Metal Science and Heat Treatment, Vol. 54, Nos. 9 10, January, 2013 (Russian Original Nos.

. 9 10, September October, 2012)

UDC 669.14.018.298.3:620.193

CORROSION DAMAGE OF OIL LINE TUBES FROM

CHROMIUM-MOLYBDENUM-CONTAINING STEELS
IN HIGHLY AGGRESSIVE PRODUCED ENVIRONMENTS
M. A. Vyboishchik,1 A. V. Ioffe,2 E. A. Borisenkova,2 T. V. Denisova,2 and A. V. Sorokin2
Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 10, pp. 29 33, October, 2012.

The effect of chemical composition and structure of the metal of oil line tubes on the evolution of corrosion
damage is studied for aggressive conditions of oil gathering. The corrosion resistance of the tubes is shown to
depend on their chemical composition and structure of corrosion products on the surface.

Key words: tube steels, corrosion resistance, corrosion products, evolution of damage.

sent work was a detailed study of the mechanism and kinetics of development of corrosion damage in steels alloyed additionally with Cr, Mo, and V and inoculated with REM for
operation under conditions of highly aggressive transported
environments.

INTRODUCTION
An urgent task of the recent period is creation of tube
steels with elevated endurance under operating conditions.
This is connected with growth in the watering and in the contents of CO2, H2S and sulfate-reducing bacteria (SRB) in
transported environments, i.e., with permanent intensification of the effect of the corrosion-active components of the
environments on the tubes. Comparative field tests [1] have
shown that oil line tubes produced from steels 13KhFChA
and 08KhMFA possess a higher corrosion resistance in environments containing elevated amounts of H2S and CO2 than
the traditionally used steels. Grade 08KhMFA combines high
mechanical properties with corrosion resistance, which determines the prospects of its application. The aim of the pre1
2

METHODS OF STUDY
We performed field tests of coils cut from tubes 219 mm
in diameter and 8 mm thick produced from steels 13KhMFA,
08KhMFChA, 20KSKh and 20. All the coils were mounted
in one pilot division into an oil-gathering header in a manner
not disturbing the laminar flow of the environment and preventing the appearance of electrochemical corrosion between
steels with different contents of carbon.
The chemical compositions of the studied steels are
given in Table 1. The heat treatment consisted of normalizing, which provided formation of fine grains in the structure

Tolyatti State University, Tolyatti, Russia (e-mail: vma@land.ru).

Samara Engineering-Technical Center, Samara, Russia (e-mail:
ioffe@eor.samara.ru).

TABLE 1. Chemical Composition of Studied Steels

Content of elements, wt.%
Steel

13KhFA
08KhMFChA-1
(37 ppm Ce)
08KhMFChA-2
(45 ppm Ce)
20KSKh
20

Si

Mn

Cr

Mo

Ni

Al

Cu

Nb

Ti

Ca

0.09

0.35

0.54

0.58

0.002

0.02

0.034

0.03

0.004

0.018

0.004

0.046

0.001

0.01

0.002

0.07

0.34

0.53

0.66

0.131

0.16

0.038

0.14

0.003

0.029

0.003

0.063

0.002

0.005

0.001

0.07
0.21
0.21

0.35
0.26
0.24

0.52
0.55
0.42

0.66
0.02
0.03

0.125
0.003
0.003

0.16
0.03
0.04

0.036
0.025
0.037

0.15
0.05
0.04

0.004
0.007
0.007

0.028
0.004
0.001

0.002
0.002
0.002

0.063
0.001
0.002

0.002

0.001

0.005
0.01
0.01

0.001
0.006
0.004

519
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520

M. A. Vyboishchik et al.

TABLE 2. Mechanical Properties of Studied Steels

Steel

13KhFA
08KhMFChA (37 ppm Ce)
08KhMFChA (45 ppm Ce)
20KSKh
20

sr , MPa

s0.2 , MPa

590
610
600
630
480

490
505
445
530
285

s0.2 /sr

0.83
0.83
0.75
0.84
0.59

KCV, MJ/m2 at test temperature, C

d, %

30.0
22.7
28.3
22.5
29.2

40

50

60

70

2.4 (100)
2.6 (100)
2.7 (100)
0.5 (0)
0.4 (0)

2.2 (100)
2.5 (100)
2.7 (100)
0.4 (0)
0.4 (0)

2.1 (100)
2.4 (100)
2.6 (100)
0.4 (0)
0.4 (0)

2.0 (100)
2.4 (100)
2.5 (100)
0.3 (0)
0.3 (0)

Note. The content of the ductile component in the fracture is presented in parentheses in percent.

TABLE 3. Corrosion Resistance of Tested Steels (NACE Standard)

HR, %
Steel

13KhFA
08KhMFChA-1 (37 ppm Ce)
08KhMFChA-2 (45 ppm Ce)
20KSKh
20

CTR

CLR

0
0
0
40
20.08

0
0
0
12
5.90

KISSC ,
MPa m1/2

41.30
42.08
43.28
35.66

Notations: HR is the resistance to hydrogen cracking (NACE TM

02842003); CLR and CTR are the coefficients of crack length and
thickness, respectively; KISSC is the threshold coefficient of stress
intensity.

of the metal and relatively high corrosion properties (all the

steels had grains of size No. 9). Each steel was studied in two
different states to obtain additional information. For example, the tests of two specimens of steel 13KhFA after operating periods of different duration (221 and 515 days) allowed
us to compare the results obtained for the rate of corrosion,
the structure and the composition of the corrosion products.
Two specimens of steel 08KhMFChA with different contents
of cerium were used to obtain data on the required content of
inoculant for chromium-containing steels. Steels 20 and
20KSKh differed in the technique of modification of nonmetallic inclusions. In the structure of steel 20 the sulfide inclusions were spheroidized.
Prior to performing field tests we determined the mechanical and corrosion properties of the steels (Tables 2 and
3). We established that the highest resistance to hydrogen
cracking and sulfide stress corrosion cracking was exhibited
by steel 08KhMFChA (Table 3).
The field tests were performed at an oil-gathering header.
Its operating parameters were as follows: working pressure
5 7 atm, volume of transported product 1170 m3/day, watering of the product 89%, content of SRB (plankton)
1 104 cells/ml, mechanical admixtures (total) 12.5 mg/liter,
product density 1.054 g/cm3, mean temperature of environment 70 80C.

The transported environments contained (in mg/liter)

2.0 H2S, 75.9 CO2, and 23.0 Fe. The total mineralization of
the environments was 75.91 g/liter, the pH = 6.6. The ion
composition of the environments (in mg/liter) was as follows:

2+
2+
0.26 HCO-3 ; 4.94 SO24 ; 46.095 Cl ; 2.52 Ca ; 0.259 Mg ;
29.9 (Na+ + K+ ).
The composition of the transported corrosion-active environment and the operating parameters of the oil-gathering
header (75 mg/liter CO2 and 2 mg/liter H2S), the watering
(98%), and the high content of corrosion-active component
(46 mg/liter Cl ) reflect high aggressiveness of the environment and allow us to expect intense carbon dioxide corrosion
in this division of oil gathering. The corrosion damage of
tube specimens manifested itself in the form of general thinning of the wall estimated by the method of ultrasonic check
and local pitting damage determined visually. The phase
composition of the corrosion products was determined by the
method of x-ray diffraction analysis performed with the help
of a DRON-3 device. The structure and composition of the
corrosion products were studied using an Inspect scanning
electron microscope (Fei) and a Edax chemical analyzer.
RESULTS AND DISCUSSION
The corrosion damage of the tubes was studied after testing steel 13KhFA for 221 days and 515 days; the other steels
were tested after 283 days. We evaluated the following characteristics:
mean and maximum rates of general corrosion, which
were determined in terms of the mean and maximum thinning of the tube wall;
mean and maximum rate of local corrosion, which
were determined in terms of the mean and maximum depth
of corrosion pits after statistical processing of the results of
50 measurements;
mean and maximum rates of growth in the diameter of
pits, which characterized indirectly the local corrosion;
total rate of corrosion damage, which was determined
in terms of the sum of the general and local components of
the damage.
The highest wall thinning is detected on the lower
generatrix of a tube (1.5 2 times higher than on the upper

Corrosion Damage of Oil Line Tubes from Chromium-Molybdenum-Containing Steels

521

Layer of corrosion products

500 mm

Metal of the tube

22%

Ca

Fe
20

40

60

80

O; Ca; Fe, wt.%

Cl; Cr, wt.%
2

Fig. 1. Structure and composition of corrosion products on the internal wall of a tube
from steel 20 after operation for 283 days in
an oil-gathering header: a) surface; b ) corrosion products in cross section of the specimen; c, d ) distribution of Fe, Ca, O2, Cr and
Cl over the thickness of the corrosion layer
(in the framed rectangular zone); e, f ) structure in the characteristic radiation of Ca and
Cl respectively (the marked regions contain
their maximum amounts).

8% l
Cr

generatrix). For this reason we made all the measurements in

the lower, most damaged, region. To reduce the results of all
the tests to one term (283 days), we recomputed the characteristics of steel 13KhFA and the kinetics of their variation
(after 221 and 515 days of testing) for 283 days. All the characteristics of the corrosion damage are given in Table 4. It
can be seen that the chromium-containing steels have much
higher resistance to carbon dioxide corrosion than the carbon
steels. In addition to the known fact of increase in the resistance to hydrogen damage [2], inoculation with REM also
lowers the manifestation of local carbon dioxide corrosion.
However, the increase in the content of Ce above 37 ppm in
steel 08KhMFChA does not produce a significant result.
Testing of tubes from steel 13KhFA for different terms
(221 and 515 days) allowed us to trace the dynamics of the
evolution of corrosion damage in chromium-containing
steels. The specimens of steel 13KhFA were taken from the
same heat and one batch of tubes. Since the testing conditions were identical, we estimated the effect of the time of
operation on the corrosion parameters. It can be seen from
the data of Table 5 that the main tendency is considerable de-

Cl

TABLE 4. Corrosion Damage of Tube Walls after 283 Days of

Testing
Steel

13KhFA
08KhMFChA-1
(37 ppm Ce)
08KhMFChA-2
(45 ppm Ce)
20KSKh
20

vtot ,
vloc ,
vp ,
vS ,
mm/year mm/year mm/year mm/year

0.23
0.51
0.21
0.35
0.23
0.40
0.28
0.43
0.36
0.56

0.30
0.41
0.27
0.36
0.21
0.33
0.44
0.55
0.40
0.53

91
.
14.6
8.2
115
.
4.3
71
.
61
.
9.0
35.2
37.5

0.54
0.92
0.48
0.71
0.44
0.73
0.72
0.98
0.76
109
.

CCr ,
%

2.9
3.7
3.6

Notations: vtot and vloc are the rates of total and local corrosions respectively; vp is the rate of growth in the diameter of pits; vS is the
total corrosion rate (general + local); CCr is the chromium content in
the corrosion products.
Note. The numerators present the mean corrosion rates; the denominators present the maximum rates.

522

M. A. Vyboishchik et al.

Layer of corrosion products

100

Metal of the tube

1.8% l

O
Ca

Fe
20

40

60

80

O; Ca; Fe, wt.%

Cl; Cr, wt.%
2

f
3.8% r

Cr
Cl

celeration of the corrosion processes upon growth in the test

time. The deceleration is the highest in maximum-size pits.
This seems to be connected with the fact that the protective
chromium-containing layer of corrosion products, which
blocks or decelerates the development of local damage, is
more concentrated in larger-size pits.
The x-ray diffraction phase analysis of the corrosion
products has also shown the presence of CaCO3 and FeCO3
carbonates, Fe3O4 oxide and FeS and ZnS sulfides in them,
which means that carbonate corrosion is the dominant corrosion mechanism for the oil field studied. The presence of
zinc sulfide seems to be connected with the special features
of the oil field and the presence of a water-insoluble zincbearing mineral that precipitates on tube walls.
The metallographic studies and local chemical analysis
of all the specimens have shown substantial inhomogeneity
of the structure and composition of the corrosion products,
which depend much on the structure and composition of the
metal of the tubes. Figures 1 and 2 present the results ob-

Fig. 2. Structure and composition of

corrosion products on the internal wall
of a tube from steel 08KhMFChA-2 after operation for 283 days in an oil-gathering header: a) surface; b ) corrosion
products in cross section of the specimen; c, d ) distribution of Fe, Ca, O, Cr,
and Cl over the thickness of the corrosion layer; d, e) structure in the characteristic radiation of Cl and Cr, respectively.

tained for steel 20 and 08KhMFChA. The corrosion products

can be divided conventionally into three layers, i.e., an external layer with dominance of sulfides in the composition, an
internal layer bearing calcium and iron carbonates, and a
layer directly adjoining the metal of the tube and represented
by a mixture of iron carbonates and iron oxide. The internal
layer of the corrosion products on chromium-containing
steels (13KhFA and 08KhMFChA) is enriched considerably
with chromium; its concentration in the layer is 4 8 times
higher than in the base metal. It is interesting that the content
of chromium in the corrosion products increases upon
growth in the term of operation (Table 5). We assume that the
chromium has the form of an amorphous phase [Cr(OH)3
chromium hydroxide]. The intermediate layers of the corrosion products are also saturated with chlorine from the transported environment. In the chromium-containing steels the
content of chlorine does not exceed 2 3%; it is distributed
relatively uniformly over the thickness of the layer without

Corrosion Damage of Oil Line Tubes from Chromium-Molybdenum-Containing Steels

TABLE 5. Corrosion Damage of the Wall of a Tube from Steel

13KhFA
ttest ,
days

vtot ,
mm/year

vloc ,
mm/year

vS ,
mm/year

hcor ,
mm

CCr ,
%

221

0.25
0.54
015
.
0.39

0.31
0.44
0.27
0.30

0.56
0.98
0.41
0.69

101

2.5

141

4.5

515

523

vcr , mm/year
0.80
0.75 1
0.70 2
0.65
0.60

Change in the characteristics after 294 days, DX, %

30 40 32 15 30 27 + 40 + 80

0.55
0.50

0.45

5
0

CCr , %

noticeable concentration at the interface of the corrosion

products and the base metal.
Growth in the chromium content in the products of corrosion decreases considerably the rate of corrosion fracture
(Fig. 3). The dynamics of development of the protective passivating chromium-containing layer and its effect on the rate
of corrosion in environments containing carbon dioxide require additional investigation. According to the data of [3, 4]
the chromium-bearing amorphous phase Cr(OH)3 possesses
a lower conductivity than iron carbonate and suppresses the
electrochemical processes leading to pitting corrosion. In addition, phase Cr(OH)3 is characterized by ion selectivity and
hinders the diffusion of Cl, CO23 , and HCO 3 ions to the
surface of the corroding steel. Ions of Cl do not accumulate
on the metal/corrosion products interface and the fracture of
the steel is decelerated.
Corrosion products on tubes from steel 20 and 20KSKh
are looser and bear a greater number of cracks and discontinuities than chromium-containing steels. The boundary between corrosion products and the base metal in steels 20 and
20KSKh is developed poorly, which indicates low adhesion
and possibility of detachment. The upper and lower layers of
corrosion deposits have a more homogeneous composition
and contain an iron oxide and calcium and iron carbonates.
Sulfides penetrate into the middle layers of corrosion products. The corrosion products are saturated with chlorine.
The highest concentration of chlorine is observed on the interface with the metal and amounts to 8% (Fig. 1), which
corresponds to the concentration of chlorine in the transported environment. Undoubtedly, this accelerates the general and local corrosion processes. On some regions the carbonates are detached, which causes pitting corrosion initiated
by the carbonates (cathode) tube metal (anode) galvanic
couple.
CONCLUSIONS
1. The rate of corrosion of chromium-containing steels
depends on the content of chromium in the corrosion products. Growth in the term of operation of tubes from steel

Fig. 3. Mean total rate of corrosion vcor (general + local) as a function

of the content of chromium in the corrosion products of steels after
different terms of operation: 1 ) steel 20, 283 days; 2 ) steel 20KSKh,
283 days; 3 ) steel 12KhFA, 221 days; 4 ) steel 08KhMFChA-1
(37 ppm Ce), 283 days; 5 ) steel 08KhMFChA-2 (45 ppm Ce),
283 days; 6 ) steel 13KhFA, 551 days.

13KhFA from 221 to 515 days increases the chromium content in the corrosion deposits from 2.5 to 4.5% and, accordingly, lowers the corrosion from 0.56 to 0.41 mm/year.
2. On tubes from steels 20 and 20KSKh a great content
of chlorides is contained in corrosion products and on their
surface, which accelerates the local and general corrosion of
the tubes.
3. On the surfaces of tubes from steels 13KhFA and
08KhMFChA chlorine does not accumulate, which seems to
be connected with the barrier action of the chromium-bearing corrosion products.
4. Inoculation of the steels with rare-earth metals decelerates local corrosion.
The authors are grateful to specialists of the VZM and
RN-Stavropolneftegaz Companies for participation in the
erection of by-pass benches and help with the organization of
field tests.
REFERENCES
1. A. V. Ioffe, T. V. Tetyueva, V. A. Revyakin, et al., Corrosionmechanical fracture of tube steels in operation, Metalloved.
Term. Obrab. Met., No. 10, 22 28 (2012).
2. A. V. Ioffe, T. V. Tetyueva, T. V. Denisova, et al., Effect of inoculation with rare-earth metals on mechanical and corrosion
properties of low-alloy steels, Vektor Nauki TGU, No. 4,
41 46 (2010).
3. C. F. Chen, M. X. Lu, D. B. Sun, et al., Effect of chromium on
the pitting resistance of oil tube steel in a carbon dioxide corrosion system, Corrosion, 61(6), 594 601 (2005).
4. M. Ueda and A. Ikeda, Effect of microstructure and Cr content
in steel on CO2 corrosion, in: Corrosion, Sumitomo Metal Ind.
Ltd., Paper No. 96013 (1996).

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