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Inhibition of steel and galvanised steel corrosion by zinc and calcium ions in
the presence of phosphate

Article  in  Corrosion Engineering Science and Technology · June 2004

DOI: 10.1179/147842204225016967

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Inhibition of steel and galvanised steel corrosion by
zinc and calcium ions in the presence of phosphate
I. M. Zin, S. B. Lyon, V. I. Pokhmurskii and M. C. Simmonds
Mixtures of zinc, calcium and phosphate ions have been found
to be effective (.90%) in inhibiting the corrosion of steel and
zinc during immersion in acid rain solution and when used as
pigment additions to organic coatings. The presence of
calcium ions, in addition to zinc ions, appears to be
fundamental in the inhibition mechanism since, in the absence
of calcium, the inhibition efficiency is 50% or less. Although
some anodic inhibition occurs, the predominant mechanism
appears to be classical cathodic inhibition caused by the
precipitation of a sparingly soluble, thin, but persistent, solid
film. Surface analysis, by XPS, confirms that phosphorus is
present in the form of phosphate species containing zinc and
calcium. Also, the atomic ratios of zinc:calcium:phosphorus
present in the inhibitive film strongly suggest that it consists
of a mixture of CaZn2(PO4)2 (Scholzite) and Zn3(PO4)2
(Hopeite) in a 1 : 1 ratio. CEST/2126
Keywords: galvanised steel, organic coating, inhibitor, XPS
I. M. Zin and V. I. Pokhmurskii are at the Karpenko
Physico-Mechanical Institute, National Academy of
Sciences, Lviv, 79601, Ukraine. S. B. Lyon is at the
Corrosion and Protection Centre, UMIST, Manchester,
M60 1QD, UK. M. C. Simmonds is at the Materials
Research Institute, Sheffield Hallam University, Sheffield,
S1 1WB, UK. Manuscript received 9 December 2003;
accepted 19 April 2004.
# 2004 IoM Communications Ltd. Published by Maney for
the Institute of Materials, Minerals and Mining.
INTRODUCTION
Inhibiting pigments are widely used components of anti-
corrosion organic coatings. The addition of inhibitors to
organic coatings can greatly increase the effective service
life by providing additional electrochemical protection to
the metal substrate after the external environment has
penetrated through the coating. Such additions function by
modification of the local electrolytic environment at the
metal surface beneath the organic coating, generally by
release of specific anions and/or cations from sparingly
soluble solid pigments dispersed within the organic coating.
These ionic species can form protective films at either
anodic or cathodic sites, by precipitation, by participation
in the electrochemical process, or by another mechanism;
also, they may plug local macrodefects within the organic
coating.1 For the protection of galvanised steel, the most
effective species currently used are chromates. However,
due their environmental toxicity they will not satisfy future
legislation as components of organic coatings. Thus,
modern manufacturers both of paint materials and metal
polymer coil coated steel are under pressure from govern-
ment and public organisations to develop realistic, effective,
and non-toxic alternatives to chromate pigments.
In previous work, we have shown that a blend of calcium
and inhibitive pigments containing phosphate in an organic
coating is a prospective substitute for the current use of
strontium chromate in coil coat applications.2,3 Using
mixtures of these inhibitive pigments dispersed in epoxy
coatings, it was found that, at through thickness coating
defects, the cathodic reaction on steel is significantly
DOI 10.1179/147842204225016967 Corrosion Engineering, Science and Technology 2004 Vol. 39 No. 2
inhibited by deposition of a compact surface film of zinc
and calcium phosphate. Gradually, this inhibitive film
covered the metal surface, greatly restricting substrate
corrosion. Importantly, each of these species, i.e. calcium
ions and phosphate ions, does not function well alone.
Thus, synergism between these two types of inhibiting
pigments appears to be critical for effective inhibition.
Fletcher noted that, for the pigment Shieldex (calcium
ion exchanged silica), both the silica support, as well as the
exchanged ion, might become mobile in the paint film
during weathering.4 This leads to the formation of a
protective calcium/silica film lying on or slightly incorpo-
rated into, any local corrosion product. Other results have
shown that, in the additional presence of phosphate species,
silica enhanced and increased the precipitation of amor-
phous calcium phosphate and dihydrated dicalcium phos-
phate, by acting as a suitable substrate.5
Other work has confirmed a positive influence of zinc
ions on the protective properties of calcium phosphate
films. Olesen et al.6 studied the composition of the species
deposited onto stainless steel during cathodic polarisation
in aqueous solutions of nitric acid saturated with tricalcium
phosphate, and/or zinc phosphate dihydrate with added
zinc ions. The adhesion of the pure calcium phosphate
coating onto the stainless steel substrate was relatively poor
but increased with increasing zinc content in the coating.
The composition was found to consist of a mixture of
different phosphates with variable solubilities: e.g.
Ca5(PO4)3OH, CaHPO4?2H2O, CaHPO4, Ca8H2(PO4)6?5H2O,
Ca3(PO4)2, CaZn2(PO4)2, 3Zn3(PO4)2?Zn(OH)2,
Zn3(PO4)2?4H2O, ZnHPO4?H2O and Zn(H2PO4)2?2H2O.
Mayer and Featherstone found that the solubility products
for hydroxyapatites containing Zn were markedly lower
than for those without Zn.7 Also, the lattice parameters of
the structures were reduced in proportion to the amount of
zinc added because Zn2z ions substituted directly for Ca2z
ions. In another study it was reported that carbonated
hydroxyapatite crystals had structural defects, dislocations
and grain boundaries, and that when such an apatite
contained zinc, the number of defects was reduced
significantly.8 Deposits formed on steel from acid solutions
of phosphates containing alkaline-earth metals often
contain pseudoamorphous Fe3(PO4)2.9 Such films are
coloured because of light interference and are commonly
iridescent. Finally, Tanizawa et al. have shown that both
Fe2z and Fe3z ions may incorporate into the structure of
calcium phosphate and inhibit crystallisation; the colour
of such deposits is often brown owing to the incorporation
of these ferric ions.10
This paper seeks to provide further understanding of the
corrosion inhibition of carbon steel and galvanised steel by
species containing phosphate and calcium in solution and
contained within an epoxy organic coating. In this work, a
multianalytical approach, with electrochemical and surface
analysis methods, was used to elucidate the mechanism in
more detail.
EXPERIMENTAL METHOD
The organic binder phase used in these experiments was a
two pack clear epoxy composition produced by H. Marcel
Guest Ltd (Manchester, UK). The coatings were applied
onto acetone degreased galvanised steel in two layers using
167
168 Zin et al. Inhibition of steel and galvanised steel corrosion
Table 1 Details of the inhibitor systems used in
the study
Active ingredients, vol.-%
Inhibitor designation ZMP* CAS{ SrCrO4 TiO2
E7 … … … 6
E8 3 3 … …
E16 7 11 … …
E17 … … 1. 5 … HNO3 (70%)
*zinc molybdatezzinc phosphate.
{calcium ion exchanged amorphous silica gel.
a drawbar; first, the primer containing inhibitor was applied
to 30 mm dry film thickness (dft) and, second, a clear
topcoat was applied to 100 mm dft. The galvanised steel
samples were of dimension 8615 cm with a hot dip zinc
coating thickness of 15 mm. Four different inhibitor
systems were used (Table 1): two contained mixtures of
zinc molyphosphate (Actirox 106, or ZMP) and calcium
exchanged silica (Shieldex CP4 or CAS) in blends of 3/3
vol.-% (designated E8) and 7/11 vol.-% (E16), one con-
tained strontium chromate at 1.5 vol.% (E17); finally, a
formulation containing TiO2 at 6 vol.-% (E7) was used as a
control. The pigments were separately introduced into the
epoxy binder and mixed for 24 h in a ceramic ball mill.
After application, the coatings were cured for 24 h at
ambient temperature (about 20uC) in a dust free environ-
ment, then post-cured at 60uC for 6 h. Solution extracts of
pigments were prepared by agitation of an excess of the
appropriate material in 1 L of acid rain solution, such that
solid material remained after 24 h, after which they were
filtered. Compositions of the resulting inhibited acid rain
solution are given in Table 2.
The corrosion behaviour of bare steel (Q-panels from Q-
panel Lab Products – 08 mm thick cold rolled steel) and
epoxy coated galvanised steel was investigated using
electrochemical impedance spectroscopy (EIS). The mea-
surements were carried out in artificial acid rain solution,
which mimics the average composition of rain in Greater
Manchester, UK in 1986, Table 3.11 Electrochemical measure-
ments were carried out using a three-electrode cell with a
sample testing area of 3.14 cm2 and with a platinum
electrode and a saturated calomel electrode (SCE) as the
auxiliary and reference electrodes, respectively. The impe-
dance measurements were carried out close to the corrosion
potential using an EG&G potentiostat Model 263A and a
Solartron frequency response analyser Model 1250 in the
10 kHz to 5 MHz frequency range. The signal amplitude
was 30 mV (rms). The instruments were under the control
of ZPlot software and impedance spectra were interpreted
with ZView (both from Scribner and Associates). Artificial
defects were introduced by making a scratch of length 1 cm
and approximate width 100 mm on the epoxy coated sample
with a fresh scalpel blade.
The surface chemistry of uncoated steel and zinc samples
(exposed area 4?8 cm2) was studied using X-ray photoelec-
tron spectroscopy (XPS). Samples were exposed in blank
acid rain solution and in acid rain solution presaturated
with the inhibitive pigments (i.e. CAS and ZMP) for 24 h.
Before exposure the samples were cleaned in acetone in an
ultrasonic bath for 5 min and then rinsed with deionised
Table 2 Compositions of ‘saturated’ solutions of pigment extracts (ppm)
Ion composition of pigment extract in acid rain solution, mg dm23
Pigment Sr Cr Ca
SrCrO4 195 224 … …
ZMP … … 0. 3
CAS … … 18.4
Corrosion Engineering, Science and Technology 2004 Vol. 39 No. 2
Table 3 Artificial acid rain solution; the average
composition of rainfall in the Greater
Manchester area in the UK in 1986
Artificial acid rain Chemical species Conc., mg dm23
(pH was adjusted to H2SO4 (98%) 3.185
4.5 with Na2CO3)
(NH4)2SO4 4.620
Na2SO4 3.195
1.575
NaNO3 2.125
NaCl 8.483
water. Constant potential polarisation of the samples was
carried out using an EG&G potentiostat Model 263A, a
saturated calomel reference electrode and a platinum
auxiliary electrode. Subsequently, XPS analysis was per-
formed with a Kratos Axis 165 instrument using mono-
chromatic Al Ka (1486.6 eV) radiation and a magnetic
snorkel lens. The samples were removed from solution,
rinsed thoroughly with deionised water and dried with
compressed nitrogen and inserted into the vacuum chamber
within 3 min. This was done to ensure that the degree of
adventitious carbon contamination was minimised.
Analysis was started after about half an hour at a pressure
of around 2–361028 mbar. Generally, by the end of the
analysis, the pressure had dropped to around
561029 mbar. Survey scans were performed at a pass
energy of 80 eV with high resolution scans over peaks of
interest performed at a pass energy of 40 eV. In this
configuration the FWHM peak width of the Ag 3d 5/2 peak
is around 0.7–0.8 eV. It was found necessary to use a
relatively high pass energy to ensure a reasonable signal on
some low intensity peaks. In addition, auger electron
spectroscopy (AES) was carried out on some zinc samples
using the same equipment, as the corresponding chemical
shifts from the XPS spectra were small.
RESULTS AND DISCUSSION
Corrosion of carbon steel in inhibited acid rain
solution
After 2 h of immersion of carbon steel in the acid rain
solution containing the two inhibitor species at saturation,
potentiodynamic polarisation shows significant inhibition
of the anodic reaction and slight inhibition of the cathodic
reaction, compared with uninhibited acid rain solution
(Fig. 1). However, this protective effect is rather short term.
Thus, results from electrochemical impedance measure-
ments, fitted to a standard circuit featuring a charge
transfer resistance Rct in parallel with a constant phase
element term CPE both of which are in series with the
solution resistance Rs, demonstrates a significant increase in
the Rct value after 2 h exposure, but a relatively large
decrease after 24 h exposure (Table 3). Initially, the charge
transfer resistance of mild steel in the inhibited solution is
approximately 90 times that of the control (uninhibited)
acid rain solution. However, after 24 h this difference
decreases to a factor of only 3.5 times, approaching the
value recorded for steel in uninhibited acid rain solution.
Thus, acid rain solution inhibited with a mixture of ZMP
Zn P Mo
… …
0. 2 6. 9 0.6
0. 2 … …
 Zin et al. Inhibition of steel and galvanised steel corrosion
1 Potentiodynamic polarisation of steel sample in unin-
hibited acid rain solution and in an inhibited acid rain
solution saturated with Shieldex and Actirox pigments
and CAS at their effective saturation concentrations shows
relatively strong inhibiting properties on mild steel, but
only during the first hours of exposure.
Electrochemical impedance of coated
galvanised steel
Electrochemical impedance was used to estimate the
anticorrosion effectiveness of various pigmented (and
scratched) epoxy coatings on zinc coated (hot dip
galvanised) steel at the open circuit potential after immer-
sion for up to 10 days in acid rain solution at laboratory
ambient temperature (20uC). The experimental impedance
spectra (not shown) generally comprised two semicircles.
The first time constant derived from a geometric effect due
to the high resistance of the electroyte, while the second
time constant gave information about corrosion processes
at the defect area. The electrical equivalent circuit used to
model the defective epoxy coatings consisted of a charge
transfer resistance for oxygen reduction Rcat in series with
a Warburg element Ws and in parallel with the charge
transfer resistance for anodic reaction Ran (i.e. zinc
dissolution) and the double layer capacitance Cdl. The
fitting procedure showed relatively low errors (less than
5%).
The addition of inhibitive pigments to the epoxy
primer increased the charge transfer resistance for the
cathodic process Rcat at the coating defect (Fig. 2), from
about 20 kV for the uninhibited coating (E7) to about
55 kV for the ZMP/CAS mixture (E16) and about 45 kV
for the coating containing strontium chromate (E17). For
the chromate free inhibitor mixture, the greater the quantity
added the better the performance; thus, E16 performed
better than E8. Notably, the Rcat for the pigment blend-
containing coatings is similar to, or larger than that for the
coatings containing strontium chromate. For the anodic
process, the chromate free pigments were less effective for
inhibition than strontium chromate (Fig. 3). Thus, the
charge transfer resistance, Ran, for coatings E16 and E8 do
not exceed 1 MV compared with 1.2 to 1.4 MV for the
2 Time dependency of Rcat at a defect on variously
inhibited epoxy coated galvanised steel
Corrosion Engineering, Science and Technology 2004 Vol. 39 No. 2
169
3 Time dependency of Ran at a defect on variously inhib-
ited epoxy coated galvanised steel
coating containing chromate, E17. The double layer
capacitance (not shown) rises rapidly for the control
coating sample E7 (i.e. only with TiO2), which suggests
that the area of active corrosion underneath the coating
increased with time. In contrast, the capacitance for the
three inhibited coatings stays at a much lower level and
does not exceed 75 nF, suggesting that an effective
inhibited film was present at the defect. Finally, it can be
concluded that the ZMP/CAS pigment blend is a more
effective cathodic inhibitor and that chromate is a more
effective anodic inhibitor.
Variation of zinc and steel corrosion potentials
with immersion time
The time dependencies of the open circuit potential for steel
and zinc exposed in inhibited acid rain solution (Fig. 4)
appear to show anodic inhibition. Thus, the corrosion
potential of zinc moves into the range 20.74 to 20.75 V
(SCE), compared with 20.92 to 20.95 V (SCE) in the
uninhibited solution. Initially, the potential of mild steel is
also more positive compared with uninhibited acid rain,
reaching a value of 20.26 V (SCE) after 2 h. However,
while the corrosion potential for zinc remains at 20.75 V
for extended times, that for steel decreases after 3 h,
eventually approaching the corrosion potential for steel in
uninhibited solution.
Potentiostatic polarisation of steel and zinc in
inhibited solutions
At galvanised steel cut edges, or similar defects, galvanic
couples between zinc and steel will play an important role in
the corrosion process. Two reactions are expected here:
first, the anodic dissolution of zinc (release of zinc ions)
and, second, oxygen reduction (generating hydroxide ions)
at the steel cathode. Thus, in considering inhibition of cut
edge corrosion, the zinc is under anodic polarisation, while
the steel is under cathodic polarisation and the restriction
(inhibition) of both reactions is critical. In order to study
these processes, zinc and steel samples were individually
4 Time dependency of the open circuit potential of steel
and zinc in inhibited and uninhibited acid rain solutions
170 Zin et al. Inhibition of steel and galvanised steel corrosion

5 Variation of cathodic current with time on steel

6 Variation of anodic current with time on zinc polarised
polarised in inhibited and uninhibited acid rain solutions
in inhibited and uninhibited acid rain solutions

polarised at constant potentials representative of the mixed

potential of a galvanic couple.
The cathodic current for steel polarized at 20.9 V (SCE)
in inhibited and uninhibited acid rain solution is shown in
Fig. 5. It is clear that in the inhibited solution (i.e. with
ZMPzCAS) the current density decreases rapidly
approaching 5 mA cm22 after about 20 h. In contrast, the
cathodic currents on steel in the uninhibited acid rain
solution and in acid rain inhibited with only one of the two
components (i.e. either ZMP or CAS) are about 10 to 15
times higher. Neither of the inhibitors singly suppresses
cathodic activity as effectively as the mixture of the two.
Consequently, it must be stressed that a highly protective
surface film can form under cathodic polarisation only in
7 Variation of anodic current with time on steel
the presence of both inhibitor species and that the mixture
polarised in inhibited and uninhibited acid rain solutions
is, hence, an effective cathodic inhibitor.
The anodic reaction on zinc can also be suppressed by the
inhibitor mixture (Fig. 6); here the currents at 20.8 V and (OCP), and at slight anodic and cathodic polarisation, were
20.6 V (SCE) in inhibited acid rain solution are signifi- investigated by XPS in order to study the surface film
cantly suppressed compared with those in the uninhibited compositions. The general film compositions (in at.-%),
solution. In contrast, anodic polarisation of carbon steel from a survey scan after exposure at the OCP, are shown
(Fig. 7), revealed that inhibition does not persist signifi- in Table 5. The investigation revealed the presence of
cantly and, after about 2.5 h, the anodic current rises the elements P, Si, O, C, Fe, and Zn on the surfaces. A
rapidly. This last result is consistent with the impedance significant carbon signal was also observed and this is
data reported in Table 4. ascribed to adventitious carbon contamination during
unavoidable exposure of the sample to air. In order to
XPS analysis of inhibitive films formed on zinc probe further the chemistry of the surfaces, high-resolution
and steel XPS scans were under-taken for O1s, P2p. Si2p, Ca2p3/2,
Fe2p3/2, and Zn2p3/2. In addition, since the XPS binding
Samples of zinc and steel exposed to the inhibited and
energy for Zn2p3/2 is relatively insensitive to chemical shifts,
uninhibited acid rain solution at the open circuit potential
a high resolution AES scan for zinc was taken. The
resulting scans were curve fitted and the results are
Table 4 Charge transfer resistance for carbon summarised in Figs. 8–12. The XPS data were charge cor-
steel in inhibited and uninhibited acid rected ascribing a binding energy of 284.8 eV using the
rain solution adventitious C–C peak. The C1s spectra are similar for all
samples and consist predominantly of C–C and C–H
Charge transfer resistance from
impedance measurements, Rct bonding; they are assumed to be due to adventitious
contamination and hence are not included.
Exposure time Acid rain solution Inhibited acid rain solution The Si2p spectrum (not shown) is rather weak and
corresponds, under all conditions to silicon being present
2h 1840 V 164 000 V
24 h 180 V 630 V as silicate. The phosphorus P2p spectrum (also not shown)
is consistent with phosphorus as phosphate, e.g. Zn3(PO4)2

Table 5 General film composition after exposure in inhibited acid rain solution at open circuit potential
derived from an XPS survey scan

Zinc in acid rain solution at OCP Steel in acid rain solution at OCP

Element Uninhibited, at.-% Inhibited, at.-% Uninhibited, at.-% Inhibited, at.-%

C 27.8 41.0 12.7 42.4

O 50.0 45.2 63.3 44.1
Zn 14.9 6. 5 0. 1 1.7
Ca 0. 1 0. 8 0. 1 0.3
Si 5. 3 2. 6 3. 6 1.0
P 0. 9 3. 3 0. 4 2.0
Fe 0. 7 0. 5 19.7 8.4

Corrosion Engineering, Science and Technology 2004 Vol. 39 No. 2

 Zin et al. Inhibition of steel and galvanised steel corrosion
8 High resolution XPS scan of Ca2p3/2 peaks for steel
exposed at open circuit potential to inhibited acid rain
solution for 24 h
(133.6 eV), Ca10(PO4)6(OH)2 (133.2 eV) and
Ca(H2PO4)2?H2O (134.3 eV).12,13 The calcium spectrum
(Fig. 8) shows a peak doublet (i.e for Ca2p3/2 and
Ca2p1/2); here, binding energies of around 347?4 eV are
consistent with the presence of calcium in a series of
phosphate compounds: e.g. Ca(H2PO4)2, Ca3(PO4)2 and
Ca5(PO4)3OH).14,15 Thus, similar phosphate species are
present on both the zinc and steel surfaces consequent upon
exposure to the inhibited acid rain solution at the OCP and
at slight anodic or cathodic potentials.
In inhibited acid rain solution at the OCP (Fig. 9), the
O1s spectrum for steel reveals three peaks at binding
energies of 529.6, 531.1 and 532.6 eV. These correspond,
respectively, to oxygen in oxide, phosphate, and hydroxide
(or bound water). Under anodic polarisation at 20.35 V
(SCE) (Fig. 10) these three peaks are still present, though
with altered intensities. However, under cathode polarisa-
tion at 20.9 V (SCE) (Fig. 11) the central peak due to phos-
phate dominates.
For zinc in uninhibited acid rain solution, the O1s
spectrum (not shown) shows one peak at a binding energy
of 531.5 eV; most probably due to overlapping carbonate
and hydroxide.16 However, in inhibited acid rain solution at
the OCP (not shown), the O1s spectrum is similar to that of
9 High resolution XPS scan of O1s peak for steel
exposed to inhibited artificial acid rain solution for
24 h at open circuit potential
Corrosion Engineering, Science and Technology 2004 Vol. 39 No. 2
171
10 High resolution XPS scan of O1s peak for steel
exposed to inhibited artificial acid rain solution for
24 h under anodic polarisation at 20.35 V
steel, with three peaks at binding energies of 529.8, 531.4, and
533.1 eV, again corresponding, respectively, to oxide, phos-
phate, and hydroxide (or bound water).17 Finally, the AES
results (Fig. 12), show chemical shifts that are consistent with
zinc phosphate being present as the majority phase.
DISCUSSION
Electrochemical testing
Potentiostatic polarisation of zinc and steel specimens in
the inhibited acid rain solution shows significant suppres-
sion of the cathodic reaction as well as the anodic reaction
on zinc. However, the inhibitor film appears to break down
after a short time during slight anodic polarisation of
carbon steel and, hence, is not very persistent under such
conditions. This result is confirmed by impedance data that
show initially strong inhibition of carbon steel at the open
circuit potential, which is not persistent over 24 h of
exposure. The open circuit potential/time data appear to
show an overall anodic inhibition of both zinc and steel.
However, in the latter case, again this is not persistent over
extended periods of immersion.
11 High resolution XPS scan of O1s peak for steel
exposed to inhibited artificial acid rain solution for
24 h under cathodic polarisation at 20.9 V
172 Zin et al. Inhibition of steel and galvanised steel corrosion
12 Stacked AES plot of zinc exposed to inhibited artificial acid rain solution for 24 h at open circuit potential and at
anodic and cathodic potentials
The situation is clearer for a simulated galvanised steel
cut edge where cathodic polarisation of steel, and anodic
polarisation of zinc, is expected. In this case, effective and
persistent inhibition (current suppression) occurs only in
the presence of both inhibitor species in solution. Under
this condition, it seems clear that the inhibitor mixture
performs as an effective cathodic inhibitor. Certainly, if the
inhibitor mixture is incorporated into an organic coating,
then rather effective inhibition of the corrosion and
disbonding process occurs at scratched defects.
What is unclear from the electrochemical data is whether
anodic or cathodic inhibition predominates, why the
inhibition process appears to be rather more effective on
zinc than on steel and why the presence of calcium as well
as zinc is required for effective inhibition.
Surface analysis
The chemical state information from XPS analysis indicates
that the inhibitive film forming on carbon steel immersed in
a calciumzzinczphosphate ion mixture contains more
zinc than calcium at the OCP and under both slight anodic
and cathodic polarisation. Within the film, phosphorus is
found to be present as phosphate under all conditions.
Also, the data are consistent with some of the oxygen being
present as phosphate at all potentials and, at cathodic
potentials, greater than 90% of the oxygen being present as
phosphate. This implies that the film composition is a
mixed zinc calcium phosphate and forms most effectively at
cathodic potentials or on cathodic sites (i.e. the mixture is
predominantly a cathodic inhibitor).
The mechanism of film deposition most probably relates
to the local increase in pH at cathodic sites, normally due
to oxygen reduction in near neutral solution. This lowers
the solubility of a particular species causing precipitation.
For example, interactions in the system CaCl2–ZnCl2–
(NH4)2HPO4–H2O at 25uC were studied by Shchegrov
Corrosion Engineering, Science and Technology 2004 Vol. 39 No. 2
et al.18 They found, using X-ray diffraction analysis, that
the deposited solid phase contains a mixture of
CaZn2(PO4)2?2H2O (Scholzite) and Zn3(PO4)2?4H2O (Hopeite).
They suggested that zinc phosphate is deposited initially
and then slowly transforms into the significantly less soluble
CaZn2(PO4)2?2H2O (the solubility products for these are,
. .
respectively, 10227 1 compared with 10234 1).19
On the inhibited steel surface, oxide, hydroxide and
phosphate species were all found, in addition to calcium
and zinc. Furthermore, on the surface of the steel at the
OCP the atomic ratios of Ca : Zn : P are 0.3 : 1.7 : 2.0,
Table 4. Assuming that all the calcium is in the form of
CaZn2(PO4)2?2H2O and the remaining zinc is present as
Zn3(PO4)2?4H2O, then surplus phosphorus is probably
bound as iron phosphate, FePO4. Furthermore, the atomic
ratios of phosphorus imply that each species is present in
approximately equimolar amounts (i.e. Scholzite:Hopeite:
iron phosphate50.6 : 0.73 : 0.67). The balance of iron in the
film is most probably present as oxide or hydroxide.
On the inhibited zinc surface, phosphate, hydroxide and
oxide species were all found as well as calcium and zinc. The
molar ratio of Ca:P in the inhibited film is about 0.25, while
the molar ratio of Zn:P is close to 2. Assuming, as for iron,
that all the calcium is present as Scholzite and that excess
phosphorus is present as Hopeite, then these two species are
again in a 1 : 1 ratio. Excess zinc is most likely to be present
as zinc hydroxide or carbonate.
It is suggested that the availability of zinc ions in solution
due to corrosion of galvanised steel could be an important
factor in the inhibition process. Thus, in the case of mild
steel, the concentration of zinc ions provided by the mixture
of ZMP and CAS appears insufficient to form an effective,
persistent film. Also, because the ZMP pigment alone is not
as effective as the pigment mixture, most probably calcium
ions, phosphate and zinc ions all need to be present in the
solution to provide a significant synergetic effect.
 Zin et al. Inhibition of steel and galvanised steel corrosion 173

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1. Potentiostatic polarisation showed that use of a blend 4. T. FLETCHER: European Coatings Journal, 1991, Sep., 553–
of zinc molybdate/phosphate and calcium ion exchanged 563.
silica leads to highly effective cathodic, and somewhat less 5. Y. TANIZAWA and T. SUZUKI: J. Chem. Soc. Faraday Trans.,
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