materials
Review
Current Downhole Corrosion Control Solutions and Trends in
the Oil and Gas Industry: A Review
Vera A. Solovyeva 1, * , Khaled H. Almuhammadi 2 and Wael O. Badeghaish 2
Citation: Solovyeva, V.A.;
Almuhammadi, K.H.; Badeghaish,
W.O. Current Downhole Corrosion
Control Solutions and Trends in the
Oil and Gas Industry: A Review.
Materials 2023, 16, 1795. https://
doi.org/10.3390/ma16051795
Academic Editor: Mingchun Zhao
Received: 13 October 2022
Revised: 11 November 2022
Accepted: 16 February 2023
Published: 22 February 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/).
Materials 2023, 16, 1795. https://doi.org/10.3390/ma16051795
1 Aramco Innovations LLC, 119234 Moscow, Russia
2 Saudi Aramco EXPEC ARC, Dhahran 31311, Saudi Arabia
* Correspondence: vera.solovyeva@aramcoinnovations.com
Abstract: In the oil and gas industry, the presence of aggressive fluids and gases can cause serious
corrosion problems. Multiple solutions have been introduced to the industry to minimize corrosion
occurrence probability in recent years. They include cathodic protection, utilization of advanced
metallic grades, injection of corrosion inhibitors, replacement of the metal parts with composite solu-
tions, and deposition of protective coatings. This paper will review the advances and developments
in the design of corrosion protection solutions. The publication highlights crucial challenges in the oil
and gas industry to be solved upon the development of corrosion protection methods. According
to the stated challenges, existing protective systems are summarized with emphasis on the features
that are essential for oil and gas production. Qualification of corrosion protection performance based
on international industrial standards will be depicted in detail for each type of corrosion protection
system. Forthcoming challenges for the engineering of next-generation materials for corrosion miti-
gation are discussed to highlight the trends and forecasts of emerging technology development. We
will also discuss the advances in nanomaterial and smart material development, enhanced ecological
regulations, and applications of complex multifunctional solutions for corrosion mitigation which
have become of great importance in recent decades.
Keywords: corrosion control methods; metal protection solutions; cathodic protection; corrosion
resistant alloys; corrosion inhibitors; composites; protective coatings
1. Introduction
In the oil and gas industry, corrosion-related failures have been reported to constitute
over 25% of total safety incidents [1,2]. The problem of corrosion in oilfield environments
is predominantly associated with the presence of dissolved acidic gases in reservoir brine
such as CO2 (causing sweet corrosion) and H2 S (causing sour corrosion); oxygen-related
corrosion is encountered in the water injection systems, other associated reservoir con-
stituents, and some as-manufactured defects on metallic components. The consequences of
corrosion have large impacts in oil and gas operations. The corroded tubing/casing string
can threaten the well integrity and affect the production rate [3]. A statistical breakdown of
oilfield corrosion-related failures is shown in Table 1 [1]. According to NACE [4], in 2013,
the global cost of corrosion-related economic losses for all industries is estimated to be USD
2.5 trillion which is 3.4% of global gross domestic product (GDP) including corrosion in
the oil and gas production industry where the total annual cost of corrosion is estimated
to be USD 1372 billion [5]. Application of best corrosion control practices can save up to
35% of corrosion-related losses, which are up to USD 875 billion annually including USD
463 million annually in downhole tubing expenses, and another USD 320 million in capital
expenditures related to corrosion [6]. Effective management of corrosion will contribute to
an essential reduction of corrosion costs and extension of the lifetime of safe operations.
https://www.mdpi.com/journal/materials
 Table 1. Cause of corrosion-related failure in petroleum-related industries [1].

Type of Failure Total Failure (%)

Materials 2023, 16, 1795 CO2-related 28 2 of 33
H2S-related 18
Preferential weld 18
Table 1. Cause of corrosion-related failure in petroleum-related industries [1].
Localized pitting 12
Erosion
Type corrosion
of Failure Total Failure (%) 9
CO2 -related
Galvanic 28 6
H2 S-related 18
Crevice
Preferential weld 18 3
Impingement
Localized pitting 12 3
Erosion corrosion 9
Stress
Galvaniccorrosion 6 3
Crevice 3
Impingement 3
Although it is not a new
Stress corrosion
problem, corrosion remains
3
the main obstacle for su
operations and commodity integrity in the oil and gas industry.
Corrosion
Although it isoccurs when
not a new water
problem, is presented
corrosion remains atthethe
mainsystem and
obstacle wets the metal
for successful
This process
operations and is composed
commodity of three
integrity elements
in the oil and gasthat form the electrochemical cell: an a
industry.
cathode, and an electrolyte (Figure 1) [3]. The anodeand
Corrosion occurs when water is presented at the system is wets the metal
the site surface.
of metal corrosion
This process is composed of three elements that form the electrochemical cell: an anode, a
it dissolves and generates positively charged metal ions [7]. At the same time, el
cathode, and an electrolyte (Figure 1) [3]. The anode is the site of metal corrosion, where
transfer from
it dissolves the anode
and generates to the cathode.
positively The ions
charged metal cathode
[7]. Atisthe
ansame
electron-acceptor
time, electrons that i
consumed.
transfer from Since the to
the anode most commonly
the cathode. used metal
The cathode in the petroleum
is an electron-acceptor industry
that is not be is carbo
consumed. Since the most commonly
the metal of corrosion is iron. used metal in the petroleum industry is carbon steel,
the metal of corrosion is iron.

Figure 1.1.Local
Figure Localcorrosion on steel
corrosion on surface [3].
steel surface [3].
Traditionally, most wells were completed with regular low-carbon steel (J-55 [8],
Traditionally,
L-80 [8,9] and C-95 [9])most wells
that has werebeen
always completed
the primarywith regular
material usedlow-carbon
in oil and gas steel (J-5
80 [8,9] and
operations C-95 of
because [9])
itsthat has always
strength, stiffness,been the primary
toughness, material
and tolerance to highused in oil and ga
tempera-
tures [3], [10]. However, as most of the metals are susceptible to corrosion,
ations because of its strength, stiffness, toughness, and tolerance to high temperatu it also causes
steel degradation that results in the loss of strength and ductility, reduction in the thickness
[10]. However, as most of the metals are susceptible to corrosion, it also causes ste
of the pipes, and sometimes even ultimate failure [11]. Such consequences are especially
radation that results
fast and noticeable in the
in a harsh loss of strength
operational environment and ductility,
with reduction
a high partial pressure inofthe
COthicknes
2
pipes,
and H2 S, at high concentrations of chloride ions, or in the presence of elemental sulfur especially
and sometimes even ultimate failure [11]. Such consequences are (S0 ).
Sweet corrosion,
noticeable in a harshwhich occurs whenenvironment
operational carbon dioxide is dissolved
with a highin water
partialto produce
pressure of C
carbonic acid, promotes the electrochemical reaction between the steel surface and the
H2S, at high concentrations of chloride ions, or in the presence of elemental sulfur
contacting aqueous phase. FeCO3 is the main corrosion product formed in a sweet corrosion
Sweet corrosion,
environment. Iron carbonate which
formsoccurs when carbon
a semi-protective film ondioxide
top of theis dissolved
steel in water
surface [12]. At to p
carbonic
a high partialacid, promotes
pressure of CO2 andtheelevated
electrochemical
temperatures, reaction between
the solubility of FeCO the steel surface
3 decreases
leading to precipitation of the iron carbonate protective scale
contacting aqueous phase. FeCO3 is the main corrosion product formed in that prevents corrosion; at a swee
low temperatures,
sion environment. the corrosion rate progress
Iron carbonate forms[1].a semi-protective film on top of the steel

[12]. At a high partial pressure of CO2 and elevated temperatures, the solubility o
decreases leading to precipitation of the iron carbonate protective scale that preve
rosion; at low temperatures, the corrosion rate progress [1].
Sour corrosion, on the other hands, takes place as hydrogen sulfide (H2S) d
in water and reacts with steel to form iron sulfide (FeS) [3]. FeS has limited solubi
forms a semi-protective layer on the steel surface. However, iron sulfide itself wo
Materials 2023, 16, 1795 3 of 33

Sour corrosion, on the other hands, takes place as hydrogen sulfide (H2 S) dissolves
in water and reacts with steel to form iron sulfide (FeS) [3]. FeS has limited solubility and
forms a semi-protective layer on the steel surface. However, iron sulfide itself works as
a cathode to steel, and such precipitate will form an electrochemical potential difference
and accelerate the corrosion. In addition to the electrochemical corrosion caused by H2 S,
the most harmful effect of H2 S is the possibility of causing mechanical chemical corrosion,
such as sulfide stress cracking (SSC) [13] and hydrogen-induced cracking (HIC) [3,7,8]. SSC
provides the highest risk for OCTG due to the fast and catastrophic failures it causes to the
system [5]. SSC is a form of hydrogen embrittlement that occurs in high-strength steels and
in localized hard zones in weldment of susceptible metals under certain stress conditions.
It depends on the amount of atomic hydrogen presented in the metal lattice as well as
on the metal composition, microstructure, and total stress level applied to steel. HIC is a
cathodic cracking mechanism that takes place without external stress when steel reacts with
hydrogen sulfide and forms iron sulfide and atomic hydrogen. Atomic hydrogen either
diffuses into bulk metal or recombines at the metal surface to form H2 . Dissolved aqueous
H2 S prevents hydrogen recombination at the surface [14]. Therefore, the part of atomic
hydrogen that diffuses into the metal matrix is essential; it causes hydrogen embrittlement
and cracking. Hydrogen-induced cracking is caused by the blistering of metal due to a high
concentration of hydrogen that collects and recombines at inclusions or impurities of steel.
Preventing corrosion in the oil industry is essential to the overall functional integrity
of the system. Fast development of smart materials and nanomaterials would allow us
to achieve this goal. To bridge the lack of a comprehensive summary of classical and
novel methods of corrosion protection and their testing techniques, this work aims to
review the most common approaches to mitigate corrosion in downhole applications and
summarize the general qualification standards and practice for evaluation of each type
of corrosion protection. The survey of corrosion control methods includes application of
protective coatings, electrochemical corrosion mitigation via cathodic protection, utiliza-
tion of corrosion-resistant alloys, and injection of corrosion inhibitors. The overview of
each protection method includes discussions of the methods and their quality evaluation.
Further, we will outline new trends and aspects to consider in the development of novel
anticorrosive materials, highlighting the most recent trends and achievements of material
science in the development of corrosion prevention solutions focused on the current indus-
trial challenges. To conclude this work, we will provide our view on future directions for
the development of advanced anticorrosive materials with special emphasis on self-healing
agents, nanocomposites, and environmentally friendly formulations.

2. Corrosion Control Methods

Commonly, corrosion control focuses on materials and environments. Corrosion
control methods aim to eliminate the elements of corrosion (an anode, a cathode, and an
electrolyte) or preventing these elements from reacting with one another [11]. Corrosion
protection could be active or passive. Active protection is the protection that works by
taking effective control of the process of corrosion, which includes the modeling of the
system, material selection, and general design. Passive protection on the other hand means
protection where corrosion is removed or its rate is reduced, by isolation of the material
from the corrosive media through the application of barrier layers of coatings, imposing
cathodic protection, injection of corrosion inhibitors, and usage of non-metallic composites
for downhole equipment protection [15]. Among the active protection methods, selection of
appropriate corrosion-resistant alloys and substitution of the metal parts with composites
should be noted. The classification of methods utilized for the protection of metals against
corrosion is shown in Figure 2.
Materials 2023, 16, x FOR PEER REVIEW 4 of 34
Materials 2023, 16, 1795 4 of 33

Figure 2. Summary
Figure 2. Summary on
on corrosion
corrosion control
control methods.
methods.

Below
Below we
we will
will focus
focus on
on each
each type
type of
of corrosion
corrosion control
control method
method in
in detail
detail along
along with
with
their qualifications.
their qualifications.
2.1. Corrosion Control by Protective Coatings
2.1. Corrosion Control by Protective Coatings
External and internal coating deposition is the most cost-effective and widely used
External and internal coating deposition is the most cost-effective and widely used
method to prevent corrosion and ensure the integrity of the downhole Oil Country Tubular
method to prevent corrosion and ensure the integrity of the downhole Oil Country Tub-
Goods (OCTG). Corrosion control by coatings and linings (of interior surfaces) is a passive
ular Goods (OCTG). Corrosion control by coatings and linings (of interior surfaces) is a
protection. Protective coatings may possess various characteristics, but they have distinct
passive protection.
advantages over theProtective coatings
other methods may possess
of corrosion various
control. characteristics,
These include: but they have
distinct advantages over the other methods of corrosion control. These include:
• Ease of application;
•• Ease of
Ease of storage
application;
and handling;
•• Range ofstorage
Ease of and handling;
acceptable ambient conditions;
•• Range
Economics;of acceptable ambient conditions;
•• Economics;
Ease of restoration.
• Ease of restoration.
2.1.1. Basic Principles
2.1.1. Basic Principles
Corrosion occurs at the steel interface and this problem is the focus of surface engineer-
Corrosion
ing (SE). Surfaceoccurs at the steel
engineering, which interface and this problem
is a multidisciplinary is thearea,
research focus of surface
aims engi-
to overcome
neering
issues of(SE). Surface engineering,
degradation and failure ofwhich is a multidisciplinary
equipment that are caused by research
surfacearea, aims to
processes over-
such as
come corrosion,
wear, issues of degradation
and erosion.and failure
Basic of equipment
principles of surface that are causedinclude
engineering by surface processes
various types
such
of as wear,
surface corrosion, (i.e.,
modifications and surface
erosion.hardening,
Basic principles
plasma ofthermochemical
surface engineering includelaser
processing, var-
ious types of surface modifications
processing) and coating application. (i.e., surface hardening, plasma thermochemical pro-
cessing, laser processing) and coating application.
2.1.2. Types of Coatings
2.1.2.The
Typesbasicof function
Coatingsof coatings is to provide a barrier of protection to a metal surface,
insulating it from
The basic functioncontactofwith moisture,
coatings electrolytes,
is to provide corrosive
a barrier gases (oxygen,
of protection soursurface,
to a metal gases),
and environmental
insulating threatswith
it from contact like moisture,
fluids flow, cuts, and contact
electrolytes, with
corrosive soil.(oxygen,
gases Functional
sourcoatings
gases),
would be selected based
and environmental on specific
threats functions
like fluids suchand
flow, cuts, as mechanical
contact withprotection [16], antifouling
soil. Functional coatings
action
would[17], corrosion
be selected resistance
based [18], functions
on specific and others. Theasbroad
such class ofprotection
mechanical anticorrosive
[16],coatings is
antifoul-
designed to eliminate corrosion. Depending on the surface to protect, the coatings
ing action [17], corrosion resistance [18], and others. The broad class of anticorrosive coat- could be
ings is designed to eliminate corrosion. Depending on the surface to protect, the coatings
als 2023, 16, x FOR PEER REVIEW 5 of 34
Materials 2023, 16, 1795 5 of 33

could be external and internal; fusion-bond epoxies (FBE) could protect both internal and
external
external surfaces and internal;
of tubulars [19,20].fusion-bond epoxies (FBE) could protect both internal and external
surfaces
The external of tubulars
coating creates a[19,20].
barrier between the tubular and the external environ-
The external
ment such as moisture, seawater,coating creates
fouling, a barrier
rocks and soils,between the tubular
cement casings, and
and so on.the external environ-
These
ment such as moisture, seawater, fouling,
coatings often provide improved mechanical protection. rocks and soils, cement casings, and so on. These
coatings often provide improved mechanical protection.
The internal coating protects the tubular internal wall from the flow media, increases
pipe smoothness and Theflow
internal coating protects
characteristics, the the
prevents tubular internal
corrosive walloffrom
action themoisture,
acids, flow media, increases
pipe smoothness
electrolytes, hydrocarbons, andand
sourflow
gas characteristics,
exposure, as wellprevents the corrosive
as reduces scale andaction of acids, moisture,
asphalting
deposition. electrolytes, hydrocarbons, and sour gas exposure, as well as reduces scale and asphalt-
ing deposition.
For downhole applications, several types of coatings are used that can be divided
For downhole
into metallic, non-metallic, applications,
and mixed severalNon-metallic
type coatings. types of coatings arecan
coatings usedbethat can be divided
either
into metallic, non-metallic,
organic or inorganic (Figure 3). and mixed type coatings. Non-metallic coatings can be either
organic or inorganic (Figure 3).

Figure 3. TypesFigure
of protective
3. Typescoatings for downhole
of protective coatingsapplications.
for downhole applications.

Metallic Coatings
Metallic Coatings
Metallic
Metallic coatings coatings
are thin layersare
of thin layers
metals of metals
deposited deposited
onto the steel onto the Insulative
surface. steel surface. Insulative
coatings consist of less reactive metals which are used to coat the
coatings consist of less reactive metals which are used to coat the base metal, for example, base metal, for example,
nickel-plated steel. A sacrificial coating consists of a more reactive
nickel-plated steel. A sacrificial coating consists of a more reactive metal that is deposited metal that is deposited
on the steel surface, e.g., zinc-coated steel. Important metals used for coating deposition deposition
on the steel surface, e.g., zinc-coated steel. Important metals used for coating
arechromium,
are nickel, zinc, nickel, zinc, chromium,
tin, aluminum, tin, aluminum,
copper, copper,
and others and
[15]. Inothers [15].
addition toIn addition to metals,
metals,
alloys could also be deposited as metal coatings; thus, NiAl, FeCr, FeCoCr, FeCoCrNi,
alloys could also be deposited as metal coatings; thus, NiAl, FeCr, FeCoCr, FeCoCrNi, and
and FeCrNi coatings [21] have been suggested for steel protection. The advantages of
FeCrNi coatings [21] have been suggested for steel protection. The advantages of metallic
metallic coatings are remarkable corrosion resistance, excellent mechanical properties,
coatings are remarkable corrosion resistance, excellent mechanical properties, uniform
uniform film deposition, very good wear resistance, high hardness, abrasion resistance,
Materials 2023, 16, 1795 6 of 33

high adhesion with excellent range of temperature and pressure resistance, as well as
tunable acid stability. Conventionally, most of the metallic coatings would be applied
via methods such as electroplating, cladding, electroless coatings, spraying, hot dipping,
galvanizing, anodizing, plating, sputtering, and chemical vapor deposition. A few of the
most common methods of metal coating deposition used in the oil and gas industry are:
• Hot-dip galvanizing—immersion of steel substrate into a bath of molten zinc [22].
Additionally, hot dipping technology could be applied for aluminum, zinc–aluminum
alloys, tin, antimony, lead, and other low-melting-point metals and alloys.
• Electroplating—deposition of a metal coating on top of other metals via reduction of
the cations of the coating metal upon application of a direct external electric current.
The most widely used electroplated metals are zinc, nickel, copper, and chromium [22].
• Electroless nickel plating [23]—autocatalytic chemical reduction that deposits a uni-
formly thick layer of amorphous nickel or nickel–phosphorus alloy on top of the
substrate. The process occurs upon dipping the substrate into a solution of nickel
salt and the reducing phosphorus agent (commonly sodium hypophosphite) with
no use of an external current. The content of the phosphorus governs the coating’s
microstructure, ductility, and rate of deposition. Rod pumps, packers, mud pumps,
collars, couplings, safety valves, and other equipment are coated with electroless
nickel plating in petrochemical applications due to its great chemical resistance [23].
• Thermal spraying—atomization of molten or semi-molten droplets by the impinge-
ment of quickly moving and continuously flowing atomization gas onto the prepared
base surface [24].
Numerous advantages of the metallic coatings listed above led to the extensive de-
velopment of advanced coating deposition methods, inventions of numerous coating
compositions, and coatings specialization; however, their cost is about 5–10 times more
expensive than carbon steel, and their application techniques involve toxic chemicals.
Considering rising environmental regulations on heavy metals, cyanides, and toxic gas
pollution, the engineering of an alternative type of coating is essential.

Non-Metallic Coatings
Thermoplastic and thermosets are the most common key components of the non-
metallic coatings that have been used for rehabilitation of the existing OCTG and for
deposition on new products. Non-metallic coatings can be subdivided into organic (poly-
mers) and inorganic (oxides, phosphates, nitrides, sulfides, carbides, etc.) [25].

Organic Coatings
Organic coatings consist of mixtures of binder, pigments, fillers, solvents, and additives
where the binder is the major component of the coating. It determines the nature of
the coating system that can be epoxy, phenolic, polyolefins, polyurethanes, polyamides,
combinations thereof, and others. Fillers serve specific coating functions, for example,
extended anticorrosive action such as zinc-rich epoxy [26] where zinc is used as a sacrificial
agent or as corrosion-inhibiting zinc phosphate fillers [27]. Solvents are optional in the
coating composition but for the multi-component liquid formulations, the solvents are the
components that help in uniformly dispersing all the other ingredients in the formulation.
Additives can serve various purposes; they may be present as reinforcement agents such as
carbon black, graphene [28], mica, clay, aramid, and carbon and glass fibers [29] to provide
strength and additional mechanical stability. Additionally, they may act as curing or flow
control agents or many other functions.
There is a wide variety of organic OCTG internal coatings including epoxy, FBE,
phenolic, modified epoxy–phenolic, modified urethanes, nylon, [30] and composite fiber-
glass coatings.
Epoxy coatings consist of diglycidyl ethers of bisphenol A [31], F, and other bisphenol
moieties. The curing agents, such as aromatic (methylene dianiline) and aliphatic diamines
(isophorone diamine) and polyamines, drastically influence the nature and the properties
Materials 2023, 16, 1795 7 of 33

of the final coating. Basic epoxies are thermosets that are stable until 175 ◦ F and are
constructed from bisphenol A and epichlorohydrin building blocks. The common examples
of classical epoxies are Epon, Durcon, and Araldite [30]. These coatings possess good
chemical resistance and excellent flexibility in thick films of 254–381 µm (10–15 mils) [32].
Phenolic coatings are thermosets based on phenol–formaldehyde with the most well-
known example being Bakelite [30]. These coatings are stabile up to 400 ◦ F and are
chemically resistant to brine containing CO2 and oxygen, or hydrochloric and hydrofluoric
acids. These coatings possess high rigidity and mechanical properties but are not as flexible
as epoxies.
Novolac resins are highly crosslinked phenol formaldehyde resins with a ratio of
phenol to formaldehyde of less than one. It often contains cresol moieties instead of or in
addition to phenol and is produced by acid-catalyzed polymerization. Hexamethylenete-
tramine is a common hardener agent to crosslink novolacs.
Epoxy–phenolic resins are phenolic resins with the aromatic hydroxyl position modified
with epichlorohydrin to introduce an epoxide functional group. This resin possesses a high
degree of crosslinking compared to the phenolic analog due to additional epoxy functions.
Modified epoxy–phenolic coatings consist of epoxy–phenolic resin components mod-
ified with inorganic fillers to increase abrasion resistance [33]. These coatings possess
general resistance to chemicals, are stable up to 400 ◦ F/204 ◦ C, and can be applied in thin
films that are 127–228.6 µm (5–9 mils) thick [32].
Urethanes or polyurethanes could be both thermoset and thermoplastic coatings.
They are formed upon reaction of di- or triisocyanates with polyols to form alternating
copolymers linked by carbamate units. For high performance coatings, fluorinated polyols
are often used.
Modified urethanes are polyurethane matrices modified with inorganic fillers like
ceramics and/or glass particles to increase wear, and corrosion and abrasion resistance.
Urethane resin coatings have high resistance to water, oil, and hydrocarbons [34] as well
as good elastic properties and are stable up to 400 ◦ F/204 ◦ C if applied as 127–228.6 µm
(5–9 mils)-thick films [32].
Nylon is a family of thermoplastic polyamide coatings. They possess chemical re-
sistance to water, carbon dioxide, and hydrocarbons with temperature stability up to
107 ◦ C/225 ◦ F [30].
Fluoropolymer-based (FP) thermoplastic downhole coatings protect OCTG at HTHP
conditions of 8000 psi, 350 ◦ F in sweet and sour media [35]. New generations of engineered
FP superhydrophobic coatings additionally prevent the formation of organic (asphaltenes
and paraffins) and inorganic (carbonates, BaSO4 ) deposits on the surface of production
pipes for both oil and gas wells. Nowadays, FP-based coating systems could address the
challenges that previously could be resolved only with the utilization of CRAs. Current FP
coatings are recommended for wells with a harsh corrosive environment, pressures above
10,000 psi, temperatures above 392 ◦ F/200 ◦ C, content of H2 S above 15%, and high salinity
of production brine.
Some of the abovementioned OCTG coatings, their stability and applications in oil
production are listed in Table 2.
The great progress in polymer design and synthesis achieved in the recent decades
led to a breakthrough in the properties of organic coating formulations that brought their
performance close to the reliability and robustness of metallic materials. Moreover, these
novel organic coatings still retain their major advantages in cost efficiency, ease of deposition
and repair, as well as being light weight and having tunable elasticity. Considering the
number and varieties of commercially available polymers and the vast possibilities for their
modifications with advanced fillers, composite coating formulations could reach further to
overcome the metals. Furthermore, tuning of organic matrices with nanomaterials allows
for noticeable improvements in the performance even at a low filler loading.
Materials 2023, 16, 1795 8 of 33

Table 2. Coating systems and their application in the protection of downhole OCTG.

Maximum Temperature, Applied Thickness,

Coating System ◦F Primary Usage
µm
Epoxy 175 [36]; 195 [37] 254–381 (10–15 mils) [36] Completions [36]
Phenolic [33] 400 127–203 Production/Injection Tubing
Novolac [36] 250 254–457 (10–18 mils) Tubing String (OCTG)
Epoxy–Novolac [33,38] 400 152–330 Production/Injection Tubing
Epoxy–Phenolic [33] 400 127–229 (5–9 mils) Drilling/Completions
Modified Epoxy–Phenolic [33] 400 127–229 Drilling/Completions
Phenolic–Novolac [33] 350 152–330 Production/Injection Tubing
Production/Injection Tubing and
Modified Epoxy [33] 225 254–508
Line Pipe
Modified Novolac [33] 300 178–381 Production/Injection Tubing
Urethanes [36] 225 127–229 (5–9 mils) Tubing String (OCTG)
Nylon [36] 225 305–635 (12–25 mils) Tubing String (OCTG)
Fluoropolymer [35] 350–392 No data Tubing String (OCTG)

Inorganic Coatings
The main methods of inorganic coating include oxidation, phosphating, enamel-
ing [15], and others. Depending on the metal nature and the spare part specifics, the
optimal coating and method of deposition should be chosen. Oxidation involves coating
of a metal with a surface oxide film by heating the metal at high temperatures in the
presence of oxygen, by chemical oxidation treatments with acids, or by anodic oxidation in
an electrolytic cell. Metals which can form non-porous oxide layers to convert steel surfaces
to be more passive are zinc, aluminum, and magnesium [39]. For austenitic and martensitic
stainless steels, corrosion resistance depends on the content of chromium and the purity
and uniformity of surface chromium oxide layers [39,40].
Phosphating involves coating of steel with a layer of porous crystalline mixed phos-
phates [41]. The nature of the coating could include hydrated zinc phosphate (Zn3(PO4)2 * 4H2O,
hopeite), iron and mixed iron–zinc phosphates (Zn2 Fe(PO4 )2 * 4H2 O, phosphophyllite),
mixed iron–manganese phosphates, and/or zinc and other phosphates [42]. Phosphates
are porous, thus offering only partial corrosion protection, and therefore are being used as
a base for liquid coatings that prevent the spread of rust under the oils and paints. There
are a number of the patented formulations of phosphate conversion coatings [43,44] that
could be applied via brushing, spraying, or immersion of the steels into the orthophosphate
solution with salts of zinc, magnesium, or manganese [45] in the presence of phosphoric
acid. In oil production, phosphate conversion coatings are used to improve the sealing
ability of casing connections [46].
Enameling implies coating of the substrate with a glass layer by dipping the metal
into a suspension of powdered glass followed by high temperature melting of the glass on
the metal surface. Groundless enamels are applicable for the internal surfaces of the pipes
and require forcing the slip under pressure into the internal space of the pipes, followed by
discharge. Thus, a uniform layer of enamel forms and slips over the entire length of the
pipe [47]. Porcelain enamel, as an inorganic material, is chemically bonded to substrate
metals by fusing glass frits at a temperature of 750~850 ◦ C. It provides good chemical
stability and corrosion resistance, as well as excellent resistance to abrasion and thermal
shocks in extreme erosion environments, far outperforming epoxy coatings [48].
High performance zinc-rich silicate inorganic coatings are well known in the oil
production industry since 1970s and have been successfully used for the protection of steel
against corrosion in extreme environments [49]. These systems offer good if not the best
Materials 2023, 16, 1795 9 of 33

thermal stability among the liquid coatings that are stable up to 400 ◦ C. For deposition
of zinc-rich silicates, conventional spaying is used. The conductive nature of the silicate
binder in combination with zinc, provides perfect cathodic protection, metal-like hardness,
and excellent adhesion to steel; however, these coatings cannot resist pHs other than the
range of 5–10. These coatings find their extended use in protective and reinforcement
coatings for drill pipes [50].
The other types of inorganic coatings, such as boronized ceramic-based tribo-corrosion
resistant systems, were proposed and showed a high efficiency of protection of oil pro-
duction equipment such as artificial lift systems, centralizers, valves, and some other
complex-shaped components of engineering tools [51].

Mixed Inorganic–Organic Coatings

The addition of inorganic species into organic coatings improve their thermal, me-
chanical, and wear resistance properties in addition to providing galvanic protection as
was shown for zinc-rich epoxy coatings [52]. Moreover, inorganic mesoporous materials
such as TiO2 can be surface modified with scale and corrosion inhibitors to serve as an
inhibitor carrier and chelating agent within the epoxy matrix to improve the corrosion
resistance and anti-scaling properties of the coating [53]. Mesoporous TiO2 whiskers were
surface modified with ethylenediamine tetra(methylene phosphonic acid) (EDTMPA), a
well-known chelating, scale reducing, and anticorrosive agent, and were further loaded
with imidazoline corrosion inhibitor into internal pores to yield multifunctional iFTiO2 (w)
carriers [53]. These iFTiO2 (w) carriers were evenly dispersed within organosilicon epoxy
coating and used to coat steel coupons. Outstanding barrier, and scale and corrosion
prevention properties were demonstrated for this blend due to synergistic protective effect
of EDTMPA and imidazoline-functionalized composite. iFTiO2 (w)-containing coatings
worked up to 35–40 times better compare to non-modified-TiO2 -loaded epoxy coatings.
The overview of the abovementioned types of protective coatings taking into con-
sideration the economic aspects of their deposition and the ecological trends in green
industrial operations allows us to conclude that the most promising and cost-efficient mate-
rial engineering efforts should be targeted at the design of polymeric and nanocomposite
formulations involving deployment of smart and stimuli-responsive additives. Metallic
coatings were previously unique due to their superior protection and mechanical resistance
but they are becoming less economically feasible compared to emerging engineered poly-
mers and composites. There are broad possibilities for the customization of epoxy, phenolic,
and other polymeric matrices towards resistance to specific temperatures, aggressive media,
and mechanical impacts, allowing polymeric and nanocomposite formulations to reach
the efficiency of metallic coatings with lower costs of deposition. The current tendency in
mixed coating engineering is to overcome the gap in the mechanical rigidity and robust-
ness of polymer-based composites and metals. Mixed coatings formulations that combine
the advantages of organic and inorganic/ceramic materials with functional nanomaterial
additives enable further improvement of their protective properties. A comparison and
evaluation of the efficiency of these coatings could be performed based on the qualification
techniques that are reviewed below.

2.1.3. Performance Qualification of Coatings

Building on the importance of the coating performance, this section is dedicated to
the quality control and coating evaluations. Various methods of nondestructive QC tests
including visual and ultrasonic coating thickness evaluations and continuity examinations
are performed at manufacturing sites upon OCTG production; however, regular inspection
of new products in the market and monitoring of the performance of applied protective
coating systems is necessary for maintaining the durability and integrity of the well in-
frastructure. Recommendations for QC industrial techniques are summarized by major
international standards such as ISO, ASTM, NACE, and others. Below we will focus on the
most common methods of coating evaluation.
Materials 2023, 16, 1795 10 of 33

Electrochemical Impedance Spectroscopy (EIS)

Electrochemical impedance spectroscopy allows characterization of heterogeneous
systems composed of multiple arrays of layers with different electrical and structural
properties by applying equivalent circuits. This method is based on the determination
of electrical impedance of a sample as a function of the frequency of applied alternating
current [54]. This technique is a non-destructive, online method to control general corrosion,
and its inhibition and coating performance in the laboratory. It has no widespread field
monitoring application due to localized zone of measurements, the complexity of the results’
analysis, and being difficult to use during wide temperature and operational changes [55].
EIS is a useful lab tool to detect areas of localized active corrosion at the metal–coating
interface [56] in order to test the self-healing processes of the coatings, to evaluate the impact
of additives like various ions into the coating matrix, and to evaluate the barrier properties
of the coatings [57]. These measurements can be used to determine the effects of the water
uptake and subsequent coatings plasticizing [58] and others. In a typical experiment, the
coated metal surface with an artificial cut in the protective layer is exposed to sea water
and immersed with a cathodic current. The changes of impedance are measured relative to
a reference electrode (saturated calomel electrode (SCE)) in the electrochemical cell [58].
Ageing and degradation of the coating system is indicated by the decay of the impedance
modulus with immersion time. Equivalent circuits are used to model and experimentally
verify the EIS data. Several software solutions such as ANALEIS with the modules BASICS
and COATFIT [59], PowerSuite [60], and others were developed to simulate and interpret
EIS spectra.

Adhesion Tests
The strength of a coating’s adherence to the substrate is its principle functional charac-
teristic. Adhesion is a measure of the force per unit area required to remove the coating
from the surface [55]. Adhesion strength tests determine what force is required for sep-
aration of two adhered parts along the interface. Typically, adhesion tests are based on
different methods of separation of a coating from its substrate at a particular load. Below
we will list the most essential adhesion tests recommended by ASTM and ISO standards.
The pull-off test is utilized for the evaluation of adhesion of single and/or multiple
coating systems on a metal surface by application of a tensile stress from a dolly to the
coating through the usage of a portable adhesion tester/automatic pull-off adhesion gauge.
The stress gradually rises until the dolly with the adhesive layer is removed. Pull-off
strength determination includes two protocols: (1) testing if the coated surface remains
intact at a defined loading and (2) testing for fracturing that determine the maximal
perpendicular force that the surface can bear until the material detaches. The test can be
performed in the field and would provide quantitative evaluation data according to11ASTM
Materials 2023, 16, x FOR PEER REVIEW of 34
D4541-17 [61], ASTM C633-13(2017) [62], and ISO 4624:2016 [63] techniques. Figure 4 shows
the pull-off test description and test instrument kit.

Figure 4. Pull-off adhesion test and required instrument kit [64,65].

Figure 4. pull-off adhesion test and required instrument kit [64,65].

An X-cut adhesion test evaluates the adhesion of single or multilayered coating

systems to a metal or another coating surface using one stroke from a knife according to
ASTM D6677-18 [66]. This technique is applicable both in the laboratory and in the field.
 Figure 4. pull-off adhesion test and required instrument kit [64,65].
Materials 2023, 16, 1795 11 of 33
An X-cut adhesion test evaluates the adhesion of single or multilayered coating
systems to a metal or another coating surface using one stroke from a knife according to
ASTMAn D6677-18 [66]. This
X-cut adhesion technique
test evaluatesisthe
applicable
adhesionboth in theorlaboratory
of single multilayeredandcoating
in the field.
The test should be performed with the cut made all the way to the
systems to a metal or another coating surface using one stroke from a knife according examined substrate
surface.
to ASTM D6677-18 [66]. This technique is applicable both in the laboratory and in the
TheThe
field. scratch test isbestandardized
test should performed with by the
ASTM D7027-20
cut made [67]
all the wayand
to the examined
equivalent ISO
substrate surface.
19252:2008 [68]. The scratch test measures the adhesion strength of the coating upon ap-
plyingThe test is standardized
scratchmachine
a scratch by ASTM
with an increasing D7027-20
amount [67] and the
of pressure untilequivalent ISO is de-
the adhesive
19252:2008 [68]. The scratch test measures the adhesion strength of the coating upon
tached. The commercial scratch test apparatus allows control of the scratch velocity and
applying a scratch machine with an increasing amount of pressure until the adhesive is
length. Detection of the critical load upon coating debonding is a quantitative character-
detached. The commercial scratch test apparatus allows control of the scratch velocity and
istic of the
length. method.
Detection of Adhesion and cohesion
the critical load between
upon coating the coating
debonding layers as
is a quantitative well as the types
characteristic
ofofdebonding is evaluated.
the method. Adhesion and cohesion between the coating layers as well as the types of
The bend
debonding test according to ASTM D522 [69] is based on producing shear stress along
is evaluated.
the coating interface
The bend by bending
test according the tested
to ASTM sample
D522 [69] overona producing
is based round pinshear
as shown in Figure 5.
stress along
the coating interface by bending the tested sample over a round pin as shown in Figure 5.

Figure 5. Adhesion bend test [64].

Figure The
5. Adhesion
shear testbend test [64].to ATSM F1044-05(2017)e1 [70] is used to determine the
according
adhesion and internal cohesion of the metal and phosphate coatings in shear parallel to the
surface
Theasshear
showntest
in Figure 6. Coated
according specimens
to ATSM are glued against[70]
F1044-05(2017)e1 the matching
is used tocounterpart
determine the
adhesion and internal cohesion of the metal and phosphate coatings in shearcause
and load up to failure. This test determines a material’s ability to resist forces that parallel to
thesurface
the coatingassystem
shown to in
slide against
Figure 6. itself, that
Coated is important
specimens are to provide
glued correct
against handling
the matchingof coun-
Materials 2023, 16, x FOR PEER REVIEW 12 of 34
the coated products. Chen [71] provides the methodology of the mechanical evaluation of
terpart and load up to failure. This test determines a material’s ability to resist forces that
coating adhesion.
cause the coating system to slide against itself, that is important to provide correct han-
dling of the coated products. Chen [71] provides the methodology of the mechanical eval-
uation of coating adhesion.

Figure 6. Tensile
Figure 6. Tensileshear
shear fatigue
fatigue testtest
[72].[72].

Abrasion Resistance
Abrasion Resistance
ASTM D4060-19 [73] is a standardized technique to measure the abrasion resistance of
ASTM
organic D4060-19
coatings [73] rigid
on a plane is a standardized technique
surface by the Taber to measure
Abraser. the abrasion
The instrument resistance
is a single
of organic coatings on a plane rigid surface by the Taber Abraser. The
rotary platform with various abrasive wheels that perform accelerating wear examinationinstrument is a
single rotary
mimicking platform
fine, with
coarse, and various
large abrasive
particle wheels
abrasion. that perform
The technique allowsaccelerating
determiningwear
the exam-
ination mimicking fine, coarse, and large particle abrasion. The technique allows deter-
mining the wear index, weight loss, and/or wearing cycles per Mil. A lower wear index
indicates better abrasion resistance of the coating.

Impact Resistance
Materials 2023, 16, 1795 12 of 33

wear index, weight loss, and/or wearing cycles per Mil. A lower wear index indicates
better abrasion resistance of the coating.

Impact Resistance
ASTM D2794-93(2019) [74] describes the technique to qualify the coatings for impact
resistance. A standard weight is dropped from a distance onto the coated metal plate
to strike an indent that deforms the coating and the substrate. By gradually increasing
the distance of the weight drops, the point at which coating failure occurs is determined.
Visible inspection of the crack with a magnifier or usage of a pinhole detector or chipping
with tape allow identification of the damage.

Immersion Test
The standard ASTM D870 [75] covers the evaluation of the stability of the coating
system in water at ambient or elevated (up to 95 ◦ C) temperatures upon immersion of the
coated specimen. The typical results of the test are “pass” or “fail”, although a degree of
failure could also be determined. Performance of the coatings immersed in a 5% sodium
hydroxide or 5% sodium chloride solution should be examined at ambient and elevated
temperatures according to NACE TM 0174 [76].

Cathodic Disbonding Test

Although original ASTM G8-96(2019) [77] was developed to test polymeric pipeline
coatings, the method has been successfully applied to evaluate the adhesion of downhole
thermoplastic and thermosets coatings [78]. A truncated version of the ASTM G8-96(2019)
technique was shown to be effective for the evaluation of the adhesive properties of coatings
with various compositions such as polyamide and different types of epoxies. The test
exposes the coated metal specimen with a coating perforation to high cathodic polarization
followed by physical examination of polymer disbonding around the perforated site and/or
the monitoring of the current drawn by the test specimen. The current that is applied
as the cathodic protection induces alkalization of the interface between the metal and
coating and may lead to cathodic disbonding of the coating [58]. Along with ASTM G8-
96(2019) that covers the standard testing of coatings for cathodic disbonding resistance at
room temperatures, ASTM G-42-11(2019)e1 [79] describes the standard testing method to
determine cathodic disbonding of pipeline coatings at elevated temperatures, and ASTM
G95-07(2013) [80] is valid for the testing of coatings where the test cell is cemented to the
coated specimen. Physical examination is used for the inspection of the coating contact
to the metal surface. The cathodic disbonding test apparatus includes an electrolytic cell,
potentiostat, and voltage meter.

Torque Testing of External Coatings

The integrity of the external coating is essential to withstanding the downhole envi-
ronment temperature, water salinity, and chemical compatibility. However, the external
coating integrity is especially important when OCTG are moved onto the rig using power
tongs. The torque that is applied to the external coating will damage the coating and it will
require the use of the fast cure epoxy on the rig to fix the dents or damage to the external
coatings.
External coating qualification using a rotational torque machine is required to evaluate
the adhesion upon exposure to an external mechanical impact. The rotational torque
machine mimics the actual rig torque and helps to evaluate the external coating integrity
on the shop as part of the qualification. This torque will check the resistance of the coating
and evaluate the damage/dents that may occur (Figure 7).
 external coatings.
External coating qualification using a rotational torque machine is required to evalu
ate the adhesion upon exposure to an external mechanical impact. The rotational torqu
machine mimics the actual rig torque and helps to evaluate the external coating integrity
Materials 2023, 16, 1795
on the shop as part of the qualification. This torque will check the resistance13ofofthe
33
coating
and evaluate the damage/dents that may occur (Figure 7).

Figure7.7.Rotational
Figure Rotational pipe
pipe torque
torque machine
machine [81]. [81].

As
Asreviewed
reviewedabove,
above,coating
coatingqualification
qualification and standardization
and standardizationprocedures
procedures are the
are the spe
special part of coating QC practice that involves a several stages of evaluation. It
cial part of coating QC practice that involves a several stages of evaluation. It include includes
primary laboratory tests as well as the qualifications at the workshop to select superior
primary laboratory tests as well as the qualifications at the workshop to select superio
materials for preliminary field investigations. Stationary field performance of the material
materials
during testsfor preliminary
provides field investigations.
an estimate of the actual work Stationary field performance
performance of the system of in the
the materia
during tests
dynamic provides conditions
ever-changing an estimate of the
in the actual
field. Thus,work
a wideperformance of isthe
variety of tests system
used for in th
dynamic ever-changing conditions in the field. Thus, a wide variety
coating evaluations to evaluate the behavior of the coating system during most of the of tests is used fo
coating challenges
possible evaluations tocould
that evaluate
occurthe
in behavior
the field. of the coating system during most of the pos
sible challenges that could occur in the field.
2.2. Corrosion Control by Cathodic Protection
2.2.1. Basic Principles
2.2. Corrosion Control by Cathodic Protection
Cathodic protection (CP) is an electrochemical corrosion mitigation technology. Its
2.2.1.principal
main Basic Principles
is based on diminishing the corrosion of a metal by making that surface
Cathodic
the cathode of anprotection (CP) cell
electrochemical is an electrochemical
[82] with the purpose corrosion mitigation
of significantly technology.
reducing the It
corrosion rate of the
main principal is metal
based[83].
on CP is intendedthe
diminishing for metal structures
corrosion of a permanently submersed
metal by making that surface
into
the sea watersof[84],
cathode structures exposedcell
an electrochemical to soil
[82][85],
withorthe
concrete suchof
purpose assignificantly
well casings [86].
reducing th
corrosion rate of the metal [83]. CP is intended for metal structures permanently sub
2.2.2. Cathodic Protection Design
mersed into sea waters [84], structures exposed to soil [85], or concrete such as well casing
There are two types of cathodic protection that can be applied—galvanic and im-
[86].
pressed current cathodic protections. The first one works as electrochemical protection in
itself, while the second one requires an external source for the current.

Galvanic Cathodic Protection

A galvanic cathodic protection system consists of a sacrificial anode fixed directly to
the metal surface. The sacrificial anode should be made of a highly active metal to prevent
the less active metal from corrosion [87]. Galvanic anodes typically could be made of
alloys of magnesium, zinc, or aluminum [88]. For some of these metals there is a risk of
passivation of galvanic anodes due to the formation of a surface oxide layer that would
diminish anode capacity. The galvanic cathodic protection has a limited lifetime until the
sacrificial anode is consumed. Once the sacrificial anode is no longer capable of protection,
the original metal surface would start to corrode.
 the less active metal from corrosion [87]. Galvanic anodes typically could be made of al-
loys of magnesium, zinc, or aluminum [88]. For some of these metals there is a risk of
passivation of galvanic anodes due to the formation of a surface oxide layer that would
diminish anode capacity. The galvanic cathodic protection has a limited lifetime until the
sacrificial anode is consumed. Once the sacrificial anode is no longer capable of protection,
Materials 2023, 16, 1795 14 of 33
the original metal surface would start to corrode.

Impressed Current
Impressed Current current cathodic protection utilizes a current from an external power
The impressed
source.The impressed
Such current
protection cathodic
converts protection
all anode areas utilizes a current
to cathodes, thusfrom an external
eliminating power
the possi-
source.
bility Such
of an protection
anodic loss ofconverts all anode
metal (Figure areas to cathodes, thus eliminating the possibility
8) [87].
of an anodic loss of metal (Figure 8) [87].

(A) (B)
Figure
Figure8.8.Impressed
Impressedcurrent
currentcathodic
cathodicprotection:
protection:(A)
(A)buried
buriedpipelines
pipelines[87],
[87],(B)
(B)well
wellcasing
casing[20].
[20].

Since
Sincethethepower
powerisisdelivered
deliveredtotothe theelectrode
electrodefromfroman anexternal
externalpower
powersource
sourceandandisis
not
notgenerated
generatedby byelectrode
electrodedegradation,
degradation,this thissystem
systemprovides
providesaamuchmuchlonger
longerprotection
protection
lifespan
lifespancompared
comparedtotothe thesacrificial
sacrificialanode
anodeand andititenables
enablescalibration
calibrationofofcurrent
currentparameters.
parameters.
Impressed
Impressedcurrent
currentcathodic
cathodicprotection
protectionworksworksdifferently
differentlyfor forburied
buriedpipes
pipesandandforforthe
thewell
well
casing.
casing.Buried
Buriedpipes
pipesandandpipelines
pipelinesare aretypically
typicallyprotected
protectedwithwithdirect
directcurrent
current(DC).
(DC).
Criteriafor
Criteria forthe
thesufficient
sufficientcathodic
cathodicprotection
protectionmethod
methodare aredifferent
differentdepending
dependingon onthe
the
typeof
type ofmetal
metaland
and environment conditions.
conditions. Formation
Formationofofacidity
acidityandandsoil resistivity,
soil presence
resistivity, pres-
of bacteria,
ence andand
of bacteria, thermal
thermaldeviations
deviations would
would require thethe
require adjustment
adjustment of of
thethe
CPCP parameters.
parame-
Below,
ters. as an
Below, example,
as an example, wewelistlist
basic
basicempirical
empiricalcriteria
criteria to
to indicate the
the corrosion
corrosioncontrol
control
effectiveness for steel and gray or ductile cast-iron piping systems
effectiveness for steel and gray or ductile cast-iron piping systems according to NACE according to NACE
SP0169 [84,85]:
SP0169 [84,85]:
• • AAminimum
minimumofof100 100mV mVofofcathodic
cathodicpolarization
polarizationbetween
betweenthe thestructure
structuresurface
surfaceandandaa
stabile reference electrode containing electrolyte. Either the formation or the decay ofof
stabile reference electrode containing electrolyte. Either the formation or the decay
polarizationmust
polarization mustbe bemeasured
measuredto tosatisfy
satisfythis
thiscriterion.
criterion.
• • AAstructure-to-electrolyte
structure-to-electrolyte potential
potential of of − 850 mV
−850 mV oror more
morenegative
negativeasasmeasured
measuredwith re-
with
spect to a saturated copper/copper sulfate (CSE) reference electrode.
respect to a saturated copper/copper sulfate (CSE) reference electrode. This potential This potential may
be either a direct measurement of the polarized potential or a current-applied potential.
• A minimum negative (cathodic) voltage shift of 100 mV or more as determined by in-
terrupting the current and measuring the voltage decay in the earth and metallic parts.
For the cathodic protection of closely spaced well casings due to interference of
currents [39], pulse current technology was demonstrated to provide superior results over
the conventional DC in certain soils and casing lengths; however, there is no absolute
solution and only 20% of the top of the casing part could be protected by CP [85,89,90].
Pulse cathodic protection uses pulse rectifiers to generate short electrical pulses several
thousand times per second with a typical frequency range between 1000 and 5000 hertz
and an output voltage of 0–300 V [85]. Advantages of this type of protection include: (1) the
current requirements are typically significantly lower than in conventional DC; (2) pulse
cathodic protection can provide a current to significantly deeper levels than conventional
DC; and (3) this system provides more uniform current distribution to the casing [90].
To conclude, CP optimization is based on synergy of electrical engineering and material
science. From the point of view of material design, the novelty in the development of
cathodic protection systems would rely on the improved composition of sacrificial anodes
Materials 2023, 16, 1795 15 of 33

to avoid their passivation due to formation of oxides, hydroxides, and carbonates on the
anode surface. Thus, the recently described galvanic coupling of mild steel with high
phosphorous pig iron (HPPI) [91] exhibited efficient cathodic corrosion protection of the
steel in concrete, soil, and seawater due to the formation of well-soluble FePO4 * 2H2 O
upon anode consumption. Incorporation of more active elements as Al, Mg, and Zn into
the HPPI resulted in hybrid anodes that improved the performance of CP even better than
ordinary HPPI via cooperative action of electrochemical effects of additives and anode
dissolution [92]. Furthermore, composite anodes with the inclusion of metal oxides as
Al2 O3 , ZnO, MnO2 , and CeO2 to Al–Zn alloys improved uniformity of anode corrosion
and thus, increased its galvanic efficiency [93]. Comparison of materials for the cathodic
protection efficiency are based on the qualification methods that are reviewed below.

2.2.3. Qualification of Cathodic Protection

Qualification of the Sacrificial Anode
For cathodic protection with a sacrificial anode, spectrometric analysis of chemical
composition, verification of anode weight, straightness, and dimensions, check of struc-
ture and surface irregularities, and testing of electrochemical efficiency and closed-circuit
potential should be performed according to DNV and NACE/AMPP standards [82,84,94].
Tests for the screening of the appropriate material for the sacrificial anode may typi-
cally use a single parameter (e.g., operating potential at a defined constant current density)
as a pass/fail criterion and are normally of a short duration (usually hours) with test
specimen weights of few tens to hundreds of grams [95].
Performance tests of sacrificial anodes are of much longer duration (from months to
years) and require close mirroring of the anticipated field operational conditions for testing
of specimen operating potential for the anode (tens to hundreds of kilograms).
For chemical quality control tests the anode material is subjected to spark emission
spectroscopy of a melted, cut, or acid-dissolved part of the specimen to determine its actual
chemical composition.
Exposure testing was first developed to act as a quality check on the efficacy of solution
heat treatment of Al–Zn–Sn alloy anodes when a simple capacity test based on measurement
of hydrogen evolved under impressed current was used as “go” or “no go” acceptance
criteria [95].

Qualification of the Impressed Current

For the impressed current CP, the NACE/AMPP standard [96] summarizes the meth-
ods of quantitative evaluations of cathodic protection efficiency. It includes methods for
voltage drop examination when structure-to-electrolyte potential measurements are made
and provides guidance to avoid vulnerable data. The qualification should include exami-
nation of the impressed current rectifier, impressed current positive and negative circuit
measurements, impressed current structure to soil potential survey, and testing of the
continuity of the impressed current [97]. The impressed current continuity survey includes
techniques of “fixed cell—moving ground test” and point-to-point continuity test.
Impressed current positive and negative circuit measurements could be performed with
an ammeter or digital multimeter at the systems where individual lead wires for each anode
are installed.
The impressed current structure-to-soil potential survey [88,98] requires a reference
electrode and voltmeter. Pipe-to-soil potential measurements are performed with an
applied protective current and are recorded over equally distributed test points. Potential
vs. test points distance provides data on the efficiency of the CP (Figure 9) [97]. The
voltage at the applied and temporarily interrupted impressed current is recorded against
the reference electrode as “On” and “Off” potential to determine pipe polarized potentials.
The acceptable values of “Instant Off” potential are tabulated [97].
 The impressed current structure-to-soil potential survey [88,98] requires a reference
electrode and voltmeter. Pipe-to-soil potential measurements are performed with an ap-
plied protective current and are recorded over equally distributed test points. Potential
vs. test points distance provides data on the efficiency of the CP (Figure 9) [97]. The volt-
age at the applied and temporarily interrupted impressed current is recorded against the
Materials 2023, 16, 1795 16 of 33
reference electrode as “On” and “Off” potential to determine pipe polarized potentials.
The acceptable values of “Instant Off” potential are tabulated [97].

Figure 9. Typical procedure for structure-to-soil potential survey [97].

Figure 9. Typical procedure for structure-to-soil potential survey [97].
The impressed current continuity survey is a point-to-point test performed with a turned
off rectifier; the leadscurrent
The impressed of the voltmeter ≥2 volts
continuity(atsurvey is aDC setting) connects
point-to-point to two testwith
test performed struc-a
tures
turnedto off
evaluate their
rectifier; theinsulation or continuity
leads of the voltmeter via
(at ≥2thevolts
voltage
DC difference. The continuity
setting) connects is
to two test
determined
structures toif evaluate
the voltage difference
their insulationis 1or
mV or less. For
continuity viathe
theentire structure
voltage protected
difference. with
The conti-
impressed current CP,if all
nuity is determined thepoints
voltage should be continuous
difference is 1 mV or [97].
less. For the entire structure pro-
For
tected wellimpressed
with casings, the methods
current CP,for
all determining
points shouldthe bespecific current
continuous density for optimal
[97].
CP can be developed according to [99] based on information from:
For well casings, the methods for determining the specific current density for optimal
CP can
(1) be developed
Casing potential according
profile—The to [99] based on information
measurements from:across a portion of well
of voltage drop
casing in service;
(1) Casing potential profile—The measurements of voltage drop across a portion of well
(2) casing
Currentindensity
service;calculations based on well completion practices;
(3) Mathematical
(2) Current density modeling including
calculations basedcurrent
on wellattenuation
completionmodeling;
practices;
(4) E-log-I test results.
(3) Mathematical modeling including current attenuation modeling;
(4) E-log-I test results.
2.3. Corrosion Control by Corrosion Resistant Alloys (CRA)
2.3.1. Basic Principles
2.3. Corrosion Control by Corrosion Resistant Alloys (CRA)
2.3.1.Corrosion-resistant
Basic Principles alloy is a commonly used term to cover a broad spectrum of alloys
with compositions of metals such as Fe, Ni, Cr, Mo, W, Ti, and others, which are capable of
Corrosion-resistant alloy is a commonly used term to cover a broad spectrum of al-
efficiently resisting corrosion compared with carbon steel. These alloys are employed in
loys with compositions of metals such as Fe, Ni, Cr, Mo, W, Ti, and others, which are
extreme oil and gas production environments that operate at HPHT (pressure exceeding
capable of efficiently resisting corrosion compared with carbon steel. These alloys are em-
1000 bar and temperatures over 177 ◦ C) and contain chlorides, CO2 , and H2 S [100]. CRAs
ployed in extreme oil and gas production environments that operate at HPHT (pressure
exhibit high resistance to uniform corrosion due to their passivity. In some cases, if the
exceeding environment
downhole 1000 bar and istemperatures
extreme, theover
best 177
way°C) and contain
to control chlorides,
corrosion COCRAs
is to use 2, and H2S
that
[100].
are CRAs
more exhibit
resistant to high resistance
degradation to structural
than uniform corrosion
steel. due to their passivity. In some

2.3.2. Types of Corrosion Resistant Alloys

The most common CRAs materials used in downhole applications [101] are 9CR, 13CR,
316L stainless steel, and Inconel® 625. 9Cr is a general-purpose chromium–manganese–
molybdenum–iron–carbon alloy with an average Cr content of 9%. It is often used for
tubular resistant to high pressure–high temperature in sweet environment service. 13Cr
(martensitic stainless steel) is a chromium–manganese stainless steel with an average Cr
content of 13% that possesses comparatively high resistance to mild sweet and sour envi-
ronments including exposure to wet CO2 containing chlorides, but its exposure to oxygen
in the presence of chlorides would result in the pitting of 13Cr as well as its exposure to
high concentrations of hydrogen sulfide. 13Cr is used for casing and tubing production and
as conventional completion material for sand screens [102]. 316L (austenitic stainless steel)
is a chromium–nickel–molybdenum–iron alloy with 0.03% carbon; it possesses great resis-
tance to acidic conditions containing CO2 and H2 S but is susceptible to local corrosion in
chloride ion-containing media [103]. 316L has a low carbon content that prevents corrosion
caused by welding; it is used for the manufacturing of tubing products [104] as well as for
expandable sand control screens [102]. Inconel® 625 is a corrosion and oxidation resistant,
nickel–chromium–molybdenum–niobium superalloy used for ESPs, valves, and cladding
manufacturing [105]. It has high strength and toughness in temperatures up to 1000 ◦ C and
outstanding chemical resistance to chlorides, seawater, alkaline media, oxidizing chemicals,
Materials 2023, 16, 1795 17 of 33

highly acidic CO2 and H2 S environments, and nitric and hydrochloric acids. The chemical
composition of the most common downhole tubing and casing materials grades is shown
in Table 3 [10].

Table 3. Composition of corrosion resistant steels and alloys for downhole tubing and casing [10].

Chemical Composition, Mass Fraction (%)

C Mn Mo Cr Ni Cu P S Si
Grade Type
Min. Max. Min. Max. Min. Max. Min. Max. Max. Max. Max. Max. Max.
H40 – – – – – – – – – – – 0.03 0.030 –
J55 – – – – – – – – – – – 0.03 0.030 –
K55 – – – – – – – – – – – 0.03 0.030 –
N80 1.0 – – – – – – – – – – 0.03 0.030 –
N80 Q – – – – – – – – – – 0.03 0.030 –
R95 – – 0.45 – 1.90 – – – – – – 0.03 0.030 0.45
M65 – – – – – – – – – – – 0.03 0.030 –
L80 1.0 – 0.43 – 1.90 – – – – 0.25 0.35 0.03 0.030 0.45
L80 9Cr – 0.15 0.30 0.60 0.90 1.10 8.00 10.00 0.50 0.25 0.02 0.010 1.00
L80 13Cr 0.15 0.22 0.25 1.00 – – 12.00 14.00 0.50 0.25 0.02 0.010 1.00
C90 1.0 – 0.35 – 1.20 0.25 0.85 – 1.50 0.99 – 0.02 0.010 –
T95 1.0 – 0.35 – 1.20 0.25 0.85 0.40 1.50 0.99 – 0.02 0.010 –
C110 – – 0.35 1.20 0.25 1.00 0.40 1.50 0.99 0.02 0.005 –
P110 – – – – – – – – – – 0.03 0.030 –
Q125 1.0 – 0.35 – 1.35 – 0.85 – 1.50 0.99 – 0.02 0.010 –

Since the 1970s, the application of CRAs in the oil and gas industry and data on the
selection of appropriate alloys for extreme conditions have been constantly expanding.
However, the initial investments cost for CRA utilization has exceed the cost of ordinary
carbon steel protected with organic coatings by several times [106]. Thus, careful decisions
should be made at the initial stage of well design with balanced considerations of CAPEX
and OPEX of implementation of alloys vs. coated carbon steel in combination with corrosion
inhibitors. Corrosion-resistant alloys that are used in extreme operational conditions despite
their superior performance should be additionally protected with corrosion inhibitors upon
production operations including acid treatments that can significantly affect CRA resistance.
Sridhar gives useful guidance for the choice of the corrosion resistant alloy according to
designated downhole conditions [100]. Until now, the service performance of CRAs and
superalloys remains the best for the extreme downhole environment; however, usage of
the composites and coated OCTG in broader cases could be more economically viable.

2.3.3. Qualification of Performance of Corrosion Resistant Alloys

Before use in oil production, CRAs should be subjected to examinations to evaluate
their stability in designated service conditions. ANSI/NACE MR0175/ISO 15156 [107]
provides a guideline for the selection of CRAs for sour service. ISO 13680 [108] covers a
full list of tests that are necessary to qualify tubular products for oil and gas production,
including examination of the chemical composition, mechanical characteristics of the CRA
products, tensile and hardness tests, impact of flattening, impact test at low temperatures,
pitting corrosion test, microstructural examinations detecting ferrite/austenite ratio, di-
mensional test, drift test, determination of length, straightness, and mass, visual inspection,
and non-destructive evaluations. Petersen [109] lists the main types of tests recommended
to qualify various classes of alloys.
Materials 2023, 16, 1795 18 of 33

For sour conditions, the important qualification parameters [110] are environmentally
assisted cracking tests that cover stress corrosion cracking (SCC) evaluation, hydrogen
embrittlement examination, and localized corrosion tests.

Stress Corrosion Cracking Test

Described in ASTM G38 [111], this test is performed by prolonged exposure of C-ring
(or U-bend) specimens to the applied constant load/deflection in corrosive conditions
that are more extreme than the expected service ones. The absence of the crack initia-
tion of the specimen while strained to yield means the successful qualification for the
alloy product. The SCC test in Cl− /H2 S + CO2 conditions performed as autoclave or
field tests are conducted in a 25% NaCl solution equilibrated with H2 S and CO2 . SCC
testing in Cl− /H2 S + S0 conditions involves autoclave testing at a high pressure of H2 S
(2000–7000 psi) in the presence of free sulfur according to expected sulfur content in the
field [110]. Alternatives are slow-strain rate and cyclic slow-strain rate tests that are based
on the maintenance of static and superimposed static-ripple loads for plastic deforma-
tion of the specimen that is required to cause stress corrosion cracking [100]. Pre-cracked
specimens are used in double cantilever beam tests where the specimen is wedge loaded
and exposed to corrosive media for 720 h, followed by cleaning and measurements of the
load–displacement curve with the tensile machine.

Hydrogen Embrittlement
This test is performed with CRAs after prolonged artificial downhole aging at elevated
temperatures depending on the downhole temperatures’ requirements [110]. The test
determines if the mechanically loaded to yield point, aged C-ring specimen would fail
either during cathodic charging at room temperature in NACE solution due to galvanic
coupling to carbon steel or upon cooling and exposure to a hot Cl− /H2 S environment
while being coupled to a surface of the carbon steel. The detailed technique of the test is
covered in NACE MR0175 [107].

Localized Corrosion Resistance

The pitting resistance equivalent number (PREN) [100] commonly evaluates the lo-
calized corrosion resistance of the CRAs. This parameter is estimated by content (wt.%
Cr + 3.3 wt.% (Mo + 0.5 W) + 16 wt.% N). The correlation of PREN to localized corrosion
perceptivity is dependent on the Cl− concentration and the corrosion potential and is
used to classify the alloys. The alloy is subjected to long-term immersion in corrosive
media and its polarization is measured starting from open-circuit potential and cycling
back to the potential at which the backward potential scan intersects the forward scan,
which is a common method to determine the extent of localized corrosion by circular po-
tentiodynamic polarization [112]. Although the test is performed in the natural conditions,
the time of testing may not be enough for the development of localized corrosion. An
alternative test is ASTM G192 [113], where the potential is raised to a value at which pitting
or crevice corrosion starts; the current is then held constant until a pre-defined charge
density is attained, then the potential is decreased in a pre-determined stepwise manner
until the measured current shows a monotonic decrease, indicating passivation. This way
the localized corrosion is controlled by galvanostatic polarization [100].

2.4. Corrosion Control by Inhibitors

2.4.1. Basic Principles
Corrosion inhibitors (CI) are chemicals that are effective in very small amounts when
added to a corrosive environment in decreasing the corrosion rate of the exposed metallic
materials [12]. Inhibitors could be added either continuously or intermittently [114] to
production fluids, acids, cooling waters, or other fluids to inhibit the corrosion reaction.
They may reduce corrosion by forming a very thin film on the metal surface, causing a
passive chemisorbed layer to form on top of the metal, by forming a oxide protective film,
 Materials 2023, 16, 1795 19 of 33

or by removing aggressive constituents from the environment and converting it into a

complex [115].

2.4.2. Types of Corrosion Inhibitors

Several chemicals including inorganic complexes, organic molecules, natural prod-
ucts, and rare earth elements were successfully identified as corrosion preventing agents
for a wide variety of metals in different corrosive environments. Inhibitors were found
to be effective and unique in action depending on the metals and environmental condi-
tions [116]. Inhibitors can be divided into two main categories—inorganic and organic.
Inorganic inhibitors are mainly used in boilers and cooling towers whereas, organic in-
hibitors are mainly used in oil field systems. Organic CIs are fatty acids, amines, quaternary
ammonium compounds, imidazolines, oxyalkylated amines, alcohols, as well as sulfur-,
phosphorous-, and oxygen-containing organic molecules bearing long hydrocarbon chains
Materials 2023, 16, x FOR PEER REVIEW
and polymers [117]. The hydrocarbon chain of organic inhibitors is oil soluble; this 20 of 34
chain
provides a barrier that keeps water away from the metal surface. Figure 10 summarizes the
classification of corrosion inhibitors [115].

Figure 10. Types of corrosion inhibitors.

Figure 10. Types of corrosion inhibitors.
The majority of oil well corrosion-preventing agents possess surfactant-like structures
withThe
polar “heads”
majority of that chelate
oil well to the metal surfaceagents
corrosion-preventing and bear long non-polar
possess alkylstruc-
surfactant-like chains
with C
tures with –C fragments
16 polar [118]. This structure helps not only to form a barrier
18 “heads” that chelate to the metal surface and bear long non-polar alkyl layer, but
chains with C16–C18 fragments [118]. This structure helps not only to form a barrier layer,of
also to emulsify and solubilize the inhibitor to keep it functional at an extended range
external
but also toconditions.
emulsify and It should be noted
solubilize that theto
the inhibitor batch
keepofitCI passes through
functional wide variety
at an extended rangeof
well conditions upon injection. It flows through temperature gradients, and fluctuations
of external conditions. It should be noted that the batch of CI passes through wide variety
of pressure and sour gas content. Thus, chemicals in CI formulations require thermal
of well conditions upon injection. It flows through temperature gradients, and fluctua-
robustness and emulsion stability at a broad range of pHs.
tions of pressure and sour gas content. Thus, chemicals in CI formulations require thermal
Inhibitors applied for corrosion prevention of well tubing are based on fatty acids,
robustness and emulsion stability at a broad range of pHs.
fatty imidazolines, film-forming imidazolines, and aminoimidazoles. In the wells with
Inhibitors applied for corrosion prevention of well tubing are based on fatty acids,
aggressive gases and acidic media, pH agents are injected to control corrosion via reduction
fatty imidazolines, film-forming imidazolines, and aminoimidazoles. In the wells with ag-
of acidity; meanwhile, sour gas scavengers such as nitrites remove the aggressive action
gressive gases and acidic media, pH agents are injected to control corrosion via reduction
of H2 S [119]. Oxygen scavengers including sodium sulfite, ammonium bisulfite, and
of acidity; meanwhile, sour gas scavengers such as nitrites remove the aggressive action
sulfur dioxide, are inactive in acidic conditions and should be injected along with pH
of H2S [119]. Oxygen scavengers including sodium sulfite, ammonium bisulfite, and sul-
agents. Among inhibitors effective in highly acidic media, guanidine derivatives, 1-benzyl
fur dioxide, are inactive in acidic conditions and should be injected along with pH agents.
imidazole, and 2-ethyl-4-methylimidazole were reported to mitigate corrosion of low-
Among
carboninhibitors
and API X65effective
steels in
in highly
a 1M HClacidic media,
solution guanidine derivatives, 1-benzyl imid-
[120].
azole, and 2-ethyl-4-methylimidazole were reported to mitigate corrosion of low-carbon
and API X65 steels in a 1M HCl solution [120].
For treatment of acidic wells at elevated temperatures, synthetic fatty acid triazoles
and oxadiazole derivatives were proposed to maintain protection of N80 and carbon steel
up to 15 wt% HCl in boiling aqueous solutions [119]. Along with inhibitors based on
amines, amides, and quaternary ammonium salts, intensifiers based on acetylenic alco-
 Materials 2023, 16, 1795 20 of 33

For treatment of acidic wells at elevated temperatures, synthetic fatty acid triazoles
and oxadiazole derivatives were proposed to maintain protection of N80 and carbon steel
up to 15 wt% HCl in boiling aqueous solutions [119]. Along with inhibitors based on
amines, amides, and quaternary ammonium salts, intensifiers based on acetylenic alcohols,
cinnamaldehyde derivatives, formic acid, and acid-soluble salts of Cu and Bi should be
injected to improve corrosion mitigation in hot conditions. Furthermore, laboratory tests of
long alkyl chains bearing derived mono- and bilayer film-forming inhibitors exhibited high
efficiency at HPHT, high salinity conditions in the presence of H2 S and CO2 .
The history of oilfield corrosion inhibitor application that started in the 1930s lead
Materials 2023, 16, x FOR PEER REVIEW
to the development of chemical formulations for a wide spectrum of oilfield conditions 21 of 34
including operations in ordinary environments or in harsh acidizing treatments of HPHT
wells. Extended action of Cis based on continuity of the films, strength of adhesion to the
metal surface, as well as the prolonged release of active chemicals is crucial for the system’s
2.4.3. Qualification of Corrosion Inhibitors
integrity. Despite the importance of oil production operations, the environmental impact of
The film-forming
the injected inhibitors’
chemicals should effects
be carefully are related to the formation of a molecular layer
considered.
adsorbed on the metal surface; their performance is based on the persistence, continuity
2.4.3. Qualification of Corrosion Inhibitors
and regeneration of this protective film. The qualification of CIs is performed with inhib
The film-forming
itor-film-covered metalinhibitors’
surfaces effects are related to theflow
in a hydrodynamic formation
regime of mimicking
a molecular the layer
field con
adsorbed on the metal surface; their performance is based on the persistence, continuity,
ditions. of the corrosion rate is determined via weight loss or electrochemical measure
and regeneration of this protective film. The qualification of CIs is performed with inhibitor-
ment of surface impedance and polarization [121]. The ASTM G-170 standard [122] covers
film-covered metal surfaces in a hydrodynamic flow regime mimicking the field conditions.
thethe
of general laboratory
corrosion equipmentvia
rate is determined and test methods
weight for evaluationmeasurement
loss or electrochemical of corrosion of inhibitors
for multiphase systems. A brief description of the most common
surface impedance and polarization [121]. The ASTM G-170 standard [122] covers the laboratory techniques
were described
general laboratoryby Sivokon and
equipment [123].
testItmethods
includesfor theevaluation
static test,
of wheel test,
corrosion bubble for
inhibitors test, test in
U-cell, rotating
multiphase cylinder
systems. A briefelectrode
description test, rotating
of the cage test,
most common impingement
laboratory techniquestest, were
and recircu
described
lating flowby loop
Sivokon
test.[123].
The It includes
static test the static test,
is based wheel test, bubble
on electrochemical ortest,
weighttest in U-cell,
loss determina
rotating cylinder electrode test, rotating cage test, impingement test, and recirculating
tion of corrosion rate in the absence of the flow of corrosive fluids. It is useful for primary
flow loop test. and
comparisons The qualitative
static test ischaracterization
based on electrochemical
of CIs. or weight loss determination
of corrosion rate in the absence of the flow of corrosive fluids. It is useful for primary
comparisons and qualitative characterization of CIs.
Wheel Test
WheelThis
Testtest is designed for the evaluation of the efficiency of a corrosion inhibitor by the
weight
Thisloss
test at low ratefor
is designed flows of the corrosive
the evaluation media. Flat
of the efficiency steel coupons
of a corrosion areby
inhibitor placed
the into a
weight loss at low rate flows of the corrosive media. Flat steel coupons are placed
wheel-shaped holder rotating inside the vessel (Figure 11) containing brine solution, into a CI
wheel-shaped holder rotating
oil and is saturated with a inside
partialthe vessel (Figure
pressure of CO11) containing brine solution, CI,
2/H2S according to service conditions
oil and is saturated with a partial pressure of CO2 /H2 S according to service conditions.
Standard testing lasts for 24 h with rotation and periodical wetting of coupons in the
Standard testing lasts for 24 h with rotation and periodical wetting of coupons in the heated
heated corrosive fluid [123].
corrosive fluid [123].

Figure11.
Figure 11.Equipment
Equipmentforfor qualification
qualification of corrosion
of corrosion inhibitors
inhibitors by the by thetest
wheel wheel test [123].
[123].

Bubble Test
This test determines the corrosion rate of the sample(s) exposed to a flow of corrosive
fluid upon CO2 bubbling using the linear polarization resistance method. Gravimetrica
measurements can also be used for the evaluation of the sample degradation [112]. The
test is performed in a glass vessel with access ports for the working, counter, and reference
 Materials 2023, 16, 1795 21 of 33

Bubble Test

Materials 2023, 16, x FOR PEER REVIEW

This test determines the corrosion rate of the sample(s) exposed to a flow of corrosive22 of 34
fluid upon CO2 bubbling using the linear polarization resistance method. Gravimetrical
measurements can also be used for the evaluation of the sample degradation [112]. The
test is performed in a glass vessel with access ports for the working, counter, and reference
electrodes, thermometer, and gas inlet and outlet tubes (Figure 12).

Figure 12. The apparatus for the bubble test [122,124].

Test in U-Cell
FigureIn
12.the
The apparatus
test in U-cell for the bubble
generates test [122,124].
an intense flow of hot corrosive medium saturated with
CO2 against the metal sample in a double chamber vessel; the weight loss of the probe is
compared
Test in U-Cellwith a control sample [123].
In theCylinder
Rotating test in U-cell generates
Electrode an intense flow of hot corrosive medium saturated with
(RCE) Test
CO2 against the metal
The rotating sample
cylinder in a double
electrode (RCE) chamber
test is onevessel;
of the the weight
most loss
popular of the probe is
laboratory
compared with a control sample [123].
methods of CI evaluation. It determines the corrosion rate of the metal sample when
exposed to aggressive fluids with temperatures ≥ 80 ◦ C at a turbulent flow by the weight
Rotating Cylinder
loss and/or Electrode curves
via polarization (RCE) Test
registration [125]. The test apparatus consists of a
rotating unit driven by a motor with a controller
The rotating cylinder electrode (RCE) test for the of
is one rotation ratepopular
the most that is attached to a meth-
laboratory
sample holder [126].
ods of CI evaluation. It determines the corrosion rate of the metal sample when exposed
toRotating
aggressive
Discfluids with(RDE)
Electrode temperatures
Test ≥80 °C at a turbulent flow by the weight loss and/or
via polarization
The rotatingcurves registration
disc electrode (RDE) [125].
test hasThe
a lottest apparatustoconsists
of similarities RCE andof a rotating
varies only unit
driven
with shape of the electrode. Electrochemical measurements in a three-electrode cell using a holder
by a motor with a controller for the rotation rate that is attached to a sample
[126].
rotating disc and rotating cylinder electrodes simulating laminar and turbulent regimes,
respectively. Registration of polarization curves by a potentiostat with and without the CI
allows for
Rotating the Electrode
Disc determination
(RDE)of the
Testfilm stability for the CI with no details regarding the
influence of flow regimes. Electrochemical impedance measurements describe the efficiency
The rotating disc electrode (RDE) test has a lot of similarities to RCE and varies only
of the CI both at laminar and turbulent flow [121].
with shape of the electrode. Electrochemical measurements in a three-electrode cell using
a Rotating
rotating Cage
disc and
Test rotating cylinder electrodes simulating laminar and turbulent regimes,
respectively. Registration
The rotating ofperformed
cage test is polarization curves
with by acoupons
flat metal potentiostat with
that are and without
installed into the the CI
allows
samplefor the determination
holder at the axis of theofrotating
the filmmotor
stability
and for the CI
dipped intowith no details
the sealed regarding
cell with the the
influence of flow regimes. Electrochemical impedance measurements describe the effi-
corrosive fluid and gas (Figure 13) [123]. Depending on the speed of the motor rotation
and dimensions
ciency of theat
of the CI both vortex formed,
laminar andvarious flowflow
turbulent regimes could be implemented such as
[121].
a homogeneous stream or turbulent flow [126]. The corrosion rate is determined by the
sample’sCage
Rotating weight loss.
Test
The rotating cage test is performed with flat metal coupons that are installed into the
sample holder at the axis of the rotating motor and dipped into the sealed cell with the
corrosive fluid and gas (Figure 13) [123]. Depending on the speed of the motor rotation
and dimensions of the vortex formed, various flow regimes could be implemented such
as a homogeneous stream or turbulent flow [126]. The corrosion rate is determined by the
Materials 2023, 16, x FOR PEER REVIEW 23 o
Materials 2023, 16, 1795 22 of 33

Figure 13. Instrument for the rotating cage test [123].

Jet Impingement Test

The jet impingement test is used for corrosion surveys of the coupon exposed to the
Figure 13. Instrument for the rotating cage test [123].
sprayed fluid. The test simulates the high-turbulence conditions at high temperatures and
Figure 13. Instrument
Jet Impingement for the rotating cage test [123].
Test and
pressures in gas, liquid, multiphase turbulent systems [126]. The jet impingement ap-
paratus includes an autoclave is
The jet impingement test forused
thefor corrosion
fluid surveys of
preparation, the coupon exposed
impingement to the
test cell with im-
Jet Impingement
sprayed fluid. The Test
test simulates the high-turbulence conditions at high temperatures and
pingement probe, a high-pressure fluid pump, and a flow meter to measure flow rates.
pressures jet in gas, liquid, and testmultiphase turbulent systems [126]. The jet impingement
The test The impingement
cell is equipped with sprayis used for corrosion
nozzles. The fluid surveys
is pumped of the coupon
from theexposed
autoclaveto
apparatus
sprayed includes an autoclave for the fluid preparation, impingement test cell with
through the fluid.
impingement nozzles Thetotest
probe, athe
simulates
probe andthe
high-pressure
high-turbulence
returns
fluid pump, (Figure 14).conditions
and a flow The probe
meter
atcontains
to measure
high temperatures
the sensor
flow rates.
pressures
element in
to measure gas, liquid,
corrosion and multiphase turbulent systems [126]. The jet impingement
The test cell is equipped withrate.
sprayThe corrosion
nozzles. rate isispumped
The fluid determinedfrom theby autoclave
the weight loss
paratus
and/or
through includes
the nozzlesan
electrochemical to autoclave
measurements
the probe and forreturns
the fluid
such preparation,
as(Figure
linear polarization
14). The probeimpingement
and thetest
electrochemical
contains cell with
sensor im-
pingement
element to probe,
measure
pedance spectroscopy [127]. a high-pressure
corrosion rate. The fluid pump,
corrosion rateand
is a flow
determined meter
by to
the measure
weight loss flow ra
The
and/ortestelectrochemical
cell is equipped with spray
measurements suchnozzles.
as linearThe fluid is pumped
polarization from the autocl
and electrochemical
impedance
through thespectroscopy
nozzles to[127].
the probe and returns (Figure 14). The probe contains the sen
element to measure corrosion rate. The corrosion rate is determined by the weight
and/or electrochemical measurements such as linear polarization and electrochemical
pedance spectroscopy [127].

Figure 14. The scheme of jet impingement cell [127].

Figure 14. The scheme of jet impingement cell [127].
Important work was done by Papavinasam [128] where he compared the abovemen-
tioned methods of CI evaluation for the reproducibility between laboratory and field test
Important
results work
for oil waspipelines.
and gas done by He Papavinasam [128] where
ranked the reliability hemethods
of the comparedfromthe abovemen-
high to
tioned
lowmethods of wheel
as follows: CI evaluation
test, bubble fortest,
thestatic
reproducibility
test, rotating between laboratory
disc electrode and field test
(RDE), rotating
results for oilelectrode
cylinder and gas(RCE),
pipelines. He ranked(JI),
jet impingement theand
reliability of the
rotating cage methods from high to low
(RC).
Figure 14.
as follows: The scheme
wheel of jet impingement
test, bubble cellrotating
test, static test, [127]. disc electrode (RDE), rotating cylin-
der electrode (RCE), jet impingement (JI), and rotating cage (RC).
Important work was done by Papavinasam [128] where he compared the abovem
tioned
3. New methods
Trends of CI evaluation
and Aspects for the
to Consider forreproducibility
Development of between
Novel laboratory andMa-
Anticorrosive field
results for oil and gas pipelines. He ranked the reliability of the methods from high to
terials
as follows: wheel test, bubble test, static test, rotating disc electrode (RDE), rotating cy
der electrode (RCE), jet impingement (JI), and rotating cage (RC).
 Materials 2023, 16, 1795 23 of 33

Materials 2023, 16, x FOR PEER REVIEW 24 of 34

3. New Trends and Aspects to Consider for Development of Novel
Anticorrosive Materials
Oil and gas reserves which are left to be explored and mined remain at challenging
Oil and gas reserves which are left to be explored and mined remain at challenging
locations with with
locations extreme extreme environmental
environmental conditions
conditions such assuch as ultra-deep
ultra-deep wells,
wells, arctic andarctic and
highly sour reservoirs, or ‘unconventional oil’ such as shale, bitumen, and tar sands [5,118].
highly sour reservoirs, or ‘unconventional oil’ such as shale, bitumen, and tar sands
Such
[5,118]. conditions
Such conditionsimply
implyexposure
exposure of ofthe
theoil
oilproduction
production equipment
equipment to high
to high pressures and
pressures
high- or ultra-low temperatures, and high concentrations of
and high- or ultra-low temperatures, and high concentrations of H2S, CO2, and chlorideH 2 S, CO 2 , and chloride ions
that cause extremal corrosion effects for metallic materials. Development
ions that cause extremal corrosion effects for metallic materials. Development of the novel of the novel
technologies for oil production such as enhanced oil recovery (EOR) and the carbon cap- capture
technologies for oil production such as enhanced oil recovery (EOR) and the carbon
and storage
ture and storagemethod
method(CCS) (CCS)are arepromoting
promotinga transition
a transitionto to more
more aggressive
aggressive production fluids.
production
fluids. Thus, OCTG, especially tubulars which are in production, are subjected toever-increasing
Thus, OCTG, especially tubulars which are in production, are subjected to ever-
corrosion
increasing challenges.
corrosion In addition,
challenges. challenging
In addition, challenging areas
areasthat
thathave
haveextreme
extremeenvironments
environ- are
mentsdifficult to access
are difficult so the so
to access exploration of these
the exploration offields
these are associated
fields with additional
are associated with addi- challenges.
tionalAchallenges.
summary A of summary
such factors is listed
of such below.
factors is listed below.

3.1. Extreme
3.1. Extreme Temperatures
Temperatures and High-Pressure
and High-Pressure Operations
Operations
Exploring
Exploring horizons horizons
beyond beyond
currentcurrent resources,
resources, deep drilling,
deep drilling, and development
and development of the of the
fields with unconsolidated sands lead to high temperatures
fields with unconsolidated sands lead to high temperatures and high-pressure exposure and high-pressure exposure
of downhole
of downhole tubulars
tubulars and equipment.
and equipment. The general
The general classification
classification of the HTHPof theoperational
HTHP operational
conditions
conditions is given
is given in Figure
in Figure 15 [5].15Exposure
[5]. Exposure of tools
of tools to extreme
to extreme environments
environments requiresrequires uti-
lization
utilization of of materials
materials with
with higher
higher mechanical
mechanical properties
properties as well
as well as implementation
as implementation of of more
morereliable
reliableengineering
engineering solutions.
solutions. Examples
Examples of such tools includes includes pressure-exposed
pressure-exposed blowup
blowup preventers,
preventers, drilling
drilling risers,
risers, andand rotary
rotary tables.
tables. In addition
In addition to the
to the environmental
environmental challenges,
challenges,
advances advances in oil production
in oil production such such as Steam
as Steam Assisted
Assisted Gravity
Gravity Drainage
Drainage technol- which is
technology,
ogy, which
used for is used for extraction
extraction of heavyofoilheavy oil and bitumen
and bitumen from deep from deep reserves,
reserves, increases increases
the ordinary oil
the ordinary
production oil production
temperatures up to 150 ◦up
temperatures to 150In°Csitu
C [129]. [129]. In situ combustion
combustion (ISC) oil (or fire
(ISC) oil production
production
flooding)(or generates
fire flooding) generates temperatures
temperatures up to 450–600up ◦ Ctoat450–600 °C at thefront
the combustion combustion
[129]. Moreover,
frontelongation
[129]. Moreover,
of the overall length of tubular structures in the deep andinultra-deep
elongation of the overall length of tubular structures the deep wells in
and ultra-deep
addition to wells
ocean in addition
waves attooffshore
ocean waves at offshore
platforms increasesplatforms increases
the tensile theon
stress tensile
the downhole
stresstubulars.
on the downhole tubulars. Deep water operations require
Deep water operations require new materials for production equipment new materials for pro- that can
duction equipment that can withstand significant temperature
withstand significant temperature differences between hot produced fluids and differences between hot cold sea
produced fluids and cold sea water [130]. Arctic and permafrost operations
water [130]. Arctic and permafrost operations provide additional challenges of freeze/thaw provide addi-
tionaldamage
challenges of freeze/thaw
of materials, damage of materials,
and difficulties in joining,and difficulties
thermal shock,inandjoining, thermal
embrittlement. Thus,
shock, and embrittlement. Thus, for operating conditions where the temperature ◦ is below
for operating conditions where the temperature is below −27 C, higher grade steels
−27 °C, higher grade steels are required to prevent embrittlement and cracking. For these
are required to prevent embrittlement and cracking. For these conditions, lightweight,
conditions, lightweight, fatigue-resistant, high strength materials are in high demand.
fatigue-resistant, high strength materials are in high demand.

Figure 15. Matrix

Figure of HPHT
15. Matrix operations
of HPHT representing
operations the main
representing operational
the main tiers—high,
operational ultra-high,
tiers—high, ultra-high, and
and extreme high [5].
extreme high [5].
Materials 2023, 16, x FOR PEER REVIEW 25 of 34

Materials 2023, 16, 1795 3.2. Aggressive Environment: H2S, CO2, and Acids 24 of 33

H2S and CO2 gases in combination with water are the main causes of corrosion in the
oil and gas industry. In addition to this, high chloride ion content can cause very high
3.2. Aggressive Environment: H2 S, CO2 , and Acids
corrosion rates and decrease production equipment durability.
H2 S and CO
Sour corrosion 2 gasesby
is caused inH combination
2S exposure with water are
and results the main
in weight causes
loss of corrosion
corrosion in sour in
the oil and gas industry. In addition to this, high chloride ion content
service, and pitting and sulfide stress cracking (SSC). SSC causes the highest risk can cause veryfor
high
corrosion rates and decrease production equipment durability.
OCTG—the exposure to H2S at a certain level of pressure, temperature, pH, and tensile
Sour corrosion is caused by H2 S exposure and results in weight loss corrosion in
stress could result in catastrophic steel failure with very fast crack propagation. Recom-
sour service, and pitting and sulfide stress cracking (SSC). SSC causes the highest risk
mendations for the steel choice depending on the severity level of the sour service is pro-
for OCTG—the exposure to H2 S at a certain level of pressure, temperature, pH, and
vided tensile
in Figure 16 [12,98]. Sweet and sour corrosions could occur while the steel is ex-
stress could result in catastrophic steel failure with very fast crack propagation.
posed Recommendations
to a mixture of H2S/CO for the2 and
steelaltering the ratio ofonHthe
choice depending 2S to CO2 in the mixture would
severity level of the sour service
shift the corrosion mechanism either to sweet or sour.
is provided in Figure 16 [12,98]. Sweet and sour corrosions Steel surface
couldmicrostructures
occur while thehavesteel is
a noticeable
exposed to a mixture of H2 S/CO2 and altering the ratio of H2 S to CO2 inincrease
effect not only on SSC and surface roughness, but they also the cor-
the mixture would
rosion shift
rate the
in acorrosion
hydrochloric acid medium
mechanism either to for
sweetboth laminar
or sour. and
Steel turbulent
surface flow regimes,
microstructures have a
so thatnoticeable
high mechanical
effect notproperties
only on SSC and
andsmooth
surfacesurface pipes
roughness, butare required
they for better
also increase dura-
the corrosion
bility [7].
rate in a hydrochloric acid medium for both laminar and turbulent flow regimes, so that
high mechanical properties and smooth surface pipes are required for better durability [7].

Figure 16. Steel materials for sour service [12].

Figure 16. Steel materials for sour service [12].
Sweet corrosion caused by exposure to CO2 was first recognized in the 1940s in
Texas [5]. Dry CO
Sweet corrosion 2 gas by
caused is non-corrosive;
exposure to CO however, if dissolved
2 was first recognized in water, it forms
in the 1940s in carbonic
Texas
acid
[5]. Dry COthat attacks steel, initiating pitting, mesa attack, and flow-induced localized corrosion.
2 gas is non-corrosive; however, if dissolved in water, it forms carbonic acid
The average
that attacks pH of CO
steel, initiating 2 -saturated
pitting, mesawater is and
attack, about 4 or slightly localized
flow-induced less. The presence
corrosion.ofTheother
inorganic or organic acids like HCl or acetic acid decreases the pH level even lower. Sweet
average pH of CO2-saturated water is about 4 or slightly less. The presence of other inor-
corrosion causes up to 60% of oilfield failures [12].
ganic or organic acids like HCl or acetic acid decreases the pH level even lower. Sweet
Additionally, formation stimulation methods introduce strong acids as HCl, HF, and
corrosion causes up to 60% of oilfield failures [12].
other mineral and organic acids to production fluids that causes equipment damage. In
Additionally, formation
practice, stimulation ofstimulation
the oil wells methods introduce
is performed strong acids
by pumping as HCl,
strong acidsHF, and
solutions
other mineral
through and organic
steel-made acids casing,
pumps, to production fluids that
and production tubingcauses
untilequipment
it reaches the damage. In
target forma-
practice, stimulation of the oil wells is performed by pumping strong acids
tion to react with [131]. However, strong acids react not only with rocks but with surfaces of solutions
through steel-made
steel and causepumps, casing,
its corrosion. andisproduction
That why corrosion tubing until it
inhibitors arereaches the target part
an indispensable for- of
mationtheto acidizing
react with [131].
fluid mix;However,
however, strong acidsfully
they cannot reactmitigate
not onlythewith rocksofbut
reaction acidswith sur-
with steel.
faces ofApplication
steel and cause
of high its permeability
corrosion. That is why corrosion
production inhibitorsstimulation
fluids in reservoir are an indispensable
are intended
part oftothe
help the production
acidizing fluid mix;equipment
however,resist
theythese
cannotconditions and require
fully mitigate development
the reaction and
of acids
implementation of reliable advanced materials.
with steel. Application of high permeability production fluids in reservoir stimulation are
intended to help the production equipment resist these conditions and require develop-
ment and implementation of reliable advanced materials.
Materials 2023, 16, x FOR PEER REVIEW 26 of 34

Materials 2023, 16, 1795 25 of 33

3.3. New Trends in Corrosion Control Technologies

3.3.1.
3.3. NewModern
TrendsTrends in Engineering
in Corrosion of Coatings
Control Technologies
3.3.1.Novel
Modern Trends in Engineering
high-performance corrosion of Coatings
control systems require high durability for OCTG
and downhole equipment. Among
Novel high-performance the corrosion
corrosion mitigation
control systems measures,
require organic protective
high durability for OCTG
coatings
and downholeare theequipment.
most widely used, the
Among andcorrosion
their costsmitigation
add up tomeasures,
two-thirdsorganic
of all anti-corro-
protective
sion expenditures
coatings are the most [132].
widelyTo used,
achieve andhightheirperformance
costs add upin to corrosion
two-thirdscontrol, design and
of all anti-corrosion
engineering
expendituresof[132]. state-of-the-art
To achieveself-healing
high performanceand smart stimuli-responsive
in corrosion coatings
control, design andareengi-
on-
going to target the action of the materials in response to the local
neering of state-of-the-art self-healing and smart stimuli-responsive coatings are ongoing environmental threats.
The healing
to target theeffects
actionofofcoatings commonly
the materials functioning
in response to the bylocal
restoring the integrity
environmental of coating
threats. The
layers
healingby sealing
effects defects or
of coatings by inhibiting
commonly corrosion
functioning by reactions
restoring at thecoating
integrity defects with layers
of coating mini-
by sealing
mal defects orphysical
or no external by inhibiting corrosion
intervention reactions
[132]. at coating
Autonomous anddefects with minimal
non-autonomous self-or
no external
healing physical have
mechanisms intervention [132]. Autonomous
been developed for smart coatingand non-autonomous
systems. An autonomous self-healing ef-
mechanisms
fect is enabled have been developed
by embedding for smart healing
polymerizable coating agents
systems. or An autonomous
corrosion inhibitorseffect
into is
enabled by embedding polymerizable healing agents or corrosion
the coating matrices [132]. Non-autonomous self-healing effects are induced by external inhibitors into the coating
matriceswhich
stimuli, [132]. Non-autonomous self-healing
trigger chemical reactions. effects autonomous
Initially, are induced by external stimuli,
self-healing effectswhich
were
trigger chemical
developed reactions.
for chromate Initially, autonomous
conversion coatings andself-healing
were basedeffects on thewere developed
reduction for
of chro-
chromate conversion
mium(VI) coatings and
corrosion inhibitors were
in the based formulation
coating on the reduction to formof chromium(VI)
a protective oxide corrosion
film
inhibitors
at the site of in damage.
the coating formulation
Other to formcorrosion
useful inorganic a protective oxide film
inhibitors thatatcanthebe
site of damage.
incorporated
into self-healing coatings are phosphates, nitrites, molybdates, tungstates, vanadates,coat-
Other useful inorganic corrosion inhibitors that can be incorporated into self-healing bo-
ings are
rates, and phosphates,
rare earth metalnitrites, molybdates,
salts. tungstates, vanadates,
Not only metal-based borates,
but also organic and rareinhibi-
corrosion earth
metal
tors salts.
can Not only metal-based
be entrapped into the coating but also organic
matrix corrosion
including inhibitors (BTA),
benzotriazole can be entrapped
mercapto-
into the coating matrix including benzotriazole (BTA),
benzothiazole (MBT), imidazoline, 8-hydroxyquinoline (8-HQ), and aliphatic mercaptobenzothiazole (MBT), imi-
amines
dazoline,
[132]. 8-hydroxyquinoline
Alternatively, methods for (8-HQ), and aliphatic
achieving autonomous amines [132].recovery
coating Alternatively, methods
by embedding
for achieving autonomous coating recovery by embedding
extrinsic microencapsulated polymerizable healing agents in the coating have been engi- extrinsic microencapsulated
polymerizable
neered. Capsules healing
ruptureagents in the coating
in response to the have
stimuli been andengineered.
release theCapsules rupture
healing agents thatin
response to the stimuli and release the healing agents that
recover the coating integrity. Isocyanates, epoxies, and amines (such as tetraethylene- recover the coating integrity.
Isocyanates,(TEPA))
pentamine epoxies,asand amines
curing (such
agents areasthe
tetraethylenepentamine
major components of(TEPA)) as curing agents
such microcapsules.
are the major components of such microcapsules.
Non-autonomous stimuli-responsive healing effects in coatings may also be facili-
Non-autonomous stimuli-responsive healing effects in coatings may also be facilitated
tated by a complementary corrosion sensing component, which would detect fine pH var-
by a complementary corrosion sensing component, which would detect fine pH variation
iation or electrochemical reactions at an early stage of corrosion. Thus, conductive poly-
or electrochemical reactions at an early stage of corrosion. Thus, conductive polymers, i.e.,
mers, i.e., polypyrrole (PPy) or polyalinine (PANI), with oxidizing properties cause steel
polypyrrole (PPy) or polyalinine (PANI), with oxidizing properties cause steel passivation.
passivation. In the case of polypyrrole which has ion-exchange properties when it is mod-
In the case of polypyrrole which has ion-exchange properties when it is modified with
ified with 3PMo 12O40 3− and HPO4 2− ions, a self-healing ability is additionally achieved ow-
PMo12 O40 − and HPO4 2− ions, a self-healing ability is additionally achieved owing to the
ing to the reaction of tetraoxomolybdate 2ions (MoO4 2−) with iron. The iron–molybdate
reaction of tetraoxomolybdate ions (MoO4 − ) with iron. The2−iron–molybdate significantly
significantly limits substrate digestion [133].2−PANI–MoO4 is an oxidizer which offers
limits substrate digestion [133]. PANI–MoO4 is an oxidizer which offers anodic galvanic
anodic galvanic protection to the substrate [134]. A self-healing effect based on commer-
protection to the substrate [134]. A self-healing effect based on commercial super-absorbing
cial super-absorbing polymers that are used as a component of protective coatings on
polymers that are used as a component of protective coatings on cold-rolled steel, can
cold-rolled steel, can considerably reduce oxygen diffusion from solution to the surface of
considerably reduce oxygen diffusion from solution to the surface of the protected material.
the
For instance, material.
protected AQALIC For CS-7Sinstance,
[135] isAQALIC
a polymer, CS-7S [135]can
which is aabsorb
polymer, which
water andcan absorb
swell. Its
water and swell. Its addition at a quantity of 5% to the polymeric
addition at a quantity of 5% to the polymeric coating helps to heal scratches on the coating coating helps to heal
scratches
upon contact on the withcoating
waterupon(Figurecontact with water (Figure 17) [136].
17) [136].

Figure 17. The scratched part of the coating with 5 wt% of SAP AQALIC CS-7S before and after 6 h
corrosion test [133].
Materials 2023, 16, 1795 26 of 33

The recent decades have provided examples of self-healing in rigid structures such as
metallic–polymeric coatings. For instance, an electrochemically produced zinc coating with
polyethylene oxide-b-polystyrene (PEO113 -b-PS218 ) nanoaggregates owes its self-healing
properties to the amphiphilic properties of the polymer, which reversibly shrink and swell
in a medium containing chloride ions [137]. Moreover, ceramic materials (TiC/Al2 O3
and Ti2 AlC) demonstrate efficient oxidation-induced self-healing properties. In this case,
healing is activated by an increase in temperature in the presence of oxygen from the
air, resulting in the oxidation of the coating components and filling of defects by formed
titanium and aluminum oxides [138,139].
Implementation of the abovementioned stimuli-responsive and autonomous self-
healing properties for industrial coating systems will drastically enrich anticorrosive per-
formance and durability of these protective systems along with engineering of novel
high-performance polymers and resins for non-metallic coatings.
Environmental sustainability and ecological regulations have brought up importance
of the utilization of natural macromolecules and biopolymers like chitosan, lignin, cellulose,
nanocellulose, etc., into coating engineering. It was recently reported [140,141] that chitosan
exhibits excellent film-forming, corrosion-protecting, and antimicrobial properties with
very good affinity to metals. In combination with an epoxy matrix, this polymer provides
synergistic effects and improved the coatings’ anticorrosive and antibacterial properties in
a sustainable manner. Lignin is known as a natural UV absorber [142] that, when mixed
with a resin matrix, improves the coatings’ UV stability and service life. Moreover, natu-
ral fibers could be used as carriers for healing agents in smart coatings. Thus, cellulose
microfibers loaded with various amines and self-healing agents [143] were used to blend
with polymeric matrices to develop smart self-healing epoxy coating formulations. Cel-
lulose nanofibers [144] can establish partial chemical interactions with amino groups of a
polyamine-based curing agent and physically adhere epoxy monomers. Upon mechanical
impact, the released epoxy monomers are cured by the amine on the surface-modified
cellulose nanofiber, promoting fracture closure.
It is worth noting that novel coating compositions often require additives of func-
tional nanomaterials [145,146] for the improvement of their texture, temperature resistance,
mechanical, adhesive, and wettability properties, as well as for better penetration of com-
ponents in the formulation. Additives of carbon-based nanomaterials, such as CNTs,
graphene, graphene oxide, and others, are known to improve mechanical stability of epoxy
and other matrices [147,148]. Nano-silica enhances corrosion protection, fracture toughness,
and tensile strength of coating matrices [149]. Combinations of polymeric matrices with
various metal oxide nanoparticles, nano-clays, nano-ceramics, and other nanofillers results
in nanocomposite coatings with superior properties vs. ordinary resins [150].

3.3.2. Current Trends in the Development of Corrosion Inhibitors

Injection of corrosion inhibitors has become a prominent method of anticorrosion
treatment in the oil industry, and the number of commercially available CI formulations is
rapidly growing. Intense injection of chemicals, especially in open systems like offshore
platforms and perforated wells, requires minimal ecological impact to maintain the sus-
tainability of ecosystems. Therefore, environmentally friendly inhibitors based on biogenic
amino acids such as methionine are of great interest for low-cost, non-toxic corrosion
protection [151]. Evaluation of L-methionine’s corrosion protective effects on 309S stainless
steel in 1M H2 SO4 via ESI, polarization, and XPS, concluded that methionine significantly
increased the charge transfer resistance, and reduced the corrosion current density due to
suppression of both cathodic and anodic reactions. To further increase the anticorrosive
efficiency of this amino acid and enhance protection of the metal surface, methionine-based
polymers were synthesized and evaluated for CI activity [152] on mild-steel coupons in a
1 M HCl solution at 60 ◦ C. The obtained polymers exhibited excellent inhibition efficiency
due to increased adsorption onto the metal surface. Moreover, comparative evaluation of
the corrosion protective action of 20 natural amino acids on iron surfaces in a 1 M HCl solu-
Materials 2023, 16, 1795 27 of 33

tion showed the best performance efficiency for sulfur-containing molecules—methionine,

cystine, and cysteine [153].
Polymers possess important structural features such as better film-forming action with
several possible attachment points and highly versatile derivatization, and thus have a great
potential in surpassing the performance of small molecule-based corrosion inhibitors while
keeping the concentration down to a minimum [154]. Biopolymers with good chelating
properties such as derivatives of chitosan are emerging candidates for readily available
and eco-friendly CI systems [155]. Additional possibilities of polysaccharide-backbone
modifications with various side chains and heteroatoms-bearing moieties can allow the
customization of the materials’ affinity to metal surfaces and film-forming behavior in a
broad variety of conditions.
Principles of chemicals’ compartmentalization and their controlled release has been
applied for extended action of corrosion inhibitors, acidizing agents, and scale dissolvers.
Hollow carbon nanospheres loaded with M16 yielded multifunctional corrosion inhibitor-
infused porous graphite carbon nanospheres (GCN@M16) [156]. Controlled release of
the M16 anticorrosive agent occurs in the response to mechanical impact and to external
pressure while the hollow nanospheres provided good dispersion and lubricating actions
for the obtained composite. As mentioned earlier, metal oxide nanoparticles, hollow silica,
halloysite, clay, and other nanocontainers were utilized for infusion of the inhibitor. The
majority of these composites were further implemented for the engineering of coatings.

4. Conclusion and Future Directions

In conclusion, this work reviewed the latest industrial and environmental challenges
that novel corrosion protection systems are facing in oil and gas downhole applications. The
broad spectrum of the existing corrosion protection systems was reviewed and described
in addition to their application features and current R&D achievements to tackle emerging
challenges. A summary of the corrosion protection systems evaluation standards illustrated
the scope of the tests that are currently implemented and that would require the extension
of methods for assessing the improved innovative protective solutions. Expanding the
horizon of oil and gas production requires the development of advanced materials that
could endure highly corrosive environments with increased mechanical challenges and
HPHT operations. Looking at the state-of-the-art, novel types of engineered corrosion
protective materials we conclude that: smart stimuli-responsive systems for self-healing
coatings, environmentally friendly formulations of corrosion inhibitors and resins, and
composites based on nanomaterials infused with corrosion inhibitors and/or healing agents
would beneficially address the prolonged durability of corrosion protective systems and
mitigate the challenges that the oil and gas industry is currently facing.

Author Contributions: Conceptualization, V.A.S., K.H.A. and W.O.B.; methodology, V.A.S., K.H.A.
and W.O.B.; writing—original draft preparation, V.A.S. and W.O.B.; writing—review and editing,
V.A.S. and K.H.A.; supervision, K.H.A.; project administration, V.A.S. and K.H.A.; funding acquisition,
V.A.S. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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