DOI 10.

1007/s11003-017-0032-8

Materials Science, Vol. 52, No. 6, May, 2017 (Ukrainian Original Vol. 52, No. 6, November–December, 2016)

CORROSION DEGRADATION OF STEEL OF AN ELBOW OF GAS PIPELINE

WITH LARGE-SCALE DELAMINATION AFTER LONG-TERM OPERATION

O. I. Zvirko,1, 2 A. B. Mytsyk,3 O. T. Tsyrulnyk,1

G. Gabetta,4 and H. M. Nykyforchyn1 UDC 622.691.4: 620.19

The electrochemical corrosion behavior of the low-carbon steel of an elbow of gas pipeline after long
term operation with extensive hydrogen-induced delamination was investigated in 0.3% (wt.) NaCl and
8.55 mM NaHCO 3 aqueous solutions. The degradation of the corrosion resistance of steel from the
pipe elbow in both investigated corrosive environments was revealed. The pipe steel of the elbow (both
from the compressed and tensioned sections) was characterized by lower corrosion resistance than the
metal of the straight section of the pipe. It was shown that the degradation of corrosion resistance of
the pipe-elbow steel correlated with the degradation of its mechanical properties. It was established that
the characteristics of corrosion resistance of the degraded material (corrosion current density and polari-
zation resistance) could be informative about changes in its state caused by long-term operation and
could be used for the diagnostics of the degradation of mechanical properties of hydrogen-affected
steels.

Keywords: pipeline steel, pipe elbow, degradation, macrodefect, electrochemical characteristics.

At present, the delaminations in pipeline steels caused by both the process of manufacturing and operational
factors constitute a well-known problem. They are formed by relatively weaker texture planes aligned parallel
to the direction of rolling. Their formation is influenced by the presence of carbide particles and inclusions,
seams, alignment of inclusions in the rolling plane, intergranular fracture, texture, banding, segregation bands,
and anisotropic plastic deformation [1, 2]. In oil and gas pipelines, absorbed hydrogen generated by internal or
external corrosion can penetrate into steels [3, 4]. The accumulation of hydrogen at imperfections, due to the
recombination of atomic hydrogen into the molecular state, generates tremendous pressure and leads to the for-
mation of macrodefects, e.g. delaminations, hydrogen-induced cracks, or blisters [5, 6]. These macrodefects
may eventually cause the failures of pipelines [7].
There is a wide range of available sources of hydrogen in both manufacturing and working environments.
The specific long-term service of oil and gas pipelines promotes the hydrogenation of pipeline steel as a result of
the evolution of hydrogen on the metal surface in the corrosion processes running under the external and/or in-
ternal environmental conditions [4, 8, 9]. Hence, the risk of hydrogen-induced macrodelamination in corrosive
environments with high hydrogenating ability, especially in the presence of hydrogen sulfide, is very high.
It should also be noted that no external stresses are usually required to cause this damage. The macrodefects of
this kind in oil and gas pipelines are often revealed as pipe-wall thinning by using ultrasonic testing [10].

1
Karpenko Physicomechanical Institute, Ukrainian National Academy of Sciences, Lviv, Ukraine.
2
Corresponding author; e-mail: zvi@ipm.lviv.ua; olha.zvirko@gmail.com.
3
“Main Gas Pipelines Administration “Lvivtransgaz,” PJSC UKRTRANSGAZ, Ukraine.
4
ENI S.p.A., Rome, Italy.

Published in Fizyko-Khimichna Mekhanika Materialiv, Vol. 52, No. 6, pp. 104–108, November–December, 2016. Original article sub-
mitted June 21, 2016.

1068-820X/17/5206–0861 © 2017 Springer Science+Business Media New York 861

862 O. I. ZVIRKO, A. B. MYTSYK, O. T. TSYRULNYK, G. GABETTA, AND H. M. NYKYFORCHYN

Recently, an extensive delamination in the body of pipe elbow revealed in the lateral pipeline of the gas-
transmission pipelines system after long-term operation was investigated and the degradation of the metal close to
the macrodefect was revealed [11]. A strong decrease in plasticity of the pipe-elbow steel was observed. The
electrochemical approach to the diagnostics of degradation of the mechanical properties of structural materials
by nondestructive methods has been recently proposed [12–14] on the basis of the correlation between the
changes in the electrochemical and mechanical properties of the material caused by its long-term service. Thus,
the focus of the present study is to investigate the electrochemical-corrosion behavior of steel of an elbow of gas
pipeline containing a macrodefect after long-term operation in order to obtain information on the changes in its
state.

Objects, Materials, and Methods

The object of the present study was a pipe elbow made of low-carbon 0.20 C pipeline steel. The pipe elbow
was a part of above-ground lateral pipeline of the gas-transmission pipelines system located behind the compres-
sor station and operated for 40 yr. It was removed from the lateral pipeline after nondestructive testing by an
ultrasound thickness meter that revealed a macrodefect in the body of the pipe [11]. The dimensions of the pipe
elbow were as follows: outer diameter D = 219 mm and the thickness of the wall t = 18 mm. The 90° elbow
was made by cold bending without any further heat treatment. The maximum working pressure was 5.5 MPa and
the working temperature of the pipe-elbow steel was up to 80°С.
The specimens (working electrodes) from three different sections of the pipe elbow were studied, including
the tensioned and compressed sections of the pipe elbow and a straight section of the pipe. The working elec-
trodes were made in the form of bars 1.5 × 1 cm with a length of 2.5 cm. All their surfaces were polished.
Prior to testing, all surfaces of the working electrodes were coated with a special waterproof dielectric isolation,
except a small area ∼ 0.35 cm 2 used for electrochemical studies. The electrochemical behavior of the speci-
mens was analyzed on the basis of the results of electrochemical tests performed by the potentiodynamic method
with the help of an IPC-Pro potentiostat controlled by a computer. The electrolytes were 0.3% (wt.) NaCl and
8.55 mM NaHCO 3 aqueous solutions used without any pretreatment. All electrochemical tests were carried out
by using a standard temperature-controlled electrochemical cell with a typical three-electrode system consisting
of the working electrode, Ag/AgCl (saturated KCl) reference electrode, and Pt auxiliary electrode. The tests
were conducted at room temperature. The potentiodynamic polarization curves were recorded by sweeping the
potential with a sweep rate of 1.0 mV⋅ sec –1. The basic electrochemical characteristics of steels (corrosion poten-
tial Ecorr , corrosion current density icorr , and Tafel constants of the anodic and cathodic reactions ba and bc )
were determined by the graph-analytic method. The polarization resistance R p was found by using the Stern–
Geary equation:

ΔE K
= Rp = ,
Δi icorr

where the constant

ba bc
K = .
2.3(ba + bc )

The characteristics of the tensioned and compressed sections of the pipe elbow were compared with each
other and with the properties of the material of the straight pipe.
CORROSION DEGRADATION OF STEEL OF AN ELBOW OF GAS PIPELINE WITH LARGE-SCALE DELAMINATION 863

Fig. 1 Potentiodynamic polarization curves of low-carbon 0.20 C steel from different sections of the pipe elbow in 0.3% (wt.) NaCl (a)
and 8.55 mM NaHCO 3 (b) aqueous solutions: (1) straight section of the pipe; (2) compressed section of the pipe elbow; (3) ten-
sioned sections of the pipe elbow.

Table 1. Electrochemical Characteristics of Low-Carbon 0.20 C Steel from Different Sections

of the Pipe Elbow in Different Corrosive Environments

Section of the pipe elbow Ecorr , V icorr , µA/cm 2 R p , kΩ ⋅ cm 2

0.3% (wt.) NaCl solution

Straight – 0.658 3.37 4.14

Compressed – 0.663 3.81 3.66

Tensioned – 0.667 3.96 3.53

8.55 mM NaHCO 3 solution

Straight – 0.686 2.84 5.56

Compressed – 0.690 3.36 4.70

Tensioned – 0.695 3.48 4.54

Results of the Tests and Discussion

The polarization curves obtained for the low-carbon steel from the straight section of the pipe elbow and
from its tensioned and compressed sections in 0.3% (wt.) NaCl and 8.55 mM NaHCO 3 aqueous solutions are
shown in Fig. 1. The values of corrosion potential ( Ecorr ) and corrosion current density ( icorr ) computed by
using the Tafel extrapolation method are presented in Table 1.
There are no passive regions observed in the potentiodynamic polarization curves (see Fig. 1) for any of the
investigated materials in any of the studied media. Thus, we observe only the process of active dissolution. For
864 O. I. ZVIRKO, A. B. MYTSYK, O. T. TSYRULNYK, G. GABETTA, AND H. M. NYKYFORCHYN

the studied potentials, the cathodic and anodic polarization curves recorded for the metal of straight pipe and for
the deformed steel of the pipe elbow (from the compressed and tensioned sections) were almost identical, with
events of slight increase in the current density for the deformed steel. The diffusion of depolarizer (oxygen) was
the limiting stage of the corrosion process, as indicated by the region of limiting diffusion current in the cathodic
polarization curves shown in Fig. 1.
For all studied materials, the values of the Tafel constant of anodic reactions bа were close to 0.046 and
0.057 V in 0.3% (wt.) NaCl and 8.55 mM NaHCO 3 solutions, respectively.
Analyzing the results obtained by electrochemical testing of the pipe-elbow steel taken from different sec-
tions (see Table 1), it is possible to conclude that the steel taken from the tensioned section is characterized by
slightly lower corrosion resistance than the steel of the compressed section. Thus, the corrosion current densities
of the materials taken from different sections of the pipe elbow, which were loaded in compression or in tension
during their long-term service, are slightly different.
The lower corrosion resistance of the pipe-elbow steel (both from the compressed and tensioned sections) as
compared with the metal of the straight section of the pipe was revealed in both investigated corrosive environ-
ments. Thus, the highest values of polarization resistance were obtained for the steel from the straight pipe:
4.14 and 5.56 kΩ ⋅ cm 2 in 0.3% (wt.) NaCl and 8.55 mM NaHCO 3 solutions, respectively (Table 1). The steel
of the straight pipe was characterized by the most positive value of corrosion potential Ecorr . At the same time,
the pipeline steel from the tensioned section of the elbow was characterized by the most negative value of corro-
sion potential among the studied steels in the analyzed corrosive environments. The obtained results revealed
the degradation of corrosion resistance of the pipe-elbow steel.
The comparison of the results obtained by electrochemical and mechanical (see [11]) testing of steels from
the three studied sections of the pipe elbow (compressed, tensioned, and straight sections of the pipe elbow)
showed good correlation between its electrochemical (corrosion current density and polarization resistance) and
mechanical (reduction in area) properties. Thus, the intense degradation of steel from the pipe elbow containing
a macrodefect was revealed by mechanical testing [11]. At the same time, the degradation of the pipe-elbow
steel was higher than for the steel taken from the straight pipe both for the tensioned and compressed sections.
However, the steel from the tensioned section of the pipe elbow was characterized by the most intense damage.
Nevertheless, the steel from the tensioned section of pipe elbow was characterized by the lowest plasticity (re-
duction in area ψ R = 30.0) and the steel of the straight section of the pipe was characterized by the highest
plasticity ( ψ R = 38.7).
With regard for the obtained results, it was established that the degradation of pipe-elbow steel caused by its
long-term service resulted in the weakening of cohesion of the elongated nonmetallic inclusions to the matrix
facilitated by the influence of hydrogen. Moreover, the high temperature (up to 80°С) of the steel of pipe elbow
caused by its location behind the compressor station intensified the diffusion of hydrogen through steel and,
in turn, contributed to the degradation of the metal. It can be assumed that the in-service degradation of pipe-
elbow steel is accompanied by the intense internal damage caused by the mutual action of working stresses and
hydrogen. Therefore, it is possible to conclude that the electrochemical properties of pipe-elbow steel, such as
the corrosion current density icorr and polarization resistance R p sensitive to changes in the state of degraded
steel and correlated with its mechanical properties could be informative about changes caused by the long-term
operation.

CONCLUSIONS

The results presented in the present work describe the electrochemical corrosion behavior of 0.20 C low-
carbon steel cut out form three different sections (compressed, tensioned, and straight) of a pipe elbow of the
CORROSION DEGRADATION OF STEEL OF AN ELBOW OF GAS PIPELINE WITH LARGE-SCALE DELAMINATION 865

above-ground lateral pipeline of the gas-transmission pipelines system in 0.3% (wt.) NaCl and 8.55 mM
NaHCO 3 aqueous solutions and reveal the degradation of the corrosion resistance of the pipe-elbow steel:

— the corrosion resistance of steel from the tensioned section was slightly lower than the corrosion re-
sistance of steel from the compressed section;

— the corrosion resistance of pipe-elbow steel (both from the compressed and tensioned sections) was
lower than for the metal from straight section of the pipe.

The degradation of the corrosion resistance of pipe-elbow steel is correlated with the degradation of its me-
chanical properties. Thus, the characteristics of corrosion resistance of the degraded material, such as corrosion
current density and polarization resistance could be informative about the changes in its state caused by the
long-term operation.

Acknowledgement. The research was partially financially supported by the Ministry of Education and Sci-
ence of Ukraine under the Project M/227-2015.

REFERENCES

1. M. S. Joo, D.-W. Suh, J. H. Bae, and H. K. D. H. Bhadeshia, “Role of delamination and crystallography on anisotropy of Charpy
toughness in API-X80 steel,” Mater. Sci. Eng. A, 546, 314–322 (2012).
2. M. A. Mohtadi-Bonab, J. A. Szpunar, and S. S. Razavi-Tousi, “A comparative study of hydrogen-induced cracking behavior in API
5L X60 and X70 pipeline steels,” Eng. Failure Anal., 33, 163–175 (2013).
3. R. A. Carneiro, R. C. Ratnapuli, and V. F. C. Lins, “The influence of chemical composition and microstructure of API linepipe
steels on hydrogen-induced cracking and sulfide stress-corrosion cracking,” Mater. Sci. Eng. A, 357, 104–110 (2003).
4. O. T. Tsyrulnyk, Z. V. Slobodyan, O. I. Zvirko, M. I. Hredil, H. N. Nykyforchyn, and D. Gabetta, “Influence of operation of Kh52
steel on corrosion processes in a model solution of gas condensate,” Mater. Sci., 44, No. 5, 619–629 (2008).
5. C. Zapffe and C. Sims, “Hydrogen embrittlement, internal stress, and defects in steel,” TMS-AIME, 145, 225–232 (1941).
6. G. Herbsleb, R. K. Poepperling, and W. Schwenk, “Occurrence and prevention of hydrogen-induced stepwise cracking and stress
corrosion cracking of low-alloy pipeline steels,” Corrosion, 36, No. 5, 247–256 (1981).
7. V. N. Polyakov, “Catastrophes of large diameter pipelines: the role of hydrogen fields,” in: Hydrogen Effects in Materials, Moran,
Wyoming, USA (1996), pp. 991–1000.
8. O. T. Tsyrul’nyk, H. M. Nykyforchyn, D. Yu. Petryna, M. I. Hredil, and I. M. Dzioba, “Hydrogen degradation of steels in gas mains
after long periods of operation,” Mater. Sci., 43, No. 5, 708–717 (2007).
9. H. M. Nykyforchyn and O. T. Tsyrul’nyk, “Specific features of the in-service bulk degradation of structural steels under the action
of corrosive media,” Strength Mater., 41, No. 6, 651–663 (2009).
10. R. Mostert and W. Sharp, “Low temperature hydrogen damage assessment in the gas and refining industries,” in: Proc. of the Mid-
dle East Nondestruct. Test. Conf. & Exhib, Manama, Bahrain (2005).
11. L. Ye. Kharchenko, O. Ye. Kunta, O. I. Zvirko, R. S. Savula, and Z. A. Duryahina, “Diagnostics of hydrogen macrodelamination in
the wall of a bent pipe in the system of gas mains,” Mater. Sci., 51, No. 4, 530–537 (2016).
12. H. M. Nykyforchyn and O. T. Tsyrul’nyk, “In-service degradation diagnostics of low-alloyed steels and aluminum alloys properties
by electrochemical methods,” Ultrasound, 64, No. 1, 46–49 (2009).
13. H. Nykyforchyn, O. Tsyrulnyk, M. Hredil, and O. Zvirko, “Correlation between degradation of corrosion and mechanical properties
of long-term operated oil and gas pipeline steels,” in: Zeszyty Naukowe, Mechanika. Politechnika Opolska, Z. 99 (2011), S. 41–43.
14. E. V. Kharchenko, L. K. Polishchuk, and O. I. Zvirko, “Estimation of the in-service degradation of steel shapes for the boom of
a clamp-forming machine,” Mater. Sci., 49, No. 4, 501–507 (2014).