716 DOI: 10.1002/maco.200805158 Materials and Corrosion 2009, 60, No.

Effect of the long-term service of the gas pipeline on the

properties of the ferrite–pearlite steel
H. Nykyforchyn, E. Lunarska, O. Tsyrulnyk, K. Nikiforov* and
G. Gabetta

The thorough mechanical, corrosion-mechanical, hydrogen permeation studies

of X52 steel in as-received condition and after 30 years of service in gas pipeline
have shown the degradation of the bulk metal properties due to the
exploitation. The structure degradation of exploited steels decreased the
resistance to crack propagation, to stress corrosion cracking (SCC), HE and HIBC.
The exploited steel exhibited specific anomalies of mechanical behaviour: (1)
decrease in resistance to brittle fracture with simultaneous decrease in
hardness; and (2) the opposite change of the plasticity parameters: decrease in
the RA accompanied by the increase in elongation. Deformation ageing and
formation of micro defects, assisted by entering and accumulated hydrogen
evolved in corrosion processes which takes place in brine deposited inside the
pipes, have been proposed to be responsible for the metal degradation and
specific modification of the properties during the long-term service of pipes.
The extent of the steel degradation not being able to be detected by the
standardized mechanical properties and routine microstructure observation
can be efficiently determined by the specially modified methods and conditions.
The information may be used in assessment of the conditions and of the life-time
of operated and newly constructed gas pipelines.

1 Introduction comparison with the as-received material [1–4] suggesting the

In the course of exploitation, the material of the pipelines has
been subjected to (1) the long-term ageing promoted by the low
cyclic stresses arising from the flowing media and from the
external factors and (2) the chemical effects of transported media,
environment and cathodic protection. Over the long time of
exploitation, effects of all those factors have been accumulated
and may cause steel deterioration.
Some recent material expertises of the transit oil trunk
pipelines and storage tanks exploited for a long time have shown a
substantial decrease in the in-bulk corrosion resistance, brittle
fracture resistance and corrosion-mechanical resistance in
H. Nykyforchyn, O. Tsyrulnyk
Karpenko Physico-mechnanical Institute of NANU, Lviv (Ukraine)
E. Lunarska, K. Nikiforov
Institute of Physical Chemistry of the Polish Academy of Sciences,
Warsaw (Poland)
E-mail: kkk@ichf.edu.pl
G. Gabetta
ENI - E&P-Unita TEMM, Milano (Italy)
degradation of the bulk material during the service. Corrosion
(internal or external) cannot itself cause the degradation of the in-
bulk material, whereas the entering hydrogen might be an
important factor producing metal deterioration, especially as
combined with stresses. In the case of oil and hydrocarbons, the
evolution of hydrogen due to their decomposition [5] and due to
corrosion processes having taken place in deposited solutions [3]
have been stated. In the case of the pipelines transporting wet gas,
the solution of a high aggressiveness (brine) has been condensed
on the pipe bottom [6]. The gas flow has usually splashed the
brine and thus, the other parts of the pipe inner surface have also
been affected [7]. Therefore, similar processes of metal
degradation during the long-term exploitation should take place
in the crude oil and the gas pipelines.
The state of the degradation of the pipe material cannot be
usually established by routine examination, as tensile tests and
metallography. Therefore, the application of other methods
should be considered. The fracture mechanics [1, 4], acoustic
emission [8], hydrogen permeation [9, 10] and internal friction
[11] measurements have been successfully applied to evaluate the
state of the metal deterioration. Fracture mechanics gives the
information on the susceptibility to cracking, easiness, and mode
of the crack propagation. Measurements of the hydrogen

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Materials and Corrosion 2009, 60, No. 9 Effect of the long-term service of the gas pipeline 717

Figure 1. Scheme of specimens cutting; a – the pipe cross-section and places of investigated materials; b – the scheme of the cutting of membranes
for hydrogen permeation and internal friction tests and of coupons for hydrogen extraction; c – the scheme of the cutting of samples for
mechanical and corrosion-mechanical tests

permeation provide the information concerning the intrinsic
hydrogen diffusivity and the efficiency of the hydrogen trapping
[12, 13]. From the data obtained for ferrite–pearlite steels,
modification of the ferrite lattice, and the development of the
structure defects serving as hydrogen traps in the course of
exploitation have been established [9, 10]. Internal friction
measurements allow estimation of the development of the certain
defects and the specific modification of the microstructure [14].
The aim of the present work was thorough examination of
the material of the gas pipeline that has been in service for about
30 years, in order to: (1) establish the steel deterioration
accumulated during its exploitation in the gas pipeline and
(2) select the methods enabling characterizing of the level of
degradation caused by the long-term exploitation.
2 Materials and experimental procedure
the possible effects of the condensate splashing [7], and the effect
of outer corrosive environment and applied cathodic protection,
the specimens were cut from up and down parts of the exploited
parts and from the inside and outside parts of the pipe walls
(Fig. 1a). The carried out tests, test conditions and parameters
evaluated from those tests are shown in Table 1. After thorough
removal of the corrosion products, deposits and unevenness of
the surface metal, the specimens were cut as schematically shown
in Figs. 1b and 1c for hydrogen and for mechanical tests,
respectively. Tensile specimens were oriented normal to the pipe
axis. In the Charpy test, the different specimens and notches
orientation were checked. The initial cracks in fracture toughness
specimens were directed along the pipe axis.
In corrosion tests, the solution containing (mg/l) 14 440 Naþ;
25 400 Cl
; 129 Kþ; 5.0 SO2
þ
4 ; 2.5 Li ; 600 Ca
2þ
; 522 HCO
3;


518 Mg ; 140 Ba ; 5.0 NO3 ; 389 Sr ; 3.6 F ; 0.25 Fe2þ;
2þ 2þ
2þ

100 Br
; 0.5 Mn2þ; 21 I
; 1.0 Al3þ; 5.0 PO3
þ

4 ; 52 NH4 ; 18 SiO2
2

The state of the ferrite–pearlite X52 steel of pipes, 275 mm in
diameter with a wall thickness of 10 and 12 mm (code X52-10 and
X52-12, respectively) being in service in the onshore section of a
gas trunk line for 30 years has been compared with a pipe (408
mm in diameter, wall thickness 12 mm) made about 20 years ago,
not being in use (code ‘‘as-receivedþ X-52). Taking into account
the effect of the condensate (brine) deposited on the pipe bottom,
(alkalinity – 455), simulating the aqueous condensate (brine) in
the gas pipes [6] was used.
The amount of hydrogen in coupons (Fig. 2) was measured by
vacuum extraction done at the step-by-step 500 ! 700 ! 900 K
increasing temperature (VHn ) or at constant temperature 900 K,
(VH), cf. Table 1. The amount of hydrogen measured in as received
steel was subtracted from the data obtained for exploited ones.

Table 1. Carried out tests, test conditions and characteristic parameters

Applied tests Specimens (Fig. 1) Temperature Environment & Test Characteristic

conditions conditions parameters

Tensile cylindrical, 4 mm diameter, RT air "´ ¼ 10
6 s
1 sY, sUTS, ef, RA, strain
25 mm gauge length (Fig. 1c) hardening rate n (s ¼ ken)
Stress corrosion tensile as above RT brine Eocp as above as above
ic ¼ 0.1mA/cm2
Fracture toughness [15] compact pre-cracked, RT air load time – crack growth resistance,
10 mm thick (Fig. 1c) displacement J crack growth rate
rate 10mm/hr (a ¼ dl/dt)
Stress corrosion as above RT brine Eocp, as above as above
cracking [16] ic ¼ 0.1 mA/cm2
Charpy test [17] 10  10 mm V-notch differently RT air impact test impact strength, KCV
oriented (Fig. 1c)
Hydrogen extraction coupons (Fig. 1b) 500 ! 700 ! 900 K vacuum vacuum extraction extraction curve, hydrogen
measurements content, Vn,V
40
Hydrogen permeation [18] membranes (Fig. 1b) RT 0.5 M H2SO4 Figure 2 Dtb, D5 , I1 , iC  (Fig. 2)
Internal friction [19] membranes (Fig. 1) 200 ! 1200K vacuum frequency 80 KHz elastic modulus, Q
1
amplitude 10
5

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718 Nykyforchyn, Lunarska, Tsyrulnyk, Nikiforov and Gabetta Materials and Corrosion 2009, 60, No. 9

Figure 2. (a) Scheme of the hydrogen permeation through the membrane of studied metal and (b) the typical curve of the hydrogen permeation
current recorded at egress side under the increased cathodic polarisation applied at the ingress side

The hydrogen permeation tests [18] were done for subjected to the highest cathodic polarization were observed by
membranes (0.1 cm thick, cf. Fig. 2). After the anodic removal SEM.
of hydrogen from the membrane and attaining the permeation Three to five tests were done for specimens cut from various
current background about 2 mA/cm2, the step-by-step increased parts of the pipes and the mean values of obtained results were
cathodic current density (from 1 to 40 mA/cm2) was applied to the taken into account.
membrane (Fig. 2) at ingress cell, filled with the 0.5 M H2SO4
solution selected as the test electrolyte. In the egress cell filled
with 0.1 M NaOH, the response hydrogen permeation current
3 Obtained results
was recorded. From the obtained build-up (at 5 mA/cm2) and
3.1 Characterization of the structure
decay permeation transients (Fig. 4b) the hydrogen diffusion
coefficients D5 ¼ 0.01/6xt0.63 (where t0.63 – time to attain the
All the studied steels had the ferrite–pearlite structure. The
value of 0.63 of the steady state permeation current J51 ) and
structure details are shown in Table 2. By optical microscopy no
Dtb ¼ 0.05/ttb, (where ttb ¼ break through time), respectively
differences were observed between the structure of material close
were calculated. The critical cathodic current corresponding to
to the wall surfaces and in the bulk, for as-received as well as for
the formation of permeation maximum (iC ) and the steady state
exploited steels.
hydrogen permeation current measured at application of
The comparison of the X-ray spectra taken from as-received
polarisation 40 mA/cm2 (J40 1
) as indicated in Fig. 2, were also
X52 and exploited X52-10 and X52-12 materials showed the
determined.
bigger lattice parameter and the larger size of the coherently
The internal friction [14] was measured using the mechan-
scattered areas of ferrite in exploited material in comparison with
ical spectrometer RAK-3 [19]. The membrane (3  1  0.1 cm3)
the as-received one. The difference of the ferrite texture in both
cut along the pipe axis (Fig. 1b) was mounted as a beam between
kinds of studied materials was also detected.
two electrodes and oscillations were excited in the bending mode
by application of sinusoidal voltage of acoustic frequency. The
measurements were done at the strain amplitude e ¼ 1  10
4 at 3.2 Mechanical properties
heating from 180 to 1000 K with a heating rate 3 K/min. The
values of the internal friction (Q-1) and of the dynamic Young Mechanical properties of the X52 steel, according to the API
modulus (E) were calculated [14, 19]. standard and according to the Polish Standard and the properties
The hardness measurements and metallographic observa- of the studied steels are shown in Table 3. It is seen that the
tion (at magnification up to 1000 X) were done on the planes mechanical properties of as- received X52 steel corresponded to
differently oriented to the pipe axis, close to the wall surfaces and the standards. For as-received steel no differences of the
in the bulk. The X-ray diffraction spectra were recorded on properties of material close to the in and out parts of the pipe
Siemens D5000 diffractometer at Cu ka radiation. The fracture wall was stated. However, such differences occurred in the case of
surface of specimens and the ingress side of the membranes pipes being in service. In exploited pipes, the tensile stress–strain

Table 2. Microstructure details of studied steels

Steel Structure Pearlite volume fraction, % Pearlite grain size mm Ferrite grain size mm Interband distance mm

X52 uniform 15 10 15
X52-12 visible bands 20 20 15 25
X52-10 bands 20 20 15 25

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Materials and Corrosion 2009, 60, No. 9 Effect of the long-term service of the gas pipeline 719

Table 3. Mechanical properties of steel X52 according to API and Polish standards, some recent literature data and the properties of studied steels

Material Place sy, MPa sUTS, MPa n RA, % e, % HRB J kN/m a mm/hr

API 5L X52 min. 358 min. 455 min. 22

Polish Standard 355 450–690 min. 22
X52 [20] 521 565
X52[21] 486 610 22.5
X52 [22] 343 453 87
X52 355 475 0.59 72,9 22.7 90 86 0.004
X52-12 down 268 451 0.74 64.4 20.8 75 50 0.016
up 255 460 62.5 22.9 77
X52-10 down 362 536 0.82 54.6 29.7 81 37 0.032
up 335 538 55.0 28.8 84

curves exhibited an apparent yield plateau not observed for as-

Figure 3. Stress–strain curve recorded in air for as received X52 and for
X52-10 steels
received steel, cf. Fig. 3. The exploited materials also revealed
larger strain-hardening coefficient n, lower reduction of area
(RA), similar or higher elongation to fracture (e f ), lower hardness
(HRB), substantially lower fracture toughness (J) and even order
of magnitude higher crack propagation rate (a) in comparison
with those parameters evaluated for as-received steel (Table 3).
Exploitation dramatically decreased the impact strength (KCV)
(Table 4), the effect being dependent on the specimen orientation:
transverse specimens cut from the exploited pipe exhibited the
impact strength even four times lower than the initial ones. In
longitudinal specimens, the notch orientation did not signifi-
cantly affect the impact strength of as-received material, whereas
in the case of exploited ones, this parameter of specimens with
notch cut from the inside surface (1) was lower than that for
specimens with the notch cut from outside (2). In the case of
transverse specimens for both, exploited and as-received steels,
the impact strength decreased in the range 1 ! 2 ! 3 of the
notch orientation.

Figure 4. Fracture surface of as received X52 steel (a, c) and exploited X52-10 steel (b, d) after fracture toughness (a, b) and Charpy (c, d) tests

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720 Nykyforchyn, Lunarska, Tsyrulnyk, Nikiforov and Gabetta Materials and Corrosion 2009, 60, No. 9

Table 4. Results of the KCV (Charpy) tests, J/cm2

Material Transverse specimens Longitudinal

specimens

Notch orientation, according to Fig. 2

1 2 3 1 2

X52 196 177 169 350 342

X52-12, down 77 73 72 189 198
X52-12, up 72 55 64 182 198
X52-10, down 60 65 43 173 195
X52-10, up 57 52 48 <145a <177a
a
Specimens with visible stratification along the pipe axis not broken
suggesting the lower KCV level.

Figure 5. Example of the normalised hydrogen extraction curves

It should be noted that all the above changes in the properties
observed in exploited materials were especially significant for the
X52-10 steel and for the down parts (Tables 3 and 4).
Figure 4 presents the appearance of the fracture surface of
the X52 and X52-10 specimens, after fracture toughness (a, b) and
Charpy (c, d) tests done in air. In both tests, as-received steel
exhibited the shear tearing fracture mode, with the flat areas, up
to 100–150 mm big (Figs. 4a and 4c). In exploited steel, the long
crevices with the visible deep cracks and the ductile fracture areas
between them can be seen (Figs. 4b and 4d).
3.3 Stress corrosion cracking (SCC) and hydrogen
embrittlement (HE)
Stress corrosion cracking (SCC) and hydrogen embrittlement
(HE) data are shown in Table 5. As follows from the comparison
of those data with the data in Table 3, immersion in the brine
produced the negligible effects on the tensile strength of studied
materials. Presence of brine did not affect the parameters
characterising the metal plasticity (RA and ef ) of as-received
material, but substantially decreased those parameters in the case
of exploited materials. Detrimental effect of aggressive solution
was observed for pre-cracked specimens. Application of the low
cathodic polarization additionally decreased the RA and e and J
values and drastically increased the crack growth rate.
3.4 Hydrogen extraction rate
Hydrogen extraction rate as recorded at 900 K was lower in
exploited than in as-received pipes (Fig. 5). Table 6 shows the
amount of hydrogen contents extracted at consequently increased
recorded for as received and exploited steels
temperature (VHn ) and the total hydrogen content (VH). Exploited
steels contained the higher total hydrogen amount than as-
received one. It should be emphasized that in exploited materials
the portion of hydrogen extracted at the higher temperature was
higher than that in the as-received steel.
3.5 Hydrogen permeation
Hydrogen permeation data are collected in Table 7. The highest
critical values of ic , the highest permeability measured at
40
polarisation 40 mA/cm2 (J1 ) and the highest values of hydrogen
diffusivity were observed for the as-received steel.
The ingress surface of the membrane subjected to cathodic
polarisation, higher than ic , exhibited the hydrogen induced
blisters (Fig. 6a) and the chipping-off of the material (Fig. 6b). The
fracture surface of blisters and chips formed in as-received and
exploited steels had the intergranular appearance (Figs. 6c
and 6d). However, in the case of exploited steel, the interphase
cracking and the secondary cracks going deep into the metal bulk
were seen (Fig. 6d).
3.6 Internal friction
Internal friction of studied steels revealed a peak (Fig. 7). Since
the occurrence of that peak was associated with the change in
the slope of the modulus vs. temperature relationship, it could be
recognised as the relaxation peak [14]. In exploited materials, the
peaks occurred at slightly higher temperature and they were
substantially higher than in as-received material.

Table 5. Results of the SCC and HE tests

Material Conditions sY MPa sUTS MPa RA % ef % J N/mm a mm/hr

X52 EOCP 370 500 70 21.7 49 0.007

X52 iC 370 487 31 11.7 38 0.011
X52-12 down EOCP 267 450 55.8 16.7 37 0.05
X52-12 down iC 290 460 21.6 8.9 24 0.13
X52-12 up iC 245 480 40.6 20.0
X52-10 down iC 350 530 27.2 22.6
X52-10 up EOCP 340 535 41.1 24.8 31 0.07
X52-10 up iC 335 530 35.9 20.0 11 1.1

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Materials and Corrosion 2009, 60, No. 9 Effect of the long-term service of the gas pipeline 721

Table 6. Amount of hydrogen desorbed gradually at increased Table 7. Results of hydrogen permeation data: critical cathodic current
temperature (VHn , ppm) and total amount of extracted hydrogen (VH, density corresponding to formation of permeation maximum (iC )
2
ppm] steady state hydrogen permeation (J40 1 ) at ic ¼ 40 mA/cm ; hydrogen
intrinsic diffusivity Dtb calculated from decay transients, hydrogen
Steel code and pipe part 500 K 700 K 900 KC total apparent diffusivity D5 calculated from build-up transient at iC ¼ 5 mA/
cm2
X-52 1.4 0.07 0.04 1.51
X52-12 down-in 0.01 1.00 0.41 1.42 Pipe iC , 40
Dtb D5
(J1 ),
X52-12 up-out 0.10 0.51 0.60 1.21
mA/cm2 mA/cm2 cm2/s cm2/s
X52-10 down-in 0.15 0.80 4.15 5.10
X52-10 up-out 0.30 0.60 0.81 1.71
X52 40 160 3.2  10S5 1.2  10S5
X52-12 down-in 7 53 1.14  10S5 7,3  10S6
X52-12 down-out 15 80 1.2  10S5 8.6  10S6
X52-12 up-in 40 160 2  10S5 1.3  10S5
4 Discussion X52-12 up-out 35 200 1.2  10S5 8.3  10S6
X52-10 down-in 6 24 8.6  10S6 7  10S7
The applied experimental programme has been designed in order X52-10 down-out 12 36 7.9  10S6 1  10S6
to obtain the information concerning: X52-10 up-in 20 56 1.6  10S5 8.4  10S6
X52-10 up-out 20 60 7.7  10S6 4.8  10S6
1. properties of studied materials (routine tensile tests, measure-
ments of hardness and total content of hydrogen, metallo- It should be noted that owing to the lack of the records of
graphy). exploitation conditions of the pipes, the high scattering of the
2. resistance to brittle fracture (fracture mechanics and Charpy results could have been expected. However, quite consistent
tests), to stress corrosion cracking (tensile and fracture trends were observed in the case of all the tests.
mechanics tests in brine at open circuit potential), to hydrogen As follows from the data in Table 3, the standardised tensile
embrittlement (tensile and fracture mechanics tests in brine at mechanical properties (sy, sUTS, ef ) of as-received steel and of the
low cathodic polarization) and resistance to hydrogen induced exploited steels were within the limits of API and Polish
blistering cracking (hydrogen permeation tests). standards and are consistent with the values given for other
3. state of material structure and its change due to the service investigated X52 steels. Therefore, evaluation of those parameters
(selected mechanical tests, evaluation of hydrogen transport, does not allow estimating the degradation of steel in the course of
hydrogen distribution, internal friction measurements, X-ray service. However, the non-standardised data showed that the
diffraction, fractography). properties of the exploited materials substantially differed from

Figure 6. Appearance of the ingress side of the membranes subjected to the cathodic polarisation above the appropriate values of iC ; a – X52;
b – X52-10 down-in; c – X52; d – X52-10 down-in

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722 Nykyforchyn, Lunarska, Tsyrulnyk, Nikiforov and Gabetta
Figure 7. The internal friction recorded for as received X52 (*) and for
X52-10 down (*) materials
those of as-received one: the latter had the lower RA, hardness
(Table 3) and impact strength (Table 4), but the higher strain
hardening rate, sUTS and the elongation to fracture (Table 3). The
above differences in the properties of the as-received and the
exploited steels could be explained by the difference in the
microstructure (Table 2), since the acicular ferrite steel showed
higher resistance to brittle fracture than the banded ferrite–
pearlite one [22]. On the other hand, the difference in the
susceptibility to hydrogen degradation has been stated in [23] for
differently heat treated X52 steels despite their similar phase
morphology. In the studied case, all the steels had the acicular
pearlite-ferrite structure of the quite similar pearlite volume
fraction and the grain size (Table 2). Moreover, the microstructure
effects could have not explained the observed differences between
the properties of steels X52-12 and X52-10, both having the
banded structure. The negligible effect of the microstructure may
be additionally confirmed by the results of Charpy tests (Table 4).
In the case of as-received and exploited steels, the orientation of
the specimens (transverse or longitudinal) and the direction of
the notches in the transverse specimens similarly affected the
obtained data. Therefore, it seems to be logical to account for
the stated differences in properties between the as-received and
the exploited steels by the modification of the metal structure as a
result of simultaneous influence of the stresses and the
environment in the course of the long-term service.
In [8, 24], the deformation ageing of the long-term exploited
steels has been stated to decrease the RA, impact strength and
fracture toughness. The appearance of the apparent yield plateau
in the studied exploited steels (Fig. 5) confirmed some
deformation ageing during the long-term service, which
strengthened the metal and resulted in the increase in the
strain-hardening rate n and in decrease in RA. However, the
following results were not consistent with the effects of
deformation ageing (Table 3):
1. substantial decrease in hardness of exploited steels was
accompanied by the increase in strength and in the strain
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Materials and Corrosion 2009, 60, No. 9
Figure 8. Relationship between the elongation to fracture and RA
evaluated in tensile tests for studied steels; & – X52~, ~ – 52-12; *, *
– X52-10; ~, * – up parts; ~, * – down parts of pipes
hardening rate, whereas the opposite relationships have been
usually observed;
2. tremendous decrease in RA in exploited steels was associated
with the increase in elongation to fracture (Fig. 8), despite the
fact that the course of the changes of those parameters
describing the metal plasticity are expected to be the same.
To explain the apparently inconsistent results assumption
can be made that in the course of the long-term exploitation the
metal not only undergoes the deformation aging but also the
intensive development of the micro defects. It should be noted
that no defects were found by the routine metallographic
observation at magnification up to 1000. However, the data of
hydrogen permeation, X-ray diffraction and internal friction tests
revealed the modification of the structure of exploited steels.
According to applied procedure of hydrogen permeation
measurements, the values of Dtb revealed the hydrogen lattice
diffusivity, whereas the values of D corresponded to the
hydrogen transport affected by the hydrogen traps [12, 13]. As
seen in Fig. 9a, both parameters are lower in the exploited than in
the as-received steel. Decrease in the lattice diffusivity should be
accounted for by some change in the metal lattice, confirmed by
the change in the ferrite lattice parameters and in the size of the
ferrite coherently scattered areas detected by the X-ray. On
the other hand, decrease in the apparent diffusivity D showed the
increase in the trapping efficiency due to exploitation. It is
supported by the data in Fig. 9b showing the decrease in
1
permeation current J40 , which also depended on the trapping [12].
The higher trapping efficiency in exploited steels might be also
confirmed by the lower rate of hydrogen extraction (Fig. 5) and by
the higher amount of deeply trapped hydrogen (Table 6). Since the
hydrogen trapping has been known to be associated with the
defects in the metal structure, the increased hydrogen trapping
efficiency in exploited steels confirmed the formation of the
micro defects in the course of service.
The internal friction peaks at 600–1050 K revealed that the
relaxation process originated by the gliding along the grain
(phase) boundaries [14]. Formation of the voids at the boundaries
has shown to inhibit that gliding and thus to increase the internal
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Materials and Corrosion 2009, 60, No. 9 Effect of the long-term service of the gas pipeline 723

Figure 9. Change of the parameters evaluated from the hydrogen permeation measurements of exploited steels in comparison with the as
received one; a – ratio of the hydrogen lattice diffusivity calculated for different parts of exploited steels to that for as received material; b – steady
state values of hydrogen permeation current density as measured for as received steel and for different parts of exploited ones

friction [11, 25]. Therefore, the observed increase in the peak (Figs. 4b and 4d) at the application of external stresses during the
height in exploited materials (Fig. 7) showed the development of tests.
defectiveness of the metal, especially along the boundaries. This From the data in Fig. 9 and in Tables 3–5 it follows that the
has been also consistent with the SEM observations. In X52-10 material exhibited the more pronounced degradation and
cathodically polarised exploited steel, the hydrogen induced contained the higher amount of hydrogen (Table 6) than the X52-
cracks were formed not only at the grain boundaries as in the case 12 one, despite the similar time of exploitation. However since
of as-received steel (Fig. 8c) but also along the ferrite–carbide
phase boundaries (Fig. 6d).
The effect of presumed micro defects on the various
parameters may differ from those of deformation ageing. The
latter may decrease the RA, while the metal micro defects may
promote the elongation to fracture, as schematically shown in
Fig. 10. It is also possible that the formation of micro defects led to
relaxation of internal stresses present in the as-received material
and formed due to the deformation ageing in the course of
exploitation. This may explain not only the increase in the
elongation to fracture but also the observed decrease in the yield
stress and in the hardness (Table 3) being the measure of the
ability of metal to plastic deformation.
The suggested specific modification of the metal structure in
the course of exploitation deteriorated the resistance to the
cracking making the crack propagation to be easier. For exploited
X52-10 steel the J values were two times lower and the crack
propagation rate almost an order of magnitude higher (Table 3) in
comparison with those parameters for as-received X52 one. In the
case of Charpy tests, the exploited steels exhibited up to three-
times lower impact strength than as received one. The assistance
of the micro defects to the cracking might be also confirmed by
the interphase crevices and cracks formed in exploited steel

Figure 11. Resistivity of studied steels to stress corrosion cracking and

Figure 10. Scheme of the effect of the micro defects formed in the
course of steel exploitation on elongation and on RA
to hydrogen embrittlement as evaluated in tensile and fracture
mechanics tests done in brine under the open circuit conditions
(RASCC, JSCC, aSCC) and at low cathodic polarisation (RAH, JH, aH); a – ratio
of RASCC and RAH measured in tensile tests for studied steels in brine to
those measured at testing the as received steel in air (RAo); b – ratio of
fracture toughness JSCC and JH evaluated for studied steels in brine to
those evaluated for as received steel at testing in air (J0); c – ratio of
crack propagation rate aSCC and aH measured for studied steels in brine
to those measured for as received material in air (a0)

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724 Nykyforchyn, Lunarska, Tsyrulnyk, Nikiforov and Gabetta
the record of exploitation conditions of those pipes are not known,
the states of X52-12 and X52-10 materials may be considered as
gradual progressive degradation.
The micro defects developed during the service affected also
the susceptibility of steel to SCC and HE as evaluated by the
comparison of the mean values of RA, J and crack propagation
rate established in tests done for exploited steels in brine under
open circuit condition and at low cathodic polarisation,
respectively, to those obtained for as received steel X52 in air.
As seen in Fig. 11 in both tests, the exploited materials showed the
increase in the susceptibility, being especially tremendous in the
case of the crack propagation rate (Fig. 11c). It is also seen that
the X52-10 steel was more susceptible to corrosion-mechanical
action than the X52-12 one.
The data in Tables 3, 4, 6, 7 and in Fig. 11 showing the higher
metal degradation in the down parts of the pipes and at the in
surface of the pipe walls, especially in the down-in sites suggested
the hydrogen to be an aggressive factor. It evolved in corrosion
processes occurred on the inner surface of pipes exposed to the
brine, enter the metal and became trapped there. This has been
confirmed by the higher hydrogen content in the exploited than in
the as-received steel (Table 6). Hydrogen accumulated during the
service and affected the structure.
Susceptibility of the metal to the hydrogen induced blistering
cracking (HIBC) has been promoted by hydrogen trapping
efficiency increased during the exploitation (see Fig. 12). The
critical cathodic current (iC ) has been evaluated in the hydrogen
permeation tests. It characterized the formation of voids under
the hydrogen action without the application of the external
stresses [26]. Values of the critical cathodic current have decreased
with the decrease in the steady state permeation rate, which in turn
corresponded to the increase in the trapping efficiency [12, 13].
As follows from the obtained data the state of material
degradation due to exploitation in the oil and gas pipelines cannot
be unambiguously characterized by the standardised parameters
Figure 12. Relationship between the critical cathodic current density
for void formation and the steady state hydrogen permeation rate for
studied metals; & – X52; ~, ~ – 52-12; *, * – X52-10; ~, * – up parts;
~, * – down parts of pipes
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Materials and Corrosion 2009, 60, No. 9
(strength and elongation measured in tensile tests) and by optical
metallography. However, the application of the Charpy and
fracture mechanics tests, the measurement of hardness and
evaluation of RA allow estimating the development of deteriora-
tion. The application of hydrogen permeation measurements
could detect the structure modification and estimate the
susceptibility to HIBC. The data obtained by the above methods
would be especially important for the prediction of the residual
life-time of the old pipelines. However, continuous monitoring of
the material state of the newly build pipelines would assist in
optimising the exploitation conditions.
5 Conclusions
From the obtained results and discussion the following
conclusions can be drawn:
1. the metal of the gas pipelines undergoes in-bulk degradation
of properties due to long-term (up to 30 years) exploitation,
similarly as has been observed in the oil pipeline materials.
2. the exploited steels revealed the specific anomalies of
mechanical behaviour: (1) the decrease in the resistance to
brittle fracture simultaneous with the decrease in hardness;
and (2) the opposite change of the plasticity parameters, the
decrease in the RA accompanied by the increase in elongation.
3. two main factors resulting from the stresses and the presence
of corrosion environment have been assumed to be
responsible for the metal degradation in the long-term service
of pipes: (1) the deformation ageing and (2) the formation of
micro defects assisted by entering and accumulated hydrogen
evolved in corrosion processes taking place in brine deposited
inside the pipes.
4. exploited steels that underwent the structure degradation had
the lower resistance to SCC, HE and HIBC.
5. the extent of the degradation not being detected by the routine
observation of microstructure or by the measurements of the
standard tensile parameters; however, may be evaluated by the
measurements of the fracture toughness, impact strength, RA,
hardness and hydrogen transport.
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(Received: September 17, 2008) W5158
(Accepted: November 18, 2008)
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