See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/236658368

Influence of activation treatment with nickel

acetate on the zinc phosphate coating
formation and corrosion...

Article in Materials and Corrosion · October 2014

DOI: 10.1002/maco.201307009

CITATIONS READS

9 108

3 authors:

Khalid Abdalla Azmi Rahmat

University of Omar Al-Mukhtar Al Bayda, Libya Universiti Malaysia Perlis
6 PUBLICATIONS 23 CITATIONS 74 PUBLICATIONS 146 CITATIONS

SEE PROFILE SEE PROFILE

A. Azizan
Universiti Sains Malaysia
63 PUBLICATIONS 502 CITATIONS

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Synergistic Analysis and CFD Modelling of Sustainable Porous Clay-Synthesized Calcium Carbonate
for Gas Adsorbent Applications. View project

Deveploment corrosion protection at potential of zero charge View project

All content following this page was uploaded by Khalid Abdalla on 07 January 2014.

The user has requested enhancement of the downloaded file. All in-text references underlined in blue are added to the original document
and are linked to publications on ResearchGate, letting you access and read them immediately.
Materials and Corrosion 2013, 64, No. 9999 DOI: 10.1002/maco.201307009 1

Influence of activation treatment with nickel acetate on the

zinc phosphate coating formation and corrosion resistance
K. Abdalla, A. Rahmat and A. Azizan*

Zinc phosphating is a chemical conversion process that has been widely used in
industry for corrosion protection and primer for painting. In this investigation, the
effect of activation treatment with nickel acetate on the microstructural evolution
and corrosion resistance of the zinc phosphate coating on mild steel was studied.
The chemical composition and morphology of the coatings were analyzed via
scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS). The
corrosion resistance of the coatings was evaluated using polarization curves and
electrochemical impedance spectroscopy (EIS) in an aerated 3.5% NaCl solution.
Surface morphology observations revealed that the activation treatment increased
the population density and refined the grain size of the coating. The electrochemical
results showed better barrier protection characteristics and corrosion resistance for
activated phosphate coatings compared with inactivated coatings.

1 Introduction due to coagulation and sedimentation of the titanium phosphate

colloids, which limits its applications [15].
Phosphating is one of the most important chemical conversion Activation of steel surface with metal salts nobler than
processes that has been widely used in many industries for iron before zinc phosphating is beneficial in accelerating the
corrosion protection, wear resistance and primer for painting coating formation. This treatment results in the deposition of
[1–5]. For corrosion protection and wear resistance, the phosphate metallic particles on the surface of steel which form many small
coating should be compact, finely structured and firmly adhered local galvanic couples with Fe and subsequently accelerate
to the metal surface [6, 7]. The reaction mechanism of zinc the coating reaction. However, their usage to activate the metal
phosphate coating is electrochemical in nature and depends on surface in phosphating technique is rarely reported. Our previous
the dissolution of the metal at local anodic sites and the work [16], investigated the effect of copper acetate pretreatment
deposition of insoluble phosphate initiates at local cathodic sites on zinc phosphate coating morphology and corrosion resistance.
[8]. Recently, many studies have been focused mainly on getting The results showed that the pretreatment plays a significant role
compact, uniform, and stable phosphate coating via different in the nucleation and deposition of the phosphate layer and in
treatment strategies including pretreatment [9], process treat- turn the corrosion resistance of the phosphated samples was
ment [10, 11], and post-treatment [12, 13]. improved after the pretreatment with copper acetate.
It has been known that, the zinc phosphate coating can be As nickel is nobler than steel, the objective of this work
refined by activation treatment before phosphating with aqueous was to study the activation effect of nickel acetate pretreatment on
dispersions of colloidal titanium phosphate. This treatment zinc phosphate coating morphology and corrosion resistance on
increases the rate of nucleation and growth of the phosphate mild steel. The surface morphology and chemical composition of
coating because the colloids act as initial nuclei for the phosphate the coatings were analyzed using scanning electron microscopy
crystals [14, 15]. However, the activation performance of colloidal (SEM), and energy-dispersive spectroscopy (EDS). The corrosion
titanium phosphate decreases with increasing dispersion age, behavior of the phosphated samples was examined using
polarization curves and electrochemical impedance spectroscopy
(EIS) in an aerated 3.5% NaCl solution.
K. Abdalla, A. Azizan
School of Material and Mineral Resources Engineering, Engineering
Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Pulau Penang 2 Experimental
(Malaysia)
E-mail: [email protected] 2.1 Sample preparation

K. Abdalla Mild steel substrates with dimensions 15 mm  10 mm  2 mm

Faculty of Engineering, Omar Almukhtar University, Al-Bayda (Libya)
were used for the experimental purpose; the chemical composi-
A. Rahmat tion of the steel in weight percent is shown in Table 1. The
School of Material Engineering, Universiti Malaysia Perlis, 02600 substrates were mechanically ground with a series of SiC papers
Jejawi, Perlis (Malaysia) up to 600 grits, then subjected to ultrasonic cleaning in acetone

www.matcorr.com wileyonlinelibrary.com ß 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
2 Abdalla, Rahmat and Azizan Materials and Corrosion 2013, 64, No. 9999

Table 1. The chemical composition of mild steel substrate reference and counter electrodes, respectively. The scan rate
for polarization was 1 mV/s.
Element Composition (wt%)
All EIS measurements were conducted at an open circuit
C 0.16 potential (OCP) after reaching a steady state, with a voltage
Al 0.07 perturbation amplitude of 10 mV and a frequency range from
Si 0.168 105 to 102 Hz.
Mn 0.18
P 0.025
Cu 0.09
3 Results and discussion
Fe Balance
3.1 Coating morphology and composition

and rinsed with deionized water. The cleaned specimens were The SEM micrographs of the bare steel surface and of the zinc
treated with a 5% nickel acetate solution for 5 s at 55  3 8C. phosphate coatings activated and inactivated with nickel acetate
For comparison, some specimens were prepared without are shown in Fig. 1. It is seen that the phosphate coating
treatment in nickel acetate solution. The specimens after that deposited as plate-like crystals on inactivated substrate, whereas
were immediately immersed into the phosphating bath for 5 min cubic-like crystals formed on activated sample. The activation
at 55  3 8C. The chemical composition and operating conditions treatment with nickel acetate markedly enhances the population
for the phosphating bath are listed in Table 2; pH of the bath density and refines the size of the phosphate crystals. The mean
was adjusted by adding a 50% NaOH solution. Eventually, the crystal size of the phosphate layers on the activated and inactivated
phosphated samples were rinsed with deionized water and samples were 7.5 and 14 mm, respectively, suggesting that
dried with compressed air. The coating weight was determined activation treatment with nickel acetate causes a decrease in the
according to the following formula: phosphate crystal size and promotes a more compact and
uniform coating compared with the coating developed on the
ðW1  W2 Þ inactivated samples. This improvement in the phosphate coating
W¼
A could be attributed to the acceleration effect of small galvanic
where W is the phosphate coating weight per unit area, W1 is the couples that formed on the metal surface between Fe and nickel
specimen weight after phosphating, W2 is the specimen weight particles which deposited from the nickel acetate solution. These
after the coating was eliminated using a 5% chromium trioxide galvanic couples accelerate metal dissolution in the early stage of
solution for 15 min at 70 8C, and A is the surface area of the phosphating process and in turn accelerate the coating reaction
phosphated sample. and uniformity. Hence, the galvanic couples act as a nucleation
The free and total acidity of the phosphating bath was agents for the phosphate coating crystals.
determined by titration a 10 ml of phosphating bath with 0.1 M Figure 2 shows SEM images of the activated and inactivated
NaOH solution. The values of free and total acidity were 2.7 and phosphate coatings obtained with a phosphating time of 10 s, in
23.3 points, respectively. The points correspond to the volumes of order to demonstrate the effect of activation treatment by nickel
NaOH solution that were used in the titration [17]. acetate on the morphology of phosphate coating. In both samples,
some well-crystallized small particles were observed. It is also
2.2 Characterization of phosphate coating observed that the activation treatment had a clear influence on the
density and crystals size of the coating at the early stage of
The surface morphology and composition of the phosphate phosphating process. The number of nuclei per unit area of the
coating were assessed by SEM using a Zeiss Supra Model 35VP phosphate crystals was higher for the activated sample compared
and EDS. to the inactivated one. According to Machu’s hypothesis, the
The corrosion performance of the phosphated samples precipitation of insoluble metal phosphates could be initiated on
was evaluated via potentiodynamic polarization curves and EIS the cathodic sites [18]. Pretreatment with nickel acetate could
using a potentiostat/frequency response analyzer (AUT 71943, activate the metal surface and increase the number of cathodic
Autolab Instruments). A sodium chloride solution (3.5% NaCl), sites, due to the formation of many small Fe–Ni local galvanic
naturally aerated and maintained at 25  2 8C, was used for couples on the metal surface, which lead to a reduction in the
electrochemical analysis. The coated steel with an area of phosphate crystal size.
1.5 cm2 was used as the working electrode, whereas a silver/ The chemical compositions of activated and inactivated phos-
silver chloride electrode and a platinum wire were used as the phate coatings obtained from EDS analysis are listed in Table 3.
The phosphate films mainly contained zinc, iron, and phosphorus.
Table 2. The chemical composition of phosphating bath and operating A low Ni content appeared on the coating after activation treatment
conditions
with nickel acetate, indicating the presence of nickel particles on
Bath composition (g/L) Operating conditions the metal surface which accelerated the coating formation.

H3PO4 (85%) 15 T ¼ 55  3 8C 3.2 Phosphate coating weight

ZnO 3.5 pH 2.50
HNO3 (65%) 26
Figure 3 shows the dependence of the phosphate coating weights
NaF 0.66
on the immersion time. The coating weight increased rapidly

ß 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.matcorr.com

Materials and Corrosion 2013, 64, No. 9999 Influence of activation treatment on zinc phosphate coating 3

Figure 2. SEM micrographs of inactivated and phosphated samples for

10 s (a), and activated for 5 s and phosphated for 10 s (b)

3.3 Electrochemical characterization

The polarization curves obtained for mild steel and phosphated

substrates, in an aerated 3.5% sodium chloride solution, are
shown in Fig. 4. The corrosion current density (icorr), corrosion
potential (Ecorr), and charge transfer resistance (Rct) obtained
from the polarization curves by Tafel extrapolation method and
EIS studies are given in Table 4. The expected predominant
reactions that could occur during the cathodic and anodic
polarization are the reduction of oxygen and metal dissolution,
respectively. The rate at which these two reactions occur

Figure 1. SEM micrographs of bare steel surface (a), inactivated and

phosphated sample for 5 min (b), and activated for 5 s and phosphated Table 3. Chemical composition of the activated and inactivated phos-
for 5 min (c) phate coatings

Element Composition (wt%)

during the early stages of immersion and the samples pretreated
with nickel acetate increased faster than the unpretreated ones. Inactivated Activated
Then the coating weight showed a slight increase at intermediate
stages, and finally reached a steady value. These results suggest O 34.46 32.02
that the treatment with nickel acetate prior to phosphating Zn 35.65 40.81
process causes an activation effect and offers more nucleation, P 15.29 15.73
Ni – 1.80
leading to the fast formation and more coverage of the phosphate
Fe 14.59 9.63
coating.

www.matcorr.com ß 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

4 Abdalla, Rahmat and Azizan Materials and Corrosion 2013, 64, No. 9999

10
a) 160
9 Inactivated 140

8 Activated
120
Coating weight (g/m²)

7 100

Z" (Ohm)
6
80
5
60
4
40
3
20
2
0
1 0 50 100 150 200 250 300 350

0 Z' (Ohm)
0 50 100 150 200
Time (s)
250 300 350 400 450
b) 3000
Acvated sample Inacvated sample
2500
Figure 3. Variation of the phosphate coating weights with the
phosphating time 2000

Z" (Ohm)
1500
determines the corrosion performance of phosphated sample [19,
20]. Compared with bare steel, both the phosphated samples own 1000
more positive corrosion potential, lower corrosion current density
and higher polarization resistance. These indicate that the 500

protection characteristics of mild steel had been improved

0
obviously by phosphating treatment which forms a protective film 0 1000 2000 3000 4000 5000 6000 7000 8000
on the metal surface. Moreover, the corrosion current density
Z' (Ohm)
for the phosphated substrate decreased from 3.15 to 1.07 mA/cm2
and corrosion potential shifted positively after activation Figure 5. Nyquist plots of (a) bare steel, and (b) the activated and
treatment with nickel acetate solution. This indicates that the inactivated coated samples

activated phosphate coating exhibited a better corrosion resis-

tance than the inactivated one, which could be attributed to the
uniform and compact structure of activated phosphate coating
[19, 21].
The EIS characteristics of mild steel and phosphated samples
in an aerated 3.5% NaCl solution are presented in Figs. 5 and 6
as Nyquist and Bode phase angle plots. The equivalent electrical
circuit models shown in Fig. 7 are used to fit the impedance data
of high frequency part, where Rs is the solution resistance, Rc is
the coating resistance, Rct is the charge transfer resistance, Cc is
the coating capacitance, and Cdl is the double layer capacitance.

60
Bare steel

Inactivated sample
50
Activated sample
Figure 4. Polarization curves for the bare steel and the phosphated
samples with and without activation treatment, obtained in an aerated 40
Phase angle (deg)

3.5% NaCl solution (potential value in V vs. Ag/AgCl electrode)

30

Table 4. Corrosion potential (Ecorr), corrosion current density (icorr), and

charge transfer resistance (Rct) evaluated by potentiodynamic polar- 20

ization studies and EIS

10
Treatment Ecorr icorr Rct
(mV) (mA/cm2) (V)
0
Bare steel 613 9.56 319.7 -3 -2 -1 0 1 2 3 4 5 6
Inactivated phosphate layer 492 3.15 1500 Log Freq (H)
Activated phosphate layer 454 1.05 7124
Figure 6. Bode phase plots for bare steel and phosphated samples

ß 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.matcorr.com

Materials and Corrosion 2013, 64, No. 9999 Influence of activation treatment on zinc phosphate coating 5

formed on activated substrate that result in enhanced surface

coverage and uniformity than the plate-like type. In addition,
electrochemical results in 3.5% NaCl showed that the activation
treatment with nickel acetate improves the corrosion resistance of
the phosphated samples.

Acknowledgements: The authors would like to acknowledge

the supports of Universiti Sains Malaysia (Incentive Research
grant number 1001/PBAHAN/8044002) and University of Omar
Al-mukhtar, Libya.

5 References

[1] T. S. N. Sankara Narayanan, Rev. Adv. Mater. Sci. 2005, 9, 130.

[2] C. H. S. B. Teixeira, E. A. Alvarenga, W. L. Vasconcelos,
Figure 7. Equivalent electrical circuits used to model the high V. F. C. Lins, Mater. Corros. 2011, 62, 853.
frequency part of impedance behavior of (a) bare steel, and (b) of [3] M. Sheng, Y. Wei, Q. Zhong, J. Coat. Technol. Res. 2009, 6, 543.
phosphated samples [4] C.-Y. Tsai, J.-S. Liu, P.-L. Chen, C.-S. Lin, Corros. Sci. 2010,
52, 3907.
It is seen that the semicircles obtained for the Nyquist plot of [5] K. Ogle, A. Tomandl, N. Meddahi, M. Wolpers, Corros. Sci.
2004, 46, 979.
the various samples are not well defined. The high frequency
[6] C. H. S. B. Teixeira, E. A. Alvarenga, W. L. Vasconcelos,
capacitance loop, which was described by the equivalent electric
V. F. C. Lins, Mater. Corros. 2011, 62, 771.
circuit in Fig. 7, can be attributed to the formation of passive film
[7] C.-M. Wang, H.-C. Liau, W.-T. Tsai, Surf. Coat. Technol. 2006,
on the metal surface, and the low frequency inductance loop has 201, 2994.
been related in literature to the corrosive attack of the exposed [8] A. S. Akhtar, K. C. Wong, K. A. R. Mitchell, Appl. Surf. Sci.
substrate [22, 23]. In contrast with bare steel, the samples with 2006, 253, 493.
phosphate coatings exhibited significantly higher resistance as [9] J. Wang, W. Zhou, Y. Du, Mater. Corros. 2012, 63, 317.
indicated in Fig. 5. This suggests that the zinc phosphate layer [10] S. Jegannathan, T. K. Arumugam, T. S. N. Sankara Narayanan,
acts to avoid as much as possible reactions at its interface in the K. Ravichandran, Prog. Org. Coat. 2009, 65, 229.
3.5% NaCl solution [24]. Moreover, the reaction resistance for [11] M. Arthanareeswari, T. S. N. Sankara Narayanan, P. Kamaraj,
phosphate coating activated with nickel acetate solution has M. Tamilselvi, Indian Chem. Technol. 2010, 17, 167.
markedly improved compared to inactivated one (Fig. 5b). This [12] E. P. Banczek, M. Terada, P. R. P. Rodrigues, I. Costa, Surf.
could be attributed to the compact and uniform structure of Coat. Technol. 2010, 205, 2503.
activated phosphate coating which serves as an effective barrier [13] B.-L. Lin, J.-T. Lu, G. Kong, Corros. Sci. 2008, 50, 962.
between the metal surface and the corrosive solution. Based on [14] T. S. N. Sankara Narayanan, Met. Finish. June 1996, 86.
the Bode plot, a larger phase angle peak at high frequencies was [15] M. Wolpers, J. Angeli, Appl. Surf. Sci. 2001, 179, 281.
observed for the coated steel compared with that of the bare [16] K. Abdalla, A. Rahmat, A. Azizan, J. Coat. Technol. Res. 2013,
steel surface, which was related to the pores’ resistance of 10, 133.
the phosphate coating to electrolyte diffusion [25]. The phase [17] J. W. Brouwer, B. Schenzle, P. Kuhm, W. Wichelhaus,
angle for the phosphated substrate activated with nickel acetate H. Endres, US Pat. 6,447,662, 2002.
was higher than that for the inactivated one at high frequencies, [18] W. Rausch, The Phosphating of Metals, Finishing Publications
which is consistent with the previous results, indicating that the Ltd., London 1990.
[19] D. Weng, P. Jokiel, A. Uebleis, H. Boehni, Surf. Coat. Technol.
activation treatment with nickel acetate improves the corrosion
1996, 88, 147.
resistance for the phosphate coating.
[20] S. Jegannathan, T. S. N. Sankara Narayanan, K. Ravichandran,
S. Rajeswari, Prog. Org. Coat. 2006, 57, 392.
4 Conclusions [21] S. M. A. Shibli, Appl. Surf. Sci. 2011, 257, 3111.
[22] E. P. Banczek, P. R. P. Rodrigues, I. Costa, Surf. Coat.
The influence of the activation treatment with nickel acetate Technol. 2006, 201, 3701.
solution on zinc phosphate coating properties on mild steel was [23] M. Sheng, Y. Wang, Q. Zhong, H. Wu, Q. Zhou, H. Lin, Surf.
investigated. It can be confirmed that using activation treatment Coat. Technol. 2011, 205, 3455.
prior to phosphating process is helpful for phosphate nucleation [24] Q. Li, S. Xu, J. Hu, S. Zhang, X. Zhong, X. Yang, Eletrochim
and leads to finer structure. The morphology of the coating Acta 2010, 55, 887.
formed on inactivated substrate consists of plate-like crystals, [25] E. P. Banczek, P. R. P. Rodrigues, I. Costa, Surf. Coat.
whereas cubic-like crystals with a compact and finer structure are Technol. 2008, 202, 2008.

(Received: January 2, 2013) W7009

(Accepted: February 1, 2013)

www.matcorr.com ß 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

6 Abdalla, Rahmat and Azizan Materials and Corrosion 2013, 64, No. 9999

Keywords: corrosion resistance

mild steel
nickel acetate
phosphating

ß 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.matcorr.com

View publication stats