine
concentration in the bath. On the other hand, the transfer coefficient α decreases with increasing
glycine concentration, implying that the charge transfer reaction is affected by the presence of glycine
(Table 1). Moreover, the exchange current density, io, is markedly increased with increasing glycine
concentration. Generally, the exchange current density io is increased when the electrochemical
reaction is accelerated [28]. This finding implies that glycine accelerates the rate of Ni2+ ion transfer
across the electrical double layer. The accelerating effect of glycine could be due to its complex
formation with Ni2+ ions, which activates the electroreduction of Ni2+ ions.
On the other hand, the effect of changing the pH values shows that the Tafel slope are high at
low pH values as a result of hydrogen overvoltage and low at high pH. At the same time the exchange
current density significantly decreases while the transfer coefficient increases. In contrast, raising the
bath temperature, results in an increase in both the Tafel slope and io and a slight decrease in the
transfer coefficient. The increase in io may be attributed to the fact that a rise in temperature favours
the complex ion dissociation, as mentioned before. Consequently, the concentration of the free Ni 2+
ions would increase and the reduction of Ni2+ ions occurs more readily.

Table 1. Tafel kinetic parameters obtained for nickel deposit in absence and presence of glycine at
different deposition conditions.

Variable i° αc -bc
(A cm-2 ) (mV decade-1)
[glycine] , g/ L

0 5.76 х 10-4 0.09 323

25 5.89х 10-4 0.06 486
50 5.99 х 10-4 0.06 502
100 6.65х 10-4 0.05 533
125 7.61 х 10-4 0.05 562
Int. J. Electrochem. Sci., Vol. 10, 2015 4954

Temp. /oC
20 3.92 х 10-4 0.06 487
30 1.05 х 10-3 0.05 554
50 5.81 х 10-3 0.05 664
60 6.04 х 10-3 0.05 685
pH
2.1 1.19 х 10-2 0.04 740
3.1 6.66 х 10-3 0.05 634
4.2 4.12 х 10-4 0.06 493
5.1 2.28 х 10-4 0.07 439
6.2 4.65 х 10-5 0.09 315
7.1 1.24 х 10-6 0.14 210
8.3 4.32 х 10-8 0.18 163
9.1 1.78 х 10-8 0.18 158

3.2.2 In situ-Anodic linear stripping voltammetry (ALSV)

ALSV is particularly useful as a simple and easy ‘in situ’ electrochemical method for
identifying the phase and composition of metal and alloy. A series of voltammetric experiments was
carried out by the deposition of nickel onto a glassy carbon electrode (GCE) at a given constant
cathodic potential (-1.15 VSCE) for a given time (100 s). Immediately after nickel deposition, the
potential was swept linearly in the positive direction at a scan rate of 10 mVs -1 and an anodic stripping
voltammogram was recorded without removing the electrode from the solution or changing the
prevailing conditions.

Figure 6. In-situ anodic linear stripping voltammetric curves during nickel deposition at different
concentrations of glycine.
Int. J. Electrochem. Sci., Vol. 10, 2015 4955

Figure 7. In-situ anodic linear stripping voltammetric curves during nickel deposition at different pH
values.

Figure 8. In-situ anodic linear stripping voltammetric curves during nickel deposition at different
temperatures.

Representative data are given in Figs. 6 -8. The voltammograms of nickel in all cases studied
has only one dissolution peak, which arises from dissolution of nickel deposited potentiostatically. No
residual nickel or nickel oxide was visible on the GCE beyond the anodic peak. Therefore, the charge
consumed through anodic stripping could be taken as a quantitative measure of the current efficiency
of nickel deposition, i.e., the area under the peak is equivalent to the amount of nickel deposited.
Int. J. Electrochem. Sci., Vol. 10, 2015 4956

The effect of adding different concentrations of glycine on the ALSV was studied and the
results are shown in Fig. 6. It is clear that increasing the glycine concentration increases the height and
the area under the stripping peak indicating clearly that glycine acts as an accelerator for nickel
deposition. This acceleration process increases with increasing glycine concentrations. These results
agree well with the data of the polarization curves (see Fig. 3). On the other hand, in the presence of
glycine, the peak of ALSV lies at more positive potential indicating that the nickel deposited in the
presence of glycine is difficult to oxidized in comparison with that deposited in absence of glycine.
Fig. 7 illustrates the ALSV curves during nickel electrodeposition at different pH values. Increasing
the pH values resulted not only in a decrease in the height of the stripping peak but also in a decrease
of the area under the peak. The results indicate that the stripping charge for nickel deposition decreases
with increasing pH. These results also agree well with the polarization curves (Fig.4).
Fig. 8 shows the ALSV during nickel electrodeposition at different bath temperatures. The
results indicate that the stripping charge for nickel deposition increases with increasing the bath
temperature which indicates that a rise in bath temperature decreases the stability constant of the
complex species leading to relatively higher concentrations of the uncomplexed Ni2+ ions.

3.2.3. Cyclic voltammetry

Cyclic voltammetry was used to determine the reduction potential regions for the
characterisation of nickel deposition process. Figs. 9 and 10 show the voltammograms of Ni
electrodeposition on GCE recorded at scan rate of 100 mVs-1. In each voltammogram there is no
difference in the oxidation wave during the anodic scan and that we have identified to study the change
in reduction wave during the cathodic scan.

Figure 9. Cyclic voltammetric curves recorded at GCE during Ni deposition at different

concentrations of glycine, scan rate = 100 mVs-1.
Int. J. Electrochem. Sci., Vol. 10, 2015 4957

Figure 10. Cyclic voltammetric curves recorded at GCE during nickel electrodeposition at different
pH values, scan rate =100 mVs-1.

Fig. 9 shows the cyclic voltammograms of nickel deposition with various concentrations of
glycine. In the presence of glycine, the potential of cathodic reduction of Ni2+ shifted to less negative
potentials. This effect of glycine could be related to its complex formation with Ni2+ ions which
indicates that the complex formed activates the electroreduction of Ni2+ ions. This implies that glycine
acts as an accelerator for nickel deposition over the copper substrate and does not block the active sites
on the electrode surface for nickel deposition. This result is consistent with the results of cathodic
polarization curves (Fig. 3).
The influence of pH on the cyclic voltammetry during nickel electrodeposition was examined
and the results are shown in Fig. 10 A, B. It was found that the potential of cathodic reduction of nickel
Int. J. Electrochem. Sci., Vol. 10, 2015 4958

is significantly shifted to more negative potential values with increasing the pH in agreement with the
results of polarization curves shown in Fig. 4.

3.3. Cathodic current efficiency

Visual observation of nickel coatings deposited from glycine baths showed that the deposit has
bright appearance all over the current densities studied and the electrolytes studied can be used to
obtain bright nickel deposits without introduction of brightening additives.

Figure 11. Effect of NiSO4 concentration on the cathodic current efficiency during nickel deposition.

Figure 12. Effect of glycine concentrations on the cathodic current efficiency during Ni deposition.
Int. J. Electrochem. Sci., Vol. 10, 2015 4959

Fig. 11 shows the effect of NiSO4 concentrations (25-100 g/L) on the cathodic current
efficiency (CCE%). The data show that, increasing Ni2+ content in the bath leads to a gradual increase
in the CCE reached a maximum value of 93.9 % at 50 g/L, and then with further increase in nickel
content in the bath, it decreases to reach 84.5% at 125 g/L. The CCE% determined from these baths is
less than 100% as a result of simultaneous hydrogen evolution. Addition of glycine to the electrolytic
bath decreases gradually the CCE% of nickel deposition as shown in Fig. 12.
This may be attributed to the fact that increasing the glycine concentration, increases the
concentration of complex ions, and decreases the concentrations of uncomplexed Ni 2+ ions, which in
turn causes an increase of the cathodic overpotential and a lowering of cathodic current efficiency. The
deposition from complex species is not so easy like the deposition from free Ni2+ ions [29].

Figure 13. Effect of pH on the cathodic current efficiency.

One of the most important operating parameters in the electroplating process is the pH value.
The data in Fig. 13 shows the influence of pH on the CCE% in the pH range from 2.1 to 9.1. The data
indicate that the CCE% increases sharply reaching maximum values at pH between 4 and 7 and
decreases with further increase in pH. The low values of CCE% for Ni deposition at low pH values
could be due to the decrease in hydrogen overpotential and consequently the enhancement of hydrogen
evolution reaction, although lowering pH increases the concentration of the free Ni2+ in the bath.
Int. J. Electrochem. Sci., Vol. 10, 2015 4960

Figure 14. Effect of current density on the cathodic current efficiency at different pH.

The effect of current density on the CCE at two different pH values (pH 6.2 and pH 8.1) was
studied and the results are given in Fig. 14. The data clearly reflect that the pH variation is still more
pronounced than that of current density. For example, at pH 6.2, the CCE increases slightly with
increasing current density and then tends to level off with further increase in the current density.
However, at pH 8.1, a significant decrease in the CCE is observed with increasing current density.

Figure 15. Effect of H3BO3 concentration on the cathodic current efficiency during Ni deposition.
Int. J. Electrochem. Sci., Vol. 10, 2015 4961

The effect of boric acid concentration on the CCE% of nickel deposited is given in Fig. 15. The
CCE incre ases from 86.1% to a maximum value of 93.9% with increasing boric acid concentration
from 10 to 30 g/L. These data show that the presence of boric acid in the bath improves the efficiency
of Ni deposition. In this case, boric acid plays a greater role than merely as a buffer. It is now believed
that boric acid complexes with Ni2+ ions acting as a homogeneous catalyst or adsorbs on the electrode
surface [30-32], which lowers the overpotential for nickel deposition. However, further increase in
concentration of boric acid ( 30 g/L) has a decreasing effect on the CCE.

Figure 16. Effect of temperature on the cathodic current efficiency at different current densities.

The effect of bath temperature on the CCE% of nickel deposited at different current densities
was studied and the results are shown in Fig. 16. The data indicate that at a given current density, the
CCE decreased with increasing the bath temperature especially at high current densities of 13.3 and 20
mAcm-2. However, at low current densities of 6.3 and 9.3 mAcm-2, the CCE decreases slightly and
then tends to level off. On other words, increasing bath temperature leads to a decrease in CCE and
this effect is more pronounced at high current densities. Similar behavior was observed during cobalt
electrodeposition from gluconate bath [33]. It is worth mentioning that, high efficiency at low
temperature could be considered as an advantage in industrial applications.

3.4. Chronoamperometric analysis

Chronoamperometry (current –time transient) measurements were conducted at GCE to obtain

more information about the initial nucleation and growth kinetic mechanism of nickel deposition in
Int. J. Electrochem. Sci., Vol. 10, 2015 4962

glycine bath. Fig. 17 shows typical potentiostatic current time transients for nickel deposition from
bath contains: 100 g/L NiSO4, 30 g/L H3BO3 and 100 g/L glycine at various deposition potentials.
During the potential step, the current-time transients are characterized by a graduall double-layer
charging current decay [34] followed by a rising current due to the formation and growth of Ni nuclei.
The current increases with increasing the applied nucleation overpotential. It has been demonstrated
that the deposition of metals onto a foreign substrate generally involves some type of three
dimensional nucleation processes. Two limiting cases for this type of metal deposition have been
classified by Scharifker and co-workers[35-37] as instantaneous nucleation and progressive nucleation.
The instantaneous model refers to the situation in which a fixed number of nucleation sites are all
activated at the same time after the potential step, whereas progressive model refers to the situation in
which the nucleation sites gradually become activated as the chronoamperometric experiment
proceeds.

Figure 17. Potentiostatic current-time transient curves during nickel electrodeposition at different
deposition potentials.

Figure 18. Relationship between the current density and t1/2 during nickel electrodeposition derived
from Fig.17 at different deposition potentials.
Int. J. Electrochem. Sci., Vol. 10, 2015 4963

Analysis of the rising part of transient is possible by representing, for the initial transient
portion, i vs t1/2 for instantaneous and i vs t3/2 for progressive nucleation. For the experimental data
shown in Fig. 17, plots of i vs t1/2 show good linearity (Fig. 18). On the other hand, plots of i vs t 3/2
show poor linearity. This indicates that under the experimental conditions, instantaneous three-
dimensional growth of nickel nucleation occurs.

3.5. Throwing power, throwing index and Wagner number

Figure 19. Metal distribution ratio M against linear ratio L at different NiSO4 concentrations.

Figure 20. Metal distribution ratio M against linear ratio L at different glycine concentrations.
Int. J. Electrochem. Sci., Vol. 10, 2015 4964

Figure 21. Metal distribution ratio M against linear ratio L at different pH values.

The throwing power values of the nickel plating baths calculated by Field's empirical formula
at a distance ratio of 1:5 under different plating conditions are shown in Table 2. Moreover, the
throwing index (TI) was determined by plotting the metal distribution ratio M, and the linear ratio L
(1:1–1:5) as shown in Figs. 19-21 as representative examples. The reciprocal of the slopes of these
lines are called the throwing index (TI) and represent a measure of bath throwing power.
Table 2 shows that the TP increases from -8.05% to 1.69 % as the nickel salt increases in the
bath from 50 to 125 g /L. The corresponding TI values are 0.86 and 1.05 respectively as deduced from
Fig. 19. The increase in TP is due to the observed increase in conductivity from 14.8 mS to 28.9 mS.
The data in Table 2 reveals that TP and TI decrease as the concentration of glycine increases
(Fig. 20). This behavior could be assigned to the observed decrease in the cathodic polarization with
increasing glycine concentration ( Fig. 3).
The influence of pH on the TP and on TI was also investigated and the results are summarized
in Table 2. Increasing pH value of the plating solution leads to a remarkable increase in TP and TI
(Fig. 21).. This improvement in TP may be attributed to the increase in the cathodic polarization as
well as the conductivity with increasing pH ( Fig. 4).
The throwing power can be expressed by Wagner number (Wa). The degree of
electrodeposition uniformity is characterized by the Wagner number Wa ]38,39], which represents the
ratio of the electrochemical reaction to the ohmic resistances. The Wa is used to characterise the
relative importance of charge transfer control on the current distribution. The current distribution is
expected to become more uniform as the Wa increases ]40[. The Wa is defined by:
Int. J. Electrochem. Sci., Vol. 10, 2015 4965

(10)
Where, is the electrolyte conductivity of the solution, is the breadth of the electrode (2.3 cm
in this work), is the slope of the potential-current density curve. The Wagner numbers calculated
for different solutions are included in Table 2. The results confirm that the current density distribution
becomes less uniform as the Wagner number decreases. The data of the throwing power, throwing
index and Wagner number are in good agreement with each other. The less uniform the current
distribution, the lower the Wagner number and consequently the lower the throwing power as well as
the throwing index.

Table 2. Throwing power, throwing index and Wagner number for nickel electrodeposition

Variable TP TI Wa
]NiSO4[, g/L
50 -8.05 0.86 -
125 1.69 1.05 -
]glycine[, g/L
0 -8.05 0.86 3.47
75 -20.00 6.04 3.06
150 -34.21 0.50 2.21
pH
2.4 -11.37 0.68 0.45
2.4 14.29 1.33 0.59
1.8 49.25 2.84 0.30

3.6. Characterization of nickel deposits

3.6.1. Surface morphology of nickel deposits

The surface morphology of the as-deposited nickel deposited from glycine-containing and
glycine-free baths was examined by scanning electron microscopy (SEM) and the results are given in
Fig. 22. The nickel deposited on copper substrate from glycine-free bath consists of grains of mud-like
structure of different sizes as shown in Fig. 22 a. However, the addition of glycine to the plating
solution (75 g / L) leads to the formation of fine and a homogenous circular grains but containing
cracks as shown in Fig. 22b. These microcraks become larger with increasing glycine concentration
(Fig. 22C). The presence of microcracks in the deposit indicates that the deposits are highly stressed as
a result of hydrogen evolution during deposition [41]. The cracking occurs if the tensile stress exceeds
the tensile strength of the film.
Int. J. Electrochem. Sci., Vol. 10, 2015 4966

Figure 22. Photomicrograph of nickel deposited in the absence and presence of different glycine
concentrations (a) 0 g/L glycine, (b) 75 g/L glycine, (c) 125 g/L glycine.

3.6.2. X-ray diffraction analysis

The XRD patterns of a typical Ni-deposited from glycine-containing and glycine-free baths are
shown in Fig. 23.
Int. J. Electrochem. Sci., Vol. 10, 2015 4967

Figure 23. X-ray diffraction analysis of nickel deposited in the absence and presence of glycine, s is
the substrate.

As shown in this figure, the Ni deposit in the absence of glycine exhibits three reflections at 2θ
characteristic for Ni(200), Ni(220) and Ni(111), respectively. However, addition of 50 g /L glycine
leads to retard the peak of Ni(200) and enhances the peak of Ni(111). Further increase in glycine
concentrations shows clearly a decrease in crystallinty of nickel deposited. For example increasing the
glycine concentration to be 100 or 125 g / L leads to decrease the degree of crystallinty as observed by
the complete disappear of Ni(200) reflection and the decrease in Ni(220) intensity.

3.7. Corrosion behavior

3.7.1 Anodic potentiodynamic polarization curves

One of the most important properties of electrodeposited coatings is their corrosion resistance.
Therefore, the corrosion behavior of the as-deposited nickel from glycine-containing and glycine-free
baths was examined in 3.5% NaCl solution by means of anodic potentiodynamic polarization
measurement.
Fig. 24 shows the anodic potentiodynamic polarization curves for nickel coating deposited on
copper substrate in 3.5% NaCl. The curves were obtained by sweeping the potential starting from -2.0
VSCE up to an anodic potential of 1.0 VSCE at scan rate of 10 mVs-1. As can be observed, all of the
samples studied exhibited an active-passive – transpassive behavior. However, the nickel deposited
Int. J. Electrochem. Sci., Vol. 10, 2015 4968

from glycine-free bath is characterized by wider range of passivity. The icorr (corrosion current density)
and Ecorr (corrosion potential) which were calculated by using linear Tafel fitting on the anodic and
cathodic Tafel regions of the potentiodynamic polarization curve are listed in Table 3. As can be
observed the corrosion current icorr increases and the Ecorr is shifted to more negative potential values,
in cases of samples prepared from glycine-containing baths. This result indicates that the Ni coating
glycine-free solution has a higher corrosion resistance relative to Ni coating from glycine-containing
solution, which corresponds to an increase of the corrosion rate of nickel.

Figure 24. Anodic potentiodynamic polarization curves for nickel deposited in the absence and
presence of different concentrations of glycine in 3.5% NaCl.

Table 3. Electrochemical parameters of nickel deposits at different glycine concentrations.

]glycine [ Icorr Ecorr

g/ L (Acm-2 ) (volts)

0 0.00014333 -0.80574
100 0.00020800 -1.1001
125 0.00044013 -1.1078
Int. J. Electrochem. Sci., Vol. 10, 2015 4969

3.7.2. Open circuit potentials

Figure 25. Free corrosion potentials vs. time for nickel deposited from glycine-free (a) and from
glycine-containing (b,c) solutions in 3.5% NaCl .

Fig. 25 shows the time variations of the free corrosion potential for nickel deposited from
glycine- containing solutions and from glycine –free solution in 3.5% NaCl solution in open circuit
conditions. The data reveal that the nickel deposited from glycine- free solution (curve a) posses nobler
potentials than that which deposited from glycine-containing solutions (curves b,c), which means that
nickel deposited from glycine-containing bath posses a lower corrosion resistance than that without
glycine. This result is in good agreement with the result obtained from the anodic polarization
measurements. All of the samples tested reached the equilibrium potential within the time range of the
measurements (approximately 4 h). To the best of our knowledge, no previously published reports
refer to the corrosion resistance of nickel deposited from glycine solutions.

4. CONCLUSIONS
Addition of glycine to the nickel plating solution leads to:
- Improve the appearance of the nickel deposits, it becomes bright.
- Formation of a complex between nickel and glycine which depends strongly on pH as
confirmed by the electronic spectra measurements.
- Glycine accelerates the Ni2+ ions reduction as confirmed by the polarization curves, the ALSV
and CV.
- Decrease the throwing power, throwing index and Wagner number.
- Increase the degree of noncrystallinity, as shown by XRD analysis.
Int. J. Electrochem. Sci., Vol. 10, 2015 4970

- Decrease the corrosion resistance of the nickel deposits.

- The formation of finer grains and the appearance of fine microcracks.

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