J. Coat. Technol. Res.
, 11 (3) 431–442, 2014
DOI 10.1007/s11998-013-9533-z
Deposition of zinc–zinc phosphate composite coatings on steel
by cathodic electrochemical treatment
C. Kavitha, T. S. N. Sankara Narayanan,
K. Ravichandran, Il Song Park, Min Ho Lee
 American Coatings Association & Oil and Colour Chemists’ Association 2013
Abstract The present work aims at the development
of an energy-efficient and eco-friendly approach for
the deposition of zinc phosphate coatings on steel. The
study describes the possibility of preparing zinc–zinc
phosphate composite coatings by cathodic electro-
chemical treatment using dilute phosphoric acid as an
electrolyte and zinc as an anode. The methodology
enables the preparation of coatings with different
proportions of zinc and zinc phosphate by suitably
varying the applied current density, pH, and treatment
time. Adhesion of the coating on mild steel and
adhesion of paint film on the phosphate coating were
found to be good. The surface morphology of the
coatings exhibited platelet-type features and small
white crystals (agglomerated at some places) which
represented zinc and zinc phosphate, respectively. An
increase in current density (from 20 to 50 mA/cm2)
increased the size of the zinc crystals, and coatings
prepared at 40 and 50 mA/cm2 resembled that of
electrodeposited zinc. Since the proportions of zinc and
zinc phosphate could be varied with applied current
Electronic supplementary material The online version of this
article (doi:10.1007/s11998-013-9533-z) contains supplementary
material, which is available to authorized users.
C. Kavitha, T. S. N. Sankara Narayanan (&)
CSIR-National Metallurgical Laboratory, Madras Centre,
CSIR Complex, Chennai 600 113, India
e-mail: tsnsn@rediffmail.com
C. Kavitha, K. Ravichandran
Department of Analytical Chemistry, University of Madras,
Maraimalai (Guindy) Campus, Chennai 600 025, India
T. S. N. Sankara Narayanan, I. S. Park,
M. H. Lee (&)
Department of Dental Biomaterials, School of Dentistry,
Chonbuk National University, Jeonju 561-756, South Korea
e-mail: lmh@jbnu.ac.kr
density, pH, and treatment time, it would be possible
to use this methodology to prepare coatings that would
offer different degrees of corrosion protection.
Keywords Cathodic electrochemical treatment,
Zinc–zinc phosphate composite coatings, Corrosion
resistance, Surface morphology
Introduction
Phosphating is the most widely used metal pretreat-
ment process for the surface treatment and finishing of
ferrous and nonferrous metals.1,2 The deposition of a
phosphate coating involves a topochemical reaction,
which enables the surface of the base metal to integrate
itself as a part of the coating. The ability to improve
adhesion of organic coatings and to localize corrosion
within the damaged zone, thus preventing it from
spreading underneath the coating, is the prime advan-
tage of applying a phosphate conversion coating. In
addition, phosphate coatings have been utilized for a
wide variety of applications, which include corrosion
protection of thermomechanically treated rebars,3,4
corrosion protection of Mg alloys,5–7 as a pretreatment
for hydroxyapatite coatings for stainless steel
implants,8 as a nonchromate alternative for improving
the corrosion resistance of hot-dip galvanized steel,9 to
improve the adhesion of electroless Ni–P coating on
NdFeB magnets,10 and to increase the adhesive bond-
ing of AZ31Mg alloy.11 As a result, studies on
acceleration of the phosphating process with the use
of chemical additives,12,13 by galvanic coupling and
electrochemical methods,14–24 development of eco-
friendly accelerators,25,26 and understanding the micro-
structural characteristics and corrosion behavior of
phosphate coatings23,27–29 assume significance to meet
the challenging needs of various applications. Cathodic
electrochemical treatment of steel in a zinc phosphat-
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J. Coat. Technol. Res., 11 (3) 431–442, 2014
ing bath has been shown to produce zinc–zinc
phosphate composite coatings.16–18,21 The presence of
zinc along with zinc phosphate in these coatings
enables them to offer corrosion resistance both by
sacrificial and barrier layer mechanisms. Deposition of
zinc as one of the constituents of the coating implies
that other metals could also be deposited along with
zinc phosphate and this opens up a new avenue for the
deposition of composite coatings with desirable char-
acteristics. Since the composition and corrosion resis-
tance of the resultant coatings depend on the type of
anode used,18 it would be of interest to study the
formation of coatings on steel using zinc as the anode
and dilute phosphoric acid as the electrolyte, and this
forms the basis of the present work. This combination
together with a variation in current density and
processing time would enable formation of zinc–zinc
phosphate composite coatings on steel with varying
fractions of zinc and zinc phosphate that would offer
different degrees of corrosion protection. This meth-
odology is a simple approach to prepare zinc–zinc
phosphate composite coatings and it has been reported
for the first time.
Experimental details
Mild steel disks (composition (in wt%)—C: 0.16%; Si:
0.17%; Mn: 0.68%; P: 0.027%; S: 0.026%; Cr: 0.01%;
Ni: 0.01%; Mo: 0.02%; and Fe: balance; 40 mm ˘ and
1 mm thick) and zinc disks (99.5% pure; 40 mm ˘ and
8 mm thick) were used as the cathodes and anodes,
respectively, for the deposition of coatings. The steel
disks were pickled in 10% sulfuric acid at 70–80C for
10 min, while the zinc disks were cleaned in 10% HCl
at 27C, followed by rinsing in deionized water. Dilute
phosphoric acid (12 mL/L) was used as the electrolyte.
The zinc anodes were placed 1 cm apart on both sides
of the steel cathode. Coating deposition was carried
out at 27 ± 1C under galvanostatic conditions using a
potentiostat/galvanostat (ACM Instruments, UK;
Model: Gill AC). Current density (10–50 mA/cm2),
pH of the electrolyte (2.00, 2.30, 2.50, 2.70, 2.90, 3.00,
and 3.5), and time (10–60 min) were used as process
variables. The surface morphology of coatings was
assessed by scanning electron microscopy.
The adhesion of the phosphate coating on the mild
steel substrate was evaluated by a pull-off adhesion test
using adhesive tape. The adhesion of the paint coating
on phosphated steel was tested by dry and wet
adhesion methods. For evaluation of the paint adhe-
sion measurements, the phosphated mild steel samples
were painted with synthetic enamel paint (white), with
a dry film thickness of 50 lm (for double coat). After
thorough curing, they were tested by adhesive tape for
adhesion in the dry state. For wet adhesion measure-
ments, the phosphated and painted samples were
scribed to the base metal both in the vertical and
432
horizontal directions to form a number of squares.
Subsequently, they were immersed in deionized water
at 45C for 240 h. After the test period, the excess
water present on the samples was carefully removed by
absorbent papers and dried. The samples were tested
by adhesion measurements using a pressure-sensitive
adhesive tape. Photographic images of the samples
before and after adhesion were acquired. Uncoated
mild steel and zinc phosphate-coated mild steel
prepared by the chemical conversion coating method
(ZnO: 5 g/L; H3PO4: 12 mL/L; NaNO2: 2 g/L; temper-
ature: 27C; time: 30 min) were used as controls to
compare the extent of adhesion.
The corrosion resistance of the phosphate-coated
mild steels in 3.5% NaCl was evaluated by potentio-
dynamic polarization studies using a potentiostat/gal-
vanostat of ACM Instruments (Model: Gill AC), the
details of which are given elsewhere.16,18,20,21 For these
measurements, only a 1 cm2 area of the coated steel
was exposed to the electrolyte. The corrosion cell
consisted of four electrodes. The coated steel formed
the working electrode, whereas a saturated calomel
electrode and a platinum gauze served as the reference
and counter electrodes, respectively. The fourth elec-
trode was a platinum foil, which is connected to the
reference electrode to reduce the noise during the
electrochemical measurement. The corrosion potential
(Ecorr) and corrosion current density (icorr) were
determined using the Tafel extrapolation method. In
order to get a better insight into the corrosion behavior
and to have a quantitative comparison of the extent of
corrosion, immersion studies were performed in 3.5%
NaCl for 24 h. Visual observation of discoloration of
the corrosive medium and the loss in weight due to
corrosion after 24 h of immersion were used as the
parameters of evaluation. Uncoated mild steel, zinc
phosphate coating deposited on mild steel and zinc-
coated steel prepared by the chemical conversion
coating method (ZnO: 5 g/L; H3PO4: 12 mL/L;
NaNO2: 2 g/L; temperature: 27C; time: 30 min), and
zinc–zinc phosphate composite coatings prepared by
cathodic electrochemical treatment in a zinc phosphat-
ing bath (ZnO: 2.04 g/L; H3PO4: 16 mL/L; NaOH:
6.7 g/L; pH: 2.90; cathode: steel; anode: graphite;
current density: 6 mA/cm2; temperature: 27C; time:
60 min) were used as controls to compare the extent of
corrosion.
Results and discussion
Effect of process variables on coating weight
Effect of current density on coating weight
Current density is the primary factor that influences
the amount of coating deposited. To study the effect of
current density on coating weight, coating deposition

was carried out at 10–50 mA/cm2, whereas the pH of
the electrolyte (pH 2.5) and treatment time (30 min)
were kept as constants. The variation in coating weight
measured as a function of applied current density is
shown in Fig. 1. A linear increase in coating weight is
observed up to 30 mA/cm2, beyond which the extent of
increase in coating weight is decreased before it
eventually reaches saturation at 40 mA/cm2. When
current is applied to the electrolytic cell, dissolution of
zinc occurs at the anodes. The discharged Zn2+ ions
react with the phosphoric acid and form soluble
primary zinc phosphate in the electrolyte. Reduction
of Zn2+ ions and protons (H+ ions) occurs at the mild
steel cathode, resulting in the deposition of zinc at the
cathode with the evolution of hydrogen. The interfacial
increase in pH following consumption of protons (H+
ions) enables conversion of soluble primary zinc
phosphate to insoluble tertiary zinc phosphate that is
co-deposited along with zinc, thus making it as a zinc–
zinc phosphate composite coating. The reactions that
occur at the anode, cathode, and cathode–electrolyte
interface are as follows:
At the anode:
Zn ! Zn2þ þ 2e
At the cathode:
Zn2þ þ 2e ! Zn
2Hþ þ 2e ! H2 "
120
110
100
Coating weight (g/m2)
90
80
70
60
50
40
30
20
10 20 30 40
Current density (mA/cm2)
Fig. 1: Variation in coating weight measured as a function
of current density during cathodic electrochemical treat-
ment of steel in H3PO4 electrolyte using zinc anodes
(conditions—pH of the electrolyte: 2.5; time: 30 min)
J. Coat. Technol. Res., 11 (3) 431–442, 2014
At the cathode–electrolyte interface:
ZnðH2 PO4 Þ2 , ZnHPO4 þ H3 PO4 ð4Þ
3ZnHPO4 , Zn3 ðPO4 Þ2 þH3 PO4 : ð5Þ
Increase in current density promotes the deposition
of both zinc and zinc phosphate and increases the
coating weight of the composite coating up to 30 mA/cm2.
With further increase in current density, the extent of
anodic dissolution and cathodic reduction of zinc will
be increased. However, the sudden increase in inter-
facial pH causes a rapid conversion of soluble primary
zinc phosphate to insoluble tertiary zinc phosphate.
Hence, the zinc phosphate crystals become powdery
and spalled off from the substrate. This explains the
decrease in the measured coating weight observed at
40 mA/cm2 and the saturation in coating weight
observed beyond this current density. According to
this reaction sequence, the proportions of zinc and zinc
phosphate in the composite coatings could be varied
with the applied current density; the higher the current
density, the richer the zinc content.
ð1Þ
Effect of treatment time on coating weight
The amount of coating deposited varies with the
treatment time. To study the effect of treatment time
ð2Þ on coating weight, coating deposition was carried out
from 10 to 60 min, whereas the pH of the electrolyte
ð3Þ (pH 2.5) and current density (30 mA/cm2) were kept as
constants. The variation in coating weight measured as
140
120
Coating weight (g/m2)
100
80
60
40
20
50 10 20 30 40 50 60
Time (min)
Fig. 2: Variation in coating weight measured as a function
of time during cathodic electrochemical treatment of steel
in H3PO4 electrolyte using zinc anodes (conditions—cur-
rent density: 30 mA/cm2; pH of the electrolyte: 2.5)
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J. Coat. Technol. Res., 11 (3) 431–442, 2014
a function of treatment time is shown in Fig. 2. A
linear increase in coating weight is observed up to
40 min, beyond which the extent of increase in coating
weight is decreased and a near saturation is reached
above 50 min. Coatings deposited from phosphoric
acid (12 mL/L) electrolyte (pH 2.5) at 30 mA/cm2
are likely to be a composite of zinc and zinc phosphate.
However, when the treatment time is increased beyond
40 min, the extent of deposition of zinc (equation (2))
and hydrogen evolution (equation (3)) is decreased as
most of the surfaces are covered by zinc phosphate.
This decreases the conversion of soluble primary zinc
phosphate to insoluble tertiary zinc phosphate (equa-
tions (4) and (5)), thus enforcing saturation in the
amount of coating deposited.
Effect of pH of the electrolyte on coating weight
Electrolyte pH is another important parameter, as it
determines the conversion efficiency of soluble pri-
mary zinc phosphate to insoluble tertiary zinc phos-
phate. To study the effect of pH on coating weight,
coating deposition was carried out using the phospho-
ric acid (12 mL/L) electrolyte after adjusting its pH
to 2.0, 2.3, 2.5, 2.7, 2.9, 3.0, and 3.5 with NaOH,
whereas the current density (30 mA/cm2) and treat-
ment time (30 min) were kept as constants. The
variation in coating weight measured as a function of
pH of the electrolyte (Fig. 3) indicates a continuous
decrease in coating weight with increase in pH.
A significant decrease in coating weight is observed
after pH 2.5, while beyond pH 2.9, the coating weight is
very low. An increase in pH of the electrolyte
decreases the extent of dissolution of zinc from the
anodes (equation (1)) and the quantity of soluble
120
100
Coating weight (g/m2)
80
60
40
20
0 current density (50 mA/cm2) and lower pH (pH 2.00)
1.8 2.0 2.2 2.4 2.6 2.8 3.0
pH of the electrolyte
Fig. 3: Variation in coating weight measured as a function
of pH of the electrolyte during cathodic electrochemical
treatment of steel in H3PO4 electrolyte using zinc anodes
(conditions—current density: 30 mA/cm2; time: 30 min)
434
primary zinc phosphates in the electrolyte, thus
decreasing the coating weight.
Mechanism of coating formation by cathodic
electrochemical treatment
The mechanism of coating formation by cathodic
electrochemical treatment is interesting, as it involves
generation of Zn2+ ions as well as soluble zinc primary
phosphate in situ. With the onset of current to the
electrolytic cell, the Zn2+ ions will be discharged at the
anode (equation (1)) and they form soluble primary
zinc phosphate at the electrolyte. Reduction of Zn2+
and H+ ions (equations (2) and (3)) occurs at the
cathode. Hence, deposition of a thin layer of zinc
(equation (2)) on the entire surface of the steel
substrate with simultaneous hydrogen evolution (equa-
tion (3)) occurs during the initial stages. The consump-
tion of available H+ ions at the metal–solution
interface would result in a progressive rise in interfacial
pH and favors the conversion of soluble primary zinc
phosphate to insoluble tertiary zinc phosphate (equa-
tions (4) and (5)). With increase in treatment time,
deposition of zinc and hydrogen evolution continue,
which enables further deposition of zinc phosphate on
adjacent areas. The continuous evolution of hydrogen,
visually observed throughout the entire duration of the
deposition, suggests the availability of metallic site
(zinc) at the surface at any given time. It is presumed
that the deposition of zinc proceeds in the form of fixed
channels surrounded by zinc phosphate throughout the
thickness of the coating.16–18 During the deposition of
zinc phosphate coatings by the conventional chemical
conversion coating method, the interfacial rise in pH is
controlled by the diffusion of H+ ions through the
pores, which limits the amount of coating formation,1,2
whereas in cathodic electrochemical treatment, the
coating formation could be extended continuously to
build thick deposits. In addition, unlike the phosphate
coatings prepared by a chemical conversion method,
the coatings prepared by cathodic electrochemical
treatment are a composite of zinc and zinc phosphate,
and their volume fraction could be varied by appro-
priate choice of experimental conditions.
Characteristics of the zinc–zinc phosphate
composite coatings
The zinc–zinc phosphate composite coatings are uni-
form and gray in color. Coatings deposited at higher
3.2 3.4 3.6 exhibit a metallic luster that resembles electrodepos-
ited zinc. Adherence of the zinc–zinc phosphate
composite coating on the steel substrate, as well as
the paint coating applied on top of the composite
coating, is good when evaluated by the pull-off
adhesion test using an adhesive tape. The photographic
 J. Coat. Technol. Res., 11 (3) 431–442, 2014

Fig. 4: Photographic images of phosphated and painted mild steel after immersion in deionized water at 45°C for 240 h
(a, c, e) and after adhesion testing (b, d, f): (a, b) uncoated mild steel; (c, d) zinc phosphate-coated mild steel prepared by
chemical conversion coating method; and (e, f) zinc–zinc phosphate-coated mild steel prepared by cathodic
electrochemical treatment

images of phosphated and painted mild steel after
immersion in deionized water at 45C for 240 h and
after adhesion testing are shown in Fig. 4. It is evident
from Fig. 4 that uncoated mild steel exhibits red rust
formation on the scribed areas (Fig. 4a) and the paint
film is removed from at least 40–50% of the area when
tested with an adhesive tape (Fig. 4b). The zinc
phosphate-coated mild steel prepared by the chemical
conversion coating method exhibits the formation of
red rust in some areas of the scribed region (Fig. 4c),
and the paint film is removed only in about 10–20% of
the area when tested with an adhesive tape (Fig. 4d).
The zinc–zinc phosphate composite-coated mild steel,
prepared by cathodic electrochemical treatment
(H3PO4: 12 mL/L; pH of the electrolyte: 2.5; current
density: 40 mA/cm2), did not exhibit any red rust
formation in the scribed areas (Fig. 4e). The presence
of a thin layer of zinc over the mild steel (as explained
in the mechanism of formation of these coatings)
prevents direct contact of the mild steel with the
deionized water. The adhesion of the paint film is good
and it is removed in less than 5% of the area when
tested by an adhesive tape (Fig. 4f). The ferroxyl test2
performed on coated steel shows no sign of Prussian
blue color spots (formed due to the reaction between
the ferrous ions in the uncoated areas and ferricyanide
present in the test solution) over the entire area. This
confirms the proposed mechanism of formation that
the entire surface of the steel sample is covered by a
thin layer of zinc over which zinc and zinc phosphate
are deposited together. The results of the ferroxyl tests

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J. Coat. Technol. Res., 11 (3) 431–442, 2014
Fig. 5: Surface morphology of the zinc–zinc phosphate composite coatings prepared by cathodic electrochemical
treatment of steel in H3PO4 electrolyte (pH 2.5) using zinc anodes at different current densities: (a) 20 mA/cm2; (b) 30 mA/
cm2; (c) 40 mA/cm2; and (d) 50 mA/cm2
suggest that coatings prepared by this methodology
could probably be considered as pore-free.
The surface morphology of coatings deposited using
the dilute H3PO4 electrolyte (12 mL/L; pH 2.5) at 20,
30, 40, and 50 mA/cm2 for 30 min is shown in Fig. 5.
For the coatings obtained at 20 mA/cm2, two types of
morphological features are evident (Fig. 5a); the
platelet-type features (marked as ‘‘s’’) represent zinc,
while the small white crystals (marked by ‘‘arrows’’)
are zinc phosphate. Agglomeration of zinc phosphate
crystals is also observed at some places (marked by
‘‘h’’ in Fig. 5a, b). With an increase in current density
from 20 to 50 mA/cm2, the increased availability of
Zn2+ ions in the electrolyte makes the coatings rich in
zinc with a corresponding decrease in zinc phosphate
content. An increase in current density also increased
the size of the zinc crystals, and coatings prepared at 40
and 50 mA/cm2 resemble that of electrodeposited zinc
(Fig. 5c, d). The surface morphology of the zinc–zinc
phosphate composite coatings deposited using the
dilute H3PO4 electrolyte (12 mL/L; pH 2.5) at
30 mA/cm2 for 10, 20, 30, and 40 min is shown in
Fig. 6. The platelet-type features (marked as ‘‘s’’ in
Fig. 6a) and white crystals either in the form of small
crystals (marked by ‘‘arrows’’ in Fig. 6b, c) or the
436
agglomerated ones (marked by ‘‘h’’ in Fig. 6c) repre-
sent zinc and zinc phosphate, respectively, and their
presence is evident at all time intervals of deposition.
At later stages of deposition, refinement of the
phosphate crystals (marked by ‘‘D’’ in Fig. 6d) by the
phosphoric acid generated in situ at the interface
(equations (4) and (5)) is also evident. The elemental
mapping of the zinc–zinc phosphate composite coating
(Fig. 7) confirms the presence of Zn, O, and P as the
major elements of the coating, and they are distributed
uniformly throughout the coating. This inference
further confirms the simultaneous deposition of both
zinc and zinc phosphate on adjacent areas of the
electrode, as explained by the mechanism of coating
formation.
Corrosion behavior of zinc–zinc phosphate
composite coating
The potentiodynamic polarization curves of zinc–zinc
phosphate-coated steel (30 mA/cm2; pH 2.5; 30 min) in
3.5% NaCl as a function of immersion time are shown
in Fig. 8. The polarization curves of uncoated mild
steel and zinc phosphate-coated mild steel prepared by

Fig. 6: Surface morphology of the zinc–zinc phosphate composite coatings prepared by cathodic electrochemical
treatment of steel in H3PO4 electrolyte (pH 2.5) using zinc anodes at 30 mA/cm2 for various treatment times: (a) 10 min;
(b) 20 min; (c) 30 min; and (d) 40 min
the chemical conversion coating method are also
included in Fig. 8 for comparison. The Ecorr and icorr
of uncoated mild steel and zinc phosphate-coated mild
steel prepared by the chemical conversion coating
method are marked as reference points while compar-
ing the change in electrochemical parameters of zinc–
zinc phosphate composite coatings measured as a
function of time (Fig. 9). It is evident from Figs. 8
and 9 that after 0.5 h of immersion, the Ecorr of zinc–
zinc phosphate-coated steel is 1129 mV vs SCE,
which is more cathodic than uncoated mild steel. The
cathodic shift in Ecorr is due to the presence of zinc
along with zinc phosphate in the composite coating.
Being sacrificial in nature, the dissolution of zinc
causes a higher icorr of 77.30 lA/cm2. The cathodic shift
in Ecorr and a higher icorr suggest that zinc dissolution is
the predominant reaction during the initial stages of
immersion (0.5 h) of zinc–zinc phosphate-composite
coated steel. With an increase in time from 0.5 to 3 h,
the zinc–zinc phosphate composite coating exhibits an
anodic shift in Ecorr (624 mV vs SCE) and a decrease
in icorr (2.20 lA/cm2), and their performance lies closer
to that of the zinc phosphate coating deposited by the
chemical conversion method (Fig. 9). This is due to the
coverage of the surface with the zinc corrosion
J. Coat. Technol. Res., 11 (3) 431–442, 2014
products, which offer resistance for the electrolyte to
directly interact with the coating/metal. It has been
reported that the nature of the corrosion products
formed on zinc-coated steels is largely a function of the
electrolyte used or the environmental conditions.
Cachet et al.30,31 have reported that the corrosion
product formed on electrodeposited and hot-dip gal-
vanized zinc coatings in 0.5 M Na2SO4 consists of two
layers; the layer adjacent to the zinc coating is an intact
ZnO film, whereas the top layer consists of a porous
zinc hydroxy sulfate. Zinc hydroxychlorides have been
identified as the main constituents of the corrosion
product formed in chloride environment,32 while a
mixed salt, 4Zn(OH)2ÆZnCl2, has been reported to
form on zinc-coated samples exposed to industrial and
marine atmospheres.33 The formation of 4Zn(O-
H)2ÆZnCl2 as a corrosion product of zinc-coated steel
sheet is further confirmed by Raman spectroscopy.34,35
Simonkolleite (Zn5(OH)8Cl2) and hydrozincite
(Zn4CO3(OH)6ÆH2O), usually found in marine atmo-
spheres, have been identified as the main corrosion
products during atmospheric corrosion of zinc exposed
to archipelagic subtropical environments.36 In the
present study, the zinc–zinc phosphate-coated steel is
immersed in 3.5% NaCl and tested for a period of 15 h.
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J. Coat. Technol. Res., 11 (3) 431–442, 2014

Fig. 7: Elemental mapping of the zinc–zinc phosphate composite coating prepared by cathodic electrochemical treatment
of steel in H3PO4 electrolyte (pH 2.7) using zinc anodes at 30 mA/cm2 for 30 min

Based on the literature reports, it can be presumed that

–500 the corrosion products formed could probably be a
mixture of Zn(OH)2 and zinc hydroxychloride. The
Potential (mV) vs. SCE)

formation of ZnCO3ÆZn(OH)2 could also be possible,

–700
since the electrolyte was not prepared by CO2-free
deionized water. In addition, the electrolyte is left open
–900 to air during corrosion testing for a period of 15 h,
A – Uncoated mild steel
B – Zinc phosphated mild steel by chemical conversion method
which might have allowed absorption of a reasonable
C to J – Zinc–zinc phosphate composite coated steel
C - after 0.5 h;
amount of CO2 from the atmosphere. With an increase
–1100 D - after 3 h
E – after 5 h;
in immersion time from 3 to 5 h, the zinc–zinc
F – after 7 h
G – after 9 h;
phosphate composite coating exhibits a cathodic shift
H – after 11 h;
I – after 13 h;
in Ecorr (689 mV vs SCE) and an increase in icorr
–1300 J – after 15 h (5.50 lA/cm2), possibly due to dissolution of the
10–4 10–3 10–2 10–1 100 coating/metal through the pores/defects in the corro-
Current density (mA/cm2) sion product layer. The stabilization in Ecorr observed
from 5 to 15 h (700 to 713 mV vs SCE) suggests the
Fig. 8: Polarization curves of zinc–zinc phosphate compos- occurrence of continuous dissolution of coating/metal
ite coatings prepared by cathodic electrochemical treatment and formation of corrosion products on the surface of
(conditions—electrolyte: 12 mL/L H3PO4; pH: 2.5; anode: the electrode. The variation in icorr measured during
zinc; current density: 30 mA/cm2; time: 30 min) in 3.5% NaCl
this period (3.0–9.0 lA/cm2) also supports this view.
as a function of immersion time in comparison with uncoated
mild steel and zinc phosphate-coated mild steel prepared by This is due to the less protective ability of the corrosion
the chemical conversion coating method product layer, which could have allowed the

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 J. Coat. Technol. Res., 11 (3) 431–442, 2014

–600

–650 Zinc phosphate coated mild steel by chemical conversion method

Uncoated mild steel

Corrosion potential (mV vs. SCE)

–700

–750

–800

–850

–900

–950

–1000

–1050

–1100
–1150
0 2 4 6 8 10 12 14 16
Time (h)

0.21

0.20
Corrosion curent density (µA/cm2)

0.19

0.18

0.17
Uncoated mild steel
0.16

0.15
Zinc phosphate coated mild steel by chemical conversion method
0.14

0.13

0.12

0.11

0.10
0 2 4 6 8 10 12 14 16
Time (h)

Fig. 9: Change in corrosion potential (Ecorr) and corrosion current density (icorr) of zinc–zinc phosphate composite
coatings in 3.5% NaCl, measured as a function of time. The Ecorr and icorr of uncoated mild steel and zinc phosphate-coated
mild steel prepared by the chemical conversion coating method are also included in these curves for an effective
comparison

permeation of the electrolyte through the pores,
defects, and cracks formed by that time.
Visual observation of the discoloration of the corro-
sive medium and the loss in weight due to corrosion
after 24 h of immersion in 3.5% NaCl are compiled in
Table 1. It is evident from Table 1 that when compared
to uncoated mild steel and zinc phosphate-coated mild
steel prepared by the chemical conversion coating
method, the loss in weight due to corrosion is much
lower for zinc–zinc phosphate composite coatings
prepared in the present study. In addition, the inferences
made on the corrosion behavior and loss in weight due to
corrosion of zinc–zinc phosphate composite coatings of
the present study are highly comparable with zinc
phosphate zinc-coated steel and zinc–zinc phosphate
composite coatings prepared by cathodic electrochemi-
cal treatment using a zinc phosphating bath. The
improved corrosion behavior exhibited by these samples
is due to the formation of a zinc corrosion product layer
on the surface of the coated steel, which offers some
resistance for the electrolyte toward the direct attack of
the coated steel. However, in the case of uncoated mild

439
J. Coat. Technol. Res., 11 (3) 431–442, 2014

Table 1: Comparison of the corrosion resistance offered by phosphated mild steel and zinc-coated steel prepared
by chemical conversion method and by cathodic electrochemical treatment method, evaluated by immersion test in
3.5% NaCl for 24 h
System studied Bath composition and operating Observations after 24 h Loss in References
conditions weight
after 24 h
(g/m2)

Uncoated mild steel – Discoloration of the 24.2 (18)

Zinc phosphate coating
deposited on mild steel by
conventional chemical
conversion method
Zinc phosphate coating
deposited on zinc-coated steel
by conventional chemical
conversion method
Zinc–zinc phosphate composite ZnO: 2.04 g/L; H3PO4: 16 mL/L
coating deposited on mild
steel by cathodic
electrochemical treatment
Zinc–zinc phosphate composite H3PO4: 12 mL/L; pH: 2.5; cathode:
coating deposited on mild
steel by cathodic
electrochemical treatment
solution; red rust
formation on the surface
of the substrate
ZnO: 5 g/L; H3PO4: 12 mL/L NaNO2: Discoloration of the 13.2 (16)
2 g/L temperature: 27C; time: solution; red rust
30 min formation on the surface
of the substrate
ZnO: 5 g/L; H3PO4: 12 mL/L NaNO2: No discoloration of the 1.0 (16)
2 g/L temperature: 27C; time: solution; no red rust
30 min formation on the surface
of the substrate
No discoloration of the 1.3 (16,18)
NaOH: 6.7 g/L; pH: 2.90; cathode: solution; no red rust
steel; anodes: graphite; current formation on the surface
density: 6 mA/cm2; temperature: of the substrate
27C; time: 60 min
No discoloration of the 1.0 Present
steel; anodes: zinc; current density: solution; no red rust study
30 mA/cm2; temperature: 27C; formation on the surface
time: 30 min of the substrate

steel and zinc phosphate coatings deposited by the
chemical conversion method, the corrosion products
formed fail to impart a large resistance toward corrosion
attack, thus resulting in a higher mass loss after immer-
sion for 24 h.
Conclusions
A simple method to prepare zinc–zinc phosphate
composite coatings of steel using zinc as the anode
and dilute H3PO4 as the electrolyte is proposed for the
first time. The ability of this methodology to deposit
zinc–zinc phosphate composite coatings using only
dilute H3PO4 without any chemical additives at 27C
makes it not only eco-friendly but also energy efficient.
The coating weight is increased linearly with current
density up to 30 mA/cm2 for a given duration of time
and up to 40 min when deposited at 30 mA/cm2. For a
given current density and time, a higher coating weight
is obtained at pH 2.3, followed by those obtained at pH
2.5. Coatings prepared at pH 3.0 are powdery and show
signs of poor adhesion to the steel substrate. Adherence
of the zinc–zinc phosphate composite coating on the
steel substrate as well as the paint coating applied on top
of the composite coating is good when evaluated by the
pull-off adhesion test using adhesive tape. Wet adhesion
measurement reveals that the zinc–zinc phosphate
composite-coated mild steel did not exhibit any red
rust formation in the scribed areas, whereas uncoated
mild steel and zinc phosphate-coated mild steel
prepared by the chemical conversion coating method
exhibit red rust formation. The adhesion of the paint
film is good on the zinc–zinc phosphate composite-
coated mild steel and it is removed in less than 5% of the
area when tested by an adhesive tape, whereas for
uncoated mild steel and zinc phosphate-coated mild
steel prepared by the chemical conversion coating
method, the extent of removal of paint film is 40–50%
and 10–20%, respectively. The surface morphology of
the coatings exhibits platelet-type features and small
white crystals (agglomerated at some places) that
represent zinc and zinc phosphate, respectively. An
increase in current density (from 20 to 50 mA/cm2)
increased the size of the zinc crystals, while coatings
prepared at 40 and 50 mA/cm2 resemble that of
electrodeposited zinc. Since the proportions of zinc
and zinc phosphate could be varied using a suitable
combination of applied current density, pH, and treat-

440

ment time, this methodology would be useful to prepare
coatings with different degrees of corrosion protection.
Acknowledgments CK and TSNSN express their
sincere thanks to Dr. S. Srikanth, Director, National
Metallurgical Laboratory, Jamshedpur, for his constant
support and encouragement to carry out this research
work and permission to publish this paper.
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