Journal of Chemical

Journal Technology
of Chemical and Metallurgy,
Technology 52, 4,52,
and Metallurgy, 2017, 766-772
4, 2017

CHEMICAL RESISTANCE OF STEEL 13CrV (RUS 13ХФА)

Anton S. Tyusenkov

Ufa State Petroleum Technological University Received 06 March 2016

450062, 1 Kosmonavtov St., Ufa Accepted 16 December 2016
Republic of Bashkortostan, Russian Federation
E-mail: anton.tyusenkov@yandex.ru

ABSTRACT

In recent years, the oil and gas pipelines for transportation of both conventional and hydrogen sulfide corrosive en-
vironments, including the Far North region, are made of low-alloy steels with a low content of chromium. For example,
the flowlines are made of steel 13CrV (rus 13ХФА) in some oil and gas fields of the Russian Federation. In this paper we
investigate the chemical resistance of this steel and analyse the experimental results.
In the present paper, the effect of chloride ions dissolved in produced water on the chemical resistance of the steel
13CrV is determined, the nature of corrosion and the passivation tendency of the steel is examined and the sulfur content
on the pipe wall is inspected using sulfur print.
Keywords: steel, corrosion, polarization diagram, potential, sulfur print, chlorine ions.

EXPERIMENTAL to study any electrochemical processes, especially the

metal deposition and dissolution processes, the electrode
Steel 13CrV (rus 13ХФА) has no analogues. It is processes in chemical current sources, the corrosion re-
classified as a constructional corrosion and cold-resistant sistance characteristics of various materials, the coulomb
alloyed steel. It is used for the production of seamless and voltammetric determination of the composition of
hot-worked tubes, as well as for the production of round the substances and other electrochemical measurements.
billets and pipe fittings (elbows, tees, flanges and other The studies were carried out in a pressing three-
parts). All these products are intended mainly for the oil electrode electrochemical cell. The working electrode
and gas industry. The chemical composition of the steel was 13CrV steel and the working environment was the
13CrV on a percentage base is as follows: model water of one of the oil fields of the Far North
C Si Mn Ni S P Cr Cu As of Russia, the composition of which is represented in
0.07 - 0.17 - 0.35 - up to up to up to up to up to up to Table 1. Platinum was used as the auxiliary electrode.
0.14 0.37 0.65 0.3 0.04 0.035 0.15 0.3 0.08
The introduction of the auxiliary electrode is related
The anodic and cathodic polarization diagrams are to the fact that the phenomenon of reference electrode
obtained using a potentiostat IPC-Pro M. polarization may occur during the electric current flow,
The potentiostat is designed to study the kinet- i.e. the change in the potential that introduces error into
ics of the electrochemical processes occurring in the the measurements [1]. The electric current in the cell
«electrode-electrolyte” system. The potentiostat IPC- flows through the auxiliary electrode and the working
Pro M is a software-hardware system, consisting of a electrode. The silver-chloride reference electrode was
potentiostat measuring unit and a personal computer used to measure the potential of the working electrode.
with installed software. The potentiostat is intended The polarization of the working electrode in the

766
 Anton S. Tyusenkov

Table 1. The composition of the model pro-

duced water.

Ions Composition, mg/l

Ca2+ 15932
HCO3- 242
Mg2+ 2063
Na+ 60837
-
Cl 127367

cathode region was undertaken up to the potential of Fig. 2. Polarization diagram of the steel 13CrV in the
-1.0 V, in the anode region - up to +0.5 V; the potential model medium containing 40 g/l Cl‾ in semi-logarithmic
sweep rate was 0.5 mV/s. coordinates.

RESULTS AND DISCUSSION

Polarization studies
As a result of these studies we determined the effect
of the chloride ions content on the corrosion resistance
of the steel 13CrV. The resulting polarization curves of
the experiments are presented in Figs. 1 - 4.
On the corrosion chart the values of anodic polariza-
tion, cathodic polarization and the ohmic potential drop
at the corrosion current I can graphically be found. The
calculation is made by Tafel extrapolation.
Fig. 3. Polarization diagram of the steel 13CrV in the
Calculation of the corrosion rate of steel 13CrV model medium containing 80 g/l Cl‾ in semi-logarithmic
in the model water coordinates.
The tangent to the cathode curve at the point of
overvoltage of -10 mV from the corrosion potential.

Fig. 4. Polarization diagram of the steel 13CrV in the

Fig. 1. Polarization diagram of the steel 13CrV in the model medium containing 120 g/l Cl‾ in semi-logarithmic
model water in semi-logarithmic coordinates. coordinates.

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 Journal of Chemical Technology and Metallurgy, 52, 4, 2017

E=
−0.554 − 0.092 lg i. (1) 0.01309 −3 mm
P
= ⋅ 8760 ⋅10= 0.01460 .
7.86 yr
The tangent to the anode curve at the point of over
The calculations of the other polarization diagrams
voltage of +10 mV from the corrosion potential
are performed similarly. The calculation results are sum-
E= −0.228 + 0.021lg i. (2)
marized in Table 2.
The polarization diagram of the steel 13CrV in the
The point of intersection of the tangents corresponds
model water (Figs. 1, 2) shows that the potential of
to the potential and corrosion current density of the two-
-0.28 V results in repassivation of the steel surface.
electrode system [2, 3]
The sharp increase in the corrosion current is due to the
−0.554 − 0.092 lg icorr =
−0.228 + 0.021lg icorr , breakdown of the protective film, which leads to active
anodic dissolution. This steel is passive in the potential
lg icorr = −2.9, range of -0.28 and -0.90 V; it is subjected to anodic
mA A dissolution at potentials more positive than -0.28 V.
icorr 10
lg= = −2.9
0.001258sin −1 θ = 0.01258 2 ,
sm 2
m However, this steel is characterized by the phenomenon
of secondary passivity (at a potential of -0.21 V) due
Mass rate of corrosion Km
to the formation on its surface of new poorly soluble
Ik ⋅ A ⋅ 3600 ik ⋅ A compounds accompanied by a drop of the anode current.
=Km = , (3)
With increase of the content chloride ions in the
F ⋅S ⋅n 26,8 ⋅ n
model water the potential of repassivation of the steel
where: Iк - corrosion current, А;
13CrV shifted to lower values (Figs. 3 - 8), which is
А - atomic mass of metal, g/mol;
associated with the activation of the anodic process.
3600 - the number of seconds in an hour;
However, the amount of metal corrosion losses in this
F = 96487 - Faraday number, C/mole (A∙s/mol);
case is reduced because the products resulting from the
S - contact surface of the metal, m2.
anodic reaction hamper the contact between the ag-
Depth rate of corrosion P
gressive environment and the rest of the steel. A small
K amount of chromium contained in the steel (0.55 %)
P = m ⋅ 8760 ⋅10−3 , (4)
can enrich corrosion products and form a dense layer
ρ
which prevents the penetration of corrosive compounds
where: n - valence of the metal;
to the metal - corrosion products boundary [4]. Due to
ρ - metal density, g/cm3;
this the steel 13CrV surpasses in corrosion resistance of
8760 - number of hours per year;
pipe steels such as Russian steel grades 09Г2С (German
10-3 - conversion factor.
analog 13Mn6), 17Г1С (German analog St 52-3), and
0.01258 ⋅ 55.8 g steel 20 (German analog C22).
=Km = 0.01309 2 ; Traditionally, in the Far North and the West Siberia
26.2 ⋅ 2 m ⋅ hr
fields, the manganese-doped steel is used for the produc-

Table 2. Results of polarization studies.

Content of icorr, К m, P,
Environment aa ba ak bk Eкорр, V
Cl‾, g/l A/m2 g/m2⋅hr mm/yr

Model water oil

-0.228 0.021 -0.554 -0.092 0.0126 0.013 0.015 -0.228
field
40 -0.213 0.034 -0.488 -0.107 0.1141 0.119 0.132 -0.213
Model water oil
field with Cl‾ 80 -0.178 0.039 -0.603 -0.118 0.0194 0.020 0.023 -0.178
120 -0.391 0.033 -0.654 -0.047 0.0054 0.006 0.006 -0.391

768
 Anton S. Tyusenkov

Table 3. The electrode potential of the steel 13CrV.

Steady potential, V (silver
Corrosive environment
chloride reference electrode)
No -0.306
Distilled water -0.374
Model water oil field -0.427

tion of pipes with high cold resistance, such as Russian
steel grades 09Г2С (German analog 13Mn6) and 17Г1С
(German analog St 52-3) [5]. Practical application of
these tubes proves their low corrosion resistance. Man-
ganese adversely affects the corrosion resistance since
it is more active than iron and promotes the formation
of manganese oxides and sulfides. The lattice param-
eters of manganese oxides and sulfides differ from the
parameters of iron oxides and sulfides, which leads to
corrosion products loosening and peeling from the metal
surface. Such loosening and peeling of corrosion prod-
ucts triggers the dissolution of carbonate crystals and,
therefore, the formation of cavities and holes through
which corrosive components penetrate the metal [6, 7].
In contrast to manganese steels, the chromium steels
are characterized by the formation of an amorphous
Cr(OH)3 layer, which is the link between the carbonate
crystals and protects the latter from dissolving by the
transported fluid. Thus, the metal surface is protected
against the penetration of corrosive components by a
dense layer of FeCO3 and Cr(OH)3 mixture.
Analysis of the steel electrode potentials
Continuous films of corrosion products forming on
the surface of the metal often do not prevent the interac-
tion of the metal with the oxidant as either or both can be
dissolved in the film simultaneously ionizing them i.e.
Me = Men+ + ne;
O + 2e = O2-,
and moving the generated ions and electrons in the
crystal lattice of the corrosion product.
Ions and electrons move in the crystal lattice of the
metal corrosion products (salts and oxides) due to the
presence of disturbances in the lattice, so they move
according to these disturbances or defects (vacancies,
cations, anions or electrons in the interstices, electron
holes, etc.) [8]. The rate of corrosion process occyring
with the participation of free electrons, as well as all of
the electrochemical processes depend on the magnitude
of the metal electrode potential according to the laws of
electrochemical kinetics.
The magnitude of the irreversible electrode potential
of a metal is determined by both internal factors associ-
ated with the metal and external factors associated with
the electrolyte and physical conditions.
Electrode potentials of the steel 13CrV in various
media are presented in Table 3.

Fig. 5. The sample appearance after the gravimetric tests.

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 Journal of Chemical Technology and Metallurgy, 52, 4, 2017
Table 4. Electrode potentials of heterogeneous surface.
Potential measuring place
Steel surface without deposits
Corrosion products of negligible thickness
Corrosion products of considerable thickness
The gravimetric test of the steel under examination
in the model water within a few days of the onset of
the experiments showed that some local areas become
covered with a thin deposit (corrosion film). The longer
the samples were exposed, the more deposit (FeCO3, and
Cr(OH)3 mixture) was formed (Fig. 4).
The results of electrode potentials measurement in
various regions of the sample surface are summarized
in Table 4.
Thus, on the 13CrV steel surface there is a galvanic
couple formation due to the surface irregularity. At the
same time, corrosion products containing chromium act
as an anode because they have higher electronegative
potential. The steel surface in this case is the cathode
and is protected from corrosion. Over time, the sample
surface is covered with a dense solid layer of corrosion
products of FeCO3 and Cr(OH)3 that protects the steel
surface from corrosive components.
Monitoring of the chemical heterogeneity by
Baumann sulfur print
The type of corrosion damage that the steel 13CrV
is prone to is pitting. Non-metallic inclusions of various
nature can act as centers of pitting in the steel. The main
reason for the abnormal corrosion rate of oil pipelines
are non-metallic inclusions introduced into the steel
during the ladle treatment at non-optimal manufactur-
ing parameters. Such inclusions are called corrosive
nonmetallic inclusions [9].
Inclusions in the steel 13CrV are biphasic and com-
prise separate oxide and sulfide parts, tightly adjacent
to each other. Sulfide part is calcium sulphide with
manganese, and sometimes grains of calcium sulphide
are observed in aluminium oxide with magnesium (most
likely magnesia spinel MgO·Al2O3).
There is calcium sulphide in magnesia spinel be-
cause sulfur can dissolve in various compounds in both
sulphide and oxide phases. Initially, oxides in the form
of magnesia spinel are formed in liquid steel and then
770
Steady potential, V (silver
chloride reference electrode)
-0.321
-0.459
-0.471
manganese sulphides become prominent on the surface
of the oxide inclusion at the start of the crystallization
[10, 11]. With further steel cooling the dissolution of
calcium sulphide takes place in oxide and sulphide
inclusions.
Inclusions of manganese sulphides or sulfoxides
are preferable centers in steel pitting. The provoking
action of MnS inclusions is caused by the fact that upon
contact with aqueous media, they are readily dissolved
to form ions S2–, which similarly to Cl– ions can displace
the passivating oxygen from the metal surface, thereby
initiating secondary phenomena leading to the stable
pitting formation.
Manganese sulfide inclusions affect the corrosion
resistance of alloyed steels ambiguously: both the inclu-
sion and the matrix around the inclusion can be dissolved
therein no change in chemical composition (especially
chromium reduction) is detected.
The sensitivity to MnS pitting in chlorine-containing
environments is attributed to preferable Cl- ion adsorp-
tion on these inclusions, which leads to a chemical or
electrochemical dissolution of manganese sulphides.
Accordingly, this dissolution is accompanied by a local
pH decrease around the inclusion. This local pH reduc-
tion and Cl– concentration increase result in the pitting
formation and formation of elements such as H+, Cl– and
HSO3–, which may be inside the pits. The growth of
pitting depends on the concentration of Cl- ions. If it is
high, then iron dissolution accelerates and subsequent
hydrolysis reactions of iron ions continue to lower the
local pH which in turn aggravates corrosion processes.
The manganese sulfide MnS is not thermodynamically
stable in acidic media, so it actively dissolves in aque-
ous environments containing hydrogen sulphide. CaS is
thermodynamically unstable within the entire pH range
and potentials. Therefore, the dissolution rates of calcium
and manganese sulphides are much higher than the metal
matrix and oxide components. Thus, localized steel cor-
rosion triggers on thermodynamically unstable sulfides.
 Anton S. Tyusenkov
Fig. 6. Prints of steel samples on photographic paper:
top - 13CrV; bottom - Ст3сп.
Baumann determination of sulfide inclusions was
conducted in accordance with the State standard GOST
10243-75 Steel test and evaluation methods of the
macrostructure.
In order to take the print of sulfur distribution in the
metal, the steel sample 13CrV was ground, polished and
degreased. Prints were taken on sized up photographic
paper. Sheets of paper were soaked for 5-8 minutes under
light exposure in 5 % sulfuric acid solution. The paper
was then imposed on the emulsion sample surface side
down. On the back side, the paper was continuously
ironed with cotton wadding avoiding shear until remov-
ing gas bubbles forming during the reaction.
Prints were taken at room temperature for 15
minutes. Ready imprint was washed thoroughly in tap
water and treated using fixative for 20 minutes (sodium
thiosulfate), then washed again and dried.
The paper is the darkest in places of sulfur inclusions
clusters in accordance with the amount of silver sulphide.
For better reliability sulphide inclusions were also
determined on the commercial quality carbon steel
sample Ст3сп (Russian steel grade).
The results of these experiments are shown in Fig. 6.
It is seen that in the steel 13CrV practically no
inclusions of sulfur compounds are visible, whereas
steel Ст3сп contains a fairly large amount of the latter.
Thus, the studied steel 13CrV is of high quality and has
low amount of sulfur, which reduces the likelihood of
pitting corrosion.
CONCLUSIONS
Steel 13CrV is passive in the potential range of
-0.28 and -0.90 V, it is subjected to corrosion at higher
potentials than -0.28V. However, this steel is character-
ized by the phenomenon of secondary passivity (at the
potential of -0.21V) due to the formation of new poorly
soluble compounds on the surface accompanied by the
anode current drop.
The repassivation potential of the steel 13CrV shifts
to more negative values with increasing of chloride ion
content in the water, which is associated with the activa-
tion of the anodic process. However, the extent of metal
corrosion losses in this case is reduced because the re-
sulting corrosion products from anodic reaction hamper
the contact of the aggressive environment with the rest
of the steel. Chromium in the steel (0.55 %) enriches the
corrosion products, whereupon a dense layer is formed
which prevents the penetration of corrosive media com-
ponents to the metal - corrosion products boundary. Due
to this, the steel 13CrV surpasses in corrosion resistance
pipe steels such as Russian steel grades 09Г2С (German
analog 13Mn6), 17Г1С (German analog St 52-3), and
steel 20 (German analog C22).
Under service conditions of the equipment and
piping made of steel 13CrV the galvanic couple may
form on the inner surface due to the inhomogeneity of
the steel substrates. Therewith corrosion products con-
taining chromium act as an anode, because they show
higher electronegative potential. The steel surface in
this case is the cathode protected from corrosion. Over
time, on the steel surface a continuous dense layer of
FeCO3 and Cr(OH)3 corrosion products is formed which
will protect the equipment from penetrating corrosive
medium components.
The steel 13CrV contains practically no impurities
of sulfur compounds which significantly reduces the
possibility of pitting corrosion.
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 Journal of Chemical Technology and Metallurgy, 52, 4, 2017
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