ELECTROCHEMICAL STUDY OF THE PROCESS OF

PHOSPHATED BY IMMERSION OF STEELS

G. ALVARADO-MACÍAS1J.C. FUENTES-ACEITUNO1A. SALINAS-
RODRIGUEZ1by F.J. RODRÍGUEZ-VARELA2
1
Metallurgical Engineering Group
2
Natural Resources and Energy Group
CINVESTAV-Saltillo, Saltillo-Monterrey Highway km.13.5, Ramos Arizpe,
Coahuila. ZIP Code 25900, Mexico.
E-mail:[Link]@[Link]

SUMMARY

Phosphating is a pre-treatment used in manufacturing of

protective coatings against corrosion on ferrous surfaces.
The process involves a topo-chemical reaction between a phosphate solution.
of primary manganese and a metallic surface, resulting in the
precipitation of an insoluble tertiary salt chemically bound to the
surface of steel. This research conducted a study
electrochemical process of phosphating steel using solutions
synthetic. The goal, in the future, is to propose a reaction model
mechanistic that allows to clarify the complex chemistry of this system and
optimize the operating conditions of the process. In this article, it
they report the results of a series of phosphating experiments where
the Open Circuit Potential (OCP) and the corrosion potentials were measured
under different conditions of temperature, pH, and concentration of Mn in the
solution. Subsequently, the phosphated steel samples are
they were characterized chemically and morphologically using electron microscopy
of sweeping (SEM) and energy-dispersive X-ray spectroscopy
(EDXS). The results clearly showed that the formation of
manganese phosphate coating not only depends on temperature and
composition of the phosphating bath, but rather depends mainly on
pH of the phosphating solution. These observations are supported
through thermodynamic diagrams of species distribution and Pourbaix.

Palabras clave: Tafel; Fosfatizado; Corrosión.

AN ELECTROCHEMICAL STUDY OF THE STEEL

PHOSPHATING PROCESS BY IMMERSION
ABSTRACT

Hot dip phosphating is a process used as a surface pretreatment to produce

coatings against corrosion of ferrous surfaces. This process involves a
topochemical reaction between a primary manganese phosphate solution
with a metal surface, promoting the precipitation of an insoluble tertiary salt.
In this work, an electrochemical study of the phosphating process on steel
was carried out using synthetic solutions in order to formulate, in the future, a
mechanistic reaction model which clarifies the chemistry complexity in this
For this purpose, phosphating experiments were performed.
measuring the OCP (Open Circuit Potential) as well as the corrosion potential
of the steel under different conditions of temperature, pH and manganese
concentration. At the end of the experiments, the phosphatized steel samples
were characterized chemically and morphologically by scanning electron
microscopy (SEM) and energy dispersive X-ray spectrometry (EDX). The
results revealed that the formation of the manganese phosphate coating on
the steel depends primarily on the pH of the phosphating solution while the
temperature and composition of the phosphating bath play secondary roles
affecting mainly the kinetics of the process and the composition of the
resulting coating. These observations are supported by species distribution
and Pourbaix thermodynamic diagrams.

Keywords: Tafel; Phosphating; Corrosion.

INTRODUCTION

MECHANISM OF COATING FORMATION

The phosphating solutions consist of metal phosphates dissolved in

phosphoric acid solutions. As long as the acidity of the solution is maintained
at a critical value, the metal phosphate remains in the solution as phosphate
soluble primary. When a metal is introduced into the solution, a
corrosion reaction on the surface, which causes the interfacial pH
exceeds the critical value and favors the formation of insoluble tertiary phosphate and
it plunges onto the surface of the metal.

The composition of the phosphating solution determines the morphology and

characteristics of the formed coating. The acidity of the bath (free acidity
(AL), total acidity (AT)) and the relationship between them (RA) must be maintained in a
optimal level required to obtain a uniform and good coating
thickness.

The conversion of soluble primary phosphates to insoluble tertiary phosphates

occurs with the regeneration of phosphoric acid. A certain amount is required.
amount of free phosphoric acid in the bath to repress hydrolysis and
keep the bath stable for effective deposition of a coating
of phosphate. However, the presence of excess phosphoric acid not only
delays the formation of the coating, but also leads to the
excessive metal loss. In contrast, the increase in temperature of
the process favors the precipitation of tertiary phosphates in short times.

Phosphating processes are generally catalyzed by the use of

of oxidizing agents or accelerators, for example, nitric acid (HNO3) the
they are important since they favor the dissolution process preventing the
physical blocking of the substrate surface by hydrogen bubbles (Hivart
and col., 1997). However, although the increase in concentration of
accelerator favors the formation of better coatings, concentrations
too high can cause the passivation of the metal surface and
inhibit growth (Narayanan, 2005).

The phosphating process has been extensively researched, particularly the

effects of the process variables on the physical characteristics of the
coatings produced, using commercial formulations of the
phosphating solutions. However, so far there is no
a reaction mechanism that accurately represents the physical phenomena
chemicals that occur during the process. This is mainly due to that
It is difficult to study a reaction mechanism in the presence of many
chemical species in the commercial solution, such as; carbonates, iron,
catalysts, oxidants, etc. Therefore, in this research work, we
it proposes to synthesize a phosphating solution that contains only
manganese and phosphates, in order to study the reaction mechanism of
phosphating of steels using manganese solutions. Once
understanding this mechanism will allow the exploration of the catalytic stage
heterogeneous, which allows minimizing the activation energy of the reaction
of precipitation on steel and thereby accelerate the process.

EXPERIMENTAL

The substrate selected to carry out the immersion phosphating process

it is a steel with the chemical composition shown in Table I.

Table I. Chemical composition of the steel used.

Yes 0.247 % Mn 0.452% Cr 1.02 %
Ni 0.075% Mo 0.885% V <0.0004 %
Cu 0.101% At 0.014% Ti 0.004 %
Nb 0.035% C 0.280 % S 0.061%

With this steel, discs of 10 mm in diameter and 0.8 mm of thickness were constructed.
thickness. The tablet was mounted on a Teflon support with silver paint
connected to a copper wire as a conductor.
The experimental work was divided into three main sections: Study
thermodynamic, electrochemical study and characterization of the samples
obtained.

THERMODYNAMIC STUDY

With the help of the HSC Chemistry 6.1 program, diagrams were constructed.
speciation of H3PO4and Pourbaix diagrams Mn-P-H 2O and Fe-P-H 2The a
90ºC to determine the effect of potential and pH on the species
predominant in the bathroom. These calculations allowed us to establish what they are
the optimal theoretical conditions for carrying out the coating of
manganese phosphate.

ELECTROCHEMICAL STUDY

PRE-TREATMENT OF THE SUBSTRATE SURFACE

The steel samples to be phosphated were prepared in different ways.

to be used later in the electrochemical tests of OCP and
linear polarization (Tafel curves) through the following procedures:

Most of the tested samples were polished to a specular finish.

Initially, the samples were roughened on SiC paper of various grits.
granulometries followed by polishing with Al powders2O3from 0.1 µm and
after being washed with alcohol. Finally, the samples were attached to the
Teflon support. Some samples were neither ground nor polished and
they only stuck to the Teflon support without any type of preparation.

Finally, some of the polished and unpolished samples were stripped in a

20% HCl solution at 80 ºC for 1 min and then rinsed with
distilled water.

All samples immediately after pretreatment were

phosphated by immersion in the different phosphating solutions.

PHOSPHATING PROCESS

Different phosphating solutions were tested, with different

H concentrations3PO4and Mn with and without the presence of catalyst (HNO3)
varying the temperature between 25 and 90ºC. Table II shows the
detailed manner the conditions of the different solutions used:

Table II. Phosphating solutions.

Concentration
H3PO4 solution Mn HNO3
5 84.25 g/L - - 3 25 - if -
6 84.25 g/L - - 3 50 - yes -
7 84.25 g/L - - 3 80 - yes -
8 84.25 g/L - - 3 90 - yes -
17 84.25 g/L - 40 90 - yes 1.26
24 9,26 gr/L 3,3 gr/L 12,61 gr/L 5 90 yes yes 1
25 9,26 gr/L 3,3 gr/L 12,61 gr/L 40 90 yes - 1
27 9,26 gr/L 3,3 gr/L 12,61 gr/L 40 90 yes - 2.57

The phosphating tests were carried out in an electrochemical cell.

conventional three-electrode setup (see Figure 1) consisting of a flask of
250 ml sphere instrumented with a thermometer, a reference electrode
of Ag/AgCl (ThermoScientific Orion) in contact with the solution through
a Luggin capillary, a high purity graphite rod (Alfa Aesar) as
counter-electrode and a port to place the working electrode (sample of
steel). The electrochemical cell was suspended in a controlling mesh of
temperature.

The procedure used to study the phosphating process was the

Next: the phosphating solution (200 ml) was poured into the cell.
electrochemistry (Figure 1), subsequently, the solution was heated to the
desired temperature (25, 50, 80, or 90ºC), once equilibrium is reached
thermic, the working electrode (steel sample) was introduced and connected
to the PGZ301 potentiostat (VoltaLab). Measurements were carried out
(OCP) to monitor the evolution of the coating and also carried out
linear polarization tests to determine the change in potential
corrosion during the phosphating time of the sample (5 and 40 min). To
At the end of the experimentation, the phosphated steel sample was removed.
(working electrode), it was rinsed with distilled water and subsequently
It was characterized by microscopy. In the following sections, we
they describe the OCP techniques, linear polarization, and characterization
microstructural used.

Figure 1. Experimental setup of the electrochemical cell used for the

phosphating experiments

OPEN CIRCUIT POTENTIAL (OCP) MEASUREMENT AND POTENTIAL

OF CORROSION (EcorrDURING PHOSPHATING

The measurements of OCP and Ecorrof steel during phosphating at different

temperatures were carried out using the experimental setup described in the
previous section. To determine these potentials, the
the following two electrochemical techniques:
OCP measurement technique: with this technique, the change of
open circuit potential of steel during phosphating. It should be noted
Note that these OCP vs time curves are related to nature and
the degree of coverage of the coatings formed during the treatment,
and are an important parameter for determining the stages of corrosion
(electrochemical attack of steel) as well as the passivation time of
process.

Measurement technique of Ecorrlinear polarization curves were made

scanning the potential from -700 mV to 50 mV vs Ag/AgCl with a
speed of 10 mV/s at different temperatures. The polarization curves
They were carried out at intervals of 4 minutes during 24 minutes of experimentation.
Subsequently, the data of E vs i (potential vs current) obtained in the
curves were converted to graphs of type E vs log i, better known as
Tafel curves and with the help of the VoltaMaster software, the evolution was calculated.
of Ecorrin acidic solutions of H3PO4.

CHARACTERIZATION OF FORMED COATINGS

The qualitative chemical composition of the coating and the morphology

they were examined using SEM by taking images of secondary electrons
and backscattered electrons. The determination of the chemical composition
EDXS was carried out in selected areas of the coatings.

RESULTS AND DISCUSSION

THERMODYNAMIC STUDY

The most important diagrams obtained for this research are

those of Mn and Fe at 90 ºC since the phosphating process takes place more
quickly at this temperature.

In the diagram of Figure 2a, it can be observed that to deposit the salt
Manganese phosphate tertiary requires the solution to have a pH
around 2.5. However, in Figure 2b it can be seen that the
the formation of iron phosphate salt occurs at pH values
acids. Therefore, from a thermodynamic point of view, when steel
phosphate is formed in solutions with an initial pH below 2, first it forms
iron phosphate and there would be no manganese phosphate on the surface of the
coating. However, from the corrosion point of view
metallic surfaces in acidic media, it is well known that the dissolution of
iron (corrosion of steel), which is an anodic electrochemical reaction,
is accompanied by the generation of hydrogen (cathodic reaction). Therefore
Thus, the hydrogen evolution reaction causes a change in pH.
interfacial above 2.5 and, according to the thermodynamic diagram
Shown in Figure 2a, the formation of manganese phosphate is observed.
 Eh (Volts) M
H
P
-m
en
2O
-0C
S
tys90-.
2.0
MnO4(-a)
1.5

1.0 MnO2 MnO4(-2a)

0.5

0.0 MnO*OH
Mn3(PO4)2
Mn3O4
-0.5
MnO2(-2a)
-1.0 Mn(+2a)
Mn(OH)2
-1.5
Mn
-2.0
0 2 4 6 8 10 12 14
C pH
ELEMENTS Molality Pressure
Mn 0.06 1.000E+00
P 0.094 1.000E+00

(a)
Eh(Volts) FP
H
e-2O
S-eym
ts90.C
2.0

1.5
FePO4
1.0 Iron(III) oxide

0.5

0.0 Fe(+2a)
-0.5 Iron phosphide
Fe3O4
-1.0 Fe3P

-1.5 Iron
-2.0
0 2 4 6 8 10 12 14
C pH
ELEMENTS Molality Pressure
Iron 0.09218 1.000E+00
P 0.094 1.000E+00

(b)
Figure 2. Pourbaix diagrams at 90 ºC for (a) Mn-P-H2O y (b) Fe-P-H2O

These results suggest that if the interfacial pH of the steel-solution system

if it reaches a value above 2.5, manganese phosphate can precipitate
on the surface of the steel. However, it is not clear why it precipitates from
of this pH, which indicates that, in some way, the process is influenced
strongly due to the speciation of phosphoric acid.
Figure 3 shows the speciation of phosphoric acid at 90 ºC
different pH values, as can be seen, the acid dissociates into three
species starting from pH 2 (H2PO4,- HPO4and
-2 -3
PO4), being the first of them
-
the predominant. It is interesting to note that the dissociation to H2PO4
it occurs at pH levels very similar to those at which manganese phosphate precipitates
(see Figure 2). Therefore, for the precipitation of the tertiary salt to occur
-
It is necessary for species H to predominate in the phosphated bath.2PO4, and
that H does not exist3PO4without dissociating. This thermodynamic result explains
because some authors point out that the presence of free acidity in the bath
It is of utmost importance for the formation of the coating. (Ghali et al.,
1972 and Narayanan, 2005) Free acidity allows for the precipitation of
coating, in fact if we do a more rigorous analysis, the free acidity
(H+it is not the only important factor, but rather it requires that there is
-
the dissociated species H2PO4, and as can be seen in Figure 3 this
The first ionization of phosphoric acid begins to occur at pH 2.

Log(kmol)
5
phosphoric acid (aqueous)
H2PO4(-a) HPO4(-2a) PO4(-3a)
0

-5

-10

-15

-20

-25

-30

-35
1 3 5 7 9 11 13 pH

Figure 3. Species distribution diagram of H3PO490 ºC

ELECTROCHEMICAL STUDY OF STEEL PHOSPHATING IN

SOLUTIONS WITH AND WITHOUT MANGANESE

One of the objectives of this work is to understand the nature of phosphating.

of steels in Mn solutions. Therefore, initially it is required
study the corrosion and passivation behaviors of steel in
solutions of phosphoric acid without Mn. Figure 4 shows the curves.
Table for an acidic solution at 25 ºC at 4-minute intervals during 24 minutes
of reaction. As can be seen, the Tafel curves are different
as the corrosion reaction progresses, that is to say, they exhibit a
displacement towards positive potentials (see curves at 0 min and 24 min).
Additionally, it can be observed that the corrosion potential is becoming
more positive: at time 0 the corrosion potential is -490 mV while
that when a time of 24 min is reached, the potential is -454 mV. This
behavior is due to the fact that the steel in this acidic solution corrodes and
they are forming passive layers of iron oxide or phosphates. This latter effect
it can be observed from 20 minutes, where the corrosion potential is already
It doesn't change, indicating that the steel is passivated. Another characteristic to
highlight is the difference in magnitude of dissolution current of steel at
the 0 min and the 24 min. As can be seen, starting from potentials of -
At 440 mV, the current is lower by 24 minutes than at the beginning, which confirms
again, during those 24-minute times, passive layers are formed that
they decrease the electrical conductivity of steel. When the temperature of the
the acidic solution increases to 90 ºC (Figure 5) the same phenomenon occurs
at 25 ºC in Figure 4 (corrosion-passivation). However, it is
It is important to note that there are differences in corrosion potentials.
from steel at 25 and 90 ºC. For example, it was found that the corrosion of steel at
ambient temperature for 24 min (Figure 4) is carried out at
potentials of -454 mV. In contrast, the corrosion of steel with the same
The solution at 90 ºC (Figure 5) occurs at -422 mV. Therefore, the increase of
the temperature causes a shift of the curves towards values of
more positive potential, indicating that the corrosion-passivation of steel is
faster at 90 ºC. If the current is compared at a potential of -390 mV, it
You can appreciate that this is lower than 90 ºC than at 25 ºC, which indicates
also that the steel becomes passive more quickly at 90 ºC. This
the phenomenon can be beneficial for the phosphating process with Mn, as
At 90 ºC, the corrosion of steel would accelerate and, therefore, it would be favored.
precipitation of manganese phosphate due to interfacial pH change
associated. The thermodynamic study described in the previous section showed
that the precipitation of manganese phosphate requires an interfacial pH of at
-2.5.

Figure 4. Tafel curves for acidic H solution3PO4without manganese at 25ºC

(solution #5) with a 4-minute interval
Figure 5. Tafel curves for acidic solution of H3PO4without manganese at 90ºC
(solution #8) with 4-minute intervals

Once it was found that the temperature of 90 ºC promotes dissolution of the

steel, OCP measurements (potential-time curves) were carried out,
using acidic solutions with manganese with and without catalyst (HNO3).
The results are presented in Figure 6. This technique allows to relate the
change of the OCP with the kinetics of the phosphating process. In the literature
open it is possible to find potential-time curves for the case of the
zinc process; however, very few researches have been conducted.
for the manganese phosphating process by immersion.

When the curves described by Ghali and Potvin (Ghali et al., 1972) are
compared to those obtained in this research, it can be observed
certain differences, however, the general behavior is very similar.
The curve corresponding to solution #17 (Table II) in Figure 6 exhibits
the typical characteristics of phosphating in a solution without accelerator.
Initially, a potential drop corresponding to the
dissolution of the substrate. With the increase in time, a change is observed.
constant increase in potential due to development and growth of the
phosphate film and finally the presence of a passive film. Without
embargo, as can be seen in Figure 6, the potential-time curve
of the phosphating process of a sample in an accelerated solution with
nitrates (solution 25, Table II) exhibits a cyclic behavior that could
associating with the formation and dissolution of the phosphate layer. This type of
behavior is observed up to 40 minutes of processing and is not observed
the passivation of the substrate.
Figure 6. Potential-time curve for acidic solutions of H 3PO4-Mn sin
HNO3(#17) and with HNO3(#25)

It was also observed that the presence of accelerator in the solution

phosphated is of utmost importance. In the solutions where it was not used
it was observed that the substrate attack is excessive, taking away
end in some cases the total consumption of it. The presence of
oxidant inhibits steel corrosion allowing for a more controlled attack
of the surface.

MICROSTRUCTURAL CHARACTERIZATION OF COATINGS

FORMED

The morphology and chemical composition of the coatings obtained in the

Different solutions were characterized by SEM-EDXS. Figure 7 illustrates the
morphology and local chemical composition of the coating obtained during 5
minutes of phosphating in solution # 24 (accelerated with nitrates). As how
You can see, the coating is made up of a relatively thin layer.
uniform with some crystals with cubic morphology dispersed over the
surface.

A semi-quantitative analysis (Table III) of the EDXS spectrograms of the

Figure 7 indicates that the cubic crystals are δ-Fe. 2O3while the layer
relatively uniform coating corresponds to an iron phosphate.
These results are consistent with those reported by Saison (Saison,
1962), who observed that in the first minutes of treatment of
phosphated by immersion of steel results in a layer of Fe3(PO4)28H2Oh yes
delta iron2O3.
 Iron O Iron

P P

S Cr Iron Iron Cr Fe
Fe S
Mn Mn

b)
c)

a)

Figure 7. Phosphated with solution #24. (a) Surface morphology

phosphatized, (b) Chemical composition of the crystal, (c) chemical composition of
the surface without glass

Table III. Composition of δ-Fe crystals2O3.

Element Wt% At%

O 24.4 50.96
P 7.83 8.45
Mn 3.41 2.07
Iron 64.37 38.52

As can be seen in Figure 8, by increasing the phosphating time

in solution # 24 (solution # 25, Table II), the iron phosphate layer
increases in thickness and it is no longer possible to observe δ-Fe crystals 2O3about
the surface of the sample.

The effect of the increase in pH of the accelerated phosphating solution with

nitrates (solution #27, Table II) on the coating formed on the sample
is illustrated in Figure 9. This coating can be compared to the
morphology of the coating achieved in the same solution but at a pH of 1
(Figure 8).
 P
O

Iron

S Cr
Iron Mn Fe
C

Figure 8. Morphology and chemical composition of the steel surface

phosphated in solution 25 (pH 1)

As can be seen, by increasing the pH to 2.57 the coating

consists of a non-uniform layer of manganese phosphate crystals
on the surface of the steel and matches what was predicted in the
Pourbaix diagrams discussed earlier. This morphology suggests
from a mechanistic point of view, that the formation of phosphate crystals
Mn occurs in cathodic areas where the reduction of the ion takes place.
H+ in the solution. The crystal-free areas correspond to areas
anodic where the dissolution of steel takes place. On the other hand, these
observations suggest that the formation of manganese phosphate coatings
in steels follows the mechanism proposed by Machu (Machu, 1950) for the
formation of zinc phosphate coatings on steels.

O P

Mn

C Mn

Figure 9. Morphology and chemical composition of the steel surface

phosphatized in solution 27 (pH 2.57)
 P Fe
O

Mn

SCl
Cr Mn
C Iron

Figure 10. Morphology and chemical composition of the substrate surface with
solution 27

Finally, Figure 10 shows that the Mn phosphate crystals are

formed in reality by aggregates of smaller crystals and that in the
the cathodic area where these crystals are formed is surrounded by a zone
anodic where the dissolution of steel occurs and the formation of a layer
thin layer of iron phosphate.

CONCLUSIONS

According to the results of the experiments conducted, the pH of the

phosphating solution controls the formation of the phosphate coating of
manganese on steel. The pH should be such that the optimal amount exists.
of free phosphoric acid but at the same time promotes precipitation
of tertiary manganese phosphate when the interfacial pH increases
due to the reduction of H ions+ in the solution.

It was observed that from a pH of 2.57, the acid begins to dissolve.

phosphoric that helps in the formation of manganese tertiary salt
(Mn3(PO4)2), which is deposited in the substrate.

In addition to pH, temperature is another factor that influences the

coating formation. As the temperature increases, the speed of the
reaction increases. In this case, the temperature of 90 ºC was ideal for the
obtaining the coating.
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