The effect of sodium citrate as an additive on properties of electroplated nickel on

SPCC steel
Rini Riastuti, Falah Herdino, Achmad Rifki, Cika Ramadini, and Sonia Taruli Siallagan

Citation: AIP Conference Proceedings 2043, 020013 (2018); doi: 10.1063/1.5080032

View online: https://doi.org/10.1063/1.5080032
View Table of Contents: http://aip.scitation.org/toc/apc/2043/1
Published by the American Institute of Physics

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 The Effect of Sodium Citrate as an Additive on Properties of Electroplated
Nickel on SPCC Steel

Rini Riastuti1,a), Falah Herdino1,b), Achmad Rifki1,c), Cika Ramadini1,d), and Sonia Taruli Siallagan1,e)

1
Dept. of Metallurgy and Materials Engineering, University of Indonesia
Kampus Baru UI Depok, 16424± Indonesia
a)
Corresponding author: riastuti@metal.ui.ac.id
b)
herdinofalah@gmail.com
c)
ahmadrifki132@yahoo.co.id
d)
cika.ramadini@gmail.com
e)
soniasiallagan@gmail.com

Abstract: The aim of this work was to investigate the effect of sodium citrate as an additive on the grain size of nickel
electroplating SPCC steel. For this purpose, nickel were deposited by direct current electrodeposition from a Watts bath
at the current density of 6 A/dm2 with adding different amount of sodium citrate (5, 15, 30, 45, 60 g/L). X-ray diffraction
(XRD) was used to determine the average gain size of the nickel coatings. Effect of adding sodium citrate on nickel
electroplating on hardness, corrosion resistance, and adhesive strength were also investigated by Vickers Hardness, salt
spray test, and bending test. The smallest grain size was obtained with grain size 36.8 nm with adding 45 g/L sodium
citrate. The hardest nickel deposit was 701 HV with presence of sodium citrate complex in the deposit. Corrosion
resistance and adhesive strength were increased by adding sodium citrate in the nickel electroplating bath.

Keywords: Electroplating, nanocrystalline, nickel, sodium citrate, grain size, SPCC steel

INTRODUCTION
In recent years, production of nanocrystalline coating with grain size less than 100 nm has been the subject of
intensive research and has important role in industrial applications due to their unique properties, especially
mechanical and chemical properties [1,2]. Various techniques, such as physical vapor deposition (PVD), chemical
vapor deposition (CVD), laser beam deposition, ion implantation, plasma and high-velocity oxygen fuel (HVOF)
spray have been developed to synthesize nanocrystalline materials. Among those methods, electroplating was the
most feasible technique and economical to produce nanocrystalline coating with low residual porosity. Compare to
the other techniques, electroplating are (a) low cost and industrial applicability, (b) easy to control as the
electrodeposition parameters can be easily adjusted to meet required grain size, microstructure and chemistry of
products and (b) high production rates [3].
Materials that have nanocrystalline structure are better in mechanical and chemical properties. For example,
materials that decreased from 100 μm to 10 nm grain size structure has seven times higher yield strength and
hardness compared to the coarse grain. Besides mechanical properties, nanocrystalline materials has better corrosion
resistance because it has higher grain size density that accelerates the formation of protective passive layer.
Whereas, a coarse grain size deposit has lower corrosion resistance because no passivation occurred [4-6].
Many parameters are involved in the electroplating, such as type of electrolyte, concentrations of ions, pH of
electrolyte, current density, and additives. Nevertheless, the results of electroplating experiments obtained by

The 6th International Conference on Science & Engineering in Mathematics, Chemistry and Physics
AIP Conf. Proc. 2043, 020013-1–020013-6; https://doi.org/10.1063/1.5080032
Published by AIP Publishing. 978-0-7354-1769-4/$30.00

020013-1
different researchers are difficult to optimize certain conditions for production nanocrystalline nickel electroplating,
because in some cases, the reported data are inconsistent or even different.
A review of literatures shows that saccharin has often added to nickel electroplating bath from the 80s [7] in
order to improve brightness and as grain refining agent. Although, saccharin has many advantages, it has
carbonaceous material and sulfur. Sulfur in saccharin acts as solid solution strengthener but may also cause
intergranular embrittlement [8]. Therefore, in this study tried to use different additive which was sodium citrate.
Sodium citrate is mainly used as food additive in food production, pharmaceutical and cosmetics industry. It is
commonly used as a buffering agent in combination with citric acid to provide precise pH control required in many
food and beverage applications. According to patent from Abdelmounam and Thomas Anand, they observed that
sodium citrate can act as grain refiner but it didn¶t get much attention. The objectives of this study were to
investigate the effect of adding sodium citrate as an additive on nickel electroplating bath on grain size, hardness,
corrosion resistance and adhesive strength of the coating.

EXPERIMENTAL
Nickel coatings were deposited by direct current electrodeposition (DC) from a Watts bath containing nickel
sulfate (300 g/L), nickel chloride (30 g/L), boric acid (30 g/L) and aquadest (1000 mL). The Watts bath then
homogenized by stirring using magnetic stirrer. Sodium citrate with different amount (5, 15, 30, 45, 60 g/L) at
temperature of 55oC, a current density of 6 A/dm2 and pH 5.5 [13]. Pure nickel (75 x 50 x 7.5 mm) was used as
anode and SPCC Steel (100 x 75 x 2 mm) as cathode. Chemical composition of SPCC steel shown in Table 1.

TABLE 1. Chemical Composition of SPCC Steel

Chemical composition (%)

Material
C (Max) Mn (Max) P (Max) S (Max)

SPCC 0.12 0.50 0.04 0.045

Prior electrodeposition process, pretreatments sample were conducted including degreasing with NaOH and
Na2CO3 for 15 minutes at 70oC, electrodegreasing, pickling with HCl 32% for 5 minutes, etching with 10% H2SO4
for 15 minutes. The pretreatments were conducted to make the surface of SPCC steel free from grease, oil and other
unwanted substance. The average grain size in the direction normal to the film plane was estimated by using
Scherrer¶s formula obtained from Xray diffraction (XRD) (equation 1).

/ .Ȝ%&RVș (1)

Where L is the grain size, K is Scherrer constant aȜ is wave length and B is half-KHLJKWZLGWKRIș
diffraction peak. Hardness of the coating was measured by Vickers hardness with diamond indentor. The force was
50 grf and time load was 10 seconds. The Vickers hardness is a quotient obtained by dividing the kgf load by the
square mm area of indentation. Corrosion resistance was tested with salt spray test with 5% NaCl for 48 hours
referred to ASTM B117. The grade of corroded products was compared to ASTM D 610 ³Standard Test Method for
Evaluating Degree of Rusting on Painted Steel Surfaces´. While adhesive strength of coating was measured by
bending test referred to ASTM B571. The SPCC steels with deposited nickel were bend 180o and then observed
whether there was peeling or flaking on electrodeposited nickel (bend area).

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 RESULT AND DISCUSSION
1. Effect of Sodium Citrate on Grain Size

Fig. 1 shows the result of grain size of nickel deposited on spcc steel with adding sodium citrate on Watts
bath (0-60 g/L) using Scherer¶s formula. The grain size of nickel deposit without adding sodium citrate was 93 nm.
On addition 5 g/L sodium citrate, the grain size decreased to 40.8 nm. Further addition of sodium citrate has no
significant effect. The smallest grain size obtained was 36.8 nm with 45 g/L addition of sodium citrate.

FIGURE 1. Effect of Sodium Citrate on Grain Size

It is suggested that addition of small amount of sodium citrate can reduce the size of grain, but with further
addition of sodium citrate has no significant effect. This happened maybe because of that the addition of sodium
citrate can form nickel complexes that may be absorbed on the cathode surface, block the active sites available and
slow down crystal production and producing fine grain nickel deposit [9]
Nickel deposit with sodium citrate addition has brighter appearance comparing to without addition of
sodium citrate in the Watts bath because of fine deposit produced, it will reflect most the light with the same angle
as the angle of arrival. When the surface is rough and has coarse grain, the ray will diffuse into different angle and
the surface will appear as matt [10].

2. Effect of Sodium Citrate on Corrosion Resistance

The type of corrosion referred to ASTM D610. The percentage of rusted area was estimated using visual
example shown ASTM D610.

TABLE 2. Effect of Sodium Citrate on Corrosion Grade

Sodium Citrate Hardness Corrosion

(g/L) (HV) Grade

5 220.6 1-G
15 231.8 4-S
30 473.06 8-S
45 701.09 10
60 440.99 10

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 Based on the salt spray result in Fig. 2, in the nickel deposit with 5 g/L sodium citrate addition on watts bath,
there was brown oxide formed on the surface and categorized as general rusting 1-G with 50% oxide content. With
15 g/L sodium citrate, it has long oxide formed in the center of the surface and categorized as spot rusting 4-S with
10% oxide content. The highest corrosion resistance obtained with 45 g/L and 60 g/L sodium citrate addition,
categorized as 10 corrosion grade because there were no corrosion or oxide formed after 48 hours of salt spray test.

a b

c d

FIGURE 2. The Result of 48 Hours Salt Spray Test with 5% NaCl with The Addition of a) 5 g/L b) 15 g/L c) 30 g/L d) 45 g/L e)
60 g/L Sodium Citrate

It suggested that corrosion resistance increased with increased the amount of sodium citrate in Watts bath.
According to LI Chao-qun [11], the presence of citrate and boric acid further increases the cathodic polarization
during nickel deposition. This behavior is caused by the formation of Ni2+ ion complexes and block effect of boric
acid and absorb on the cathode surface and block the active sites available hence there is an inhibition process
occurred and no corrosion occurred.

3. Effect of Sodium Citrate on Hardness

FIGURE 3. Effect of Sodium Citrate on Hardness

020013-4
 Fig. 3 shows a graph of relation between variation sodium citrate on hardness number of nickel deposit. It shows
that more addition of sodium citrate amount increased the hardness number of nickel deposit. There was an
increased hardness number 0 g/L (220 HV), 15 g/L (231.8 HV), 30 g/L (473.06 HV), 45 g/L (701.09 HV) sodium
citrate addition but there was a decreased with 60 g/L (441 HV) sodium citrate addition. Nickel deposit with the
highest number of hardness obtained from 45 g/L sodium citrate addition. The highest number of hardness obtained
with nickel smallest grain size deposit.
The hardness dependence on the average grain size can be described by Hell Petch equation where there was a
relationship between grain size and hardness:

+9 +9RN¥G (2)

Where HV is the hardness of material, d is grain size, and HVo and k is constant. With a decreased grain size,
there are more grain boundaries can hinder dislocations movement. The smaller grain size has a larger surface area
to volume ratio, which means the greater the grain boundary ratio to the dislocations. The more grain boundaries
that exist, strength and hardness increases.
According to Tadashi Doi and Kazunari Mizumoto, increased hardness of the deposit, beside its nano grain
size, it can be caused by a (Ni(HCit)]- complex exist because the reaction between nickel and sodium citrate. The
presence of the complexes linked to specific deposit characteristics. One particularly clear example of this is the
increased hardness obtained in the bath pH region where the [Ni(Cit)]- complex exists predominantly. It appears that
this specific complex contributes much to the crystallization of the nickel deposits [11].

4. Effect of Sodium Citrate on Adhesive Strength

Adhesion of the nickel deposit with SPCC steel is tested by bend (bending the film with substrate to 180 o).
The result showed that nickel deposit with sodium citrate addition have good adhesion with the spcc steel because
there were no peeling or flaking occurred on bend area in any sodium citrate addition. Based on experimental results,
it can be suggested that the process parameter favouring fine grain at the substrate/deposit interface produced
deposits with high adhesive strength. According to A. Murray, H. Khakbaz [12], a plausible mechanism for the
difference in the adhesive strength with change in crystal size is based on mechanical interlocking of the deposited
crystals have greater ability to interlock with the spcc steel, and thereby maximizing the area of direct substrate
attachment, hence increasing the adhesive strength.

CONCLUSION
Effects of addition sodium citrate as additive on Watts bath in nickel electroplating on SPCC steel were studied.
It was found that the addition of sodium citrate can reduce the grain size of nickel deposits to 36.8 nm with 45 g/L
sodium citrate addition. Sodium citrate also can improve on properties of electroplated nickel on SPCC steel.
Sodium citrate improved corrosion resistance of electroplated nickel by act as inhibitor because it reacted with
nickel forming nickel citrate complexes that absorbed in cathode surface. Sodium citrate also improved hardness by
forming nitrate complexes and it made the hardness of the electroplated nickel increased. The adhesive strength of
the coating increased because there was good interlocking between nickel and SPCC steel.

ACKNOWLEDGEMENTS
The authors would say thanks to PT. Utama Raya Motor Industry and PITTA UI for all facilities and their
financial support that offered to perform this work.

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