CORROSION SCIENCE SECTION

Oxidation of Steel Surfaces in Water Solutions

A.A. Efimov,‡,* L.N. Moskvin,** and O.Yu. Pykhteev*

ABSTRACT when protective films are formed on steel surfaces

in contact with aqueous solutions containing special
Oxide film formation on the surface of carbon steels during reagents, which initiate formation of protective oxide
contact with solutions of reagents such as oxygen, hydrogen films with a certain phase composition. In particular,
peroxide (H2O2), hydrazine-hydrate (N2H4·H2O), ammonium those in the nuclear and heat power engineering fields
acetate (CH3COONH4), and ethylene-diamin-tetraacetate use oxygen (O2),5 hydrogen peroxide (H2O2),6 and com-
(Na2H2Y2) was studied. By means of a number of physical and
plexants,7 etc., as such reagents.8
chemical methods (radioactive indicators, spectrophotometry,
Up to now, there has been no single point of view
gel-chromatography, and Mössbauer spectroscopy, etc.), it has
been proven that iron compounds in the solution contacting the surrounding the mechanism of the formation of oxide
steel surface play the decisive role in the formation of oxide films on steel surfaces in water media. Convention-
films. Oxide films on steels with maximal protective properties ally, oxidation is deemed to involve the oxidation of
are shown to form in water solutions of Fe(III) complexes or surface iron atoms starting from the oxygen molecule
solutions containing polymer forms of its hydrolysis products adsorption on the steel surface.1 However, as long ago
with the number of iron atoms in the molecule being <13. as the 1970s, we obtained data using radioactive trac-
ers on the inclusion into the oxide film of iron ions
KEY WORDS: carbon steel, iron, hydrogen peroxide, hydroly-
sis products, oxidation, oxide films, oxygen, polymers, water in the water solution in contact with the steel. These
solutions data have remained unnoticed by corrosion special-
ists because they have been published strictly in a
difficult-to-access Russian-language report.9 Numer-
INTRODUCTION
ous investigations of the mechanisms of the formation
Among well-known methods of protecting steel struc- of protective oxide films on steel surfaces in contact
tures against corrosion, one of the most widespread with water solutions, investigations that we have
and effective techniques is planar oxidation.1-3 Even performed during subsequent years, have proved the
the oxide layers spontaneously formed at room tem- results of the first experiments and suggested new
perature on steel surfaces contacting water without methods of directed steel oxidation to reduce corro-
special reagent additives reduce the rate of corro- sion rate. This article summarizes the results of the
sion.4 The corrosion rate is reduced to a greater extent research we have conducted, explaining the mecha-
nism of the formation of oxide films on steel surfaces.
Submitted for publication September 2002; in revised form, June
‡
2004. EXPERIMENTAL PROCEDURES
Corresponding author. E-mail: efi[email protected].
* Alexandrov Research Institute of Technology, 188540, Sosnovy
Bor, NITI, Leningrad region, Russia. Samples of carbon steels (CS) of pearlitic and
** St. Petersburg State University. austenitic classes have been investigated in parallel
0010-9312/05/000063/$5.00+$0.50/0
CORROSION—Vol. 61, No. 4 © 2005, NACE International 317
CORROSION SCIENCE SECTION

6 + yOH ↔ [Fe[(OH) y (H 2 O)6– y ]

experiments. From the first steel class, samples of the Fe(H2O)3+ – (3y)+
+ yH + (1)
following Russian steels have been investigated: Steel
3 ([mass%] ≤2 C; 0.3 to 0.7 Mn; 0.2 to 0.4 Si; 0.005 where y can take the value of 1 or 2.
to 0.01 P; 0.17 to 0.04 S; an analog of the A533 steel The concentrations of various species have been
according to the AISI[1] nomenclature) and Steel 20 calculated for different concentrations of Fe(III) and
([mass%] 0.17 to 0.24 C; 0.35 to 0.65 Mn; 0.17 to pH for equilibrium conditions at room temperature.
0.37 Si; 0.25 Cr; an analog of the A501 [UNS The results of calculations, which are given in Figure
K03000](2) steel according to the AISI nomenclature). 1, served as the basis for selecting the conditions for
From the second steel class: stainless steel (SS) the preparation of solutions with the given EHP com-
OCr18Ni10Ti ([mass%] 0.008 C; 17 to 19 Cr; 9 to position.
11 Ni; 0.65 Ti; bal. Fe; an analog of the Type 304 To prepare solutions of certain fractions of Fe(III)
[UNS S30400] steel according to the nomenclature hydrolysis products (HP), these fractions were prelimi-
AISI). The shape of samples changed depending upon narily isolated from the total HP mixture (the proce-
experimental conditions and research methods used: dure of their preparation is described below) using the
discs ([∅30.0; d = 2.0] mm), rings ([∅30.0; h = 2.0; method of gel-chromatography on sefadexes.11 The
d = 0.5] mm), and cylinders ([∅7.0; h = 30.0] mm). solutions for obtaining HP fractions were prepared
Corrosion tests of the samples have been conducted using dissolution of the specific amount of the over-
potentiostatically in a three-electrode electrochemical crystallized salt ferric nitrate (Fe[NO3]3·9H2O) in deion-
cell, with the potentials being equal to 0.7 V (passive ized water containing a certain amount of nitric acid
region), –0.3 V (anode dissolution region), and –0.8 V (HNO3), so that after dissolution of the Fe(III) nitrate
(cathode protection region) with respect to the normal shots at pH<1, the iron concentration in the solution
hydrogen electrode (NHE). should be equal to (2 × 10–1 to 1 × 10–2) mole/dm3.
The steel oxidation processes have been studied The EHP fraction was isolated from the solutions ob-
in contact with water media within the pH range of tained by means of gel-chromatography on G-10 sefa-
3.0 to 7.5. Observations of the spontaneous formation dexes. The preparatory chromatographic column filled
of oxide films have been performed in high-purity with sefadex had a height of 200 mm, a diameter of
deaerated water with the following parameters: con- 10 mm, and a total volume of 16 cm3. The EHP isola-
ductivity χ = 0.2 µS/cm; Cl– ion concentration is less tion procedure included the following consecutive
than 20 µg/dm3; and O2 concentration is less than operations. The column filled with G-10 sefadex was
10 µg/dm3. To investigate the steel oxidation process washed with an eluent having the same composition
in the presence of reagents affecting the forms of iron and acidity as the solution with the HP mixture but
existence in solution, high-purity water has been used not containing the latter. An aliquot of one of the HP
with the following content: solutions prepared with a volume of 50 mL was
—dissolved oxygen [O2] = 0.02 mg/dm3 to passed through the column. The column was flushed
8.0 mg/dm3 with 30 mL of eluent. The first 25 mL of the filtrate
—hydrogen peroxide [H2O2] = 5 mg/dm3 to including the column’s free volume and the exclusion
100 mg/dm3 volume, in which the polymer hydrolysis products
—Fe(III) nitrate in terms of [Fe(III)] = 5.6 mg/dm3 (PHP) are isolated, were discarded. The next 35 mL of
to 560 mg/dm3 the filtrate contained EHP cleaned from PHP that had
—hydrazine [N2H4·H2O] = 500 mg/dm3 been formed in solutions at the stage of dissolution of
—complexants in the form of a disodium salt of the iron nitrate shot. The EHP isolation degree accord-
ethylene-diamine-tetraacetatic acid [Na2H2Y2], ing to this procedure was about 75% of their total
where Y = C2H4N2-(CH2COO)4, 33.6 g/dm3 content in the aliquot of the solution prepared. The
—ammonium acetate [NH4Ac] = 7 g/dm3 iron concentration in the EHP solutions obtained was
—lactic acid [HLac] = 9 g/dm3 equal to 4 × 10–3 to 10–4 mole/L, which was monitored
All solutions, unless especially stipulated other- according to the method of the photocolorimetric de-
wise, have been prepared using deionized water with termination of iron with 0-phenanthroline. The ion
the oxygen concentration being ≤0.02 mg/dm3 ob- strength of µ = 1.0 was maintained in the solutions
tained by argon bubbling. prepared by adding calculated shots of sodium nitrate
The experimental studies followed calculations of (NaNO3). The excessive content of NO3– ions in the so-
the content of hydrolysis products in equilibrium with lutions under investigation provided practically equal
hexaquo Fe3+ ions (EHP) using known equilibrium re- influence on the probability and energy of electronic
action constant values for:10 transitions in all EHP forms in case of a possible coor-
dination of NO3– ions with Fe3+.
(1)
American Iron and Steel Institute (AISI), 1140 Connecticut Ave., The preparation of solutions for the isolation of
Ste. 705, Washington, DC 20036. Fe(III) PHP fractions was carried out by adding sodium
(2)
UNS numbers are listed in Metals and Alloys in the Unified Num-
bering System, published by the Society of Automotive Engineers hydroxide (NaOH) solution with a concentration of
(SAE International) and cosponsored by ASTM International. (10–2 to 10–1) mole/dm3 to the initial [Fe(H2O)6]3+ solu-

318 CORROSION—APRIL 2005

 CORROSION SCIENCE SECTION

FIGURE 1. Calculated dependence of the percentage content of Fe(H2O)63+ ions and EPH depending on the concentration
of OH– ions (pHorig) and the total concentration of Fe(III) [CFe tot] at 25°C CFe tot: (a) –10–4 mole/L; (b) –10–3 mole/L;
(c) –10–2 mole/L; (d) –1.0 mole/L. (A) Fe(H2O)63+; (B) Fe(OH)2+; (C) Fe2(OH)3+; (D) Fe2(OH)24+; (E) Fe(OH)2+.

tion. In this case, the final pH value was chosen in indicator was introduced into the initial [Fe(H2O)6]3+
preparatory experiments, which established depen- solution until PHP was formed in it. The PHP solu-
dencies of the content of various PHP fractions upon tions prepared with the radioactive indicator were
pH in the conditions of maintaining constant ion held at room temperature for 30 days, after which a
strength within the solution with respect to NaNO3. It repeated gel-chromatographic isolation of the corre-
has been established that the main parameter deter- sponding PHP fraction was performed, and, by radio-
mining the degree of Fe(III) HP polymerization is the activity of the last filtrate fraction of the corresponding
[OH]/[Fe(III)] ratio in the solutions.12 EHP, their appearance in the PHP solution under
The isolation of specific PHP fractions was car- investigation was tested. In parallel, the absence of
ried out by sequential filtration of PHP mixture solu- Fe(OH)3 + FeOOH (mixture) sediments was tested
tions obtained through gel-chromatographic columns using filtration through a dense paper filter. The ref-
with sefadexes of G-25 (limit of exclusion of polymers erence experiments conducted have shown that no
containing 100 PHP iron atoms [100]), G-15 (limit of noticeable changes have occurred for the given time in
exclusion of PHP[33]), and G-10 (limit of exclusion of the iron PHP fractional composition. The time interval
PHP[13]). The procedure for their exclusion included of 30 days selected for testing the PHP solution stabil-
filtration of the PHP mixture solution aliquot at the ity securely overlapped with the storage period of PHP
selected pH value through the first column. At that, solutions from the moment of their preparation until
the first 10 mL of the filtrate corresponding to the free they are used in subsequent experiments.
column volume were discarded. The solution further The processes of mass exchange between steel
eluting contained EHP and PHP with the iron atom samples and water solutions in contact with them
number being less than the limit of exclusion for the were monitored using 59Fe and 55Fe radioactive indica-
given gel. This filtrate fraction was collected and used tors; the former was determined using the method of
for isolation of the following PHP fractions: PHP(33) γ-spectroscopy on Ge-Li detectors, while γ-spectrosco-
on the column with G-15 PHP(13) on the column with py on silicon detectors was used for determining 55Fe.
G-10. In both cases, the PHP(100) fraction was iso- The steel corrosion rate K (mg/dm2-h) was calculated
lated from the corresponding column with G-25 in the using the formula:
second 10 mL of the filtrate.
The stability of the PHP solutions prepared with
0.693t/T1/2
respect to time was tested in special experiments m o A t Vn e
K= (2)
using an 59Fe radioactive indicator. The radioactive S·τ

CORROSION—Vol. 61, No. 4 319

CORROSION SCIENCE SECTION

Phase analysis of hydrolytic sediments was per-

formed using the adsorption version of Mössbauer
spectroscopy.13 The processes of formation of oxide
film layers and loose deposits on steel sample sur-
faces were observed visually and by means of a scan-
ning electron microscope. The phase composition of
surface layers was determined by means of the ra-
diography method and using a version of conversion
Mössbauer spectroscopy (dispersion geometry with
conversion electrons recording).14 Oxide layer thick-
nesses were determined using optical microscopes on
transverse metallographic sections of metal samples
with oxide film.
In the following, spontaneous oxidation is under-
stood as the process of forming oxide phases on the
steel surface when they were in contact with water
media that were initially free of dissolved iron com-
pounds or any reagents that could additionally initi-
ate the steel dissolution process, except a minimum
amount of oxygen remaining in the water after deaera-
tion. Respectively, directed oxidation is understood as
the process of the formation of oxide phases on steel
surfaces when in contact with aqueous solutions of
FIGURE 2. Anodic polarization curves for steels under investigation special reagents affecting the process of oxide phase
in various solutions. (A) CS 20 in the solution of 1.0 mole/dm3 NaNO3; formation on steel surfaces.5-7
pH = 3.3; t = 20°C. (B) CS 20 in the solution of 1.0 mole/dm3 NaNO3; Such differentiation is conventional, because
pH = 3.3; CO2 = 5 mg/dm3 to 8 mg/dm3; t = 20°C. (C) CS 20 in the when pearlite steels are in contact with water free of
solution of 0.5 mole/dm3 H3BO3 + 0.05 mole/dm3 NaOH, pH = 7.5;
any reagents, one can still observe the emergence and
CO2 = 5 mg/dm3 to 8 mg/dm3. (D) CS 20 in the solution of Item C,
gradual growth in the concentration of dissolved forms
t = 100°C. (E) CS 20 in the solution of Item C, t = 150°C. (F) Steel
OCr18Ni10Ti in the solution of the same composition as in Item C, of irons in water, beginning with hexaquo Fe(II) ions.
t = 20°C. (G) CS 20, having preliminarily been oxidized in the
solution of NH4Ac (0.1 mole/dm3, t = 180°C) in the solution of Item C, RESULT AND DISCUSSION
t = 20°C.
The anodic polarization curves for CS samples
not subjected to prior oxidation had regions of active
where mo is a normalization factor for converting the anode dissolution, passivation, and transpassivity
units of solution-specific activity in terms of 59Fe or that is typical of iron (Figure 2). In the case of austen-
55
Fe reference radionuclides to the units of iron con- ite SS of the OCr18Ni10Ti type, the active dissolution
centration in the solution, g/dm3 (Here, mo is deter- region cannot be discerned. A similar picture also can
mined experimentally for each irradiated steel sample. be seen in the case of preoxidized CS samples (Curve
Parallel radiochemical and chemical analyses of the G). Preoxidation was carried out in NH4Ac solution by
solution are conducted in the initial experiments with keeping the samples in an autoclave at a temperature
the samples.) Also, t is the time from the moment of of 180°C for 3 h.
measuring mo to the moment of measuring the solu- Sample surface blackening from the formation
tion sample activity; τ is the time of solution contact of oxides phase fixed firmly on the steel surface was
with steel, h; At is the specific activity of the reference seen at all potentials except for the full passivation
radionuclide in the sample of solution that contacted region. The beginning of CS surface oxidation at room
the steel sample under study, Bq/dm3, at the moment temperature becomes noticeable after 0.5 h to 1.0 h
of activity measurement; S is the area of the solution of steel contact with the solution. An equilibrium film
contact with the steel, dm2; T1/2 is the reference thickness of 1 µm to 2 µm is reached in 3 h to 4 h.
radionuclide half-life period, h; Vn is the volume of Corrosion potential (Efr) is established after 1 h to 2 h
the sample of the solution that was in contact with within (–0.45 ± 0.05) V, regardless of conditions of ox-
steel, dm3. ide film formation on the CS surface.
For studying the chemical transformations of To elucidate the mechanism of oxide film forma-
dissolved corrosion products, in addition to the ra- tion on steel surfaces, a series of experiments was
diochemical method and the gel chromatography on conducted under conditions similar to those of Ex-
sefadexes, the methods of pH-metry and spectropho- periment 2 in Figure 2. However, unlike Experiment
tometry were used. 2, the water solution in contact with steel contained

320 CORROSION—APRIL 2005

 CORROSION SCIENCE SECTION

Fe(NO3)3 with the 59Fe radioactive indicator. It was

found in this experiment that the process of oxide
film formation on the steel surface involves, for all
potentials, not the oxidation of metal atoms, but dis-
solved iron compounds passing to the metal surface
into the oxide phase being formed (Figure 3). The
latter conclusion is confirmed by the fact that, after
the mechanical removal of black oxide film from the
metal, the radioactivity of the metal surface decreased
to background values, and the γ-spectrum of the ox-
ide powder that was separated from the metal corre-
sponded to 59Fe. Measurements of the specific activity
of iron included in the oxide films that formed on steel FIGURE 3. Change of radioactivity of the CS 20 sample surface
surfaces at any potentials, after they are mechanically at the contact with the solution of 1 mole/dm3 NaNO3; pH = 3.3;
separated and dissolved (Asp, Bq/dm3), yielded practi- CO2 = 5 mg/dm3 to 8 mg/dm3; t = 20°C, containing a radioactive 59Fe
cally the same values for this property as the value for indicator in the Fe(NO3)3 solution depending upon the contact time in
the initial Fe(NO3)3 solution that contacted the steel the conditions of anode polarization of the sample: (A) area of active
(Table 1). anode dissolution (ϕNHE* = –0.3 V); (B) area of cathode polarization
The data obtained indicate that, at any potentials, (ϕNHE = –0.8 V); (C) area of passivation (ϕNHE = –0.7 V).
the oxide film formation process is due not to the
oxidation of metal atoms on the sample surfaces, but
to dissolved iron compounds passing into the oxide they correspond to those real conditions that can be
phase being formed. In this process, as follows from provided in the oxidation of the working surfaces of
Figure 3 (A and B), in the active anode dissolution heat power equipment by adding special reagents to
and cathode polarization regions, the rate of dissolved water media that are in contact with the surfaces.
iron passing to the oxide phase being formed practi- Participation of dissolved iron forms in the pro-
cally does not depend on the potential. In the passive cess of oxide films formation on the steel surface is in
region, this passage is at a minimum (Figure 3 [C]). direct correlation with the known fact of a drastic
The data presented in Table 1 and Figure 3, on drop in the steel corrosion rate in time. Figure 4 shows
the one hand, confirmed the fact established earlier corrosion rates of CS 20 against the time of the steel
that oxide films are formed on steel surfaces from contact with water solutions of various compositions.
iron compounds dissolved in the solution with which In all the curves, one can note similar initial por-
they are in contact.9 On the other hand, a new result tions (the first 2 h of contact) corresponding to the
is evidence that the oxidation process in the cathode period of establishing a steady-state corrosion poten-
polarization and active anode dissolution regions runs tial. During this period, hexaquo Fe(II) ions are first
independently of values for metal electrochemical accumulated in the contacting solution to equilibrium
potential. concentrations resulting from metal dissolving. The
For pearlite class steels, the free corrosion poten- arrival at an equilibrium condition in the case of oxy-
tial value in the solutions studied (Efr), as a rule, cor- gen-free solutions is indicated by the stabilization of
responds to the active anode dissolution region (Table the corrosion rate. In the presence of oxygen, some
1), where the oxidation process runs most intensely. portion of [Fe(H2O)6]2+ is oxidized to [Fe(H2O)6]3+, which
Therefore, further investigations into the oxidation disturbs the equilibrium and can result in new peri-
mechanism were carried out at Efr without special su- ods of the corrosion rate growth (peaks in Curves B
perposition of external polarization. In addition, such and D). By this time, the formation of oxide layers can
data are of the greatest practical interest, because be observed visually on steel surfaces contacting oxy-

TABLE 1
Variation of 59Fe Specific Activity (Asp) in Labeled Fe(NO3)3 Solutions Contacting CS 20
in Relation to Potential (ϕ) of External Polarization of Steel Samples at Room Temperature
ϕ Value of Time of Steel
Materials Contact with Asp Asp
Potential Region (NHE) Solution (Bq/dm3) (% of initial value) Note
— — 0 270 ± 20 100 Initial 59Fe solution
Cathode polarization region –0.8 3.0 80 ± 20 29 —
Active anode dissolution region –0.3 3.0 95 ± 20 35 —
Passivation region 0.7 3.0 230 ± 20 85 —
Corrosion potential
(without external polarization) ≈ –0.44 3.0 75 ± 20 28 —

CORROSION—Vol. 61, No. 4 321

CORROSION SCIENCE SECTION

agreement with what is known about using H2O2 as

an additive to aqueous coolants for the reduction of
corrosion rate of heat power equipment.15 At the same
time, these data were the first evidence that a sig-
nificant factor for the process of oxide film formation
on steel surfaces are chemical forms in which Fe(III)
is in the contacting solution. The reason for such a
conclusion is the fact that the role of oxygen in aque-
ous solution is merely oxidation of Fe(II) to Fe(III).
[Fe(H2O)6]3+ ions produced in this process undergo
further complex hydrolytic transformations from EHP
to hydrolytic sediments. At the same time, aquoxohy-
droxo complexes16 are formed in H2O2 solutions; they
prevent the formation of hydrolytic sediments, and,
respectively, as will be shown below, generate loose
deposits on steel surfaces that do not protect steels
against corrosion.
FIGURE 4. Time behavior of the corrosion rate for CS 20 in deionized The influence of the chemical forms of Fe(III) to
water depending upon the concentration of oxygen in it and the which hexaquo Fe(II) ions pass (which have formed as
temperature: CO2 ≤ 0.02 mg/dm3 (A, C); CO2 = 8 mg/dm3 (B, D); 20°C a result of the corrosion of steel in contact with solu-
(A, D); 98°C (B, C). tions) during oxide film formation processes can be
learned from the character of dependencies shown in
Figure 5. Equilibrium concentrations of 55Fe radionu-
gen-containing water: black at 98°C and a mixture of clides in solutions produced after their contact with
black and rust-colored at 20°C. No such phenomenon CS 20 samples previously irradiated by thermal neu-
has been found for the same period of steel contact trons vary with the growth temperature, depending
with oxygen-free water. Therefore, there are grounds on the compositions of the solutions. Steel samples
for believing that the subsequent drastic decrease in withdrawn from autoclaves after being heated to
the corrosion rate during steel contact with oxygen- temperatures corresponding to ascending branches
containing solutions, which is especially pronounced of the curves, to maximum levels have no noticeable
at 98°C, is connected with participation, in protective oxide films on their surfaces. Oxide films do not ap-
oxide film formation on steel surfaces, and of aquohy- pear on the surfaces of the steel samples under study
droxo compounds of Fe(III) accumulated in the solu- until the temperatures corresponding to descending
tion contacting with steel. branches of the curves in Figure 5 are reached. Their
At the initial stages of pearlite steel corrosion, appearance is especially pronounced after the curves
significant differences can be noted in oxygen and reach the plateau.
H2O2 effects on the corrosion rate, which are especial- The results obtained are attributable to the fact
ly pronounced at room temperature (Table 2). Thus, that, regardless of the composition of the solutions,
when in contact with oxygen-free water-containing the corrosion rate increases with temperature, which
50-mg/dm3 H2O2, the corrosion rate of CS 20 at initial leads to an increase in equilibrium concentrations of
stages is significantly higher than it is in oxygen- iron ions in the solution until they reach their maxi-
containing water. However, the corrosion rate of CS mum values. A reduction of equilibrium concentra-
20 in contact with H2O2 solutions becomes consider- tions of iron compounds in the solution begins after
ably lower with time. The data obtained are in good reaching a specific temperature inherent to each solu-

TABLE 2
Corrosion Rate (K) of CS 20 in Water Solutions of O2 and H2O2
Depending on Their Composition, Temperature, and Time of Steel Contact with Solutions(A)
Corrosion Rate of CS 20 in Water (K mg/m2-h)
Depending on Oxygen and H2O2 Content of Water and Temperature
CO2 ≤ 0.02 mg/dm3
Time of Steel CO2 ≤ 0.02 mg/dm3 CO2 = 8 mg/dm3 CH2O2 = 50 mg/dm3
Contacting Water
Solution (h) 20°C 98°C 20°C 98°C 20°C 98°C
1.0 40 80 60 100 190 200
3.0 10 20 50 20 55 50
8.0 8 15 80 4 25 5
(A)
K was calculated from the results of measuring 55Fe activity in solutions, in experiment with steel samples irradiated by neutrons.

322 CORROSION—APRIL 2005

 CORROSION SCIENCE SECTION

tion composition; at this temperature, the interaction

of the dissolved iron species with the steel surface
intensifies. As a result of the interaction, oxide phases
are formed on the steel surface, and the equilibrium
iron species concentration in the solution decreases
until new equilibrium values are reached (plateau re-
gions on the curves after maximums in Figure 5) that
correspond to the conditions where corrosion rates
of metal protected by the oxide film formed becomes
equal to the rate of the reverse process of iron release
from the solution into the oxide film. If we adopt this
explanation of the nature of the dependencies seen in
Figure 5, they can be regarded as additional confirma-
tion that dissolved iron species participate in oxide
phase generation on the steel surface. An analysis of
the phase composition of the films produced for all
solution compositions has shown that the final prod-
uct of chemical transformations of iron compounds on
the steel surface is magnetite (Fe3O4), because conver-
FIGURE 5. Effect of temperature dependence on equilibrium
sion electron Mössbauer spectroscopy (CEMS) of steel
concentration of 59Fe (1) radio-nuclides in water solutions of hydrazine
surface layers after oxidation, regardless of the com- with ([N2H4Y] = 500 mg/dm3) (Curve A); sodium ethylene-diamine-
position of contacting solutions, are approximated by tetraacetate with ([N2H4Y] = 31.4 g/dm3) (Curve B); hydrogen peroxide
the superposition of a doublet and four sextets with ([H2O2] = 50 mg/dm3) (Curve C); ammonium acetate ([CH3COONH4]
the parameters presented in Table 3. The process of = 7 g/dm3) (Curve D). Measured after contact during 1 h with CS 20
oxide film formation on the steel surface is illustrated samples irradiated by thermal neutrons at each temperature. Values
in Figure 6, which shows the results of observation of of equilibrium concentrations of 59Fe in solution were normalized on
surface changes on CS 20 samples against the time the area of the steel sample.
of contact with H2O2 solutions. It can be seen that as
early as after 0.5 h of contact, an oxide film (Figure
6[b]) forms on the initial metal surface (Figure 6[a]). —Solution A: initial solution of PHP mixture, and
The oxide film consists of two layers: the lower layer solutions of individual PHP fractions containing
(black color) snug against metal, and the upper layer different numbers of iron atoms in the polymer
(gray grains in Figure 6) located over a compact Fe3O4 molecule
layer (Figure 6[b]). In 1 h, buildup of the two-layer —Solution B: from 3 to 13 Fe atoms
oxide film is completed (Figure 6[c]). It can be seen —Solution C: from 13 to 33 Fe atoms
that the upper, grainy oxide layer does not ideally cov- —Solution D: from 33 to 110 Fe atoms
er the lower layer that is firmly adhered to the metal. Solutions were prepared by dissolving PHP fractions
Therefore, it can be suggested that protective proper- separated by the gel-chromatography method in de-
ties of the two-layer oxide film are defined only by the ionized water, to a 56-mg/dm3 iron concentration.
inner layer that is strongly adhered to the metal. After holding CS 20 samples in contact with the
A series of special experiments was carried out above-listed solutions in autoclaves at 200°C for 1 h,
to find an interconnection between the forms of iron the following results were obtained:
species in solutions and the phase composition of iron —After contact with Solution A, two layers of
oxides formed on the steel surface. oxide phases were found on the steel surface:
The above-described procedure was used to 3-µm- to 5-µm-thick Fe3O4 film snug against
prepare a series of Fe(III) PHP labeled with 59Fe metal, and a loose layer of hematite (α-Fe2O3)
radionuclide: deposits over the film.

TABLE 3
Parameters of Mössbauer Spectra on Conversion Electrons of Oxide Phases on CS 20 Surface
Spectral Parameters of Spectral Fragments at 295 K Identification of Oxide
Fragment ISFe (mm/s) Q (mm/s) Hef (T) Film Components6
Doublet 0.32 ± 0.03 0.55 ± 0.05 0 γ-FeOOH
Sextet A 0.25 ± 0.04 0.1 ± 0.1 49.0 ± 0.2 Fe3O4
Sextet B 0.67 ± 0.05 0.25 ± 0.07 46.0 ± 0.4 Fe3O4
Sextet C 0 0 33.0 ± 0.2 α-Fe
Sextet D 0.44 ± 0.05 0.21 ± 0.05 51.7 ± 0.5 α-Fe2O3

CORROSION—Vol. 61, No. 4 323

CORROSION SCIENCE SECTION

—After contact with Solution B, only Fe3O4 film

3 µm to 5 µm thick was found on the steel
surface.
—After contact with Solutions C and D, only loose
α-Fe2O3 deposits were found on the steel surface.
The data indicate that, in the presence of polymer
HP forms in the solutions, ultradispersed polymers
with (3 to 13) iron atoms in the molecule play the
critical role in the process of formation of Fe3O4 films
having the best protective properties on steel surfaces.
A comparison of the data obtained in this work with
the results of earlier investigations into the phase
composition and protective properties of oxide films
(a) formed during contact with solutions of reagents sta-
bilizing Fe(III) in the solution in the dimer, trimer, and
other polymer forms with a lower degree of polymer-
ization (respectively, acetate, ammonia, and ethylene-
diamine-tetraacetate solutions) allows us to assert
that, for the intentional production of good-quality
protective oxide films on steel surfaces, one should
select, as oxidizing additives to water media, the re-
agents that promote the formation of iron compounds
with a minimum number of iron atoms in the mol-
ecule, or add such compounds directly to the oxidiz-
ing solutions. The nature of chemical processes
running during the interaction of dissolved iron forms
with iron atoms located in the surface metal layer re-
mains unclarified so far.
It can be suggested that the heterogeneous re-
action of dissolved Fe(III) species with iron atoms in
“active” centers on the steel surface proceeds in accor-
dance with the following pattern:

...OH–.. Fe– →
(b)
Fe ...OHADS... –Fe–
o
[ OH .
]
q/2
H2 O

(3)
[
→ Fe–O– –Fe–O–Fe– ... ] + H2O
OH q/

where Fe are iron atoms in “active” centers on the

steel surface.
Active centers of heterogeneous interaction on
steel surfaces can be surface iron atoms with uncom-
pensated valence electrons. From the chemical point
of view, the reaction is a heterogeneous reaction of
Fe° oxidation by Fe(III). A ring structure formed in the
process and containing, formally, two Fe(III) atoms
and one Fe(II) atom is a nucleus of Fe3O4. Further
growth of Fe3O4 film can proceed by way of a continu-
ing interaction of surface elementary iron atoms (that
have not been blocked by Fe3O4 nuclei) with Fe(III)
ions diffused to the surface.
Within the framework of the suggested mecha-
(c) nism of protective oxide film formation on steel sur-
faces, many facts known earlier can be explained. In
FIGURE 6. Scanning electron microscope images of the surface of particular, it is known that oxide films that are formed
CS 20 (a) before (500X) and (b and c) after the contact with the spontaneously on steel surfaces in contact with water
solution of CH2O2 = 50 mg/dm3. (b) 30 min after the contact (500X);
are not continuous and uniform, and, therefore, not
(c) 60 min after the contact (750X).
very protective. This fact can be explained by a rela-

324 CORROSION—APRIL 2005

 CORROSION SCIENCE SECTION

tively low share of 3 to 13 polymers in the mixture of ❖ The formation of the oxide phase on steel surfaces
Fe(III) hydrolysis products, since they are an interme- is observed at potentials of cathode polarization and
diate form in the chain of hydrolytic transformations active anode dissolution and does not take place in
of iron. the region of full passivation potentials.
In addition to explaining the mechanism of oxide ❖ The phase composition of the oxide film formed on
phases formation on steel surfaces, the data have a steel surface and the uniformity of surface coating
important practical consequences. It becomes clear depend on the forms of iron species in the solution
that to protect CS against corrosion in water media, contacting the steel. For formation of a Fe3O4 film
the proper selection of additives is necessary, which chemically bonded to the surface of steel and uniform-
would ensure the existence of iron therein in the form ly covering the entire surface, it is necessary for iron
of complex Fe(III) compounds preventing profound hy- to be present in the solution in the monomer form or
drolytic transformations of iron. Theoretically, one can in the form of polymers with a minimum number of
assume the existence of conditions under which iron iron atoms in the molecule.
species in solutions will exist in the form of ultradis- ❖ For the intentional oxidation of pearlite steels with
persed hydrolytic polymers with a minimum number the formation of oxide films providing maximum pro-
of iron atoms in the molecule. Practically, it is difficult tection against corrosion, it is reasonable to use water
to realize such a scheme, because a mixture of PHP solutions of Fe(III) compounds not subject to hydroly-
with different numbers of iron atoms is always formed sis with the formation of polymer hydrolysis products
in real hydrolysis processes. containing a number of iron atoms in the molecule
The addition of the necessary polymer fraction exceeding 13.
prepared to the solution beforehand also seems un-
reasonably complicated. Regardless of the composi- REFERENCES
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