metals
Article
Corrosion Resistance of 13Cr Steels
Artem Davydov 1, * , Ekaterina Alekseeva 1 , Vladislav Kolnyshenko 1 , Darya Strekalovskaya 1 , Oleg Shvetsov 1 ,
Natalia Devyaterikova 2 , Konstantin Laev 2 and Aleksey Alkhimenko 1
Citation: Davydov, A.; Alekseeva, E.;
Kolnyshenko, V.; Strekalovskaya, D.;
Shvetsov, O.; Devyaterikova, N.;
Laev, K.; Alkhimenko, A. Corrosion
Resistance of 13Cr Steels. Metals 2023,
13, 1805. https://doi.org/10.3390/
met13111805
Academic Editor: Belén Díaz
Fernández
Received: 28 September 2023
Revised: 13 October 2023
Accepted: 20 October 2023
Published: 26 October 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Metals 2023, 13, 1805. https://doi.org/10.3390/met13111805
1 Scientific and Technological Complex “New Technologies and Materials”, Institute of Advanced Engineering
Technologies, Peter the Great St. Petersburg Polytechnic University, 195251 St. Petersburg, Russia;
alekseeva_el@spbstu.ru (E.A.); kolnysh_vv@spbstu.ru (V.K.); strekal_da@spbstu.ru (D.S.);
shvetsov_ov@spbstu.ru (O.S.); a.alkhimenko@spbstu.ru (A.A.)
2 TMK Pipeline Solutions LLC (TMK), 40/2a Pokrovka Street, 101000 Moscow, Russia;
n.devyaterikova@tmk-group.com (N.D.); konstantin.laev@tmk-group.com (K.L.)
* Correspondence: davydov_ad@spbstu.ru
Abstract: Super 13Cr steels, which combine high strength and excellent corrosion resistance, are the
optimal choice for developing and exploiting complex oil and gas wells, particularly in high-CO2
environments. In this study, we conducted a corrosion assessment of several high-strength steels
of the 13Cr type with different alloying systems. We identified the primary parameters responsible
for the corrosion resistance of these steels based on our research findings and suggested ways to
optimize their chemical composition and select the most economically viable option. We demonstrate
the importance of selecting the appropriate alloying system and the impact of non-metallic inclusions
(NMIs) on the corrosion properties of the high strength 13Cr material.
Keywords: corrosion; super 13Cr; stress corrosion cracking; non-metallic inclusions; autoclaves;
electrolytic etching
1. Introduction
In most cases, pipe failures in the oil and gas industry occur due to internal corro-
sion [1]. With traditional oil and gas reserves depleting, the production of hard-to-recover
oil is increasing, leading to the utilization of new methods [2–7]. This development leads to
the exploitation of materials in extreme conditions [8–12], resulting in premature equipment
failure [13–18] when operating in aggressive environments containing chlorine ions (Cl− ),
carbon dioxide (CO2 ), and hydrogen sulfide (H2 S). Sulfide stress corrosion cracking (SSC),
which is typical for materials in a hydrogen sulfide-containing environment, causes metal
cracking under the action of corrosion and tensile stresses in the presence of moisture and
hydrogen sulfide [9,18–21].
Economic challenges have led to a new impulse for the development of new materials
for tubing which possess high mechanical characteristics and increased resistance to sulfide
stress corrosion cracking and general and local corrosion in CO2 -saturated environments.
Consequently, the current state of development of the oil and gas complex demands
that consumers require high-quality and reliable tubular products [22] with constantly
increasing requirements [23].
In challenging downhole environments characterized by high temperature, high
pressure, and CO2 saturation, along with the possibility of low H2 S concentrations, 13Cr
corrosion-resistant steels (API 5CT) are commonly used as tubing and casing materials. In
such aggressive conditions, the use of low-alloy steels is not recommended as hydrogen
from H2 S diffuses into the metal and significantly reduces the fracture resistance of carbon
steels [24]. Additionally, the resistance of steels to sulfide stress corrosion cracking is
dependent on the environmental pH. For example, at pH < 3.0, crack initiation can occur at
a chloride concentration of 600 ppm [25,26]. Therefore, careful selection of materials and
operating conditions is crucial for ensuring the reliability and safety of oil and gas wells.
https://www.mdpi.com/journal/metals
Metals 2023, 13, 1805 2 of 14

In the pipe industry, martensitic corrosion-resistant steels are commonly used for
aggressive downhole conditions saturated with CO2 and H2 S at high pressure and high
temperature. Currently, two subclasses of martensitic corrosion-resistant steels are utilized
in the pipe industry. The well-known steels AISI 410S and AISI 420 have a simple alloying
system and low cost but are limited in strength (L80, R95), corrosion resistance, and impact
strength, especially at low temperatures. On the other hand, low carbon supermartensitic
steels contain several expensive alloying elements that provide high cost, increased tensile
strength (R95, P110, Q135), high impact strength, and corrosion resistance. However,
these materials are not economical solutions for end users. Alternatively, highly resistant
alloyed steel grades, such as duplex (22Cr-5Ni-3Mo) or super duplex (25Cr-7Ni-3Mo),
are considered, but they are even more expensive and could be implemented for specific
applications [27].
The properties of supermartensitic 13Cr steels are greatly improved compared to tradi-
tional martensitic-ferritic stainless steel (such as AISI 410S) due to the presence of residual
austenite in the matrix structure of low-carbon martensite without δ-ferrite. These steels typ-
ically contain 12–14% Cr, 4–6% Ni, 0.5–2% Mo, and less than 0.03% carbon, with additional
elements, such as titanium, vanadium, and niobium, to prevent softening during tempering
and improve impact strength, especially at low temperatures [1,2,8,13,14,19,28]. Tungsten
and copper are also added for further enhancement of the mechanical properties [3,4,9].
The properties of 13Cr steels are significantly influenced by the carbon content. With
a decrease in the carbon content, the ductility of the steel increases, the impact resistance
increases, and the machinability improves, while the hardness and strength decrease.
Additional alloying of steels of the supermartensitic 13Cr type with strong carbide-forming
elements in an amount of up to 0.05% contributes to a significant increase in strength
properties due to secondary hardening without a negative effect on the ductile and corrosion
properties [29–31].
The carbon content significantly affects the ductility, impact resistance, machinability,
hardness, and strength of steel [32]. Steels with a low carbon concentration, known as
supermartensitic 13Cr, exhibit better properties but are expensive to produce and not
suitable for tubing applications. The studied steels have a transitional composition between
conventional 13Cr and supermartensitic 13Cr, and this work aims to determine the optimal
chemical composition of 13Cr steels for corrosion resistance and mechanical properties.
The study evaluates the corrosion resistance of martensitic 13Cr P110 tubing after
operation. For studying steel options that exhibit satisfactory properties, several new
grades of martensitic 13Cr stainless steel types were developed (13Cr-4Ni-1Mo (P110),
13Cr-3Ni-1Mo (P110), 13Cr-5Ni-2Mo (P110), and 13Cr-5Ni-2Mo (Q135)) and manufactured
without the vacuum oxygen degasser (VD/VOD) processes, with [C] = 0.06–0.09%. The
entire life cycle, from melting to the final pipe, was simulated during the laboratory sample
production process. Corrosion properties of the samples during laboratory testing were
assessed under simulated operational conditions. The objectives are to evaluate corrosion
properties, electrochemical performance, resistance to sulfide cracking, and non-metallic
inclusions and their effect on corrosion resistance.

2. Materials and Methods

At the beginning, studies were conducted on samples of a production tubing made of
13Cr-2Ni steel with a strength group of P110 (Table 1) after operation. Numerous pittings
were observed on the tubing after operation (Figure 1). The tubing was used in an oil well.
The operating conditions involved a combination of approximately 1% H2 S, 1.5% CO2 , and
a total mineralization of produced water at 50,000 mg/L.

Table 1. The mechanical properties.

Type of Steel HRC YS, MPa TS, MPa δ5 , %

13Cr-2Ni 29 804.8 917.1 17
 Metals 2023, 13, x FOR PEER REVIEW 3 of 14

Table 1. The mechanical properties.

Metals 2023, 13, 1805 3 of 14
Type of Steel HRC YS, MPa TS, MPa δ5, %
13Cr-2Ni 29 804.8 917.1 17

(a) (b)

Figure 1. Figure
Surface1.ofSurface of the
the tubing tubing
after after operation:
operation: (a) local corrosion,
(a) local corrosion, ×50; (b)
×50; (b) local local corrosion,
corrosion, ×25. ×25.

For comparison,
For comparison, experimental
experimental closest analogues
closest analogues with additional
with additional Ni and Mo-alloyed
Ni and Mo-alloyed
13Cr stainless
13Cr stainless steels weresteels wereThe
chosen. chosen. The properties
properties of the investigated
of the investigated steels are in
steels are presented presented
in Table
Table 2. For 2. For a preliminary
a preliminary assessmentassessment of theresistance,
of the corrosion corrosionweresistance,
calculatedwethecalculated
pitting the pit-
resistance equivalent
ting resistancenumber (PREN).
equivalent numberNumbers,
(PREN).shown in Table
Numbers, 3, based
shown on 3,
in Table the actual
based on the ac-
chemicaltual
composition, according to the
chemical composition, formulatoPREN
according = % CrPREN
the formula + 3.3 (%
= %MoCr++ %
3.30.5
(%W)Mo+ +%% 0.5 W)
16 N, where
+%% 16 is
N,the mass%fraction
where of the
is the mass element,
fraction of expressed
the element,as expressed
a percentage.
as a percentage.

Table
Table 2. The 2. The mechanical
mechanical propertiesproperties of the investigated
of the investigated steels. steels.

Type of SteelType of Steel

PREN PREN
HRC HRC
YS, MPa YS, MPa
TS, MPa TS,
δ5 ,MPa
% δ5, %
13Cr-4Ni-1Mo
13Cr-4Ni-1Mo (P110) (P110)
18.5 18.5
28 28840 840
912 912
21.5 21.5
13Cr-5Ni-2Mo
13Cr-5Ni-2Mo (P110) (P110)
21.4 21.4
33 33905 905
965 965
22 22
13Cr-5Ni-2Mo (Q135)
13Cr-5Ni-2Mo 19.9
(Q135) 33
19.9 33980 1035
980 21
1035 21
13Cr-3Ni-1Mo (P110)
13Cr-3Ni-1Mo16.3
(P110) 27
16.3 27780 870
780 24
870 24

The
Table 3. Results specimens
of chemical wereofetched
analysis by Vilella
corrosion productss from
etchant, which
the EDS contained 5 mL hydrochloric
data.
+ 4 g picric acid + 100 mL ethyl alcohol. The microstructure was assessed using optical
Spectrum O Si S
microscopy at Cl Ca
×500 magnifications on aCrReichert-Jung
Mn MeF3A5Fe Ni Depew, NY,
(Reichert Inc.,
1 38.41 0.96 USA)
0.31 microscope.
4.31 Microstructures
0.43 of35.76
the samples were evaluated 17.18 at different
2.64 distances
2 38.29 0.82 0.61 the external
from 6.12 wall of 0.29
the tubing.39.06
For metallographic analysis 12.57 of corrosion
1.99 products,
3 44.01 1.08 0.93
longitudinal 5.04
specimens were obtained 36.92
from the pitting depicted 11.24in Figure0.78
1a. The extrac-
4 37.48 0.93 1.06 4.54 37.01 17.41 1.57
tion was carried out using an erosion machine with a corrosion-neutral cutting fluid to
5 0.54 13.53 0.64 83.04 2.26
6 1.50 0.47 minimize the deleterious effects of corrosion 13.37 products.
0.61 Studies81.34of corrosion
2.71 products on
the surface of the tubing were conducted using electron microscopy on a TESCAN VEGA
scanning electron microscope (SEM, TESCAN, Brno, Czech Republic) equipped with an
TheINCA
specimens wereenergy
X-Max-50 etcheddispersive
by Vilella’sX-ray
etchant, which contained
spectrometer 5 mL hydrochloric
(EDS, Oxford Instruments, Oxford,
+ 4 g picric
UK). acid + 100 mL ethyl alcohol. The microstructure was assessed using optical
×500 magnifications
microscopy atElectrochemical onwere
studies a Reichert-Jung
carried out MeF3A5 (Reichert
using a Versa Inc., Depew,
Princeton AppliedNY,Research
USA) microscope. Microstructures of the samples were evaluated at different
potentiostat (AMETEK Inc., Berwyn, PA, USA) equipped with specialized software distances
from the(AMETEK
external wallInc.,ofBerwyn,
the tubing.
PA, For
USA) metallographic analysis
on three-electrode cellsofaccording
corrosionto products,
ASTM G3, G59,
longitudinal specimens were obtained from the pitting depicted in Figure 1a.
and G102. A 3% NaCl solution was used as the working electrolyte under conditions ofThe extraction
was carried out using
natural an erosion
electrolyte machine
deaeration with
and at aroom
corrosion-neutral
temperature cutting
(~23 °C)fluid
withtoaminimize
pH of 3, 6.5, and
the deleterious effects of corrosion products. Studies of corrosion products
11. When the cell was saturated with CO2 or H2S, the solution was deaerated. on the surface
Based on the
of the tubing
results were conducted
of these using
tests, the mostelectron microscopy
aggressive on a TESCAN
environment was chosen VEGA scanning critical-
for subsequent
electron microscope (SEM, TESCAN, Brno, Czech Republic) equipped with an INCA
condition tests. Thus, evaluation of the electrochemical characteristics presented in Table
X-Max-50 energy dispersive X-ray spectrometer (EDS, Oxford Instruments, Oxford, UK).
2 was carried out in a 3% NaCl solution saturated with CO2 with a pH value of 2.8–3.0 at
Electrochemical studies were carried out using a Versa Princeton Applied Research po-
a temperature of 60 °C on samples in the form of plates. The analyzed surface area of all
tentiostat (AMETEK Inc., Berwyn, PA, USA) equipped with specialized software (AMETEK
Inc., Berwyn, PA, USA) on three-electrode cells according to ASTM G3, G59, and G102. A 3%
NaCl solution was used as the working electrolyte under conditions of natural electrolyte
deaeration and at room temperature (~23 ◦ C) with a pH of 3, 6.5, and 11. When the cell
was saturated with CO2 or H2 S, the solution was deaerated. Based on the results of these
Metals 2023, 13, 1805 4 of 14

tests, the most aggressive environment was chosen for subsequent critical-condition tests.
Thus, evaluation of the electrochemical characteristics presented in Table 2 was carried out
in a 3% NaCl solution saturated with CO2 with a pH value of 2.8–3.0 at a temperature of
60 ◦ C on samples in the form of plates. The analyzed surface area of all samples was 1 cm2 .
Surface preparation was carried out by grinding and polishing. The research procedure
consisted of immersing the sample in the test environment, measuring the equilibrium
corrosion potential (Eq) for 55 min (3300 s), and carrying out subsequent linear polarization
in the potential range from −250 to 250 mV with a sweep rate of 0.16 mV/s to obtain a
polarization curve. The corrosion current density was determined graphically to determine
the corrosion rate using the Tafel equation.
The operating conditions were simulated using an autoclave; 50 by 30 by 5 mm plate
samples were immersed in a solution of 5% NaCl and 0.5% acetic acid with a solution pH
of 3–4. The vessel was sealed, deaerated with nitrogen, saturated with carbon dioxide up to
a total pressure of 3 MPa, and heated to a temperature of 80 ◦ C. The tests were carried out
for 240 h. After exposure, the samples were removed from the autoclave and rinsed with
flowing water to remove corrosion products. Subsequently, they were dried using paper
and organic solvents (acetone). Any remaining corrosion residues were removed using
gentle abrasives (erasers). The weight loss of the samples was determined and visually
evaluated (according to ASTM G1).
The corrosion rate was calculated using the formula:

m0 − m1 mm
K = 1.129· , (1)
S·t year

where 1.129 is the coefficient for steels of the martensitic class of type 13Cr for converting
the dimension of the rate of general corrosion in g/m2 h into the dimension of mm/year;
m0 is the mass of the sample before testing, g; m1 is the mass of the sample after testing, g;
S is the surface area of the sample, m2 ; and t-test duration, hours.
Sulfide stress corrosion cracking resistance was evaluated according to NACE TM0177,
method A, on cylindrical samples in a solution of 5% NaCl plus 0.5% acetic acid, with pH of
3, and then saturated with 10% H2 S. The duration of the tests was 720 h. The applied stress
on the samples was 80% of the standard minimum yield strength (SMYS). After testing, it
was assessed visually for cracks.
The influence of the type and composition of non-metallic inclusions (NMIs) on the
quality of the steel was evaluated using electrolytic etching, which involves the dissolution
of the matrix and residue analysis.
Metal samples were used for three-dimensional (3-D) investigations of non-metallic
inclusions extracted using the electrolytic extraction (EE) technique. The electrolytic ex-
tractions were carried out at the KTH Royal Institute of Technology (Stockholm, Sweden)
by using the following extraction parameters: electrolyte, 10%AA (10% acetylacetone-1%
tetramethyl-ammonium chloride-methanol); electric current, 40~60 mA; voltage, 2.9~3.8 V.
After an electrolytic dissolution of metal matrix, the non-metallic inclusions, which did not
dissolve in the given electrolyte, were collected on a surface of a membrane polycarbonate
film filter (with a 0.4 µm open-pore diameter) during filtration of the electrolyte after the
completed EE [20,31]. The characteristics of inclusions (such as size, morphology, and
chemical composition) were analyzed by using an SEM combined with EDS. The NMIs
were investigated on film filters and on surfaces of metal samples after EE.
The types of inclusions, their sizes, and the coefficient of dissolution of the metallic
matrix around the inclusion (K D ) were determined:

Acr
KD = (2)
Aincl

where Aincl is the areas of inclusion, and Acr is the areas of craters.
Metals 2023, 13, 1805 5 of 14

3. Results
3.1. Investigations of the Pipe Sample after Operation
During the investigation of the microstructure of the samples at different distances
Metals 2023, 13, xMetals 2023, REVIEW
FOR PEER 13, x FOR PEER REVIEW
from the external wall of the pipe, no critical structural features were observed. The 5steel
of 14

structure corresponded to tempered martensite (Figure 2).

(a) (a) (b) (b)

Figure Figure 2.in

Figure2.2.Microstructure
Microstructure Microstructure
inthe
thesample, in the(a)
sample,××200:
200: sample,
(a) inthe
in ×200: (a)(b)
themiddle;
middle; in on
(b) the middle;
onthe
the (b) on the surface.
surface.
surface.

Figure
Figure33showsFigure
showsan 3 showsphotograph
anelectronic
electronic an electronic
photograph ofofphotograph
corrosion of corrosion
corrosiondamage,
damage, while
whiledamage,
Table while
Table33lists
liststheTable 3 li
the
chemical chemical
compositions compositions
of the of
corrosion the corrosion
products.
chemical compositions of the corrosion products. products.

Figureof
Figure 3. SEM image 3. corrosion
SEM image of corrosion products.
products.
Figure 3. SEM image of corrosion products.
Table 3. Results of chemical
Table
The3. Results of chemical
corrosion productsanalysis
contain theanalysis
of corrosion of corrosion
products
following products
from the
elements: SEDS from the EDS data.
data.
is found in the products
resulting 2−
Spectrum Spectrum
O SiO from S the
Si interaction
ClSof iron withCaClH2 S or SOCr 4 ; Ca replaces
Ca MnCr iron andFe nickel atoms
Mn Ni Fe
during corrosion; an increase in Cr concentration above the specified 13% is attributed
1 1
38.41 38.41
0.96 0.96
0.31 0.31
4.31 4.31
0.43 0.43
35.76 35.76 17.18 2.64to
17.18
iron dissolution; Cr, Fe, O and S are present as iron and chromium oxide oxidation products
2 2
38.29 38.29
0.82 0.82
0.61 0.61
6.12 6.12
0.29 0.29
39.06 39.06 12.57 1.9912.57
(Cr2 O3 , FeS, FeO and FeCO3 ). These components in the table indicate the existence of two
3 3
44.01 44.01
1.08 1.08
0.93 0.93
5.04 5.04 36.92 36.92 11.24 0.7811.24
gases in the operating environment—H2 S and CO2 with the presence of chlorides. For 13Cr
4 4
37.48 37.48
0.93 0.93
1.06 1.06
4.54 4.54 37.01 37.01 17.41 1.5717.41
steels, these conditions can lead to premature failure. To assess the impact of the operating
5 5 0.54 0.54 13.53 13.53
0.64
environment parameters as well as the presence of hydrogen sulfide and carbon dioxide, 0.64
83.04 2.2683.04
6 6
1.50 1.50
0.47
electrochemical 0.47
tests were conducted under variable 13.37conditions. 13.37
0.61 0.61
81.34 2.7181.34
Figure 4 depicts polarization curves plotted in coordinates of potential versus cur-
The corrosion
rent density. The
The studies corrosion
products products
were contain
conducted the to contain
following
assess thethe following
elements:
influence iselements:
S of Sthe
is products
found in the pro
found inparameters—
various
resulting from the interaction of iron with H S or SO 2−; Ca replaces iron and nickel
resulting from the interaction of iron with H2S or SO4 ; Ca replaces iron and nickel atoms
2− 2 4

during
during corrosion; an corrosion;
increase inan Crincrease in Cr concentration
concentration above the specifiedabove 13% the specified 13%to
is attributed is attribu
ironCr,
iron dissolution; dissolution;
Fe, O and Cr,
S areFe,present
O and as S are present
iron as iron and
and chromium chromium
oxide oxidation oxide oxidation
prod-
uctsFeO
ucts (Cr2O3, FeS, (Cr2and
O3, FeS,
FeCO FeO and FeCO
3). These 3). Thesein
components components in the table
the table indicate indicate of
the existence the existe
twooperating
two gases in the gases in the operating environment—H
environment—H 2S and CO2 with 2S and CO2 withof
the presence the presenceFor
chlorides. of chlorid
 becomes more general.
In an environment with pH 11 and CO2 saturation, the metal remains passive and
corrosion-resistant. Nevertheless, when the pH is reduced to 6.5, the corrosion rate in-
creases to 0.02 mm/year, and corrosion exhibits a pitting. With a pH decrease to 3, along
with CO2 saturation, the corrosion rate escalates to 2.2 mm/year, and corrosion becomes
Metals 2023, 13, 1805 more general. 6 of 14
In an environment with pH 11 and H2S saturation, the metal remains passive, and
the corrosion rate is 0.001 mm/year. However, when the pH is lowered to 7-3, the corro-
sion rate increases
presence to2 S0.86–1.5
of CO2 , H mm/year,
or in the open celland corrosion
(without proceeded
saturation and more through
deaeration, the gen-
“air”) with
eral mechanism
different rather than
pH values—on the the local. resistance of the samples from the investigated pipe.
corrosion

(a) (b) (c)

Figure 4. Polarization curves for 13Cr-2Ni sample: (a) in open cell, (b) saturated with CO2, (c) satu-
Figure 4. Polarization curves for 13Cr-2Ni sample: (a) in open cell, (b) saturated with CO2 , (c) saturated
rated with H2S.
with H2 S.
Subsequently, the theoretical
The results revealed corrosion
high corrosion rates of
resistance of the
the investigated samples
P110-13Cr steel were calcu-
in an environment
lated and recorded in Table 4.
with pH 11 and no gas saturation. However, when the pH is lowered to 6.5, the corrosion
rate increases to 0.04 mm/year, and corrosion exhibits a localized nature. Further reduction
Table 4. Results of electrochemical studies.
of pH to 3 significantly elevates the corrosion rate to 1.5 mm/year, and corrosion becomes
more general. Average Corrosion Rate,
№ In an environment
Sample with pH 11 andmm/year
CO2 saturation, the metal Ecorr, mV passive
remains Epit, mVand
corrosion-resistant. Nevertheless, when the pH is reduced to 6.5, the corrosion rate in-
1 13Cr-pH3-air 1.5730 −460 –
creases to 0.02 mm/year, and corrosion exhibits a pitting. With a pH decrease to 3, along
2 13Cr-pH3-CO2 2.2215 −447 –
with CO2 saturation, the corrosion rate escalates to 2.2 mm/year, and corrosion becomes
3 13Cr-pH3-H2S 1.5790 −623 –
more general.
4 13Cr-pH6.5-air
In an environment with pH 11 and H20.0353 −271 passive,−93
S saturation, the metal remains and the
5 13Cr-pH6.5-CO
corrosion 2
rate is 0.001 mm/year. However,0.0284
when the pH is lowered −511 −185
to 7-3, the corrosion
6 increases
rate 13Cr-pH6.5-H 2S
to 0.86–1.5 0.8690
mm/year, and corrosion proceeded more−678 –
through the general
7
mechanism 13Cr-pH11-air
rather than the local. 0.0011 −349 364
8 13Cr-pH11-CO
Subsequently, 0.0015
the2theoretical corrosion rates of the investigated −251
samples were6calcu-
lated
9 and recorded in2STable 4.
13Cr-pH11-H 0.0099 −435 25

Table 4. Results of electrochemical studies.

From the results presented in Figure 4 and Table 4, it is evident that pH critically
influences the material s resistance in Average
the environment.
Corrosion In the case of low pH, this steel
№ Sample Ecorr, mV Epit, mV
Rate, mm/Year
1 13Cr-pH3-air 1.5730 −460 –
2 13Cr-pH3-CO2 2.2215 −447 –
3 13Cr-pH3-H2 S 1.5790 −623 –
4 13Cr-pH6.5-air 0.0353 −271 −93
5 13Cr-pH6.5-CO2 0.0284 −511 −185
6 13Cr-pH6.5-H2 S 0.8690 −678 –
7 13Cr-pH11-air 0.0011 −349 364
8 13Cr-pH11-CO2 0.0015 −251 6
9 13Cr-pH11-H2 S 0.0099 −435 25

From the results presented in Figure 4 and Table 4, it is evident that pH critically
influences the material’s resistance in the environment. In the case of low pH, this steel
did not exhibit stainless properties and dissolved in any medium. The highest average
corrosion rate (~2.2 mm/year) was observed for the investigated steel in a CO2 environment
at pH 3. This environment was selected for further testing.
Steel with a chromium content of 13% forms a passive protective film on its surface,
preventing the dissolution of the base metal in the electrolyte medium. However, this film
can be damaged and dissolved in the presence of chlorides. This process accelerates as
 did not
did not exhibit
exhibit stainless
stainless properties
properties and and dissolved
dissolved in in any
any medium.
medium. The The highest
highest average
average
did not
corrosion exhibit
rate (~2.2 stainless
(~2.2 mm/year)properties and
was observed
observed dissolved
for the in any
theininvestigatedmedium.
investigated The
steel highest
inhighest average
did not exhibit
corrosion rate stainless
mm/year)properties
was and dissolvedfor any medium. The
steel in aa CO environ-
CO22 environ-
average
corrosion
ment at
corrosion pH rate
3.
rate (~2.2
This
(~2.2 mm/year)
environment
mm/year) was
was
was observed
selected
observed for
for
for the
further
the investigated
testing.
investigated steel
steel in
in aa CO
CO 2 environ-
environ-
ment at pH 3. This environment was selected for further testing. 2
ment at
at pH
Steel 3.
3. This
with environment was selected for
for further testing.
Metals 2023, 13, 1805 mentSteel pH with aa chromium
This chromium
environment content
wasof
content of 13% forms
selected
13% forms aa passive
passive
further protective film
testing.
protective film onon its
its surface,
surface,
7 of 14
Steel
preventing
Steel with
the
with aa chromium
dissolution
chromium ofcontent
the
contentbase of
of 13%
metal
13% forms
in
formsthe a passive
electrolyte
a passive protective
medium.
protective film on
However,
film on its
its surface,
this film
surface,
preventing the dissolution of the base metal in the electrolyte medium. However, this film
preventing
can be damaged
damaged
preventing the
the dissolution
and dissolved
dissolution of
of the
dissolved theinbase metal
metal in
the presence
base presence in the electrolyte
of chlorides.
thechlorides.
electrolyte medium.
This processHowever,
medium. accelerates
However, this
asfilm
this the
film
can be and in the of This process accelerates as the
can
pH
can be
of
bepHdamaged
the solution
damaged and
and dissolved
decreases.
dissolved in
The the
in the presence
authors of [33]
presence of
[33] chlorides.
ofof demonstrated
chlorides. This process accelerates
that reducing
This processreducing the pH
accelerates as
pH
as the
be-
the
pH of
the the solution
of the solutiondecreases. The
decreases. authors
The of
authors demonstrated
[33] demonstrated that that the
reducing thebe-pH
pH
low
pH of
of the
3.5,
the solution
down
solutionto decreases.
1, leads
decreases. to The
the
The authors
deceleration
authors of
of [33]
and,
[33] demonstrated
sometimes,
demonstrated that reducing
complete
that the
exclusion
reducing the pH
of
pH be-
the
be-
low 3.5, down
below 3.5, down to 1,toleads to the
1, leads deceleration
to the deceleration and,and,sometimes,
sometimes, complete
complete exclusion
exclusion of of
thethe
low 3.5,
3.5, down
repassivation to
process1,
1, leads
of ofto
the the
Cr 2O
deceleration
3 film on theand,
and, sometimes,
material complete exclusion of the
low downprocess
repassivation
repassivation toprocessleads
of to
the
thethe
Cr 2O
Cr deceleration
2 3Ofilm
3 onon
film thethe material
material’s ss surface.
sometimes, surface.
surface.The
complete
TheThebreakdown
exclusion
breakdown
breakdown of of
of the
thethe
repassivation
passive film
repassivation inprocess
anan
processaeratedof
of the
the Cr
Cr22OO33 film
electrolyte on
on the
results
film inin
the material
the formation
material ss surface.
ofof
pits
surface. The
and
The breakdown
anan increased
breakdown of the
rate
ofrate
the
passive
passive film in
film an
in aerated
aerated electrolyte
electrolyte results
resultsin thetheformation
formation of pits and
pits andan increased
increased rate
passive
of film
material
passive in an
dissolution.
filmdissolution. aerated
indissolution. electrolyte results in the formation of pits
an aerated electrolyte results in the formation of pits and an increased rate and an increased rate
of material
of material
of
of material
material dissolution.
dissolution.
3.2.
3.2. Autoclave
3.2. Autoclave
Autoclave Tests
TestsTests
3.2.
3.2. Autoclave
Autoclave Tests
Tests
Corrosion
Corrosion
Corrosion rate
rate
rate resistance
resistance
resistance autoclave
autoclave
autoclave test results
test
test results
results are
are provided
are provided
provided ininTable
in Table 5.5.
Table5.
Corrosion
Corrosion rate rate resistance
resistance autoclave
autoclave test test results
results are are provided
provided in in Table
Table 5.
5.
Table 5. 5.
Table
Table 5. Corrosion
Corrosion rate
Corrosion
rate after
rate
after autoclave
after
autoclave in in
autoclave
in 5%5%
5% NaCl
NaCl plus
NaCl
plus 0.5%
plus acetic
0.5%
0.5% acid
acetic
acetic with
acid
acid pH
with
with pH 3–4.
pH 3–4.
3–4.
Table
Table 5.
5. Corrosion
Corrosion rate
rate after
after autoclave
autoclave in
in 5%
5% NaCl
NaCl plus
plus 0.5%
0.5% acetic
acetic acid
acid with
with pH
pH 3–4.
3–4.
Type of
Type of Steel
Steel Average Corrosion
Average Corrosion Rate, mm/Year
Rate,
Average Corrosion mm/Year
Rate, Photo of
Photo of Specimen
Specimen
Type Type of Steel Average Corrosion Rate, mm/Year Photo of Specimen
Specimen
Type of of Steel
Steel Average Corrosion Rate, mm/Year
mm/Year Photo
Photo of
of Specimen

13Cr-4Ni-1Mo (P110)
13Cr-4Ni-1Mo (P110) 0.0019 ±± 0.0010
0.0019 0.0010
13Cr-4Ni-1Mo
13Cr-4Ni-1Mo (P110)
(P110)
13Cr-4Ni-1Mo (P110)
0.0019
0.0019 ±± 0.0010
0.0019 0.0010
± 0.0010

13Cr-5Ni-2Mo (P110)
13Cr-5Ni-2Mo (P110) 0.0007 ±± 0.0004
0.0007 0.0004
13Cr-5Ni-2Mo (P110)
13Cr-5Ni-2Mo (P110) 0.0007 ±
0.0007 ± 0.0004
0.0004
13Cr-5Ni-2Mo (P110) 0.0007 ± 0.0004

13Cr-5Ni-2Mo
13Cr-5Ni-2Mo (Q135)
(Q135)
13Cr-5Ni-2Mo (Q135) 0.0025
0.0025 ±± 0.0015
0.0025 0.0015
± 0.0015
13Cr-5Ni-2Mo
13Cr-5Ni-2Mo (Q135)
(Q135) 0.0025
0.0025 ±± 0.0015
0.0015

13Cr-3Ni-1Mo (P110)
13Cr-3Ni-1Mo
13Cr-3Ni-1Mo (P110)
(P110) 0.0106
0.0106
0.0106 ± 0.0020
±± 0.0020
0.0020
13Cr-3Ni-1Mo
13Cr-3Ni-1Mo (P110)
(P110) 0.0106
0.0106 ±± 0.0020
0.0020

The
TheThe13Cr-3Ni-1Mo
13Cr-3Ni-1Mo
13Cr-3Ni-1Mo specimens
specimens
specimens after
after
after autoclave
autoclave
autoclave testing
testing
testing have
have
have aa dark
dark
a darklayer of of
layer
layer of nearly
nearly
nearly uni-
uni-uni-
form
formThe 13Cr-3Ni-1Mo
corrosion
corrosion products
productsspecimens
onon the
the after
surface
surface autoclave
that
that testing
indicates the
the have a
absence
absence dark
of
of layer of
passivation
passivation nearly uni-
state
state in in
formThe 13Cr-3Ni-1Mo
corrosion productsspecimens
on the surface after that
autoclave testing
indicates the have
absencea dark layer of nearly
of passivation uni-
state inthe
form
the
form corrosion
testing
testing products
conditions.
conditions.
corrosion After
products on
After
on the
cleaning, surface
cleaning,
the surfacethere that
therewere
that indicates
wereno no
visually
no
indicates the
visually absence
thedetected
detected
absence of passivation
corrosion damages
corrosion
of passivation state in
state(pits).
damages in
the testing conditions. After cleaning, there were visually detected corrosion damages
the testing
(pits).
the All
testing conditions.
samples,
conditions. After
except
After cleaning,
for the
cleaning, last there
one,
there were no
exhibited
were no visually
low
visually detected
corrosion
detected corrosion
rates, with
corrosion damages
occasional
damages
(pits).
(pits).
instances
(pits). of pitting
All samples,
samples, corrosion.
except for the
the lastTheone,
last 13Cr-5Ni-2Mo
one, exhibited low (P110)
low steel type
corrosion rates,performed the best
with occasional
occasional
All except for exhibited corrosion rates, with
All
among
instances
All samples,
all
of samples.
pitting
samples, except
except for
corrosion.
for the
the Thelast
last one, exhibited
13Cr-5Ni-2Mo
one, exhibited low
(P110)
low corrosion
steel
corrosion type rates, with
performed
rates, with occasional
the best
occasional
instances of pitting corrosion. The 13Cr-5Ni-2Mo (P110) steel type performed the best
instances
among
instancesBased
all of pitting
on
samples. the corrosion.
results of The
autoclave13Cr-5Ni-2Mo
tests (P110)
conducted insteel
an type
acidic performed
environment the best
with the
among all of pitting corrosion. The 13Cr-5Ni-2Mo (P110) steel type performed the best
samples.
among
presence
among all
Based samples.
of carbon
on the dioxide,
the results
all samples. results of all variants
of autoclave
autoclave tests of martensitic
tests conducted
conducted in 13Cr
in an alloying
an acidic demonstrate
acidic environment
environment with resistance
with thethe
Based on
in Based
terms
presence of on
of the
carbon results
dissolution. of
dioxide, autoclave
Pits allon thetests
variants conducted
samples
of are one
martensitic in an
of acidic
the
13Cr environment
factors
alloying for with
assessment
demonstrate the
and
re-
presence of carbon dioxide, all variants of martensitic 13Cr alloying demonstrate the
Based on the results of autoclave tests conducted in an acidic environment with re-
presence
comparison.
sistance
presencein of carbon
inofterms
terms Thus,
carbon dioxide,
the
of dissolution.
dissolution. all
presence
dioxide, allPits variants
Pits of
on the
variants of
surface martensitic
defects,
theofsamples
samples are one
martensitic 13Cr
local
one
13Cr alloying
structural
of the
the demonstrate
heterogeneity,
factorsdemonstrate
alloying for assessment
assessment re-
and
re-
sistance of on are of factors for
sistance
and in
non-metallic terms
comparison.
sistance in terms of dissolution.
inclusions
Thus, thecan
presence
of dissolution. Pits
be Pits on
potential
of the samples
thecauses
surface
onsurface are
for are
defects,
samples one
thelocal of
formation
one the
of the of
structuralfactors for
pitting. assessment
heterogeneity,
factors and
for assessment
and comparison. Thus, the presence of defects, local structural heterogeneity, and
and comparison.
non-metallic
and comparison. Thus,
inclusions the
can
Thus, the presence
be of
potential surface
causes defects,
for the local structural
formation of heterogeneity,
pitting. and
non-metallic inclusions
3.3. Electrochemical canpresence
Tests be potential of surface
causesdefects, local structural
for the formation heterogeneity, and
of pitting.
non-metallic
non-metallic inclusions
inclusions cancan be
be potential
potential causes
causes for
for the
the formation
formation of of pitting.
pitting.
The calculated
3.3. Electrochemical
Electrochemical values can be used provided that the corresponding elements are in
Tests
3.3. Tests
3.3. Electrochemical
solid solution. The
3.3. Electrochemical TestsTests
results are presented in Table 6 and Figure 5.
Metals 2023, 13, x FOR PEER REVIEW 8 of 14

Metals 2023, 13, 1805 8 of in

The calculated values can be used provided that the corresponding elements are 14
solid solution. The results are presented in Table 6 and Figure 5.

Table 6. Results
Table 6. Results of
of electrochemical tests.
electrochemical tests.
Average Corrosion
Average Rate,
Corrosion
Type
Typeof
of Steel
Steel PREN
PREN Ecorr,
Ecorr, mV mV Epit,
Epit, mV
mV
mm/Year
Rate, mm/Year
13Cr-4Ni-1Mo
13Cr-4Ni-1Mo (P110)
(P110) 18.5
18.5 0.156
0.156 −455 −455 −170
−170
13Cr-5Ni-2Mo
13Cr-5Ni-2Mo (P110)
(P110) 21.4
21.4 0.100
0.100 −425 −425 −130
−130
13Cr-5Ni-2Mo (Q135)
13Cr-5Ni-2Mo (Q135) 19.9
19.9 0.056
0.056 −420 −420 −85−85
13Cr-3Ni-1Mo (P110) 16.3 0.409 −475 −190
13Cr-3Ni-1Mo (P110) 16.3 0.409 −475 −190

Figure
Figure 5.
5. Polarization
Polarization curves.
curves.

The potential
potential sweeps
sweeps obtained
obtained during
during the
the research
research process are nearly constant over
time, exhibiting
exhibiting minimal
minimaldeviations
deviationsnot notexceeding
exceeding2020mV mVfrom
fromthethe mean
mean corrosion
corrosion poten-
potential.
tial.
ThisThis stability
stability signifies
signifies the corrosion
the corrosion potential
potential’s s resilience
resilience forinvestigated
for the the investigated materi-
materials in
als
thisinenvironment,
this environment,
enabling enabling an evaluation
an evaluation of the material
of the material’s s corrosion
corrosion resistanceresistance ca-
capability.
Based on the obtained corrosion potential data, it can be hypothesized that the 13Cr-
pability.
3Ni-1Mo
Based steel
on samples exhibit
the obtained lower corrosion
corrosion potentialresistance
data, it cancompared to the others
be hypothesized thatinthe
the13Cr-
same
environment. In this context, the corrosion resistance
3Ni-1Mo steel samples exhibit lower corrosion resistance compared to correlates well with the PREN. When
others in the
comparing
same other characteristics,
environment. In this context, such
theascorrosion
theoretical corrosion
resistance rate andwell
correlates pitting
withpotential,
the PREN. no
significant
When observations
comparing can be made. such as theoretical corrosion rate and pitting po-
other characteristics,
Onno
tential, thesignificant
polarization curves for can
observations all the
be studied
made. steels, there is a passive region (plateau),
typically
On thewithin the potential
polarization curvesrange all−the
for of mV to −
350studied 150 mV.
steels, This
there is region
a passiveis characterized
region (plat-
by a relatively constant current as the potential increases. The presence
eau), typically within the potential range of −350 mV to −150 mV. This region is character- of such a plateau
on the polarization curve indicates the onset of passivity in the examined
ized by a relatively constant current as the potential increases. The presence of such steel. Thus, it cana
be inferred that these steel grades exhibit passivity, signifying their
plateau on the polarization curve indicates the onset of passivity in the examined steel. corrosion resistance
underitthe
Thus, canstudy conditions.
be inferred that these steel grades exhibit passivity, signifying their corrosion
In theunder
resistance case ofthethe 13Cr-5Ni-2Mo
study conditions. (Q135) sample (red curve), it is noteworthy that
thereInare several breakdowns
the case of the 13Cr-5Ni-2Mo before (Q135)
reaching the passive
sample region.
(red curve), it This could be attributed
is noteworthy that there
to the presence of non-corrosion-resistant inclusions on the surface.
are several breakdowns before reaching the passive region. This could be attributed Initially, during the
to the
active passivation process of the surface, a breakdown occurred involving
presence of non-corrosion-resistant inclusions on the surface. Initially, during the active the dissolu-
tion of the inclusion,
passivation process of characterized by a sharp occurred
the surface, a breakdown change in the current
involving density direction
the dissolution of the
inclusion, characterized by a sharp change in the current density direction towards the
towards an increase. Subsequently, the passivation process continued until reaching an
pitting potential.
Therefore, based on the results of the conducted electrochemical investigations, it can
be concluded that the 13Cr-5Ni-2Mo (P110) steel exhibits the lowest corrosion rate in a
CO2 -saturated environment.
 13Cr-4Ni-1Mo (P110) 758 720 Small pittings
13Cr-5Ni-2Mo (P110) 758 150 Many cracks
13Cr-5Ni-2Mo (Q135) 980 170 Pittings, many cracks
Near to the end of the
13Cr-3Ni-1Mo (P110) 758 250
Metals 2023, 13, 1805 working9 of
part
14

The results of the study demonstrated the susceptibility of the examined steels—
3.4. Resistance
namely, to Sulfide of
13Cr-5Ni-2Mo Stress Cracking
both strength grades and 13Cr-3Ni-1Mo—to sulfide stress
crackingThe test conditions
(SSC). were according
Visual examination oftothe
NACE MR0175,
samples Section 3.the
revealed Testpresence
results made
of on
multiple
triplicate specimens are provided in Table 7. Images of samples after testing are
cracks and pittings on their surfaces, as illustrated in Figure 6b–d. However, the 13Cr-4Ni- provided
1Moinsamples
Figure 6.
exhibited a crack-free surface, although some pittings were observed (Figure
6a). Table 7. SSC test results.
It should be noted that while pittings are not considered a definitive criterion for SSC
accordingType to of
NACE Average Time before
Steel TM0177, YS,their
MPa presence suggests lower corrosion resistance in the
Comments
Failure, Hours
tested environment and may serve as potential stress points for further crack initiation, as
13Cr-4Ni-1Mo (P110) 758 720 Small pittings
depicted in Figure 6c. Interestingly,
13Cr-5Ni-2Mo (P110) 758
no pittings were150
observed on the surface of the 13Cr-
Many cracks
5Ni-2Mo specimen
13Cr-5Ni-2Mo following the
(Q135) 980testing procedure. 170 Pittings, many cracks
Even though(P110)
13Cr-5Ni-2Mo Near to the end of the grade),
13Cr-3Ni-1Mo 758specimens have250 the highest strength level (Q135
working part
the time before failure was longer for 13Cr-5Ni-2Mo (P110) (170 h and 150 h, respectively).

(a) (b)

(c) (d)
Figure 6. Specimens
Figure after
6. Specimens SSC
after SSCtest:
test:(a)
(a)13Cr-4Ni-1Mo (P110),
13Cr-4Ni-1Mo (P110), (b)(b) 13Cr-5Ni-2Mo
13Cr-5Ni-2Mo (P110),
(P110), (c) 13Cr-5Ni-
(c) 13Cr-5Ni-
2Mo 2Mo
(Q135), (d) 13Cr-3Ni-1Mo (P110).
(Q135), (d) 13Cr-3Ni-1Mo (P110).

The results of the study demonstrated the susceptibility of the examined steels—
namely, 13Cr-5Ni-2Mo of both strength grades and 13Cr-3Ni-1Mo—to sulfide stress crack-
ing (SSC). Visual examination of the samples revealed the presence of multiple cracks
and pittings on their surfaces, as illustrated in Figure 6b–d. However, the 13Cr-4Ni-1Mo
samples exhibited a crack-free surface, although some pittings were observed (Figure 6a).
It should be noted that while pittings are not considered a definitive criterion for
SSC according to NACE TM0177, their presence suggests lower corrosion resistance in the
tested environment and may serve as potential stress points for further crack initiation,
as depicted in Figure 6c. Interestingly, no pittings were observed on the surface of the
13Cr-5Ni-2Mo specimen following the testing procedure.
Even though 13Cr-5Ni-2Mo specimens have the highest strength level (Q135 grade),
the time before failure was longer for 13Cr-5Ni-2Mo (P110) (170 h and 150 h, respectively).
In addition to convenient SSC cracks directed perpendicular to tensile stresses, cracks
parallel to the direction of the applied load were found for 13Cr-3Ni-1Mo, as shown
in Figure 6. This type of cracking is attributed to stress-oriented hydrogen-induced
cracking (SOHIC).
 In addition to convenient SSC cracks directed perpendicular to tensile stresses, cracks
parallel to the direction of the applied load were found for 13Cr-3Ni-1Mo, as shown in
Metals 2023, 13, 1805 10 of 14
Figure 6. This type of cracking is attributed to stress-oriented hydrogen-induced cracking
(SOHIC).
As we can see from Figure 7, the dissolution of the material exhibits a selective pass.
As we can see from Figure 7, the dissolution of the material exhibits a selective pass.
Studies
Studiesofofnon-metallic
non-metallic inclusions nearthe
inclusions near themetal
metalsurface
surface using
using electrolytic
electrolytic extraction
extraction
methods allow for determining their influence on environmental resistance.
methods allow for determining their influence on environmental resistance. They also They also en-
able the assessment
enable of the
the assessment degree
of the degreeofofmaterial
material dissolution underenvironmental
dissolution under environmental exposure.
exposure.

(a) (b)
Figure 7. 7.
Figure Damages
Damagesand
andpits
pits on
on the sample13Cr-3Ni-1Mo
the sample 13Cr-3Ni-1Mo after
after SSCSSC tests:
tests: (a) side
(a) side #1;side
#1; (b) (b) #2.
side #2.

3.5.3.5.
TheThe AssessmentofofNMIs
Assessment NMIs Using
Using the
theElectrolytic
ElectrolyticExtraction
ExtractionMethod
Method
Table8 8presents
Table presents thethe results
results of ofinclusion
inclusionextraction
extractionusing electrolytic
using extraction
electrolytic and and
extraction
subsequent analysis using SEM. In all steels, manganese sulfide inclusions were found.
subsequent analysis using SEM. In all steels, manganese sulfide inclusions were found. In
In the 13Cr-3Ni-1Mo steel, MnS inclusions have an irregular shape and reach a length of
the 13Cr-3Ni-1Mo steel, MnS inclusions have an irregular shape and reach a length of 14.6
14.6 µm, while in the 13Cr-4Ni-1Mo and 13Cr-5Ni-2Mo steels, the inclusions are rounded
µm, while
with in the 13Cr-4Ni-1Mo
a diameter not exceeding 6.5and µm.13Cr-5Ni-2Mo
The 13Cr-5Ni-2Mo steels, the inclusions
samples are rounded
are characterized by the with
a diameter
presence ofnot exceeding
manganese 6.5 µm.
sulfides andThe 13Cr-5Ni-2Mo samples
molybdenum-containing are which
carbides, characterized
can reduce by the
presence of manganese sulfides and molybdenum-containing carbides,
pitting resistance. Meanwhile, the 13Cr-4Ni-1Mo sample exhibits more characteristic which can reduce
pitting resistance.
titanium Meanwhile,
and niobium nitride the 13Cr-4Ni-1Mo
inclusions, which havesample exhibits
a lesser effectmore
on thecharacteristic
reduction of tita-
corrosion
nium resistance.
and niobium nitride inclusions, which have a lesser effect on the reduction of corro-
Inclusions in steels act as stress concentrators and deteriorate their mechanical proper-
sion resistance.
ties. The stronger
Inclusions the deviation
in steels of the concentrators
act as stress inclusion shapeandfromdeteriorate
spherical and the mechanical
their larger its size,prop-
the more it reduces the mechanical properties of the steel. Additionally, some non-metallic
erties. The stronger the deviation of the inclusion shape from spherical and the larger its
inclusions can act as pitting nucleation sites—corrosion-active non-metallic inclusions. The
size, the more it reduces the mechanical properties of the steel. Additionally, some non-
values of the metal matrix dissolution coefficient around the inclusions (KD ) in the 13Cr-
metallic
3Ni-1Mo inclusions
steel (KDcan act as pitting
(a)~4.5–5.0; nucleation
KD (b)~2.1–5.4) sites—corrosion-active
on average non-metallic
exceed the corresponding valuesinclu-
sions. The values of the metal matrix dissolution coefficient around the
for the steels 13Cr-4Ni-1Mo (KD ~1.5–4.1) and 13Cr-5Ni-2Mo (KD ~1.7–3.3), indicating that inclusions (KD) in
thethe
13Cr-3Ni-1Mo
composition ofsteel these(K D(a)~4.5–5.0;
inclusions may K D(b)~2.1–5.4)
have on average
a greater influence exceed
on the the correspond-
corrosion process.
ing values
The for the of
results steels 13Cr-4Ni-1Mo
electrolytic (KD~1.5–4.1)
etching should and 13Cr-5Ni-2Mo
be carefully (KD~1.7–3.3),
assessed in conjunction with indi-
the results of electrochemical studies. For instance, in the case of the 13Cr-5Ni-2Mo
cating that the composition of these inclusions may have a greater influence on the corro- (Q135)
samples,
sion process.sulfides with molybdenum-containing carbo-nitride inclusions are observed. This
confirms the earlier assumptions regarding the influence of inclusions on passivation
processes. In comparison,
Table 8. Electrolytic etching: 1a,the 13Cr-3Ni-1Mo sample
2a—13Cr-3Ni-1Mo; exhibits less favorable
1b, 2b—13Cr-4Ni-1Mo; inclusion
3—13Cr-5Ni-2Mo.
characteristics than the 13Cr-4Ni-1Mo sample, including size and dissolution coefficient.
Type NMI on Filter Surface NMI on
The high values of KSample
D , as wellSurface Composition
as the presence of large inclusions,Size (µm)
explain the occur-KD
rence of pits on the surface of the 13Cr-3Ni-1Mo steel sample after SSC testing.

1a MnS ~4.6–14.6 ~4.5–5

 size,
size,the
themore
moreititreduces
reducesthethemechanical
mechanicalproperties
propertiesofofthe
thesteel.
steel.Additionally,
Additionally,some
somenon-non-
metallic
metallicinclusions
inclusionscancanact
actasaspitting
pittingnucleation
nucleationsites—corrosion-active
sites—corrosion-activenon-metallic
non-metallicinclu-
inclu-
sions.
sions.The
Thevalues
valuesofofthe
themetal
metalmatrix
matrixdissolution
dissolutioncoefficient
coefficientaround
aroundthetheinclusions
inclusions(K(KD)D)inin
the
the13Cr-3Ni-1Mo
13Cr-3Ni-1Mosteelsteel(K
(KD(a)~4.5–5.0;
D(a)~4.5–5.0;KKD(b)~2.1–5.4)
D(b)~2.1–5.4)on
onaverage
averageexceed
exceedthe thecorrespond-
correspond-
Metals 2023, 13, 1805 ing
ingvalues
valuesfor
forthe
thesteels
steels13Cr-4Ni-1Mo
13Cr-4Ni-1Mo(K (KD~1.5–4.1)
D~1.5–4.1)and
and13Cr-5Ni-2Mo
13Cr-5Ni-2Mo(K (KD~1.7–3.3),
D~1.7–3.3),indi-
indi-
11 of 14
cating
catingthat
thatthe
thecomposition
compositionofofthese
theseinclusions
inclusionsmay
mayhave
haveaagreater
greaterinfluence
influenceon onthe
thecorro-
corro-
sion
sionprocess.
process.
Table 8. Electrolytic etching: 1a, 2a—13Cr-3Ni-1Mo; 1b, 2b—13Cr-4Ni-1Mo; 3—13Cr-5Ni-2Mo.
Table
Table8.8.Electrolytic
Electrolyticetching:
etching:1a,
1a,2a—13Cr-3Ni-1Mo;
2a—13Cr-3Ni-1Mo;1b,
1b,2b—13Cr-4Ni-1Mo;
2b—13Cr-4Ni-1Mo;3—13Cr-5Ni-2Mo.
3—13Cr-5Ni-2Mo.

Type
Type
Type NMI
NMI on
onFilter
NMIon Filter
FilterSurface
Surface NMI
Surface NMI
NMIon
onSample
onSampleSurface
Sample Surface Composition
Surface Composition Size (µm)
Composition Size (µm) KD KKDD
Size(µm)

Metals
Metals
Metals
Metals
Metals
1a1a
1a13,
2023,
2023,
2023, 13,
13,
2023,
2023, 13,
13,
x
x xFOR
FOR
FOR
xFOR
FORPEER
PEER
PEER
PEERREVIEW
REVIEW
REVIEW
REVIEW MnS
MnS
MnS ~4.6–14.6
~4.6–14.6~4.5–5
~4.6–14.6 ~4.5–5
11~4.5–5
1111
11of
ofof
of14
1414
14
Metals
Metals2023, 13,xxxFOR
2023,13, PEER
FORPEER REVIEW
PEERREVIEW
REVIEW 11
11ofof
11 14
of14
14

1b
1b
1b
1b
1b Not
Not
Notobserved
Not
Not observed
observed
observed
observed MnS
MnS
MnS
MnSMnS ~0.5–2.0
~0.5–2.0
~0.5–2.0
~0.5–2.0
~0.5–2.0 -- ---
1b
1b 1b Not
Not
Not observed
observed
observed MnS
MnS
MnS ~0.5–2.0
~0.5–2.0
~0.5–2.0 - --

AlAl
Al
Al
Al22O
22O
22O
O 33+
O
33++33++
Al2Al
O 32O
Al + O3+ +
2a2a
2a2a
2a Ti,Nb-N,C+
Ti,Nb-N,C+
Ti,Nb-N,C+
Ti,Nb-N,C+
Ti,Nb-N,C+ ~3.2–12
~3.2–12
~3.2–12
~3.2–12
~3.2–12 2.1–5.4
2.1–5.4
2.1–5.4 2.1–5.4
2.1–5.4
2a
2a 2a Ti,Nb-N,C+
Ti,Nb-N,C+
Ti,Nb-N,C+ ~3.2–12
~3.2–12 2.1–5.4
~3.2–122.1–5.42.1–5.4
MnS
MnSMnS
MnS
MnS
MnS
MnS MnS

Al
Al2O
2O
3+3+
Al2Al
Al
Al
O 2O
Al
32O
Al + 3+
O
222O
O ++
333+
3+
2b
2b2b
2b2b
2b Ti,Nb-N+
Ti,Nb-N+
Ti,Nb-N+
Ti,Nb-N+
Ti,Nb-N+
Ti,Nb-N+ ~3.2–6.2
~3.2–6.2
~3.2–6.2
~3.2–6.2
~3.2–6.2 1.5–4.1
1.5–4.1
1.5–4.1
~3.2–6.21.5–4.11.5–4.1
1.5–4.1
2b2b Ti,Nb-N+
Ti,Nb-N+ ~3.2–6.2
~3.2–6.21.5–4.1 1.5–4.1
MnS
MnS MnS
MnS
MnS
MnS
MnS
MnS

Al2Al
Al
Al
OAl
Al
Al
2O2O
322O
+ 33+
O
222O
O +333+++
3+
Al O 3+
33
333 Ti,Nb-N,C+
Ti,Nb-N,C+
Ti,Nb-N,C+
Ti,Nb-N,C+
Ti,Nb-N,C+ ~2.5–6.4
~2.5–6.4 1.7–3.3
~2.5–6.41.7–3.3
~2.5–6.4
~2.5–6.4 1.7–3.3
1.7–3.3
1.7–3.3
333 Ti,Nb-N,C+
Ti,Nb-N,C+
Ti,Nb-N,C+
MnS
~2.5–6.4
~2.5–6.4
~2.5–6.4 1.7–3.3
1.7–3.3
1.7–3.3
MnS
MnS
MnS
MnS
MnS
MnS
MnS

The
The
The
4. DiscussionThe
The results
results
results
results
results of
ofof
ofelectrolytic
electrolytic
electrolytic
electrolytic etching
etching
etching
etching should
should
should
should be
be
bebe carefully
carefully
carefully
carefully assessed
assessed
assessed
assessed in
inin
in conjunction
conjunction
conjunction
conjunction with
with
with
with
The resultsofof
Theresults electrolytic
ofelectrolytic
electrolyticetching etching
etchingshould should
shouldbe be carefully
becarefully
carefullyassessed assessed
assessedinin conjunction
inconjunction
conjunctionwith with
with
the
the
the
the
the results
results
results
results
results of
of of
ofelectrochemical
electrochemical
electrochemical
electrochemical studies.
studies.
studies.
studies. For
ForFor
For instance,
instance,
instance,
instance, in
inin
inthe
the
thethe case
case
case
case of
of of
ofthe
thethe
the 13Cr-5Ni-2Mo
13Cr-5Ni-2Mo
13Cr-5Ni-2Mo
13Cr-5Ni-2Mo (Q135)
(Q135)
(Q135)
(Q135)
the
the resultsofof
results
Electrochemical electrochemical
ofelectrochemical
studies of studies.
electrochemical studies.
the samples
studies. ForFor instance,
Forinstance,
of inin
P110 tubing
instance, the
inthethecasecase
caseofof
made the
the
of
of 13Cr-5Ni-2Mo
13Cr-5Ni-2Mo
13Cr-2Ni-grade
the 13Cr-5Ni-2Mosteel (Q135)
(Q135)
(Q135)
samples,
samples,
samples, sulfides
sulfides with
with molybdenum-containing
molybdenum-containing carbo-nitride
carbo-nitride inclusions
inclusions are
are observed.
observed.
servicesulfides
samples,
samples,
samples,
aftersamples, sulfides
sulfides
sulfides
sulfideswith
revealed with
thatmolybdenum-containing
with
with
with molybdenum-containing
molybdenum-containing
molybdenum-containing
pH critically affects the material’s
molybdenum-containing
carbo-nitride
carbo-nitride
carbo-nitride
carbo-nitride
carbo-nitride
inclusions
inclusions
inclusions
inclusions
resistance in the
inclusions
are
areare
are observed.
observed.
observed.
observed.
corrosion-
are observed.
This
This
This
This
This confirms
confirms
confirms
confirms
confirms the
the
thethe
the earlier
earlier
earlier
earlier
earlier assumptions
assumptions
assumptions
assumptions
assumptions regarding
regarding
regarding
regarding
regarding the
the
thethe
the influence
influence
influence
influence
influence of
ofof
ofinclusions
inclusions
inclusions
inclusions on
on on
on passivation
passivation
passivation
passivation
active
This
This environment.
confirms
confirmsthe The
theearlier most
earlier aggressiveregarding
assumptions
assumptions environment
regarding the for
theinfluence
influence ofof
this material inclusions
ofinclusionswas found
inclusions on
on passivation
to be a
onpassivation
passivation
processes.
processes. InIn comparison,
comparison, the the 13Cr-3Ni-1Mo
13Cr-3Ni-1Mo sample
sample exhibits
exhibits less
less favorable
favorable inclusion
inclusion char-
char-
3%processes.
processes.
processes.
NaCl solution
processes.
processes.
In
In In
In comparison,
saturatedthe
comparison,
comparison,
Incomparison,
comparison, the
the
with
the 13Cr-3Ni-1Mo
CO2 , with a sample
13Cr-3Ni-1Mo
13Cr-3Ni-1Mo
the13Cr-3Ni-1Mo
13Cr-3Ni-1Mo pHsample
sample
value
sample
sample
exhibits
exhibits
exhibits
less than
exhibits
exhibits
less
less
less
less
less
favorable
3.0 favorable
favorable
favorable
favorable
inclusion
inclusion
inclusion
at a temperature
inclusion char-
inclusionchar- char-
char-
of
char-
acteristics
◦acteristics
acteristics
acteristics
acteristics than
than
than
than
than the
thethe
the
the 13Cr-4Ni-1Mo
13Cr-4Ni-1Mo
13Cr-4Ni-1Mo
13Cr-4Ni-1Mo
13Cr-4Ni-1Mo sample,
sample,
sample,
sample,
sample, including
including
including
including
including size
size
size
size
size and
and
and
and
and dissolution
dissolution
dissolution
dissolution
dissolution coefficient.
coefficient.
coefficient.
coefficient.
coefficient.
60acteristics
C. In thisthan
acteristics environment,
thanthe four experimental
the13Cr-4Ni-1Mo
13Cr-4Ni-1Mo sample,
sample,including closest
including analogs
size
sizeand of
and 13Cr-Ni-Mo-alloyed
dissolution
dissolutioncoefficient. coefficient. steels
The
The
The high
high
high values
values
values of
ofof K
KK ,,DD,as
,, as
aswellwell asas thethe presence
presence of of large
large inclusions,
inclusions,
(P110),explainexplain the
the occur-
occur-
The high values of K ,Das, as
well
well asas
as the thepresence
presence of of large
large inclusions,
inclusions, explain
explain the
the occur-
occur-
D
were tested The
The
Thehighhigh
for
high values
valuesofof
comparison:
values ofKK
DD
KD13Cr-4Ni-1Mo
as well
aswell
wellas asthe the presence
the(P110),
presence
presence ofof large
13Cr-5Ni-2Mo
oflarge inclusions,
largeinclusions,
inclusions, explain
13Cr-5Ni-2Mo
explain
explainthe the occur-
theoccur-
occur-
rence
rence
rence
rence
rence
(Q135), of
of
andof
of
of pits
pits
pits
pits
pits on
onon
on
on
13Cr-3Ni-1Mothe
the
thethe
the surface
surface
surface
surface
surface of
of
(P110). of
of
of the
the
thethe
the 13Cr-3Ni-1Mo
13Cr-3Ni-1Mo
13Cr-3Ni-1Mo
13Cr-3Ni-1Mo
13Cr-3Ni-1Mo
Based on the steel
steel
steel
steel
steel
results sample
of sample
sample
sample
sample
the after
after
after
after
after
conducted SSC
SSC
SSC
SSC
SSC testing.
testing.
testing.
testing.
testing.
electrochemical
rence of pits on the surface of the 13Cr-3Ni-1Mo
rence of pits on the surface of the 13Cr-3Ni-1Mo steel sample after SSC testing. steel sample after SSC testing.
investigations, it can be concluded that 5Ni-2Mo (P110/Q135) steels exhibit the lowest
4.
4.4.
Discussion
Discussion
Discussion
4. Discussion
4.4. Discussion
corrosion rate in a CO2 -saturated environment (0.056–0.100 mm/year), while 13Cr-3Ni-1Mo
4.Discussion
Discussion
Electrochemical
steel shows Electrochemical
the highest corrosion
Electrochemical
Electrochemical
Electrochemical studies
studies
studies
studies
studies of
ofof
ofthe
ratethe
thethesamples
samples
(0.409
samples
samples of
ofof
mm/year).
ofP110
P110
P110
P110 tubing
Thetubing
tubing
tubing made
made
corrosion
made
made ofof13Cr-2Ni-grade
rate
ofof 13Cr-2Ni-grade
of 13Cr-4Ni-1Mo
13Cr-2Ni-grade
13Cr-2Ni-grade steel
steel
steel
steel
Electrochemical
Electrochemicalstudies studiesofof the
ofthe samples
samplesofof
thesamples P110
ofP110
P110tubingtubing
tubingmade made
madeofof 13Cr-2Ni-grade
of13Cr-2Ni-grade
13Cr-2Ni-gradesteel steel
steel
after
steelafter
afterwas
after
after service
service
the
service
service
service revealed
revealed
median—0.156
revealed
revealed
revealed that
that
that
that
that pH
pH pH
mm/year.
pH
pH critically
critically
critically
critically
critically affects
affects
affects
affects
affects the
the
the
the
the material
material
material
material
material s
s s
sresistance
resistance
resistance
s resistance
resistance in
in in
in
in the
thethe
the
the corrosion-
corrosion-
corrosion-
corrosion-
corrosion-
after
afterservice
servicerevealed
revealedthat thatpH pHcritically
criticallyaffects affectsthe thematerial
materials sresistance resistanceininthe thecorrosion-
corrosion-
active
active
active
active environment.
environment.
environment.
environment. The
The
TheThe most
most
most
most aggressive
aggressive
aggressive
aggressive environment
environment
environment
environment for
for
forfor this
this
this
this material
material
material
material was
was
was
was found
found
found
found to
toto
to be
bebe
beaaa
active
active environment.
activeenvironment.
environment.The The
Themostmost aggressive
mostaggressiveaggressiveenvironment environment
environmentfor for this
forthis material
thismaterial
materialwas was
wasfoundfound
foundtototobe beaaaa
be
3%
3%3%
3% NaCl
NaCl
NaCl
NaCl solution
solution
solution
solution saturated
saturated
saturated
saturated with
with
withwith CO
COCO
CO 22,,22with
,, with
withaaaaapH
with pHpH value
value
value less
less
less than
than
than 3.0
3.03.0 at
atataaatemperature
temperature
temperature of
ofof60
60 60
3%
3% NaCl
3%NaCl solution
NaClsolution saturated
solutionsaturatedsaturatedwith with
withCO CO
CO , with
2,22,withwitha apH pH
pH value
value
pHvalue
valueless less
less than
than
lessthanthan3.0 3.0
3.0 at
ataaaatemperature
3.0atat temperature
temperature
temperatureofof of 60
60
of6060
°C.
°C.
°C.
°C.
°C. In
InIn
In
In this
this
this
this
this environment,
environment,
environment,
environment,
environment, four
four
four
four
four experimental
experimental
experimental
experimental
experimental closest
closest
closest
closest
closest analogs
analogs
analogs
analogs
analogs of
ofof
of
of 13Cr-Ni-Mo-alloyed
13Cr-Ni-Mo-alloyed
13Cr-Ni-Mo-alloyed
13Cr-Ni-Mo-alloyed
13Cr-Ni-Mo-alloyed steels
steels
steels
steels
steels
°C. In this environment, four experimental closest
°C. In this environment, four experimental closest analogs of 13Cr-Ni-Mo-alloyed steels analogs of 13Cr-Ni-Mo-alloyed steels
were
were
were
were
were tested
tested
tested
tested
tested for
for
for
for
for comparison:
comparison:
comparison:
comparison:
comparison: 13Cr-4Ni-1Mo
13Cr-4Ni-1Mo
13Cr-4Ni-1Mo
13Cr-4Ni-1Mo
13Cr-4Ni-1Mo (P110),
(P110),
(P110),
(P110),
(P110), 13Cr-5Ni-2Mo
13Cr-5Ni-2Mo
13Cr-5Ni-2Mo
13Cr-5Ni-2Mo
13Cr-5Ni-2Mo (P110),
(P110),
(P110),
(P110),
(P110), 13Cr-5Ni-2Mo
13Cr-5Ni-2Mo
13Cr-5Ni-2Mo
13Cr-5Ni-2Mo
13Cr-5Ni-2Mo
were
weretestedtestedfor forcomparison:
comparison:13Cr-4Ni-1Mo 13Cr-4Ni-1Mo(P110), (P110),13Cr-5Ni-2Mo
13Cr-5Ni-2Mo(P110), (P110),13Cr-5Ni-2Mo
13Cr-5Ni-2Mo
(Q135),
(Q135),
(Q135),
(Q135),and and
and 13Cr-3Ni-1Mo
13Cr-3Ni-1Mo
and13Cr-3Ni-1Mo
13Cr-3Ni-1Mo(P110). (P110).
(P110). Based
(P110).Based Based
Basedononthe onon the
the results
results
theresults of
resultsofofthe ofthe
the conducted
conducted
theconducted electrochemical
electrochemical
conductedelectrochemical
electrochemical
Metals 2023, 13, 1805 12 of 14

The results of autoclave tests in a 5% NaCl and 0.5% acetic acid solution with a pH
of 3–4 at a temperature of 80 ◦ C for 240 h showed that the samples of 13Cr-4Ni-1Mo steel
(0.0019 mm/year), 13Cr-5Ni-2Mo—P110 (0.0007 mm/year), and 13Cr-5Ni-2Mo—Q135
(0.0025 mm/year) exhibited low corrosion rates without critical pittings. For the samples
of 13Cr-3Ni-1Mo steel, passivation was absent under the conditions of the autoclave tests,
which was manifested by the presence of a uniform layer of corrosion products on the
surface. The corrosion rate of 13Cr-3Ni-1Mo steel was 0.0106 mm/year.
The resistance to sulfide stress cracking (SSC) was evaluated according to NACE
TM0177, Method A, on cylindrical samples immersed in a solution of 5% NaCl and 0.5%
acetic acid, saturated with 10% H2 S, for 720 h. The results showed that only the sample of
13Cr-4Ni-1Mo steel did not fracture during the testing. The samples of 13Cr-5Ni-2Mo (P110),
13Cr-5Ni-2Mo (Q135), and 13Cr-3Ni-1Mo (P110) steels exhibited a high susceptibility to
SSC, fracturing after 150, 170, and 250 h of testing, respectively. Secondary cracks were
observed on all fractured samples, and pitting was observed on the samples of 13Cr-5Ni-
2Mo (P110) and 13Cr-3Ni-1Mo steels.
The evaluation of non-metallic inclusions (NMIs) using the electrolytic extraction
method showed that the samples of 13Cr-4Ni-1Mo steel contained inclusions of more favor-
able shape, size, and chemical composition compared to the other steels. The occurrence of
pitting in 13Cr-3Ni-1Mo steel after SSC testing can be attributed to the presence of large
manganese sulfide inclusions. The pitting in 13Cr-5Ni-2Mo (Q135) steel after SSC testing
can be attributed to the presence of corrosion-active molybdenum carbide inclusions.
Based on the results of the study, increasing the nickel and molybdenum content in
steels of this class does not lead to a directly proportional increase in corrosion resistance in
a model environment approximating operational conditions. The research has shown that
high-strength 13Cr materials, slightly inferior to supermartensitic ones, due to increased
carbon content, may still exhibit satisfactory resistance in CO2 environments and low con-
centrations of H2 S. Furthermore, metallurgical quality and chemical composition influence
the formation of specific non-metallic inclusions, relevant to this type of material, which
have a significant impact on the corrosion resistance of stainless steel.
Thus, among the investigated steel types, 13Cr-4Ni-1Mo steel proves to be the most
optimal, demonstrating high resistance to SSC, low corrosion rates under aggressive auto-
clave test conditions, satisfactory results in electrochemical testing, and containing more
favorable types of small-sized non-metallic inclusions.

5. Conclusions
Tests were carried out to determine the corrosion characteristics of experimental
steel grades with the determination of resistance to sulfide stress corrosion cracking, the
determination of the corrosion rate in autoclave tests under conditions close to opera-
tional, and the determination of the corrosion-electrochemical characteristics in a CO2 -
saturated environment. The influence of the chemical composition, structure and metallur-
gical quality, and production technology on the corrosion properties of the studied steels
is determined.
1. Tests were carried out to determine the corrosion characteristics of experimental steel
grades with the determination of resistance to sulfide stress corrosion cracking, the
determination of the corrosion rate in autoclave tests in conditions close to opera-
tional, and the determination of the corrosion-electrochemical characteristics in a
CO2 -saturated environment.
2. When tested to determine the resistance to sulfide cracking under stress in accordance
with NACE TM-0177, Method A, at a load of 80% of the minimum yield strength, all
test steels showed a tendency to crack. However, steel 13Cr-4Ni-1Mo (P110) did not
fracture during the tests, although there are cracks on two of the three samples.
3. According to the results of electrochemical studies carried out in a CO2 -saturated
environment at pH 2.8–3 and a temperature of 60 ◦ C, it was shown that 13Cr-4Ni-
Metals 2023, 13, 1805 13 of 14

1Mo (P110), 13Cr-5Ni-2Mo (P110), and 13Cr-5Ni-2Mo (Q135) steels have the lowest
corrosion rate.
4. The results of autoclave tests at a pH of 3–4 and a partial pressure of carbon dioxide
of 3 MPa at a total pressure of 5 MPa in a CO2 -saturated solution at a temperature of
80 ◦ C are consistent with the results of electrochemical tests. It has also been shown
that steel 13Cr-4Ni-1Mo (P110), 13Cr-5Ni-2Mo (P110), and 13Cr-5Ni-2Mo (Q135) have
the highest corrosion resistance in a CO2 -saturated environment. Steel 13Cr-3Ni-1Mo
(P110) had the lowest corrosion resistance during autoclave tests.
5. The metallurgical quality, shape, size, and type of non-metallic inclusions allow one
to obtain an economically alloyed 13Cr-type steel of martensitic class with satisfactory
resistance in CO2 and H2 S environments: 13Cr-4Ni-1Mo.

Author Contributions: Conceptualization, A.D. and E.A.; data curation, O.S., N.D. and K.L.; investi-
gation, A.D., E.A. and V.K.; methodology, A.D. and D.S.; project administration, A.D., E.A., N.D. and
A.A.; resources, O.S., N.D. and K.L.; supervision, A.D., E.A. and K.L.; validation, A.D.; visualization,
A.D. and V.K.; writing—original draft, A.D. and V.K.; writing—review and editing, A.D. and E.A. All
authors have read and agreed to the published version of the manuscript.
Funding: The research was financially supported by the Ministry of Science and Higher Education
of the Russian Federation under the World Class Research Centre Program: Advanced Digital
Technologies (Agreement No. 075-15-2020-311 dated 20 April 2022).
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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