Corrosion Inhibitors

CHEMISTRY RESEARCH AND APPLICATIONS
CORROSION INHIBITORS
PRINCIPLES, MECHANISMS
AND APPLICATIONS
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CHEMISTRY RESEARCH
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CHEMISTRY RESEARCH AND APPLICATIONS
CORROSION INHIBITORS
PRINCIPLES, MECHANISMS
AND APPLICATIONS
ESTHER HART
EDITOR
New York
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CONTENTS
Preface vii
Chapter 1 Organic Corrosion Inhibitors and Industrial
Applications 1
Gözde Tansuğ and Tunç Tüken
Chapter 2 Application of Polymer Composites and
Nanocomposites as Corrosion Inhibitors 27
Saviour A. Umoren
and Moses M. Solomon
Chapter 3 Uses of Environmentally Friendly Corrosion
Inhibitors in Amine-Based CO2 Absorption
Processes 59
Amornvadee Veawab, Sureshkumar Srinivasan
and Adisorn Aroonwilas
Chapter 4 The Effectiveness of Copaiba Oil Loaded
into a Microemulsion System as a Green Corrosion
Inhibitor 79
Denise P. Emerenciano, Ana Carla C. Andrade,
Melyssa L. de Medeiros,
Maria de Fátima V. de Moura
and Maria Aparecida M. Maciel
Chapter 5 Corrosion Mechanism and Inhibitors for Al Based
Particulate Metal Matrix Composite (APMMCs) 105
Ajay Singh Verma, Sumankant and N. M. Suri
vi Contents
Chapter 6 Electrochemical Study of 1,3,4-Triazolium-2-Thiol

as a Corrosion Inhibitor of Mild Steel in Saline
Medium 117
Jardel D. Cunha, Cátia G. F. T. Rossi,
Djalma R. Silva, Ewerton R. F. Teixeira,
Aurea Echevarria and Maria Aparecida M. Maciel
Index 153
PREFACE
This book discusses principles, mechanisms and applications of corrosion

inhibitors. Chapter One focuses on organic corrosion inhibitors and their
industrial applications. Chapter Two explores the application of polymer
composites and nanocomposites as corrosion inhibitors for different metal
substrates in different corrosive media. Chapter Three provides a review of
corrosion inhibitors and a progress towards use of environmentally friendly
corrosion inhibitors in the amine-based CO2 absorption process for acid gas
treatment and carbon capture. Chapter Four studies the effectiveness of
copaiba oil loaded on microemulsion systems as green corrosion inhibitors.
Chapter Five addresses the mechanism of corrosion for APMMCs, and
discusses different methods of inhibition to corrosion for APMMCs. Chapter
Six focuses on the electrochemical study of 1,3,4-triazolium-2-thiol as a
corrosion inhibitor of mild steel in saline medium.
Chapter 1 – Organic corrosion inhibitors have been frequently studied,
since they offer simple solution for protection of metals against corrosion in
aqueous environment. Thus, there are many commercialized corrosion
inhibitors for industrial applications like; cooling systems, pipelines, oil and
gas production units, boilers and pickling process etc. The largest amount of
inhibitor is demanded by cooling water systems and it is the fact that inorganic
inhibitors (phosphates, tungstate, molybdate etc.) are still widely used in this
area. For such engineering purposes, the required inhibitor is anticipated to
assemble chemisorbed film (preferably monolayer), either by direct adsorption
on metal surface or forming insoluble complex with metal ions existing at the
interface. For copper and its alloys, there have been numerous chemical
formulations based on organic inhibitors. However, steel has been the most
widely used material, and there is a need for further development in the
viii Esther Hart
application of organic inhibitors for protection of steel against corrosion. On

the other hand, there has been an increasing concern about the use of “green”
chemicals for such purposes and this consideration also urges the
investigations subjecting the organic corrosion inhibitors. For this purpose,
molecular design and synthesis of novel organic inhibitors have been
pronounced as a promising way, for tailoring one compound equipped with
multitasking. On the other hand, it is necessary to develop new approaches
(methods) for the assessment of corrosion inhibitor performance, in practical
application conditions. Because, there are many parameters (temperature, pH,
composition of corrosive media, etc.) that should be evaluated carefully for
success of the application, in order to avoid excess chemical use or insufficient
protection. Possible interference between the critical parameters should also be
taken into account, for convenient application. For this reason, statistical
evaluations should be carried out with data obtained from various routes
employed to determine the corrosion rate. Generally, the preferred method is
based on electrochemical techniques, and utilizes Tafel and Stern-Geary
methods. Solution assay analysis, weight loss measurements have also been
widely employed, since they offer simplicity for quantification of corrosion
rate. This paper focuses on the interpretations of these addressed issues, with
the theory and review of recently published studies in relevant field.
Chapter 2 – Corrosion commonly defined as the deterioration of a material
(usually a metal) or its properties because of a reaction with its environment is
a global problem. NACE International, The Corrosion Society, estimates that
global corrosion costs can be about 3–5% of GDP or GNP. Methods
commonly adopted to combat corrosion include coatings and linings, cathodic
protection, materials selection and corrosion inhibitors. Corrosion inhibitors
are chemicals that, when present in very low concentrations, retard corrosion.
Corrosion inhibitors form a layer over the metallic substrate and protect the
metal from corrosion, thereby enhancing the life of the metal. Polymers, both
naturally occurring and synthetic have been tested for metal corrosion
inhibitors as replacement for the toxic inorganic and organic corrosion
inhibitors. Interest in polymers stems from their availability, cost
effectiveness, and eco-friendliness in addition to the inherent stability and
multiple adsorption centers. However, it is found that most polymer materials
studied are moderate corrosion inhibitors. Several attempts such as
copolymerizing, addition of substances that exert synergistic effect, cross
linking, blending, and most recently incorporation of inorganic substances in
nano size into the polymer matrix have been made to improve the inhibition
ability of polymers. Composites are materials consisting of two or more
Preface ix
chemically distinct constituents on a minute-scale, having a distinct interface

separating them, and with properties which cannot be obtained by any
constituent working individually. The production of composite materials is
either by ex-situ or in-situ formation through chemical synthesis although
electrochemical method had been used recently. The application of polymer
composites and nanocomposites as anticorrosion materials have shown
promising results and are believed to form metal chelate which could barricade
metal surfaces from corrosive agents. In this chapter, the application of
polymer composites and nanocomposites as corrosion inhibitors for different
metal substrates in different corrosive media is explored.
Chapter 3 – Corrosion is a severe operational problem in the carbon
dioxide (CO2) absorption process using aqueous solutions of amines, when
carbon steel is used for plant construction. Past experiences with these plants
have provided practitioners with a number of recommendations to keep
corrosion under acceptable levels. Among these, the application of corrosion
inhibitors is the most widespread because it is economical and requires small
or no process modifications to existing plants. Various corrosion inhibitors
have been developed, patented and commercialized by many major chemical
companies for uses in amine treating plants. The patented organic inhibitors
include thiourea and salicyclic acid, while inorganic inhibitors are vanadium,
antimony, copper, cobalt, tin and sulfur compounds. The inorganic inhibitors
are in practice more favored than the organic compounds because of their
superior inhibition performance. Vanadium compounds, particularly sodium
metavanadate (NaVO3), are the most extensively and successfully used in
amine treating plants. Despite the successful use of the inorganic corrosion
inhibitors, concerns about impacts of their toxicity on human health and the
environment have increased in past decades. To respond to the environmental
concerns on the use and disposal of harmful chemicals, a number of initiatives
were taken around the world. In Canada, usage of toxic substances is regulated
by the Canadian Environmental Protection Act (CEPA). Inorganic arsenic and
cadmium inhibitors are classified as carcinogenic and considered toxic. As a
result, their usage was banned. In the US, the Environmental Protection
Agency (EPA) regulates the usage of chemicals through Clean Water Act
(CWA) and Clean Air Act (CAA). In Europe, an environmental regulatory
mechanism OSPAR was established by fifteen Northeast Atlantic nations to
protect the marine environment which was later broadened to cover land based
sources and offshore industry. Based on the OSPAR guidelines, most
corrosion inhibitors that are used, tested and patented for amine-based CO2
absorption processes are non-environmental friendly. Hence, to respond to the
x Esther Hart
environmental concerns and reduce the cost of waste disposal as well as

prepare for more stringent regulations for chemical uses, application of
effective and environmentally friendly corrosion inhibitors is necessary. The
objective of this book chapter is to provide a review of corrosion inhibitors
and a progress towards use of environmentally friendly corrosion inhibitors in
the amine-based CO2 absorption process for acid gas treatment and carbon
capture. The chapter is divided into four sections. Section 1 provides
background information of the amine-based CO2 absorption process, including
process description and type of amine used. Section 2 describes typical
corrosion problems taking place in the process and provides historical
corrosion cases in actual plant operations. Section 3 provides a compiled list of
corrosion inhibitors that have been patented, tested and applied in this plant
operation, discusses the use of environmentally friendly corrosion inhibitors
and provides an update on research related to environmentally friendly
corrosion inhibitors in the amine-based CO2 absorption process.
Chapter 4 – Corrosion inhibitors have been applied on protection of steel
structures and their alloys in industry. In this sense, natural inhibitors become
as an important alternative to sustainable technological development. As
advantage, natural corrosion inhibitors reduce the toxic effects observed for
synthetic organic compounds, and depending on their formulation could range
from lower toxicity to nontoxic commercial products. Additionally, green
inhibitors are attractive in function of the low cost procedures, inhibition
performances are closely related to plant extracts, fractions, oil, and even,
isolated compounds. In this present work a commercial copaiba oil sample
(CO) belonging to the vegetal species Copaifera L., was loaded into a O/W
self-microemulsion system (SMEDDS colloidal-type) composed with CO
(1.0% as oil phase), Tween® 80 (10.0% as surfactant) and water (89.0%),
affording the green sample SME-CO. The SME-CO formulation was applied
as a natural corrosion inhibitor measured at different concentrations (ranging
from 5 ppm to 150 ppm), in a saline corrosive medium (3.5% of sodium
chloride). The best SME-CO corrosion inhibition efficiencies (77.15%) was
observed at 100 ppm by electrochemical method of linear polarization curves
with Tafel extrapolation, and obeys Langmuir model isotherm. The greatest
inhibitory effect of the tested green sample (SME-CO) could be correlated
with the SMEDDS adsorption phenomena on the metal surface (steel AISI
1018), being herein considered as a eco-friendly corrosion inhibitor. In the
other hand, CO-corrosion efficiency could be correlated with the synergistic
effect of its phytocompounds of which diterpenes and sesquiterpenes with
Preface xi
different functional groups are adsorbed on the metal surface, forming a stable
plant source-metal complex, reducing metal damage.
Chapter 5 – Corrosion in metals is gradual degradation by oxidation in
hostile environment. APMMCs are the materials which developed by
combining two distinguish parts namely matrix and reinforcement phases
fabricated by different casting techniques. Corrosion in APMMCs happens due
to pitting initiation at the interface of the fabricated APMMCs and crevices on
the surface of the fabricated APMMCs. Corrosion mechanism in APMMCs is
due to galvanic reaction between the matrix phase and its reinforcement phase.
Formation of new compounds at the interface of the APMMCs is also a reason
of selective corrosion. Pitting action occurs in APMMCs as localize corrosion.
Potential gradient elevate the oxidation of metal in hostile environment results
in pitting phenomenon. Generally APMMCs are more susceptible to corrosion
as compare to its base alloys but superior in strength in terms of mechanical
properties. Cognition behind this is reinforcement is hurdle for preserve the
passive film which is on the surface of aluminum. Aluminum having strong
thin passive film on the surface which brakes, it recovers itself. In APMMCs
reinforcements shatter the oxide film, allowing pitting and crevice corrosion.
Hence, inhibition of corrosion becomes necessary to protect the APMMCs
from the hostile environment and to increase the life of fabricated APMMCs.
Polymer coating, anodizing, surface modification and chemical passivity are
the inhibitor process for the fabricated APMMCs. Among these inhibitors
anodizing is the best method to protect APMMCs from corrosion in hostile
environment. This chapter addresses the mechanism of corrosion for
APMMCs. Different methods of inhibition to corrosion for APMMCs are also
discussed.
Chapter 6 – The mesoionic compound 1,3,4-triazolium-2-thiol (MI) was
solubilized in an oil-in-water microemulsion (OCS-ME) containing saponified
coconut oil (OCS) as surfactant, butan-1-ol as cosurfactant, kerosene as oil
phase and saline solution as aqueous medium. The MI-loaded system (OCS-
ME-MI) was evaluated as corrosion inhibitor at lower concentrations (ranging
from 12.5 ppm to 100 ppm) using the electrochemical and gravimetric
methods, Linear Polarization Resistance (LPR) and Mass Loss (ML),
respectively. The corrosion inhibition of OCS-ME-MI was evidenced on the
AISI 1018 steel, in saline solution (NaCl 1%) showing higher inhibitory effect,
such as 92.60%, at 75 ppm of OCS-ME-MI sample by LPR technique, and
92.68% at 75 ppm of OCS-ME-MI sample by ML technique. According to the
electrochemical method applied, linear polarization curves with Tafel
extrapolation, OCS-ME-MI obeys Frumkin adsorptions isotherm.
In: Corrosion Inhibitors ISBN: 978-1-63485-791-8
Editor: Esther Hart © 2017 Nova Science Publishers, Inc.
Chapter 1
ORGANIC CORROSION INHIBITORS

AND INDUSTRIAL APPLICATIONS
Gözde Tansuğ1 and Tunç Tüken2,

1
Cukurova University, Ceyhan Engineering Faculty,
Chemical Engineering, Adana, Turkey
2
Cukurova University, Sciences and Letters Faculty,
Chemistry Department, Adana, Turkey
ABSTRACT
Organic corrosion inhibitors have been frequently studied, since they
offer simple solution for protection of metals against corrosion in aqueous
environment. Thus, there are many commercialized corrosion inhibitors
for industrial applications like; cooling systems, pipelines, oil and gas
production units, boilers and pickling process etc. The largest amount of
inhibitor is demanded by cooling water systems and it is the fact that
inorganic inhibitors (phosphates, tungstate, molybdate etc.) are still
widely used in this area. For such engineering purposes, the required
inhibitor is anticipated to assemble chemisorbed film (preferably
monolayer), either by direct adsorption on metal surface or forming
insoluble complex with metal ions existing at the interface. For copper
and its alloys, there have been numerous chemical formulations based on
organic inhibitors. However, steel has been the most widely used
material, and there is a need for further development in the application of

Corresponding Author address E-mail: ttuken@cu.edu.tr.
2 Gözde Tansuğ and Tunç Tüken
organic inhibitors for protection of steel against corrosion. On the other

hand, there has been an increasing concern about the use of “green”
chemicals for such purposes and this consideration also urges the
investigations subjecting the organic corrosion inhibitors. For this
purpose, molecular design and synthesis of novel organic inhibitors have
been pronounced as a promising way, for tailoring one compound
equipped with multitasking. On the other hand, it is necessary to develop
new approaches (methods) for the assessment of corrosion inhibitor
performance, in practical application conditions. Because, there are many
parameters (temperature, pH, composition of corrosive media, etc.) that
should be evaluated carefully for success of the application, in order to
avoid excess chemical use or insufficient protection. Possible interference
between the critical parameters should also be taken into account, for
convenient application. For this reason, statistical evaluations should be
carried out with data obtained from various routes employed to determine
the corrosion rate. Generally, the preferred method is based on
electrochemical techniques, and utilizes Tafel and Stern-Geary methods.
Solution assay analysis, weight loss measurements have also been widely
employed, since they offer simplicity for quantification of corrosion rate.
This paper focuses on the interpretations of these addressed issues, with
the theory and review of recently published studies in relevant field.
Keywords: organic inhibitors, corrosion, cooling water systems, green

chemistry
1. INTRODUCTION
The corrosion inhibitors have widespread application in various industries
(oil & gas, steel industry, general cooling water systems etc.), and the global
market was reported to be 5.20 billion US$ and forecasted to reach 7.4 billion
by the end of 2019 [1]. Within this market, the application of corrosion
inhibitors in cooling water system takes noteworthy part, because of the
variety of industries involving such cooling water systems. In these systems,
widely used commercial products are chemical formulations based on
inorganic corrosion inhibitors. These formulations also include some co-
additives (biocides, dispersant agents etc.), because ground/lake/sea water is
necessarily used in cooling water systems for various chief industries. In all
cases, the cooling water is subjected to various pretreatments, but still should
be considered as a matrix including various inorganic/organic species within.
Organic Corrosion Inhibitors and Industrial Applications 3
For cooling water systems, chromates and nitrates have long been utilized
as efficient inhibitors, until their use have been restricted due to environmental
concerns. Then, the silicates, molybdates, phosphates have been widely used
in commercialized formulations, since they offer remarkable efficiency and
they are friendly against the environment [2]. Of course, the cost of chemicals
is another important issue for designing such inhibitor formulations. For this
reason, molybdate and tungstate like chemicals have been frequently
employed for closed water cooling systems, since these kinds of systems that
require less chemicals. It is noted that well-conditioned water with efficient
corrosion inhibitor could be used for a long time in such systems, over and
over again. However, in open cooling water systems, there is water loss due to
evaporation in each cycle, as well as contamination (suspended solids, grease
etc.). Therefore, there is necessity for feeding the chemicals to tune the water
quality, after each cycle. Thus, inhibitor formulations using cheaper chemicals
like phosphate derivatives are widely commercialized with the aid of co-
additives like dispersive agents, biocides etc.
In the following sections, the application of organic inhibitors will be
discussed, in the aspects of potential for commercialization, requirements of
industrial cooling water systems, and recent developments.
2. INHIBITORS IN INDUSTRIAL APPLICATIONS

Inhibitor application is simply based on the fact that the surface of
substrate should be shielded with stable and compact thin films, in order to
hinder the attack of corrosive environment. For this purpose, molybdate and
silicate anions directly react with the metal ions of corroding metal/alloy,
which are released at the interface due to corrosion of material itself. On the
other hand, phosphate derivatives are not easy to form protective films with
dissolved Fe (II, III) ions, since they require remarkably high pH values for
direct deposition of stable complex between phosphate and iron ions. Highly
alkaline conditions bring the risk of intense scale deposition on steel. The
solution has been found with chemical deposition of zinc phosphate
(Zn3(PO4)2) on steel surface, this compound has extremely low solubility
product, 9.0×10–33. The use of phosphate derivatives (sodium salts of
hexametaphosphate and tripolyphosphates, Figure 1) offer versatility, low cost
and good efficiency under circulating water conditions. However, phosphate
based chemical formulations involve high dosages and well-adjusted water
parameters. In order to avoid bulk scale deposition on the surface, especially in
heat exchangers or hydrothermal plants, water hardness and ionic species

(hydroxide and carbonate) should be carefully managed for success of
inhibitor application.
Abd-El-Khalek and Abd-El-Nabey studied on evaluation of sodium
hexametaphosphate (SHMP) as scale and corrosion inhibitor in cooling water,
by using electrochemical techniques and comparing with polyacrylic acid.
SHMP is more efficient as antiscalant than polyacrylic acid, SHMP delays
nucleation period and thus hinder scale formation. A critical concentration of 4
ppm SHMP was required to obtain 81% of scale inhibition. In presence of 2
ppm of polyacrylic acid and SHMP, the scale inhibition efficiencies were
30.1% for polyacrylic acid and 55.9% for SHMP [3]. Moudgil et al.
investigated synergistic effect of antiscalants: 1-hydroxyethane-1,1-
diphosphonic acid (HEDP), sodium hexametaphosphate (SHMP), sodium
tripolyphosphate (STPP) and trisodium phosphate (TSP) in different
combinations for carbon steel in industrial cooling water system. When HEDP
was mixed with other antiscalants, the corrosion inhibition increased with the
following order; HEDP/SHMP (97.6%) >HEDP/STPP (91.4%) >HEDP/TSP
(59.8%) [4].
In another research, inhibition efficiencies of hydroxyl carboxylate-based
corrosion inhibitors (e.g., gluconate, citrate, tartarate) and zinc sulfate
heptahydrate have been studied in the pipeline of reclaimed water supplies and
in downstream recirculating cooling water system. It was reported that the
appropriate combination of phosphate and zinc ions reduce the cost and
environmental risk of excess phosphorus release. With 2.0 mg/L phosphate
concentration and 0.5 mg/L zinc ions, the corrosion rate was lower than 0.1
mm/year. In the same study, a non-phosphorus formulation was also reported,
using hydroxyl carboxylates as the main corrosion inhibitors, zinc ions as
additive, PESA as anti-scaling and LN-104B as dispersant. The corrosion rate
decreased down to below 0.075 mm/year, with hydroxyl carboxylate dosage in
range of 4-8 mg/L, PESA and LN-104B dosages were 6-10 mg/L [5]. In
another work, the influence of inhibitors and biocides were investigated for
mild steel and copper-nickel alloys in a power plant cooling water system with
help of electrochemical and weight loss measurements. The formulation
included sodium hypochlorite, 1-hydroxyethylidene-1,1-diphosphonate,
maleic anhydride homopolymer, 2-phosphonobutane-1,2,4-tricarboxylic acid
as scaling inhibitors, and zinc ions, 2-mercaptobenzothiazole as corrosion
inhibitors. The results showed that corrosion rate of carbon steel was 3.88 mpy
(mil per year) and 0.76 mpy was reported for copper-nickel, in presence of
inhibitor formulation [6].
Figure 1. Structures of the mostly used commercial phosphate compounds.
Figure 2. Structures of the mostly used commercial phosphonic acids.
The good performance of phosphate compounds is simply related to their

superior functional group which is capable of complexing many metal ions, so
similar compounds have been researched frequently. Moreover, phosphonates
and various anionic polymers have found application in commercial chemical
formulations. For instance, 1-hydroxyethane-1,1-diphosphonic acid (HEDP)
has partaken in formulation of various commercial corrosion inhibitor
products (Figure 2). Mohammedi et al., [7] investigated the inhibition
efficiency of a mixture formulation based on HEDP and sodium metasilicate,
on carbon steel in industrial hard water. They showed that HEDP and calcium
ions synergistically support passivity of the metal, reported inhibition
efficiency is 94% at pH 7. This kind of compounds have grabbed much
attention due to their rare properties like; stability, strong adsorption on metal
surface, complexing many metal ions and dispersant activity. Phosphonates
are good chelating agents, thanks to their ability to bind strongly to di- and
trivalent metal ions. In the case that the molecule tailored with an amine
group, the chelating capability increases. Examples for such compounds are
amino (trimethylene phosphonic acid), ethylene diamine tetra
(methylphosphonic acid) (Figure 2).
Sodium salt of polyaspartic acid (PASP) and amino trimethylene
phosphonic acid (ATMP) were investigated as scale inhibitors in circulating
cooling water system for stainless steel. The reported corrosion inhibition
efficiency is 83%–89%, up to 20 mg/L concentration range ATMP. It was also
reported that scale inhibition efficiency of PASP was three times greater than
ATMP [8].
Jin et al. [9] reported a new water treatment formulation for carbon steel
surface in a pilot-scale cooling system with reclaimed wastewater as the
makeup water. The optimized composition of scale and corrosion inhibitor
was 12.5% 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA), 21.8%
ZnSO4, 18.7% polyaspartic acid (PASP), 9.4% 2-hydroxyl phosphonoacetic
acid (HPAA), 18.8% acetic acid (AA) - amino trimethylene phosphonic acid
(ATMP) - 2-hydroxyl phosphonoacetate (HPA) polymer, and 18.8%
hydrolyzed polymaleicanhydride (HPMA). For this formulation, the reported
inhibition efficiencies against scale deposition and corrosion were 93.3 and
94.4%, respectively.
Of course, the stability of metal complexes increases with increasing
number of phosphonic acid groups. These types of species are well known
with their scale prevention effect, when they are used in cooling water with
notable hardness. However, the chemistry of these phosphonate based metal
complexes does not allow forming compact and reasonably thin protective
films on steel surface. Therefore, the dosage should be high, in order to utilize
this type chemicals for achieving both scale prevention and inhibition. The
corrosion inhibition mechanism is explained with strong adsorptive interaction
with the surface, in the case that metal surface is not occupied by other species
like; scale, corrosion products etc. The inhibition efficiency of such
compounds is highly sensitive against the pH and composition of corrosive
aqueous environment. They are very successful on bare metal surface, i.e.,
when the pH is low enough for prevention of deposits like quasi-stable (non-
protective) corrosion products on the surface. Another consideration is the
presence of diverse anions like Cl- or OH-. In this case, the competitive
adsorption between these anions and inhibitor molecules generally limits the
success of corrosion inhibition. As a conclusion, the chelating performance

and scale prevention capability of phosphonates step forward, when they are
utilized in corrosion inhibitor formulations to be used in cooling water
systems.
3. ORGANIC INHIBITORS
3.1. Why Organic Inhibitors?
The reason that there is gradually increasing concern about the use of
environmentally friendly chemicals, there is a necessity for developing new
“organic” inhibitors with better efficiency. Of course, the versatility, cost and
efficiency should be taken into account. Even though there have been some
effort about development of inorganic corrosion inhibitors, for example there
have been many studies focused on Schiff base compounds, organic inhibitors
are easy to functionalize with multitasks and they offer “green” solutions. The
corrosion inhibitor must be “green” (biodegradable and harmless for the
environment), because sooner or later these chemicals are released to
environment, one way or another.
It is not surprising that almost all organic compounds exhibit inhibition
efficiency against corrosion in aqueous media, especially when they possess
heteroatoms like; nitrogen, sulphur, phosphorous and oxygen. The organic
molecules simply adsorb on the metal surface by displacing water molecules.
So, the forces involved in this process can be summarized as; organic
molecule-electrode forces and lateral interactions (i.e., intermolecular forces
between the adsorbed organic molecules). Then inhibition efficiency arises
due to one or more of the following routes: preferential adsorption on anodic
or cathodic sites and blocking the reaction, assembling a protective barrier film
on the surface. According to inhibition mechanism, the inhibitors are classified
as anodic, cathodic or mix-type. Various electrochemical experimental studies
should be realized carefully, and collected data should also be evaluated
properly for defining the type of inhibitor. This is not within the targeted topic
of this paper; however an example will be discussed briefly in the section
titled assessment of corrosion inhibition efficiency.
OH SH
N OH
A B C
Figure 3. Molecular structures for (A) hydroxybenzene, (B) benzenethiol, (C) nicotinic
acid.
Going back to adsorptive interaction of organic inhibitors with the surface,

availability of lone pair electrons and/or π-bonding electrons in the molecule
enables formation of coordinate covalent bond involving electron transfer
from inhibitor to the metal. In this case, the adsorption type shifts from
physisorption to chemisorption, soon, and the adsorption strength depends on
the electron density on the donor atom of the functional group and the
polarizability of the group. To conclude, structure, size and orientation of the
organic molecule are the essential factors influencing the adsorption type and
strength. For example, linear (or branched) hydrocarbon chains can exhibit
weak interaction with water molecules and electrode surface. Aromatic
compounds are generally anticipated to interact strongly with the metal surface
and neighboring adsorbed molecules (lateral interactions), due to their π-
electrons. The type of molecule and functional groups alter greatly the
orientation of organic molecule at the interface. As an example,
hydroxybenzene (phenol) molecule (Figure 3A) is preferentially held to the
surface in a flat orientation, because of strong attraction between delocalized
π-bonding system and the surface, rather than –OH group. On contrary,
benzenethiol (phenyl mercaptan) molecules (Figure 3B) attach to the surface
through the sulphur atoms, and then the benzene rings are aligned towards the
solution side of the interface [10]. In the latter case, the benzene rings also
interact with each other and provide extra stability and hydrophobic surface.
Therefore, it is not surprising to obtain higher inhibition efficiencies with
organic molecules tailored with mercaptan groups. It should also be noted that
the orientation (with respect to surface) of organic molecules may change
depending on the surface charge of metal. A typical example is nicotinic acid
(Figure 3C), which could interact with negatively charged surface through its
nitrogen atom; the adsorption happens through aromatic nitrogen and
carboxylate groups, at positively charged surface. For such interpretations,
quantum chemical methods and molecular modeling techniques could also be
useful for characterizing the orientation, and binding properties of inhibitor

molecules [11]. However, the details of these methods are not within the scope
of this work.
3.2. Organic Inhibitors in Cooling Water Systems
There is necessity for novel organic corrosion inhibitors to be employed in

chemical formulations to protect steel against corrosion, in nearly neutral
conditions. Adapting an organic inhibitor to cooling water systems is a great
challenge, since the cooling water is a matrix with points of considerations
like; hardness, suspended solid materials, grease etc. Therefore, lab-scale
experimental results may indicate to excellent inhibition efficiency, but the
inhibitor may not work in a real circulating cooling water system. Scale
deposition is the major problem to be handled, because the organic inhibitors
are generally successful on bare metal surfaces. This is also the reason that
most of the studies reporting outstanding protection efficiency with organic
inhibitor are mostly in acidic environments. At this point, it should be noted
that the greatest demand for corrosion inhibitors is for cooling water systems,
where the pH value is generally in between 6.5-8.5. One may ask the question:
why the pH value should be in this range? Scale deposition is directly related
with the pH and ionic composition of water (hardness). Generally, it is easy to
adjust the parameters for prevention of scale deposition; taking into account
the Langelier Saturation index (LSI). This value is an equilibrium model
which could be simply given with the following equation.
LSI = pH - pHs (1)
As can be seen, this index is related with the degree of saturation of water
with respect to calcium carbonate. In this equation; pH is the measured value
and pHs is the value at which saturation of calcium carbonate is reached in
that water sample. The value pHs could be directly determined with help of a
simple experiment with water samples or calculated theoretically, with help of
water parameters [12].
Mostly, the operators try to adjust the water parameters in such a way that
the LSI index value is < 0, then there is no risk for scale deposition. In this
case, the risk of corrosion increases (for mostly used material: steel) and
therefore it is generally preferred to keep the index in slightly greater than
zero, this is also frequently recommended by suppliers and also in the

Literature [13-15].
However, this route could only be achieved by tuning the pH of cooling
water and is not so easy in practice, since the parameters are quite changeable,
especially in open water cooling systems. For this reason, various dispersive
agents are added to chemical mixture formulation of corrosion inhibitor.
Biocides are also inevitably necessary for controlling the microbial activities,
because microorganisms (bacteria, fungi and algae) may lead to formation
biofilms on the surface, in presence of organic compounds. The metabolism of
these species could produce corrosive compounds (acids or aggressive species)
then the result is generally severe corrosion under the biofilm. So the organic
inhibitor should also be compatible with such co-additives [6, 16-18].
3.3. Plant Extracts
Plant extracts are generally considered as green corrosion inhibitors and

the extract includes a part of phytochemicals, depending on the extraction
procedure parameters (solvent type, pretreatments, temperature etc.). The
chemical compounds that occur naturally in plants are named as
phytochemicals. The said phytochemicals are of course related with the type of
plant, but generally they are phenolic compounds, organic acids, esters,
alkaloids, flavonoids, tannic acids etc. It is generally assumed that plant
extracts are biocompatible due to their biological origin, i.e., green corrosion
inhibitors. However, the studies aiming to research green inhibitors should be
better accomplished with detailed analysis of degradability of organic
inhibitors in the nature. Because the biodegradation is a complicated process
occurring under influence of microbial activity, water, UV-visible light etc.
The organic compound itself may be green, however the intermediates of
degradation mechanism could be unsafe for the environment.
El Hamdani et al. investigated alkaloids extract of Retama monosperma
(L.) Boiss seeds used as novel eco-friendly inhibitor for carbon steel corrosion
in 1 M HCl solution. They reported 94.4% inhibition efficiency for 400 mg/L
concentration [19]. Gerengi worked on mimosa extract for AA6060 alloy in
acid rain solution, the inhibition efficiency is 45% at 2750 ppm [20]. Al-Otaibi
et al. [21] studied on alcoholic extract of eight different plants and examined
their corrosion efficiencies on mild steel. The extracts (0.01g/100 ml) of
Artemisia sieberi and Tripleurospermum auriculatum exhibited about 91%
efficiency in 0.5 M HCl. The protection efficiency of the Calligonum
comosum (CC) extract was investigated on Cu corrosion in 2 M HCl solution.

The polarization studies showed that maximum efficiency is 80%, with 0.8g/L
CC extract [22]. The aqueous extract of Coriandrum sativum L. (CSE) seeds
was studied as an eco-friendly green inhibitor for corrosion control of
aluminium in 1 M phosphoric acid solution. 500 ppm CC showed the highest
inhibition efficiency (71.51%), at 30oC [23].
As a conclusion, there are hundred thousands of plant species on the earth
and each one of them could be studied as potential green corrosion inhibitor. It
is difficult to say that all of them should necessarily be investigated. Because
most of these plant extracts have shown to be effective corrosion inhibitor
under acidic conditions, then these could be useful for pickling or chemical
cleansing processes involve utilization of high acid concentrations. It should
be noted that the chemistry of plant extracts are not customary. Also, there is a
problem for commercialization of such plant extracts as commodity material to
be used in inhibitor formulations. The fact that most of the corrosion inhibitors
are demanded by cooling water systems, it is very difficult to employ these
plant extracts in such systems. These extracts generally exhibit mixed type
inhibitor behavior, through physisorption on the metal surface. Industrial
cooling water systems involve circulation of water with a constant flow rate.
The efficiency of such inhibitors could be very limited in such circumstances,
since the weakly adsorbed inhibitor molecules could easily detach from the
surface, due to the drifting effect of running water. Increasing the inhibitor
concentration is not a reasonable way for enhancing the efficiency, because
one can’t go through this way easily in a practical application. For this reason,
the most appropriate choice still appears to be design and synthesis of specific
organic molecules, for the purpose of cooling water systems.
3.4. Molecular Designing and Synthesis
Designing an organic inhibitors molecule is challenging task because of

the variety and complexity of corrosive environment. Steel and copper are
mostly used metals for engineering purposes; pipelines, heat exchangers etc.
Azole and thiolate containing organic compounds have been designed,
synthesized and studied frequently; finally some of them have found
application in commercial formulations. This is due to their ability for
chemisorption and film assembling on the surface, via coordination with
unfilled d orbitals of metal. Generally, sulphur and nitrogen containing
functional groups exhibit strong metal-chelating (electron donor) capability,
thus they are highly compatible with vacant d-orbitals of many metals. For this
reason, various organic compounds tailored with these atoms have been
studied frequently; of course the efficiency varies with the orientation and
bond type within the molecular structure (Figure 4). The presence of an
aromatic ring improves remarkably the stability of adsorption layer and the
molecule itself. Based on these facts innumerous derivative compounds with
these functional groups have been synthesized and investigated, since it was
recognized that chemisorption is possible via these centers.
Especially for copper, nitrogen atoms (with free electron pairs) of azole
compounds constitute active center for bonding with copper (I), thus long-
lasting polymeric Cu(I) complex film is formed on the surface. This film is
highly protective, inert and insoluble in a wide pH range. Since it is
chemically adsorbed on the surface and compatible with cuprous/cupric oxide,
good protection efficiency is guaranteed even under elevated temperature.
Typical example is benzotriazole which consisted of benzene and triazole ring,
the triazole ring enables chemical bonding with copper (I) and responsible for
inhibitory effect of BTA [24-45].
Figure 4. Functional groups of mostly used for designing corrosion inhibitors.

Following the physisorption of molecule on copper surface via

electrostatic attraction, Cu(I)BTA complex is formed in the first step copper
dissolution mechanism. It was reported that the pH increase favors complex
formation on the surface.
Cu(s) + BTAH(aq) → Cu:BTAH(ads) + H +(aq) (2)
Cu:BTAH(ads) → Cu(I)BTA(s) + H +(aq) + e (3)
Self-assembled monolayers (SAM) of a series of thiol compounds with

benzene ring have been investigated for copper protection. Because the
mercapto group (-SH) has strong affinity for copper and the inhibitor
molecules attach to copper surface via the thiolate bond. The formation of
protective chemisorbed film occurs via Cu(I)-thiolate complex, the mechanism
is analogous with that discussed for azole compounds [46-60].
Innumerous organic compounds have been synthesized and investigated
for protection of copper, under illumination of previously mentioned
discussions. Methyl 3-((2-mercaptophenyl)imino)butanoate, a newly
synthesized compound, exhibited very high inhibition efficiency against
copper corrosion in acidic chloride environment [61]. The inhibition
mechanism was explained with complex formation between the inhibitor and
Cu(I) ions at the interface. The molecule is functionalized with both azole and
thiol groups. These groups generate strong adsorptive interaction with
metals/alloys, especially in acidic environment. The thiol group of the
molecule improves the adsorptive interaction with the copper surface. Also,
the carboxylate end group has significant dipole character and results with
important intermolecular interaction between the adsorbed inhibitor molecules.
Once the adsorbed molecules interact with each other along the carboxylate
tails, a film like adsorption layer could be formed on the surface. The
protection efficiency increased with increasing inhibitor concentration, and
99.30% efficiency of 10 mM concentration. The durability of protective film
was found to be good against temperature increase; the efficiency was 92.70%
at 55oC. The protection efficiency was also good for extending periods,
96.60% efficiency was determined, after 7 days exposure to 10 mM inhibitor
containing test solution. Also, the SEM results proved that the inhibitor could
successfully protect the copper surface for considerably 7 days exposure
period. In the literature, 90.80% inhibition efficiency was reported for 10 mM
benzotriazole (BTA) in 0.1 M HCl acid solution [24]. Higher efficiency values
were reported when a thiol group is also attached to inhibitor molecule, for
example 4-amino-4H-1,2,4-triazole-3-thiol exhibits 91.38%, in acidic chloride

solution [25]. In another study, the efficiency of 5-methyl benzotriazole was
reported to be 97.87% [24]. The inhibition efficiency of MMBP is quite well,
when compared to others reported in the literature. Also, it was shown that the
efficiency of MMBP was not to diminish with extending exposure periods. In
another study, the inhibition efficiency of 2-aminoethanethiol (2-AEE) was
reported as effective inhibitor against steel corrosion [62]. The molecule
possesses -SH and -NH2 functional groups that offer strong adsorption
behavior on steel surface (Figure 5). The inhibition efficiency increased
regularly with concentration and 93% value reported for 10 mM 2-AEE.
Figure 5. The schematic illustration for 2-AEE adsorption on steel/0.1 M HCl

interface.
Also, methyl 3-((2-mercaptophenyl)imino)butanoate (MMPB) compound

was synthesized and studied as corrosion inhibitor for steel and 97% efficiency
was reported for 10 mM inhibitor concentration [63]. The intermolecular
attraction forces between carboxylate tail groups are also important for
efficiency, as well as major azole and thiol groups. The said attractions
between the tail groups consolidate the stability of adsorbed inhibitor
molecules on the surface. The sulfur atom with unshared electrons can easily
coordinate with vacant d orbitals of iron atoms aligned through the bare
surface. The best auxiliary groups are those can modify the solution side of
organic layer, in order to obtain less hydrophobic and/or permeable nature. In
the case that the auxiliary groups increase intermolecular attraction between
the adsorbed molecules, a polymer like layer could be obtained on the surface.
In the literature, 97.9% and 97.2% inhibition efficiencies were reported for 10
mM 2,5-bis (4-dimethylaminophenyl)-1,3,4-thiadiazole and 2,5-bis (4-
dimethylaminophenyl)-1,3,4-oxadiazole in 1 M HCl acid solutions [64]. Also

lower efficiency values were reported for 20 mM (2,5-bis (2-pyridyl)-1,3,4-
thiadiazole [65] and 20 mM (2,5-bis (3-pyridyl)-1,3,4-thiadiazole [66] in 1 M
HCl solutions as 84.4% and 94.5% respectively. Considering similar inhibitors
reported recently, the synthesized MMPB has good inhibition efficiency and
its molecular design offers good stability, too.
2,5-dimercapto-1,3,4-thiazole (DMTD) was studied against copper
corrosion in 0.5 M HCl solution . The inhibition efficiency reached to the
highest value at 7.5 mM DMTD-ethanol solution by self-assembling for 10 h.
From molecular simulation, it was shown that DMTD molecule tends to be
adsorbed on copper surface in a closely parallel by virtue of the interaction
between three S atoms of DMTD and Cu+ or Cu+2 to form coordinate bonds
[67]. Rochdi et al. studied corrosion inhibition of oxadiazole derivatives using
electrochemical techniques on low carbon steel in simulated cooling water
system. Mixture of 2,5-bis(n-methylphenyl)-1,3,4-oxadiazole (n=2,3,4)
compounds and cetyltrimethylammonium bromide exhibited better inhibition
efficiency (99.8%) than each product solely. The addition of biocide in
oxadiazole mixture formed the most protective film against corrosion [68]. A
new imidazole derivative named {[(benzimidazol-2-ylmethyl)imino]
bis(methylene)} was synthesized by insertion of phosphonate functional
groups into structure as an environmental friendly corrosion and scale
inhibitor. It was showed that the performance of this organic compound was
comparable to sodium tungstate, against carbon steel corrosion in simulated
cooling tower water [69]. Singh et al. investigated non-toxic quinolone
derivatives as corrosion inhibitors for mild steel in 1 M HCl. The inhibition
efficiency varied in between 90-98%, depending on concentration.
Electrochemical measurements revealed that inhibitor functioned via
physisorption with pre-adsorbed chloride ions and chemisorption with vacant
d-orbital of iron atoms, surface analysis proved the formation of a protective
film on the metal surface [70].
Dithiocarbamate compounds (DTCs) are good chelating agents against
variety of metal ions, due to presence of –C = S and -C-S – sites [71-74]. Their
polymeric complexes with different metal ions are highly stable and sparingly
soluble in water [75]. As a class of nontoxic material, diethyldithiocarbamate
(DDTC) offer favorable alternative for designing green corrosion inhibitors for
copper alloys [76]. Moreover, DDTC has been reported as efficient inhibitor
against steel corrosion [77]. Liao et al. studied the inhibition behavior of
DDTC for inhibition of copper [78] and brass corrosion [79] in 3% NaCl. It
was reported that both anodic and cathodic processes are controlled by
strongly adsorbed DDTC molecules. Li et al. have reported the use of

diethyldithiocarbamate as corrosion inhibitor for cold rolled steel in 0.5 M HCl
corrosive solution [80]. In another study, sodium phenylcarbamodithioate
(PDTC) was designed and synthesized, from aniline and carbondisulfide
starting materials. Electrochemical studies showed that this compound is an
efficient adsorption type inhibitor. This good efficiency was explained with
capability of both physisorption and chemisorption on steel surface. The
phenyl group also presents a hydrophobic surface, when the molecule is
adsorbed via its thiocarbamate end. It was shown that the inhibitor molecules
were chemically bonded to surface, in the form of monomolecular layer. The
inhibition efficiency was shown to increase slightly with the temperature,
98.65% at 55oC. Also, the inhibition efficiency was shown to remain stable
with extending exposure time, it was 85.93%, three days later than employing
single dose (500 ppm) inhibitor. This was an important result for the purpose
of practical applications [81].
3.5. Polymeric Inhibitors
Water soluble polymers have also been investigated as corrosion

inhibitors, natural or synthetic in the origin. It is easy to modify the polymer
backbone with appropriate functional groups, in order to enhance chelating
capability against metal ions and adsorption on metal surfaces. The size of
macromolecules may appear as a disadvantage for adsorption strength on the
surface, but the number and type of functional groups could easily be adjusted
in order to improve the stability of adsorption layer. For application of
polymers in practice, the molecular weight and chain length are also crucial
parameters, as well as solubility. The solubility of natural polymers could
easily be improved via further modification of backbone with appropriate
hydrophilic functional groups like; -OH, -NH2, -COOH, -SO3 etc. Since these
macromolecules cover a large surface area, thus blocking the surface and
hinder the attack of corrosive environment. For this purpose natural polymeric
materials have long been studied by many authors.
Guar Gam was reported as an effective corrosion inhibitor for C-steel in 1
M sulphuric acid environment, 1500 ppm compound showed 93% inhibition
efficiency [82]. Some sulfated water-soluble natural polymer (carrageenan)
compounds on the corrosion of iron in 1 M HCl possess 80% inhibition
efficiency for 500 ppm concentration [83]. Umoren investigated corrosion
protection efficiency on mild steel and aluminum exposed to sulphuric acid
solution of a natural polymer named Gum arabic. Gum Arabic controlled the
corrosion more effectively on aluminum (inhibition efficiency is 76.69%)
rather than mild steel (inhibition efficiency is 37.88%) [84]. Polyethylene
glycol methyl ether was reported to exhibit remarkable inhibition efficiency
(84.2% at 298 K for 10-3 M) for mild steel corrosion in acidic medium with
respect to gum Arabic [85]. The effect of naturally occurring exudate gum
(from Raphia hookeri) on the corrosion of mild steel in H2SO4 was
investigated. The inhibition efficiency reached a maximum of 71.9% at 0.5 g/L
exudate concentration, at 30oC [86]. The inhibition efficiencies of kraft lignin
and soda lignin were studied against corrosion of mild steel in 3.5% (w/v)
sodium chloride. Kraft lignin exhibited maximum inhibition efficiency of 95%
and 92% at pH 6 and 8, respectively, whereas soda lignin had 97% and 95%
efficiencies [87].
4. ASSESMENT OF CORROSION INHIBITON

The conventional corrosion rate measurement methods (electrochemical
and non-electrochemical) are employed for the assessment of inhibition
efficiency. Thereby, the same methods are necessarily utilized for illuminating
the corrosion inhibition mechanism and defining the type of inhibitor (anodic,
cathodic or mix-type). At this moment, surface examinations with various
spectroscopic techniques are also necessarily used, for example FT-IR, XPS,
XRD, Raman, SEM-EDX etc. Spectroscopic analyses are generally regarded
as complementary methods which provide additional data and corroborate the
electrochemical testing results. These spectroscopy techniques are very useful
for identification of the composition of corrosion products and adsorption
layer, type of adsorption, orientations of inhibitor molecules with respect to
the surface or synergistic effect between the inhibitor other species present on
the surface. Solution assay analysis also involves spectroscopy devices (AAS
or ICP), which based on the quantitative analysis of corrosion products in test
solution. This method frequently appears in publications subjecting corrosion
inhibitors and it should be noted that it could only give meaningful results in
the lab-scale. Therefore, this method has not found application in in-situ
corrosion rate measurement in industrial water systems.
On the other hand, “ellipsometry” has been recently shown to be a direct
method for evaluation of corrosion rate, where the corroding metal is
convenient for the formation of stable corrosion products (oxides, sulfides,
insoluble salts etc.) accumulating on the surface. Of course, the studied
corrosive environment is also important for success of this method. In such

cases, the thickness of surface film is directly proportional with the amount of
metal ions released due to corrosion, thus the protective film should be
consisted of an insoluble compound of these ions [88].
For uniform corrosion, weight loss/gain measurement has still been the
most prevalent method, at which the collected data average the loss/gain over
the exposure period. The test is simply performed by immersing coupons in
test solution either in laboratory or in-situ industrial water system. Laboratory
tests should necessarily simulate the water chemistry and operating conditions
of real process, for acquisition of meaningful data. In-situ testing is conducted
in pilot plants for monitoring the success of water treatment, regarding the
effect of operating parameters. Metal coupons are mounted in pipe plugs and
exposed to water flowing in metal piping, and then the corrosion averages the
specimens’ corrosion rate over its surface. It should be noted that meaningful
data may require a couple of months, depending on the test specimen and
corrosive environment. Many details should necessarily be taken into account
when conducting coupon test; required pretreatments for coupons, placement,
supports, exposure time and cleaning. In order to eliminate the possible errors
and enhance the accuracy a standard method should be followed. For this
purpose, ASTM G1 standard describes each point of consideration, in details.
Electrochemical testing methods give the opportunity for measuring
instant corrosion rate; linear polarization resistance measurement,
potentiodynamic measurements, impedance spectroscopy and noise
measurements. Even though, it is still very difficult to employ one of these
methods under in-situ conditions, this route provides fast and reliable data for
assessment of corrosion rate. For accuracy of data collected by this route, the
measurement conditions/parameters should be carefully handled. Linear
polarization resistance and potentiodynamic measurements are regularly used
with Tafel equation and famous Stern-Geary equation, in order to quantify
corrosion rate. However, the parameters employed during these measurements
have vital effect on accuracy of collected data and requires great attention. For
this purpose, ASTM G52 defines the standard method for conducting linear
polarization resistance measurement and ASTM G5-14 explains the
requirements for potentiodynamic anodic polarization. Finally, ASTM G102
standard describes the calculation of corrosion rate with help data collected
from electrochemical measurements, including Tafel extrapolation and linear
polarization resistance [89].
Potentiodynamic measurements are widely used for interpretation of
corrosion inhibition mechanism, in order to define its type; anodic, cathodic or
mixed type. Simply, the shift of corrosion potential (Ecorr) and alteration of
anodic/cathodic current values are compared for the absence and presence of
inhibitor. Therefore, the scan rate and initial-final potential values have great
importance. For the assessment of corrosion rate, generally, the scan
measurement is performed by polarizing the specimen about 300-500 mV
anodically (positive with respect to the Ecorr) and cathodically (negative with
respect to the Ecorr). For each branch, the initial point should be better chosen
as the measured Ecorr value. Thus the cathodic and anodic branches are
obtained in two separate measurements with the same specimen. However, it
is frequently seen that the measurement is conducted in single experiment,
where the scan starts from a cathodic initial value and terminated in anodic
domain. Does it make a difference with the collected data and relevant
interpretations about corrosion inhibition efficiency and mechanism? The
answer is absolutely yes. A specimen at its Ecorr has both anodic and cathodic
currents present on its surface, so the anodic and cathodic reactions occur
simultaneously. Since these currents are exactly equal in magnitude, there is
no net current to be measured. During polarization towards slightly more
positive than Ecorr, the anodic process (thus anodic current) predominates at the
expense of the cathodic event, and vice versa. When potentiodynamic
measurement starts from cathodic initial value (about 300-500 mV negative to
Ecorr), it will take considerable time to reach the measured Ecorr value, since
quite low scan rates (< 1 mV/s) are necessarily involved. During this period
only cathodic reaction (hydrogen evolution or oxygen reduction etc.) will take
place on the surface. So the surface may change dramatically, and the data
collected for anodic region will include significant error. For example,
adsorbed inhibitor (or metal ion-inhibitor complex film) may detach from the
surface during cathodic polarization. Then, immediately taken anodic
measurement gives misleading current values which cannot be relied on for
assessing the inhibitor interaction with surface, considering spontaneous
corrosion conditions natural corrosion.
To conclude, it is strongly recommended that two or more methods should
be utilized for determination of corrosion inhibition efficiency and the
collected data should be evaluated comparatively. At this point, it is also
important to use statistical evaluations for ensuring that the measured
difference is meaningful, between inhibited and un-inhibited conditions. For
this purpose, chi-square, T and F testing methods could be realized and such
approximations would certainly improve the significance and impact of the
results. The statistical approach could also be used for development of
mathematical model between the corrosion inhibitor efficiency and effective
independent variables (pH, temperature, water composition etc.) of system. It

is also possible to establish an equation between the corrosion rate and varying
conditions (flow rate, inhibitor concentration, suspended solids etc.) of system.
This allows making trustworthy predictions for practical applications and the
model includes a mathematical equation between the output (efficiency) and
variables of system. Actually it could be named as a fitting model for
inhibition efficiency; the success of model could also be tested with basic
statistical arguments, residual and variance analysis, T and F tests, and R2
value. For engineering applications of corrosion inhibitors, such a fitting
model will certainly help to avoid from excess chemical use or insufficient
protection [90-94]. Thus optimization of industrial inhibitor applications
becomes possible.
Figure 6. Efficiency versus pH and concentration (C) diagram.
As an example, 2-aminoethanethiol (2-AEE) was reported to have

efficiency against steel corrosion in a pH range between 1 and 3.5. Response
surface methodology (RSM) was employed to explain the relation between
pH, inhibitor concentration and the efficiency. The regression analysis was
realized for development of an equation between independent variables and
the output. In this study, inhibitor concentration (0.5 – 10mM) and pH (1-3.5)
were independent variables and the percent inhibition efficiency (φ) was the
dependent output. The success of fitting model was tested with basic statistical
arguments, residual and variance analysis, T and F tests, R2 value. It was

shown that this equation could successfully explain the experimental data, in a
95% confidence level. The statistical evaluations showed that the obtained
polynomial equation can be successfully used for optimization of applications
involving the use of 2-AEE as inhibitor. This method could also provide
important information for realization of any application from lab scale to
industrial processes [62].
CONCLUSION
Even though they have been widely pronounced as green inhibitors, due to
their biological origin, the plant extracts are still not adaptable for
development of commercial corrosion inhibitor products. The fact that most of
the corrosion inhibitors are demanded by industrial cooling water systems, and
most effort should be paid for green organic inhibitors for these applications.
For such purposes, inhibitors are required to produce highly stable
chemisorbed films on metal surface, which cannot be succeeded with
physically adsorbed non-selective organics. For copper systems, there have
already developed products including organic inhibitors, while there is still a
need for developing eco-friendly high performance inhibitors to be used for
steel. Increasing the inhibitor concentration is not a reasonable way for
enhancing the efficiency, because one can’t go through this way easily in a
practical application. For this reason, the most appropriate choice still appears
to design and synthesize specific organic molecules, with minimum toxicity
and good efficiency.
An inhibitor could not be considered as 100% green, just because it is
biological source, like phytochemical. More detailed investigations are needed
for “green” inhibitor studies, including the analysis of degradation in
environmental conditions. The organic compound itself may be green,
however the intermediates of degradation mechanism could be unsafe for the
environment.
The statistical approach could also be used for development of
mathematical model between the corrosion inhibitor efficiency and effective
independent variables (pH, temperature, water composition etc.) of system. It
is also possible to establish an equation (fitting model) between the corrosion
rate and varying conditions (flow rate, inhibitor concentration, suspended
solids etc.) of system. This allows making trustworthy predictions for practical
applications and the fitting model will certainly help to avoid from excess
chemical use or insufficient protection, thus optimization could be succeeded.
REFERENCES
[1] Transparency Market Research (2015). Green Corrosion Inhibitors to
Open New Opportunity for Global Corrosion Inhibitors Market.
http://www.transparencymarketresearch.com/corrosion-inhibitors.html.
[2] Dariva, C. G.; Galio, A. F. Developments in Corrosion Protection;
Aliofkhazraei, M.; ISBN 978-953-51-1223-5, InTech; 2014; pp 365-379.
[3] Abd-El-Khalek, D. E.; Abd-El-Nabey, B. A. Desalination 2013, 311,
227-233.
[4] Moudgil, H. K.; Yadav, S.; Chaudhary, R. S.; Kumar, D. J Apl
Electrochem. 2009, 39, 1339-1347.
[5] Wang, J.; Wang, D.; Hou, D. J Env Sci. 2016, 39, 13-21.
[6] Rahmani, Kh.; Jadidian, R.; Haghtalab, S. Desalination 2015, in press.
[7] Mohammedi, D.; Benmoussa, A.; Fiaud, C. Material and Corrosion
2004, 55, 837-844.
[8] Liu, F.; Lu, X.; Yang, W.; Lu, J.; Zhong, H.; Chang, X.; Zhao, C.
Desalination 2013, 313, 18-27.
[9] Jin, J.; Li, M.; Guan, Y. Desalin Water Treat. 2016, 1–15, in press.
[10] Bockris, J.; Reddy, A. K. N.; Gamboa-Aldeco, M. Modern
Electrochemistry; Kluwer Academic/Plenum Publishers: New York,
NY, 2000; vol 2A, pp 978-980.
[11] Gece, G. Corros Sci. 2008, 50, 2981–2992.
[12] Shankar, B. S. Sch J Eng Tech. 2014, 2, 123-127.
[13] Zhang, B.; He, C.; Chen, X.; Tian, Z.; Li, F. Corros Sci. 2015, 90, 585-
596.
[14] Choudhury, M. R.; Hsieh, M. K.; Vidic, R. D.; Dzombak, D. A. Corros
Sci. 2012, 61, 231-241.
[15] Liang, J.; Deng, A.; Xie, R.; Gomez, M.; Hu, J.; Zhang, J.; Ong, C. N.;
Adin, A. Desalination, 2013, 322, 76-83.
[16] Dkhireche, N.; Dahami, A.; Rochdi, A.; Hmimou, J.; Touir, R.; Ebn
Touhami, M.; El Bakri, M.; El Hallaoui, A.; Anouar, A.; Takenouti, H. J
Ind Eng Chem. 2013, 19, 1996-2003.
[17] Belakhmima, R. A.; Dkhireche, N.; Touir, R.; Ebn Touhami, M. Mat
Chem Phys. 2015, 152, 85-94.
[18] Pillay, C., Lin, J. Corros Sci. 2014, 80, 416-426.
[19] El Hamdani, N.; Fdil, R.; Tourabi, M.; Jama, C.; Bentiss, F. App Surf
Sci. 2015, 357, 1294-1305.
[20] Gerengi, H. J Adh Sci Tech. 2015, 29, 36-48.
[21] Al-Otaibi, M. S.; Al-Mayouf, A. M.; Khan, M.; Mousa, A. A.; Al-
Mazroa, S. A.; Alkhathlan, H. Z. Arabian J Chem. 2014, 7, 340-346.
[22] Shabani-Nooshabadi, M.; Hoseiny, F. S.; Jafari, Y. Metall Mater Trans.
A 2015, 46, 293-299.
[23] Prabhu, D.; Rao, P. J Env Chem Eng, 2013, 1, 676-683.
[24] Antonijevic, M. M.; Petrovic, B. M. B. Int J Electrochem Sci. 2008, 3, 1-
28.
[25] Sudheer; Quraishi, M. A. Corros Sci. 2013, 70, 161-169.
[26] El-Sayed, M.; Sherif, R. M.; Erasmus, J. D.; Comins, J Colloid Interf
Sci. 2007, 311, 144-151.
[27] Matos, J. B.; D’Elia, E.; Barcia, O. E.; Mattos, O. R.; Pébère, N.;
Tribollet, B. Electrochim Acta 2001, 46, 1377-1383.
[28] Khaled, K. F.; Amin, M. A. Corros Sci. 2009, 51, 2098-2106.
[29] Zucchi, F.; Trabanelli, G.; Fonsati, M. Corros Sci. 1996, 38, 2019-2029.
[30] Finšgar, M. Corros Sci. 2013, 77, 350-359.
[31] Gopi, D.; Govindaraju, K. M.; Prakash, V. C. A.; Sakila, D. M. A.;
Kavitha L. Corros Sci. 2009, 51, 2259-2265.
[32] Subramanian, R.; Lakshminarayanan, V. Corros. Sci. 2002, 44, 535-554.
[33] Trachli, B.; Keddam, M.; Takenouti,; H. Srhiri, A. Corros Sci. 2002, 44,
997-1008.
[34] Huynh, N.; Bottle, S. E.; Notoya, T.; Schweinsberg, D. P. Corros Sci.
2000, 42, 259-274.
[35] Milić, S.; M. Antonijević, M. M. Corros Sci. 2009, 51, 28-34.
[36] Abdullah, M.; Al-Kharafi, F. M.; Ateya, B. G. Scripta Mater. 2006, 54,
1673-1677.
[37] Finsgar, M.; Milosev, I. Corros Sci. 2010, 52, 2737-2749.
[38] Huynh, N.; Bottle, S. E.; Notoya, T.; Trueman, A.; Hinton, B.;
Schweinsberg D. P. Corros Sci. 2002, 44, 1257-1276.
[39] Chen, Z.; Huang, L.; Zhang, G.; Qiu, Y.; Guo, X. Corros Sci. 2012, 65,
214-222.
[40] Lalitha, A.; Ramesh, S.; Rajeswari, S. Electrochim Acta 2005, 51, 47-55.
[41] Obot, I. B.; Madhankumar, A.; Umoren, S. A.; Gasem, Z. M. J Adhes
Sci Technol. 2015, 29, 2130-2152.
[42] Curkovic, H. O.; Stupnisek-Lisac, E.; Takenouti, H. Corros Sci. 2010,
52, 398-405.
[43] El-Naggar, M. M. Corros Sci. 2000, 42, 773-784.
[44] Curkovic, H. O.; Stupnisek-Lisac, E.; Takenouti, H. Corros Sci. 2009,

51, 2342-2348.
[45] El-Sayed M. S.; Erasmus, R. M.; Comins, J. D. Corros Sci. 2008, 50,
3439-3445.
[46] Tuken, T.; Kicir, N.; Elalan, N. T.; Sigircik, G.; Erbil, M. Appl Surf Sci.
2012, 258, 6793-6799.
[47] Antonijevic, M. M.; Milic, S. M.; Petrovic, M. B. Corros Sci. 2009, 51,
1228-1237.
[48] Rao, B. V. A.; Iqbal, M. Y.; Sreedhar, B. Corros Sci. 2009, 51, 1441-
1452.
[49] Tan, Y. S.; Srinivasan, M. P.; Pehkonen, S. O.; Chooi, S. Y. M. Corros
Sci. 2006, 48, 840-862.
[50] Li, C.; Li, L.; Wang, C.; Zhu, Y.; Zhang, W. Corros Sci. 2014, 80, 511-
516.
[51] Cui, F. Y.; Guo, L.; Zhang, S. T. Mater Corros. 2014, 65, 1194-1201.
[52] Benabdellah, M.; Tounsi, A.; Khaled, K. F.; Hammouti, B. Arab J
Chem. 2011, 4, 17-24.
[53] Tian, H.; Li, W.; Cao, K.; Hou, B. Corros Sci. 2013, 73, 281-291.
[54] Ye, X. R.; Xin, X. Q.; Zhu, J. J.; Xue, Z. L. Appl Surf Sci. 1998, 135,
307-317.
[55] Qin, T. T.; Li, J.; Luo, H. Q.; Li, M.; Li, N. B. Corros Sci. 2011, 53,
1072-1078.
[56] Sherif, E. M.; Park, S. M. Electrochim Acta 2006, 51, 6556-6562.
[58] Finšgar, M.; Merl, D. K. Corros Sci. 2014, 80, 82-95.
[60] Zhang, D.; Gao, L.; Zhou, G. Corros Sci. 2004, 46, 3031-3040.
[61] Tansug, G.; Tuken, T.; Giray, E. S.; Findikkiran, G.; Sigircik,, G.;
Demirkol, O.; Erbil, M. Corros Sci. 2014, 84, 21–29.
[62] Tansug, G.; Tuken, T.; Kicir, N.; Erbil, M. Ionics 2014, 20, 237-294.
[63] Tansug, G.; Tuken, T.; Sigircik, G.; Findikkiran, G.; Giray, E. S.; Erbil,
M. Ionics 2015, 21, 1461-1475.
[64] Bentiss, F.; Traisnel, M.; Vezin, H.; Hildebrand, H. F.; Lagrenée, M.
Corros Sci. 2004, 46, 2781-2792.
[65] El Azhar, M.; Mernari, B.; Traisnel, M.; Bentiss, F.; Lagrenée, M.
Corros Sci. 2001, 43, 2229-2238.
[66] Bentiss, F.; Lebrini, M.; Vezin, H.; Lagrenée, M. Mater Chem Phys.
2004, 87, 18-23.
[67] Qin, T. T.; Li, J.; Luo, H.; Li, Q.; Li, M. N. B. Corros Sci. 2011, 53,
1072-1078.
[68] Rochdi, A.; Touir, R.; El Bakri, M.; Ebn Touhami, M.; Bakkali, S.;
Mernari, B. J. Env Chem Eng. 2015, 3, 232-242.
[69] Borghei, S.; Dehghanian, C.; Yaghoubi R.; Yari, S. Res Chem Intermed.
2016, 42, 4551-4568.
[70] Singh, P.; Srivastava, V.; Quraishi, M. A. J Mol Liq. 2016, 216, 164-
173.
[71] Kanchi, S.; Singh, P.; Bisetty, K. Arab J Chem. 2014, 7, 11-25.
[72] Faraglia, G.; Sitran, S.; Montagner, D. Inorg Chim Acta 2005, 358, 971-
980.
[73] Amin, E.; Saboury, A. A.; Mansouri-Torshizi, H.; Zolghadri, S.;
Bordbar, A. K. Biochim Pol. 2010, 57, 277-283.
[74] Kicir, N.; Tansug, G.; Erbil, M.; Tuken, T. Corros Sci. 2016, 105, 88-99.
[75] Singh, A. K.; Puri, B. K.; Rawley, R. K. Indian J Chem. 1988, 27, 430-
433.
[76] Aljinovic, L. J.; Gudic, S.; Smith, M. J Appl Electrochem. 2000, 30,
973-979.
[77] Hong-bo, F.; Hui-long, W.; Xing-peng, G.; Fia-shen, Z. Anti-Corros
Method M. 2002, 49, 270-276.
[78] Liao, Q. Q.; Yue, Z. W.; Yang, D.; Wang, Z. H.; Li, Z. H.; Ge, H. H.; Li,
Y. J. Corros Sci. 2011, 53, 1999-2005.
[79] Liao, Q. Q.; Yue, Z. W.; Li, Y. J.; Ge, H. H. Corrosion 2010, 66,
125002-125006.
[80] Li, L.; Qu, Q.; Bai, W.; Yang, F.; Chen, Y.; Zhang, S.; Ding, Z. Corros
Sci. 2012, 59, 249-257.
[81] Tansug, G.; Kicir, N.; Demirkol, O.; Giray, E. S.; Tuken, T. J Adh Sci
Tech. 2016, 30, 1984-2000.
[82] Abdallah, M. Port Electrochim Acta 2004, 22, 161–175.
[83] Zaafarany, I. Curr World Environ. 2006, 1, 101–108.
[84] Umoren, S. A. Cellulose 2008, 155, 751–761.
[85] Umoren, S. A. Open Corros J. 2009, 2, 175–188.
[86] Umoren, S. A.; Obot, I. B.; Obi-Egbedi, N. O. J. Mater Sci. 2009, 44,
274–279.
[87] Akbarzadeh, E.; Ibrahim, M. M.; Rahim, A. A. Int J Electrochem Sci.
2011, 6, 5396–5416.
[88] Goller, K. (2011) Spectroscopic ellipsometry study on the oxide films
formed on nickel-base alloys in simulated boiling water reactor
environments. Determination of oxide film thickness. https://www.
kth.se/polopoly_fs/1.469671!/Spectroscopic%20ellipsometry%20study
%20on%20the%20oxide%20films%20formed%20on%20nickel-base%
20alloys%20in%20simulated%20boiling%20water%20reactor.pdf/.
[89] Baboian, R. Corrosion Tests and Standards: Application and
Interpretation (2nd Edition): ASTM International, West Conshohocken,
PA, 2005; 107-340.
[90] Oraon, B.; Majumdar, G.; Ghosh, B. Mater Des. 2006, 27, 1035–1045.
[91] Zhao, X.; Jiang, R.; Zu, Y.; Wang, Y.; Zhao, Q.; Zu, B.; Zhao, D.;
Wang, M.; Sun, Z. Appl Surf Sci. 2012, 258, 2000-2005.
[92] Guo, R.; Ren, X.; Ren, H. J Hazard Mater. 2012, 237, 270-276.
[93] Baş, D.; Boyacı, I. H. J Food Eng. 2007, 78, 836-845.
[94] Perfetti, G.; van der Meer, D. E. C.; Wildeboer, W. J.; Meesters, G. M.
H. Adv Powder Technol. 2012, 23, 64-70.
Chapter 2
APPLICATION OF POLYMER COMPOSITES

AND NANOCOMPOSITES AS CORROSION
INHIBITORS
Saviour A. Umoren1,* and Moses M. Solomon2

1
Centre of Research Excellence in Corrosion, Research Institute,
King Fahd University of Petroleum and Minerals,
Dhahran, Saudi Arabia
2
Corrosion Research Laboratory, Kaynasli Vocational College,
Duzce University, Kaynasli, Duzce, Turkey
ABSTRACT
Corrosion commonly defined as the deterioration of a material
(usually a metal) or its properties because of a reaction with its
environment is a global problem. NACE International, The Corrosion
Society, estimates that global corrosion costs can be about 3–5% of GDP
or GNP. Methods commonly adopted to combat corrosion include
coatings and linings, cathodic protection, materials selection and
corrosion inhibitors. Corrosion inhibitors are chemicals that, when
present in very low concentrations, retard corrosion. Corrosion inhibitors
form a layer over the metallic substrate and protect the metal from
corrosion, thereby enhancing the life of the metal. Polymers, both
naturally occurring and synthetic have been tested for metal corrosion
*
Corresponding author: umoren@kfupm.edu.sa (S.A. Umoren).
28 Saviour A. Umoren and Moses M. Solomon
inhibitors as replacement for the toxic inorganic and organic corrosion

inhibitors. Interest in polymers stems from their availability, cost
effectiveness, and eco-friendliness in addition to the inherent stability and
multiple adsorption centers. However, it is found that most polymer
materials studied are moderate corrosion inhibitors. Several attempts such
as copolymerizing, addition of substances that exert synergistic effect,
cross linking, blending, and most recently incorporation of inorganic
substances in nano size into the polymer matrix have been made to
improve the inhibition ability of polymers. Composites are materials
consisting of two or more chemically distinct constituents on a minute-
scale, having a distinct interface separating them, and with properties
which cannot be obtained by any constituent working individually. The
production of composite materials is either by ex-situ or in-situ formation
through chemical synthesis although electrochemical method had been
used recently. The application of polymer composites and
nanocomposites as anticorrosion materials have shown promising results
and are believed to form metal chelate which could barricade metal
surfaces from corrosive agents. In this chapter, the application of polymer
composites and nanocomposites as corrosion inhibitors for different metal
substrates in different corrosive media is explored.
Keywords: polymers, composites, nanocomposites, corrosion inhibitor
1. INTRODUCTION
In industries, particularly oil and gas industry, acid solutions are
commonly employed in practices like acid pickling, oil-well acidizing,
industrial cleaning, acid descaling, etc. This exercise usually promotes the
corrosion of metals deployed in service in the environment. As a preventive
measure, anti-corrosive agents (inhibitor) are always added to the acid
solutions to lower the metal’s corrosion rate and reduce acid consumption. A
metal corrosion inhibitor is a substance that, even at low concentration in a
corrosive environment can interrupt and slow down corrosion reactions.
Substances, both organic and inorganic origins have used to accomplish this
task of suppressing metal dissolution in aggressive corrosive environments but
the mode of action differs, hence inhibitors are classed into different groups as
shown in Figure 1. However, mere suppression of the rate of metal dissolution
in an aggressive environment does not qualify a substance to be used as an
inhibitor. Other requirements abound and this include: (i) availability and cost
effectiveness – the substance has to be readily available and inexpensive; (ii)
Application of Polymer Composites and Nanocomposites … 29
durability – should be able to protect the metal surface for a reasonable length
of time; and (iii) toxicity – should be safe in handling and non-toxic to the
natural environment.
Although inorganic compounds like chromates, silicates, phosphates,
molybdates, and nitrates as well as organic compounds containing heteroatoms
(N, O, and S) and/or π-electrons in their molecules have enjoyed high
patronage as metal corrosion inhibitor for decades [1-4], the adverse effect of
inorganic compounds on the ecosystem and the exorbitant prices of the
organic counterparts have come under severe criticism particularly in the 21st
century. A cursory search on corrosion literature revealed that the corrosion
scientists are now focusing attention on exploring plant extract and polymers
as possible replacement for inorganic and organic corrosion inhibitors. Interest
in polymers essentially arose from their availability, cost effectiveness, and
eco-friendliness added to their inherent stability and multiple adsorption
centers. However, it is found that most polymer materials studied are moderate
corrosion inhibitor and tends to be unstable at elevated temperatures [5-7].
Abandoning this material and engaging in a search for alternative materials
might not be a profitable venture; as such, corrosion scientists have resorted to
modifying polymers so as to enhance their inhibitive ability and stability at
higher temperature. Approaches employed in recent times include;
copolymerizing [8, 9], addition of substances that exert synergistic effect [10,
11], cross linking [12], blending [13], and most recently incorporation of
inorganic substances in nano size into the polymer matrix [14, 15].
Composite is a term used to describe a material that contains two or more
chemically distinct constituents on a minute-scale, separated by distinct
interface, and having properties which are different from the properties of the
components working individually.
2. GLOBAL DEMAND OF CORROSION INHIBITORS

In the present age, corrosion inhibitors are accorded top priority during
project design and implementation particularly in areas where metals are used.
The reason is simple; they can help elongate the lifespan of a material and by
so doing maximize profit. The corrosion inhibitors’ market has thus witnessed
an increase in demand. Corrosion inhibitors’ market is grouped based on
application, functionality, and geography. The application segment include:
power generation, pulp and paper, oil and gas industries, metal and mining,
chemical processing, and the others. By functionality, corrosion inhibitors’
market is divided into organic and inorganic inhibitors. Geographically, the

market is segmented into North America, Europe, Asia-Pacific, and the rest of
the world. According to the report of Transparency Market Research
(www.transparencymarketresearch.com/corrosion-inhibitors), corrosion
inhibitors demand globally stood at 4,425.9 kilo in 2012 with the cost pinned
at US$ 5.20 billion. Of this amount, power generation had 29.1%, pulp and
paper 12.3%, chemical processing 6.1%, oil and gas 19.4%, metal and mining
10.9%, and others 22.1% (Figure 2). The organic corrosion inhibitors led the
market by almost 70% and Asia-Pacific held the largest share (>35%) in terms
of demand while the North American and European corrosion inhibitors
markets jointly held more than 50%. In 2013, inhibitors demand increased to
4,659.8 kilo and is predicted that the global inhibitors’ market would grow at
5% during 2015-2022 market year with the cost estimated to be US$9.2 billion
by 2022 (www.grandviewresearch.com/industry-analysis/corrosion-inhibitors-
market).
3. POLYMER COMPOSITES AND NANOCOMPOSITES

3.1. Methods of Preparation
There are several methods of synthesizing polymer composites and

nanocomposites. They can be grouped into two broad groups: in-situ and ex-
situ methods. The in-situ technique is simple, effective and involves one-step
fabrication and as such enjoyed higher patronage than ex-situ method. In this
method, one of the components (mostly the inorganic) is generated in-situ
from corresponding precursors and are grown inside the polymer matrix. The
merit of this technique is that it prevents particle agglomeration while
maintaining a good spatial distribution in the polymer backbone. However, the
major shortcoming of this method is that the un-reacted educts of the in-situ
reaction might affect the properties of the composite formed. Some
metal/polymer composites reported to have been prepared by in-situ approach
include poly(methacrylic acid)/silver nanoparticles (PMAA/AgNPs)
composite [14, 16], polypropylene glycol/silver (PPG/AgNPs) nanoparticles
composite [17, 18], nanocomposites of aniline and CeO2 nanoparticles [19],
etc.
Ex-situ method, on the other hand, involves the dispersion of pre-made
particles directly into polymer to form composites. The ex-situ synthesis
technique is more suitable for large-scale industrial productions. This method
allows for precise control of the size, shape, and density of the inorganic
particles that are used to form composites. However, the major
challenge of this method is the difficulty in preparing inorganic components
that possess higher dispersibility in the polymer backbone and have long-term
stability against aggregation. Guo et al. [20] reported that this challenge can be
overcome by using sonication methods in the dispersion process.
Classification of Inhibitors
Interface Inhibitors: These are Scavengers (Environmental

inhibitors in which inhibition is Conditioners): These are inhibitors
caused by specific adsorption that inhibit by removing the corrosive
forming two-dimensional (2-D) agents from the medium
layers on the corroding metal
surface. They perform the task of
inhibition by either geometric
blocking, deactivation of active
sites or reactive 2-D coverages
Vapour Phase Liquid Phase
Anodic: This class of inhibitors Cathodic: This category of Mixed Adsorption: This class
acts by forming a protective oxide inhibitors performs by either inhibits by reducing both the
layer on metal surface causing the suppressing the cathodic cathodic and anodic reactions.
corrosion potential to shift reactions or selectively Silicates and phosphates are the
significantly in anodic direction; precipitating on cathodic areas common examples
forcing the metal surface into the to obstruct the diffusion of
passivation region. Examples are corrosive species to the surface.
Chromates, nitrates, tungstate, Sulphite and bisulphate are
molybdates, etc. typical examples
Physical: This Chemical: Film
involves involves
electrostatic electron
forming
interaction sharing or
between transfer from
Poison Precipitators charged the inhibitor
molecules and molecules to
a charged the metal
metal surface. surface to
Increase in form a
temperature coordinate
decreases the type of bond.
inhibitive Increase in
power temperature
increases
inhibition
efficiency
Figure 1. 1:Classification
Figure Classification ofof corrosion
corrosion inhibitors.
inhibitors
(Source: Goldman, Sachs, Virtus Global Partners, Delloite, ICS, EPA, Primary
Interviews, Transparency Market Research)
Figure 2. Global corrosion inhibitors’ market volume share, by end-use, 2012.
3.2. Application of Polymer Composites as Corrosion Inhibitors
The primary feature that makes polymers to be investigated for

anticorrosive effect is the present of heteroatom(s) and/or unsaturated bond(s)
in their molecule. Organic compounds generally inhibit metal corrosion by
adsorption onto the surface and heteroatom and/or π-bond is accepted [10, 21]
to serve as the adsorption site. Polymers are macromolecules consisting of
multiple repetitions of one or more atoms or groups linked to each other in
sufficient amount capable of providing the molecule a set of properties. They
have been extensively studied as metals corrosion inhibitor in various
aggressive environments [22, 23] because of the numerous advantages
mentioned in the introductory section. However, as mentioned before, they are
moderate inhibitors and some authors [10] have attributed this to the influence
of methylene group which characterized them on their solubility. Compositing
is one of the many approaches employed by corrosion scientists to improve the
inhibition efficiency of polymers and tremendous successes have been
recorded. For instance, Zhu et al. [24] reported that perfluorinated
lubricant/polypyrrole composite coated on low alloy steel can afford
99.8978% protection to the metal surface in 3.5% NaCl solution. It was
demonstrated by Zou et al. [25] that bridged cyclodextrin (β-CD-PEG)
synthesized by the reaction of cyclodextrin and polyethylene glycol possessed

better inhibiting ability for Q235 steel in HCl environment than cyclodextrin
and polyethylene glycol due to its excellent solubility in water. Experimental
results showed that 110 mg/L β-CD-PEG afforded 97% protection to the metal
surface and scanning electron microscope (SEM) and energy dispersive x-ray
(EDX) indicated that the high inhibition efficiency was due to the adsorption
of inhibitor molecules and protective film formation on the metal surface
(Figure 3).
Syed et al. [26] prepared water-soluble polyaniline−poly(acrylic acid)
(PANI−PAA) composites by a one-step in-situ polymerization technique and
found that PAA did not only enhanced the solubility of PANI in water but also
prevented the formation of macroscopic PANI clusters. The corrosion-
inhibition performance of PANI−PAA composites tested for 316 stainless steel
(316SS) in 0.5 M HCl by electrochemical measurements revealed that
PANI−PAA acted as a mixed-type inhibitor, and its inhibition efficiency
increased with inhibitor concentration. The optimum concentration (200 ppm)
showed a marked inhibition efficiency of 91.68%. The authors attributed the
enhanced efficiency to an insulating interfacial layer formed by the adsorption
of PANI−PAA, which obstructs the corrosion reaction at the interface. In
Table 1 is presented polymer composites reported as metals’ corrosion
inhibitors.
Figure 3. SEM images and EDX spectra of Q235 carbon steel exposed to 0.5 M HCl
solution (a) without and with (b) bridged -CD-PEG (Adapted from Zou et al. [25]).
Table 1. Polymer composites reported as metals corrosion inhibitors
S/N Composite Metal/Alloy Environment Highest Reference

Protected Used Reported
Percentage
Protection
1 Aminothiourea-modified 304 steel Acetic acid 92 [27]
chitosan
2 Chitosan salicyadehyde Mild steel HCl 75.35 [28]
Schiff base
3 Polyaniline/silver/cerium Coating H2SO4 68.08 [22]
nitrate ternary material for
metals
4 Poly(vinyl alcohol-o- Mild steel HCl 72.99 [29]
methoxy aniline)
5 Poly(vinyl alcohol- aniline) Mild steel HCl 92 [30]
6 Poly (vinyl alcohol- Mild steel HCl 84 [15]
sulphanilic acid)
7 Poly(vinyl alcohol-histidine) Mild steel HCl 95 [31]
8 Poly(vinyl alcohol-leucine) Mild steel HCl 95 [32]
9 Polyaniline/polyacrylic acid 316 stainless HCl 91.68 [26]
steel
10 Pectin-g-polyacrylamide; Mild steel NaCl 85 [12]
Pectin-g-polyacrylic acid
11 β-cyclodextrin-polyethylene Q235 carbon HCl 94 [25]
glycol steel
12 Perfluorinated Low alloy NaCl 99.93 [24]
lubricant/polypyrrole steel
13 Pyrrole/2-amino-4- Mild steel HCl 75 [33]
phenylthiazole
Outstandingly, three factors are identified from reports to have influence

on the efficiency of composites when used as metals corrosion inhibitor. These
are: concentration of inhibitor; exposure time; and temperature of the system.
Increasing the concentration of inhibitor is found to cause an increase in the
inhibitive ability of the composites and the reverse is true for decreasing the
concentration of composites. For instance, Menaka and Subhashini [28] noted
that, in 1 M HCl solution, 1500 ppm of a natural biopolymer chitosan
modified into its Schiff base derivative with salicylaldehyde (CHSA) inhibits
mild steel corrosion maximally but behaved poorly (43.30%) at a
concentration of 100 ppm. Karthikaiselvi and Subhashini [29] reported that the
optimum concentration of a water soluble composite, poly(vinyl alcohol-o-
methoxy aniline) (PVAMOA) required to achieve inhibition efficiency of
86.91% at 323 K for mild steel in 1 M HCl is 2000 ppm. Karthikaiselvi et al.
[30] observed that 100 ppm of poly (vinyl alcohol-aniline) (PVAA) composite
could only protect the surface of mild steel immersed in 1 M HCl solution by
37.67% but could be stepped-up to 92.00% if the concentration is raised to
2000 ppm. Also, an optimum concentration of 0.6% of poly (vinyl alcohol-

histidine) and poly (vinyl alcohol-leucine) composites respectively is needed
to achieve protection of more than 95% to mild steel surface deploy in service
in 1 M HCl environment [31, 32]. Syed et al. [26] recently documented that,
for a water-soluble polyaniline-poly(acrylic acid) composite to effectively
extend the life span of 316SS steel utilized in 0.5 M HCl environment by
91.68%, 200 ppm of the inhibitor is required. This is in agreement with the
findings of Geethanjali et al. [12] on the use of pectin-grafted polyacrylamide
and pectin-grafted polyacrylic acid respectively for the protection of mild steel
in 3.5% NaCl medium. This effect of composite concentration on its inhibition
efficiency (IE) might not be far from the availability of the inhibitor molecules
for adsorption. Metals corrosion inhibition by organic inhibitor is initiated by
the displacement of adsorbed water molecules by the inhibitor species
resulting in specific adsorption of the inhibitor molecules on the metal surface
[34]. By increasing inhibitor concentration, higher number of water molecules
is substituted and larger area of the metal surface covered and the effect is high
inhibition.
The length of time upon which metal is exposed to a corrosive medium
containing inhibitor is another factor identified to affect inhibition efficiency.
Menaka and Subhashini [28] studied the influence of immersion time on the
performance of chitosan Schiff base as inhibitor for mild steel in 1 M HCl and
found that IE varies directly as immersion time and reached a maximum value
of 91% at 24 h of immersion time (Figure 4(a)). Karthikaiselvi and Subhashini
[29] noticed that IE of PVAMOA increased at first instance and reached a
maximum value of 97.21% at 3 h immersion but thereafter decreased to
92.02% at 24 h of exposure time. Karthikaiselvi et al. [30] equally found that,
for any concentration of PVAA studied, IE increased with time and maximum
inhibition was obtained at 12 h of immersion time (Figure 4(b)). In the work of
Srimathi et al. [15] on polyvinyl alcohol–sulphanilic acid (PVASA) composite
as corrosion inhibitor for mild steel in 1 M HCl medium, the authors noticed
that IE increased during the first one hour and reached the highest value of
90.5% for 6000 ppm of PVASA but thereafter decreased steadily to 79.9% at
24 h and finally 63.0% at 48 h of exposure to the investigated corrosive
environment (Figure 4(c)). As earlier stated, inhibition of metal corrosion by
organic inhibitor is an adsorption process whereby inhibitor species replaced
adsorbed water molecules on the metal surface. However, the effectiveness of
an adsorbed inhibitor layer in protecting metal surface from aggressive agents
present in an environment depends to a large extent on the thickness, stability,
and rigidity of the adsorbed layer. It is deduced from the reports that, adsorbed
composite films, at prolonged exposure to corrosive environment become

relatively unstable and gradually loses its efficacy as efficient metals corrosion
inhibitor.
Figure 4. Variation of inhibition efficiency of different composites with immersion

time (Re-plotted with permission from (a) Karthikaiselvi and Subhashini [28] (b)
Karthikaiselvi et al. [30] and (c) Srimathi et al. [15]).
Figure 5. Variation of inhibition efficiency of different composites with temperature

(Adapted from (a) Karthikaiselvi and Subhashini [29], (b) Menaka and Subhashini [28]
and (c) Karthikaiselvi et al. [30].
In inhibited corrosive environment, many changes such as rapid etching,

desorption and decomposition of inhibitor, etc. take place on metal surface as
temperature of the environment changes. Research findings have shown that
temperature change has serious influence on the inhibition efficiency of
inhibitors. The study on the influence of temperature on the performance of
PVAMOA [29] and PVAA [30] on mild steel exposed to 1 M HCl
environment revealed that IE increased with rise in temperature up to 323 K
and then decreased beyond this temperature (Figure 5 (a and c)). Srimathi et
al. [15] found that PVASA behaved in like manner as PVAMOA and PVAA
when the temperature of the PVASA inhibited acid system was raised. Menaka
and Subhashini [28] however observed that the inhibition efficiency of CHSA
varies directly with temperature up to 333 K before decreasing thereafter
(Figure 5(b)). The structural orientation of these polymers would have a lot to
do with this observation. As noted by Solomon et al. [34], polymers are mostly
extended (rod-like) at low temperatures but at elevated temperatures, the
molecules overlap and coil up and then, entangle to become a thermoreversible
gel. This means that, at lower temperatures the adsorbed inhibitor molecules
on the metal surface appreciably cover the surface but at higher temperatures,
the thermoreversible gel which could also dissolve from the surface expose
some areas to corrosive agent and the resultant effect is the reported lesser IE
at elevated temperatures (Figure 5).
3.3. Application of Polymer Nanocomposites as Corrosion

Inhibitors
Recently, nanocomposites have gain global attention due to the fact that
their properties (optical, electrical, magnetic, etc.) uniquely differ from those
of the conventional composites. By definition, nanocomposites are those
composites in which the diameter of one of the constituents is below micron
dimension (generally less than 0.1 µm i.e., 100 nm). The endearing feature of
nanocomposites is the dependency of their properties on the size of the
nanoparticle. Decrease in the particle size increases the ratio of surface-to-
volume and the effect is good surface properties.
Metals/polymer nanocomposites are of special interest because they have
excellent flexibility, high compatibility, and strong adhesive power than other
forms of nanocomposites [35, 36]. Corrosion scientists have noted that
nanocomposites possess excellent inhibiting ability for metals in different
media than their corresponding polymers and should be utilized in full scale
for commercial purposes. Solomon and Umoren [17] and Solomon et al. [18]
reported that polypropylene glycol/silver nanoparticles (PPG/AgNPs)
composite has the efficacy to effectively inhibit the corrosion of mild steel and
aluminium in sulphuric acid environment. According to the reports,
PPG/AgNPs could protect mild steel surface in sulphuric acid solution by 94%
at temperature as high as 333K and Al surface by 85.6% at 303 K. Figure 6
illustrates the synthetic step of PPG/AgNPs and its effectiveness as inhibitor
for mild steel in acid solution. Solomon et al. [14, 16] documented that poly
(methacrylic acid)/silver nanoparticles (PMAA/AgNPs) composites prepared
in-situ using natural honey as the reducing and capping agent can be used for
safeguarding the life of mild steel and Al in acid medium. It was noted that
PMAA/AgNPs interrupted both anodic and cathodic corrosion reactions and
can offer protection of more than 80% to the metal surfaces in the aggressive
environment. Atta et al. [37] and [38] reported that poly (ethylene glycol)
thiol, poly (vinyl pyrrolidone) self-assembled monolayer Ag nanoparticles and
Ag/2-acrylamide-2-methylpropane/N-isopropylacryamide nanocomposite
respectively were effective corrosion inhibitor for steel in HCl environment.
Also, polyaniline-α-Fe2O3 nanoparticle composite [39], polypyrrole-clay
nanocomposite [40], chitosan/ZnO nanoparticle composite [41], and
polyaniline/CeO2 nanocomposite [19] had been reported to have inhibitive
ability towards the corrosion of 316LN steel, cold rolled steel, and mild steel
in NaCl and HCl media respectively. Recently, Hefni et al. [42] advocated for
the use of chitosan grafted poly (ethylene glycol) assembled on silver
nanoparticles (ch-g-PEG/AgNPs) for the corrosion inhibition of carbon steel in
HCl medium. The authors stated that inhibition efficiency of 92.75% can be
achieved at 298 K with 3 mM ch-g-PEG/AgNPs. Table 2 summarized polymer
nanoparticles composites reported as efficient corrosion inhibitor for metals in
different corrosive environments.
3.4. Mechanism of Corrosion Inhibition by Composites

and Nanocomposites
The effectiveness and interaction of an organic inhibitor with a metal

surface depend to a large extent on the adsorption ability of the inhibitor
molecules [43]. However, certain factors namely, concentration of electrolyte,
nature of inhibitor, and the charge on the metal surface influence the
adsorption as well as efficiency of inhibitor molecules [44]. Depending on the
concentration of the electrolyte, organic inhibitors exist as charged species,
neutral species, or both and adsorption is a function of metal surface charge.

The metal surface charge is defined by the position of corrosion potential
(Ecorr) with respect to the potential of zero charge (PZC) Eq = 0. When the
difference (ψ) between Ecorr and Eq = 0 is negative, the metal surface acquires a
net negative charge and adsorption of positively charged inhibitor species are
favored but adsorption of negatively charged inhibitor species is favored if
Ecorr minus Eq = 0 is positive [45].
Table 2. Polymer nanocomposites reported as metals corrosion inhibitors
S/N Composite Metal/Alloy Environment Highest Reference

Protected Used Reported
Percentage
Protection
1 Poly (methacrylic Al H2SO4 85.6 [14]
acid)/silver
Nanocomposite
2 Poly (methacrylic Mild steel H2SO4 81.8 [16]
acid)/silver
nanocomposite
3 Polypropylene glycol- Mild steel H2SO4 94 [17]
silver nanoparticle
4 Polypropylene glycol- Al H2SO4 85.6 [18]
silver nanoparticle
5 Polyaniline/CeO2 Mild steel HCl 69.25 [19]
nanocomposite
6 Poly(ethylene glycol) Carbon steel HCl 90.95 [37]
thiol and poly(vinyl
pyrrolidone)
self assembled monolayer
silver nanocomposite
7 2-acrylamido-2- Steel HCl 81.46 [38]
methylpropane/N-
isopropylacrylamine
silver nanocomposite
8 Polyaniline-α-Fe2O3 316LN NaCl – [39]
nanocomposite stainless
steel
9 Polypyrrole-clay Cold rolled NaCl – [40]
nanocomposite steel
10 Chitosan/ZnO Mild steel HCl 73.80 [41]
nanocomposite
11 Chitosan-g-Polyethylene Carbon steel HCl 92.75 [42]
glycol assembled silver
nanocomposite
Figure 6. Synthesis route and characterization of PPG/AgNPs and its effectiveness as

mild steel corrosion inhibitor in sulphuric acid solution (Solomon and Umoren [17]).
Generally, the adsorption of organic inhibitor onto metal surface is a

quasi-substitution process whereby inhibitor molecules in the solution (Inhsol)
replace adsorbed water molecules (H2Oads) on metal according to Equation 1
[45]:
Inh sol  xH 2 O ads  Inh ads  xH 2 Osol (1)
where Inhads is the adsorbed inhibitor on the metal surface and 𝑥 is the
number of water molecules replaced by the inhibitor molecules. There are
therefore three possible ways in which composite molecules can substitute
adsorbed water molecules: (i) by sharing of electrons between their
heteroatoms and the metal surface, (ii) through π-electron interaction between
unsaturated bonds and metal surface, and (iii) through electrostatic attraction
between charged inhibitor species and charged metal surface. Menaka and
Subhashini [28] explained that the mechanism of adsorption of chitosan Schiff
base onto mild steel surface in acid environment was through both electrostatic
interaction and chemical electron sharing according to Figure 7. However, the
mechanism of metals corrosion inhibition by inorganic nanocomposite is more

complex than that of organic composite as corrosion scientists believed that
the inorganic nanoparticles play significant role in the adsorption and
inhibition process. According to Solomon and Umoren [17], metal
nanoparticles can be chemisorbed on metal surface and decrease the
hydrophilicity of metal surface and as effect promotes the adsorption of
organic component of the composite. Hefni et al. [42] explained in their work
on ch-g-PEG/AgNPs as inhibitor for steel in HCl solution that when iron is
immersed in ch-g-PEG/AgNPs inhibited acid solution, adsorption of the
nanocomposite molecules happened in two ways: (i) by monomethylated PEG
and (ii) through adsorption of AgNPs directly on the metal surface which is
possible because of the active properties of the nanoparticles. Sasikumar et al.
[19] equally opined that the mechanism of corrosion inhibition of mild steel in
acid environment by PANI/CeO2 nanocomposite occurred by the formation of
inhibitor film due to redox reaction of iron and PANI and also by secondary
reaction of formation of cerium-iron complex. According to the authors, the
protection of the metal surface takes place through the reduction of polyaniline
emeraldine salt to polyaniline leucoemeraldine salt with the concomitant
release of cerium ions which formed iron-cerium complex along with the
passive film formed by PANI.
3.5. Challenges on the Use of Composites and Nanocomposites as

Metals Corrosion Inhibitors
Two issues are most likely to hamper the commercial utilization of

polymer composites and polymer-nanoparticles composites. These are: (i)
difficulty in dispersing added component uniformly in polymer matrix and (ii)
the cost of production on a commercial scale. Composites and nanocomposites
in which the added component is well dispersed in the polymer matrix perform
better. However, the fact that the added particles particularly inorganic
particles have the tendency to agglomerate always poses difficulty during
synthesis. The cost of production is another issue; at present, the price of
synthetic polymers depends on the price of crude oil. Utilizing synthetic
polymers on large scale production of composites and nanocomposites for
commercial application as metal corrosion inhibitor might not be cost
effective. Also, already there are expressions of fear over petroleum-based
products since crude oil is non-renewable resource. Scientists [28, 34] are
advocating for the use of naturally occurring polymers but availability in a

commercial scale is still in doubt.
Figure
Figure 7: Schematic
7. Schematic representationofofplausible
representation plausible interaction
interactionofofchitosan Schiff
chitosan basebase
Schiff withwith
mild
steel surface in acid medium (Menaka and Subhashini, [28])
mild steel surface in acid medium (Menaka and Subhashini, [28]).
CONCLUSION
This chapter focused on the application of polymer composites and
nanocomposites as metal corrosion inhibitors in various aggressive
environments. It is evident from reports that polymer composites and
nanocomposites can effectively protect metal surface deployed in service in a
corrosive environment. However, the extent of protection depends principally
on the concentration of the inhibitor, exposure duration, and temperature of the
environment. Nevertheless, the utilization of polymer composites and
nanocomposites on an industrial scale might be hampered by the difficulty
involved in producing a well and uniformly dispersed composites and
nanocomposites and the financial implication of large scale production.
REFERENCES
[1] Li, X; Deng, S; Fu, H; Mu, G. Synergistic inhibition effect of rare earth
cerium(IV) ion and 3,4-dihydroxybenzaldehye on the corrosion of cold
rolled steel in H2SO4 solution, Corros. Sci., 51, (2009), 2639–2651.
[2] Li, X; Deng, S; Fu, H; Mu, G. Synergistic inhibition effect of rare earth
cerium(IV) ion and anionic surfactant on the corrosion of cold rolled
steel in H2SO4 solution, Corros. Sci., 50, (2008), 2635–2645.
[3] Gunasekaran, G; Palniswamy, N; Apparao, BV; Muralidharan, VS.
Enhanced synergistic inhibition by calcium gluconate in low chloride
media. Part 1: kinetics of corrosion, Proc. Indian Acad. Sci (Chem. Sci.),
108, (1996), 399 – 405.
[4] Qu, Q; Hao, Z; Jiang, S; Li, L; Bai, W. Synergistic inhibition between
dodecylamine and potassium iodide on the corrosion of cold rolled steel
in 0.1 M phosphoric acid, Mater. Corros., 59(11), (2008), 883-888.
[5] Bayol, E; Gurten, AA; Dursun, M; Kayakirilmaz, K. Adsorption
behavior and inhibition corrosion effect of sodium carboxylmethyl
cellulose on mild steel in acidic medium, Acta Physco-Chim. Sin., 24,
(2008), 2236.
[6] Arukalam, IO; Nleme, KI; Anyanwu, AE. Comparative inhibitive effect
of hydroxyethylcellulose on mild steel and aluminium corrosion in 0.5
M HCl solution, Academic Res. Int., 1(3), (2011), 492-498.
[7] Rajeswari, V; Kesavan, D; Gopiraman, M; Viswanathamurthi, P.
Physicochemical studies of glucose, gellan gum, andhydroxypropyl
cellulose - inhibition of cast iron corrosion, Carbohyd. Polym., 95,
(2013), 288-294.
[8] Govindaraju, KM; Gopi, D; Anver, K. Basha, Synthesis,
characterization, and electrochemical evaluation of anti-corrosive
performance of poly((N-Methacryloyloxymethyl) benzotriazole-co-
NVinylpyrrolidone) coatings, J. Appl. Electrochem., 43, (2013), 1043–
1054.
[9] Xu, Y; Zhang, B; Zhao, L; Cui, Y. Synthesis of polyaspartic acid/5-
aminoorotic acid graft copolymer and evaluation of its scale inhibition
and corrosion inhibition performance, Desalination, 311, (2013), 156–
161.
[10] Umoren, SA; Solomon, MM. Effect of halide ions on the corrosion
inhibition efficiency of different organic species - A review, J. Ind. Eng.
Chem., 21, (2014), 81 – 100.
[11] Jeyaprabha, C; Sathiyanarayanan, S; Venkatachari, G. Influence of
halide ions on the adsorption of diphenylamine on iron in 0.5 M H2SO4
solution, Electrochim. Acta, 51, (2006), 4080–4088.
[12] Geethanjali, R; Ali Fathima Sabirneeza, A; Subhashini, S. Water-soluble
and biodegradable pectin-grafted polyacrylamide and pectin-grafted
polyacrylic acid: electrochemical investigation of corrosion-inhibition
behaviour on mild steel in 3.5% NaCl media, Ind. J. Mater. Sci., 2014,
(2014), 1-9.
[13] Umoren, SA; Eduok, UM; Solomon, MM. Effect of
polyvinylpyrrolidone – polyethylene glycol blends on the corrosion
inhibition of aluminium in HCl solution, Pigm. Resin Technol., 43 (5),
(2014), 299–313.
[14] Solomon, MM; Umoren, SA. Performance assessmentof poly
(methacrylic acid)/silver nanoparticles composite as corrosion inhibitor
for aluminiumin acidic environment, J. Adhes. Sci. Technol., 29(21),
2311-2333.
[15] Srimathi, M; Rajalakshmi, R; Subhashini, S. Polyvinyl alcohol–
sulphanilic acid water soluble composite as corrosion inhibitor for mild
steel in hydrochloric acid medium, Arab. J. Chem., 7, (2014), 647–656.
[16] Solomon, MM; Umoren, SA; Abai, EJ. Preparation and evaluation of the
surface protective performance of poly (methacrylic acid)/silver
nanoparticles composites (PMAA/AgNPs) on mild steel in acidic
environment. J. Mol. Liq., 212, (2015), 340–351.
[17] Solomon, MM; Umoren, SA. In-situ preparation, characterisation, and
anticorrosion property of polypropylene glycol/silver nanoparticles
composite for mild steel corrosion in acid solution. J. Coll. Interf. Sci.,
462, (2016), 29–41.
[18] Solomon, MM; Umoren, SA; Israel, AU; Ebenso, EE. Polypropylene
glycol - silver nanoparticles composites prepared in-situ as corrosion
inhibitor for aluminium in acidic environment, J. Mater. Eng. Perform.,
24, (2015), 4206 - 4218.
[19] Sasikumar, V; Madhan Kumar, A; Gasem, ZM; Ebenso, EE. Hybrid
nanocomposite from aniline and CeO2nanoparticles: Surface protective
performance on mild steel in acidic environment, Appl. Surf. Sci., 330,
(2015), 207–215.
[20] Guo 1, Q; Ghadiri, R; Weigel, T; Aumann, A; Gurevich, EL; Esen, C;
Medenbach, O; Cheng, W; Chichkov, B; Ostendorf, A. comparison of in
situ and ex situ methods for synthesis of two-photon polymerization
polymer nanocomposites, Polymers, 6, (2014), 2037-2050.
[21] Umoren, SA; Solomon, MM. Recent developments on the use of
polymers as corrosion inhibitors-A review, The Open Mater. Sci. J., 8,
(2014), 30 – 45.
[22] Li, Y; Li, Z; Zheng, F. Polyaniline/silver/cerium nitrate ternary
composite: synthesis, characterization and enhanced electrochemical
properties, J. Appl. Polym. Sci., 2015, DOI: 10.1002/APP.42785.
[23] Mobin, M; Khan, MA; Parveen, M. Inhibition of mild steel corrosion in

acidic medium using starch and surfactants additives, J. Appl. Polym.
Sci., 121, (2011), 1558–1565.
[24] Zhu, H; Hou, J; Qiu, R; Zhao, J; Xu, J. Perfluorinated
lubricant/polypyrrole composite material: preparation and corrosion
inhibition, J. Appl. Polym. Sci., 131(9), (2014), 1-7.
[25] Zou, C; Liu, Y; Yan, X; Qin, Y; Wang, M; Zhou, L. Synthesis of
bridged β-cyclodextrin-polyethylene glycol and evaluation of its
inhibition performance in oilfield wastewater, Mater. Chem. Phys., 147,
(2014), 521-527.
[26] Syed, JA; Tang, S; Lu, H; Meng, X. Water-soluble
polyaniline−polyacrylic acid composites as efficient corrosion inhibitors
for 316SS, Ind. Eng. Chem. Res., 54, (2015), 2950−2959.
[27] Li, M; Xu, J; Li, R; Wang, D; Li, T; Yuan, M; Wang, J. Simple
preparation of aminothiourea-modified chitosan as corrosion inhibitor
and heavy metal ion adsorbent, J. Coll. Interf. Sci., 417, (2014), 131–
136.
[28] Menaka, R; Subhashini, S. Chitosan Schiff base as eco-friendly inhibitor
for mild steel corrosion in 1 M HCl, J. Adhes. Sci. Technol., 30, (2016),
1622 – 1630.
[29] Karthikaiselvi, R; Subhashini, S. Study of adsorption properties and
inhibition of mild steel corrosion in hydrochloric acid media by water
soluble composite poly (vinyl alcohol-o-methoxy aniline), J. Assoc.
Arab Univer. Basic Appl. Sci., 16, (2014), 74-82.
[30] Karthikaiselvi, R; Subhashini, S; Rajalakshmi, R. Poly (vinyl alcohol –
aniline) water soluble composite as corrosion inhibitor for mild steel in 1
M HCl, Arab. J. Chem., 5, (2012), 517–522.
[31] Sabirneeza, AAF; Subhashini, S. A novel water-soluble, conducting
polymer composite for mild steel acid corrosion inhibition, J. Appl.
Polym. Sci., 127, (2013), 3084–3092.
[32] Sabirneeza, AAF; Subhashini, S; Rajalakshmi, R. Water soluble
conducting polymer composite of polyvinyl alcohol and leucine: An
effective acid corrosion inhibitor for mild steel. Mater. Corros., 64 (1),
(2013), 74-82.
[33] Sayyah, SM; El-Deeb, MM. Electrocopolymerization of a binary
mixture of pyrrole and 2-amino-4-phenylthiazole: kinetic studies,
copolymer structure, and applications as corrosion protection for mild
steel in acid medium, J. Appl. Polym. Sci., 103, (2007), 4047–4058.
[34] Solomon, MM; Umoren, SA; Udousoro, II; Udoh, AP. Inhibitive and
adsorption behavior of carboxymethyl cellulose on mild steel corrosion
in sulphuric acid solution, Corros. Sci., 52, (2010), 1317 – 1325.
[35] Taryba, M; Lamaka, SV; Snihirova, D; Ferreira, MGS; Montemor, MF;
Wijting, WK; Towes, S; Grundineier, G. The combined use of scanning
vibrating electrode technique and micro-potentiometry to assess the self-
repair processes in defects on ‘smart’ coatings applied to galvanized
steel, Electrochim. Acta, 56, (2011), 4475–4488.
[36] Ramezanzadeh, B; Attar, MM. An evaluation of the corrosion resistance
and adhesion properties of an epoxy-nanocomposite on a hot-dip
galvanized steel (hdg) treated by different kinds of conversion coatings,
Surf. Coat. Technol., 205, (2011), 4649–4657.
[37] Atta, AM; Allohedan, HA; El-Mahdy, GA; Ezzat, ARO. Application of
stabilized silver nanoparticles as thin films as corrosion inhibitors for
carbon steel alloy in 1M hydrochloric acid, J. Nanomater., 2013, (2013),
1-8.
[38] Atta, AM; El-Mahdy, GA; Al-Lohedan, HA; Ezzat, AO. Synthesis and
application of hybrid polymer composites based on silver nanoparticles
as corrosion protection for line pipe steel, Molecules, 19, (2014), 6246-
6262.
[39] Umare, SS; Shambharkar, BH. Synthesis, characterization, and corrosion
inhibition study of polyaniline-a-Fe2O3 nanocomposite, J. Appl. Polym.
Sci., 127, (2013), 3349–3355.
[40] Yeh, JM; Chin, CP; Chang, S. Enhanced corrosion protection coatings
prepared from soluble electronically conductive polypyrrole-clay
nanocomposite materials, J. Appl. Polym. Sci., 88, (2003), 3264–3272.
[41] John, S; Joseph, A; Jose, AJ; Narayana, B. Enhancement of corrosion
protection of mild steel by chitosan/ZnO nanoparticle composite
membranes, Prog. Organic Coat., 84, (2015), 28–34.
[42] Hefni, HHH; Azzam, EM; Badr, EA; Hussein, M; Tawfik, SM.
Synthesis, characterization and anticorrosion potentials of chitosan-g-
PEG assembled on silver nanoparticles, Int. J. Bio. Macromol., 83,
(2016), 297–305.
[43] Doner, A; Solmaz, R; Ozcan, M; Kardas, G. Experimental and
theoretical studies of thiazoles as corrosion inhibitors for mild steel in
sulphuric acid solution, Corros. Sci., 53, (2011), 2902−2913.
[44] Badr, GE. The role of some thiosemicarbazide derivatives as corrosion
inhibitors for C-steel in acidic media, Corros. Sci., 51, (2009),
2529−2536.
[45] Gerengi, H; Ugras, HI; Solomon, MM; Umoren, SA; Kurtay, M; Atar,
N. Synergistic corrosion inhibition effect of 1-ethyl-1-
methylpyrrolidinium tetrafluoroborate and iodide ions for low carbon
steel in HCl solution, J. Adhes. Sci. Technol., DOI: 10.1080/
01694243.2016.1183407.
BIOGRAPHICAL SKETCH
Name: SOLOMON, Moses Monday
Affiliation: Corrosion Research Laboratory, Department of Mechanical
Engineering, Duzce University, Turkey
Education: PhD (Polymer Chemistry)
Research and Professional Experience: Research is focused on polymer
synthesis, characterization, modification, and extensively on investigating
materials corrosion and corrosion inhibition mechanisms on conventional
polycrystalline as well as nanocrystalline surfaces.
Professional Appointments: Postdoctoral Research Fellow, Department
of Mechanical Engineering, Duzce University, Turkey (TUBITAK 21514107-
115.02-56312), 13th May, 2016 to 13th May, 2017
Publications Last 3 Years:
(A) Journals
1. Gerengi, H., Ugras, H. I., Solomon, M. M., Umoren, S. A., Kurtay,

M. and Atar, N. (2016). Synergistic corrosion inhibition effect of 1-
ethyl-1- methylpyrrolidinium tetrafluoroborate and iodide ions for low
carbon steel in HCl solution. J. Adhes. Sci. Technol., 30 (21):2383-
2403
2. Solomon, M. M. and Umoren, S. A. (2016). In-situ preparation,
characterisation, and anticorrosion property of polypropylene
glycol/silver nanoparticles composite for mild steel corrosion in acid
solution. Journal of Colloid and Interface Science, 462: 29–41
3. Solomon, M. M., Umoren, S. A., Israel, A. U., and Etim, I. G. (2015).
Synergistic inhibition of aluminium corrosion in 0.5 M H2SO4
solution by polypropylene glycol in the presence of iodide ions.
Pigment Resin Technology, DOI:10.1108/PRT-01-2015-0010
4. Solomon, M. M., Umoren, S. A. and Abai, E. J. (2015). Preparation
and evaluation of the surface protective performance of poly
(methacrylic acid)/silver nanoparticles composites (PMAA/AgNPs)
on mild steel in acidic environment. Journal of Molecular Liquids,

212: 340–351
5. Solomon, M. M., Umoren, S. A., Israel, A. U., and Ebenso, E. E,
(2015). Polypropylene glycol - silver nanoparticles composites
prepared in-situ as corrosion inhibitor for aluminium in acidic
environment. Journal of Materials Engineering & Performance, 24:
4206 - 4218
6. Solomon, M. M. and Umoren, S. A. (2015). Electrochemical and
gravimetric measurements of inhibition of aluminium corrosion by
poly (methacrylic acid) in H2SO4 solution and synergistic effect of
iodide ions. Measurement, 76: 104 - 116
7. Umoren, S. A., Solomon, M. M. Israel, A. U., Eduok, U. M. and
Jonah, A. E. (2015). Comparative study of the corrosion inhibition
efficacy of polypropylene glycol and poly (methacrylic acid) for mild
steel in acid solution. Journal of Dispersion Science and
Technology, 36(12): 1721-1735
8. Jonah, A. E., Solomon, M. M. and Ano, A. O. (2015). Assessment of
the physico-chemical properties and heavy metal status of water
samples from Ohii Miri river in Abia State, Nigeria. Merit Research
Journal of Environmental Science and Toxicology, 3(1): 001 – 011
9. Solomon, M. M. and Umoren, S. A. (2015). Performance evaluation
of poly (methacrylic acid) as corrosion inhibitor in the presence of
iodide ions for mild steel in H2SO4 solution. Journal of Adhesion
Science and Technology, 29 (11): 1060 – 1080
10. Jonah, A. E., Solomon, M. M., Ikpe, D. I., and Etim I. G. (2015).
Macro nutrients determination and bacteriological status assessment
of water and sediment samples from Ohii Miri River in Abia State,
Nigeria. International Journal of Engineering Innovation &
Research, 4(3): 383 – 389
11. Solomon, M. M. and Umoren, S. A. (2015). Enhanced corrosion
inhibition of mild steel by polypropylene glycol in the presence of
iodide ions in acid solutions. Journal of Environmental Chemical
Engineering, 3: 1812–1826
12. Solomon, M. M. and Umoren, S. A. (2015). Performance assessment
of poly (methacrylic acid)/silver nanoparticles composite as corrosion
inhibitor for aluminium in acidic environment. Journal Adhesion
Science and Technology, 29: 21, 2311-2333
13. Osu, S. R., Solomon, M. M., Abai, E. J. and Etim, I. G. (2015).
Human health risk assessment of heavy metals intake via cassava
consumption from crude oil impacted soils with and without palm
bunch ash additive. International Journal of Technical Research
and Applications, 3 (4): 140-148
14. Umoren, S. A., Solomon, M. M., Eduok, U. B., Obot, I. B. and Israel,
A. U. (2014). Inhibition of mild steel corrosion in H2SO4 solution by
coconut coir dust extract obtained from different solvent systems and
synergistic effect of iodide ions: Ethanol and acetone extracts.
Journal of Environmental Chemical Engineering, 2: 1040 – 1060
15. Umoren, S. A. and Solomon, M. M. (2014). Recent developments on
the use of polymers as corrosion inhibitors-A review. The Open
Material Science Journal, 8: 30 – 45
16. Jonah, A. E., Solomon, M. M. and Ano, A. O. (2014). Study on the
physicochemical properties and heavy metal status of sediment
samples from Ohii Miri River in Abia State, Nigeria. Fountain
Journal of Natural and Applied Science, 3 (1): 29 – 49
17. Umoren, S. A., Eduok, U. B. and Solomon, M. M. (2014). Effect of
polyvinylpyrrolidone-polyethylene glycol blends on the corrosion
inhibition of aluminium in HCl solution. Pigment and Resin
Technology, 43(5): 299 – 313
18. Umoren, S. A. and Solomon, M. M. (2014). Effect of halide ions on
the corrosion inhibition efficiency of different organic species - A
review. Journal of Industrial Engineering Chemistry, 21: 81 – 100
19. Umoren, S. A., Obot, I. B., Isreal, A. U., Asuquo, P. O., Solomon, M.
M., Eduok, U. M. and Udoh, A. P. (2014). Inhibition of mild steel
corrosion in acidic medium using coconut coir dust extracted from
water and methanol as solvents. Journal of Industrial Engineering
Chemistry, 20: 3612 – 3622
(B) Book/Book Chapter:
1. Umoren, S. A., Solomon, M. M. “Polymer Characterization: Polymer

Molecular Weight Determination” In: Polymer Science: Research
Advances, Practical Applications and Education Aspects (A. Méndez-
Vilas, A. Solano-Martin (Eds)), Formatex Research Centre, Badajoz,
Spain (To be published in summer 2016)
2. Umoren, S. A., Solomon, M. M. “Polypropylene (PP)/Starch Based
Biocomposites and Bionanocomposites” In: Propylene Based
Composites and Bionanocomposites (P. M. Visakh, Matheus Poletto
(Eds), (To be published by Wiley and Sons, USA).
3. Abasiekong, B. O. and Solomon, M. M. (2015). Rudiments of

Chemistry, Ikot Ekpene: Gift Printers (Nig.).
Name: Dr. Saviour A. Umoren

Affiliation: King Fahd University of Petroleum and Minerals, Dhahran,
Saudi Arabia
Education: PhD (Polymer Science)
Research and Professional Experience:
(a)Research Experience:
Research Interests
 Electrochemical investigation of corrosion phenomena in different

aqueous aggressive environments.
 Development of environmentally friendly corrosion inhibitors for oil
and gas industry
 Development of corrosion inhibitors for high temperature
applications.
 Interface characterization, including adsorption and biosorption
studies.
 Polymer synthesis and characterization/additives in polymer.
 Organic coatings (Alkyd resins)
 Nanotechnology
 Development of polymer-nanoparticles composites for corrosion
protection.
Research Grants
1. Studies On Corrosion Inhibition Potential of Extracts of Coconut Coir

Dust Obtained from Different Solvent Systems for Mild Steel in
Different Environments. (Project #: 10−107RG/CHE/AF/AC-G;
Value: $23,860; Role: PI) Grant for Research Units from TWAS, the
Academy of Sciences for the Developing World, May, 2011.
2. Development of Environmentally Friendly Corrosion and Scale
Inhibitors from Indigenous Plants of Saudi Arabia (Project #: 14-
ADV2452-04; Value: $533,213.33; Role PI) (Grant from NSTIP,
Saudi Arabia)
3. Computer-Aided Design of Ecofriendly Organic Inhibitors for Steel

Corrosion (Project #: 14-ADV2448-04; Value: $406,314.67; Role:
Co-I) (Grant from NSTIP, Saudi Arabia)
Postgraduate Supervision: Supervised and graduated 11 MSc and 1 PhD

students
(b) Professional Experience:
(i) University of Uyo, Uyo, Nigeria

(a) Assistant Lecturer, Department of Chemical/Petroleum
Engineering, University of Uyo, March 1998 – October 1998.
(b) Assistant Lecturer, Department of Chemistry, University of Uyo,
Oct. 1998- September 2002
(c) Lecturer II, Department of Chemistry, University of Uyo,
October1, 2002 –September 2004.
(d) Lecturer I, Department of Chemistry, University of Uyo, October
1, 2005 - September 2007.
(e) Senior Lecturer, Department of Chemistry, University of Uyo,
Oct. 1, 2008 – September, 2011
(f) Associate Professor, Department of Chemistry, University of
Uyo, October 1, 2011 – Date.
(ii) King Fahd University of Petroleum and Minerals (KFUPM),
Saudi Arabia
(a) Research Scientist II (Associate Professor), December 2012 -
Date
University Administration
Head of Department, Department of Chemistry, UNIUYO (2010 – 2012)
Journal Review:
I have served as a reviewer to more than 70 international journals which
include Corrosion Science, Carbohydrate Polymers, Journal of Solid State
Electrochemistry, Industrial and Engineering Chemistry Research,
International Journal of Biological Macromolecules, Journal of Applied
Electrochemistry, Green Chemistry Letters and Reviews, Journal of Molecular
Liquids, Research on Chemical Intermediates, Pigment and Resin Technology,
Anti Corrosion Methods and Materials, Ionics, Materials Chemistry and
Physics, Arabian Journal of Chemistry, Cellulose, Journal of Industrial and
Engineering Chemistry, Journal of Polymer Technology, Journal of

Environmental Chemical Engineering amongst others.
Professional Appointments:
Membership of Journal Editorial Board
(a) American Journal of Chemistry (Scientific and Academic Publishing),

USA
(b) International Scholarly Research Notices (ISRN) (Materials Science),
USA.
(c) Journal of Materials and Environmental Science, Morocco.
(d) International Journal of Environment and Bioenergy, Florida, USA
(e) Journal of Composites and Biodegradable Polymers
(f) Physical Chemistry Communications
(g) Innovations in Corrosion and Materials Science
(h) Journal of Adhesion Science and Technology (Taylor and Francis)
(i) Recent Patents on Materials Science Journal
Honors:
 TWAS-UNESCO Associateship appointment (2011 – 2013)

 CAS-TWAS Postdoctoral Fellowship (2009 - 2010)
 Akwa Ibom State Government of Nigeria Postgraduate Scholar (2002,
2005)
 Federal Government of Nigeria Postgraduate Scholar (1992)
 Akwa Ibom State Government of Nigeria Scholar (1988 - 1990)
 Mary Lot’s Prize for the best Science Student in Year II, Faculty of
Natural Sciences, University of Jos (1989)
 University of Jos Award for the best Year II Chemistry Student
(1988)

2016
1. Solomon, M. M., Umoren, S. A. (2016). In-situ preparation,

characterization and anticorrosion property of polypropylene
glycol/silver nanoparticles composite for mild steel corrosion in acid
solution, Journal of Colloid and Interface Science 462: 29 – 41.
2. Ahovan, M., Nasr-Esfahani, M., Umoren, S. A. (2016). Inhibitive

effect of 1-[(2-hydroxyethyl) amino]-2-(salicylideneamino) ethane
towards corrosion of carbon steel in CO2 saturated 3.0% NaCl
solution, Journal of Adhesion Science and Technology 30 (1): 89 –
103.
3. Umoren, S. A., Eduok, U. M. (2016). Application of carbohydrate
polymers as corrosion inhibitors for metal substrates in different
media: A review, Carbohydrate Polymers 140: 314 – 341.
4. Inam, E. I., Etim, U. J., Akpabio, E. G., Umoren, S. A. (2016).
Simultaneous adsorption of lead (II) and 3,7-bis(Dimethylamino)-
phenothiazin-5-ium chloride from aqueous solution by activated
carbon prepared from plantain peels, Desalination and Water
Treatment, 57 (14): 6540-6553.
5. Essien, E. E., Umoren, S. A., Effiong, E. E. (2016). Synthesis and
characterization of luffa cylindrica fatty acids-based alkyd resins,
Research on Chemical Intermediates 42(3): 2177-2189.
6. Umoren, S. A. (2016). Polypropylene glycol: A novel corrosion
inhibitor for X60 pipeline steel in 15% HCl solution, Journal of
Molecular Liquids 219: 946 – 958.
7. Umoren, S. A. (2016). Biomaterials for Corrosion Protection:
Evaluation of Mustard Seed Extract as Eco-friendly Corrosion
Inhibitor for X60 Steel in Acid Media, Journal of Adhesion Science
and Technology 30 (17): 1858-1879.
8. Umoren, S. A., Essien, E. E., Effiong, E. E. (2016). The utilization of
Lagenaria breviflorus seed oil in the synthesis of alkyd resins,
Journal of Materials and Environmental Science 7 (6): 1846-1855.
9. Gerengi, H., Ugras, H. I., Solomon, M. M., Umoren, S. A., Kurtay,
M., Atar, N. (2016). Synergistic corrosion inhibition effect of 1-Ethyl-
1-methylpyrrolidinium tetrafluoroborate and iodide ions for low
carbon steel in HCl solution, Journal of Adhesion Science and
Technology 30 (21): 2383–2403
10. Inam, E. I., Etim, U. J., Akpabio, E. G., Umoren, S. A. (2016). Process
optimization for Plantain peels carbon application in dye abstraction.
Journal of Taibah University for Science, http:// dx.doi.org/ 10.1016/
j.jtusci. 2016.01.003
11. Solomon, M. M., Umoren, S. A., Israel, A. U., Etim, I. G. (2016).
Synergistic inhibition of aluminium corrosion in H2SO4 solution by
polypropylene glycol in the presence of iodide ions, Pigment and
Resin Technology doi: 10.1108/PRT-01-2015-0010
2015
12. Solomon, M. M., Umoren, S. A., Abai, E. J. (2015). Poly(methacrylic

acid)/silver nanoparticles composites: In-situ preparation,
characterization and anticorrosion property for mild steel in H2SO4
solution. Journal of Molecular Liquids 212: 340 – 351.
13. Umoren, S.A, Inam, E.I, Udoidong, A. A., Obot, I. B., Ubong, U. M,
Kim, K. W. (2015). Humic acid from live stocks dung: ecofriendly
corrosion inhibitor for 3sr aluminium alloy in alkaline medium.
Chemical Engineering Communications. 202 (3): 206 – 216.
14. Solomon, M. M., Umoren, S. A., Israel, A. U., Ebenso, E. E. (2015).
Polypropylene glycol - silver nanoparticle composites: A novel
anticorrosion material for aluminium in acid medium. Journal of
Materials Engineering and Performance 24 (11): 4206 – 4218.
15. Solomon, M. M., Umoren, S. A. (2015). Electrochemical and
gravimetric measurements of inhibition of aluminium corrosion by
poly (methacrylic acid) in H2SO4 solution and synergistic effect of
iodide ions, Measurement 76: 104 – 116.
16. Salimi, S., Nasr-Esfahani, M., Umoren, S. A., Saebnoori, E. (2015).
Complexes of imidazole with poly(ethylene glycol) as corrosion
inhibitor for carbon steel in sulphuric acid, Journal of Materials
Engineering and Performance 24 (12): 4696 – 4709.
17. Umoren, S. A., Solomon, M. M. (2015). Effect of halide ions on the
corrosion inhibition efficiency of different organic species – A
Review. Journal of Industrial and Engineering Chemistry 21(1): 81 –
100.
18. Odewunmi, N. A., Umoren, S. A., Gasem, Z. M. (2015). Utilization of
watermelon rind extract as a green corrosion inhibitor for mild steel in
acidic media. Journal of Industrial and Engineering Chemistry 21(1):
239 – 246.
19. Umoren, S. A., Obot, I. B., Madhankumar, A., Gasem, Z. M. (2015).
Effect of degree of hydrolysis of polyvinyl alcohol on the corrosion
inhibition of steel: theoretical and experimental studies. Journal of
Adhesion Science and Technology 29 (4): 271 – 295.
20. Umoren, S. A., Obot, I. B., Gasem, Z. M., Odewunmi, N. A. (2015).
Experimental and theoretical studies of red apple fruit extract as green
corrosion inhibitor for mild steel in HCl solution, Journal of
Dispersion Science and Technology 36 (6): 789 – 802.
21. Odewunmi, N. A., Umoren, S. A., Gasem, Z. M. (2015). Watermelon

waste products as green corrosion inhibitors for mild steel 2 in HCl
solution. Journal of Environmental Chemical Engineering 3(1): 286 –
296.
22. Umoren, S. A., Gasem, Z. M. Obot, I. B., (2015). Date palm (Phoenix
dactylifera) leaf extract as eco-friendly corrosion inhibitor for mild
steel in 1 M hydrochloric acid solution, Anticorrosion Methods and
Materials 62(1): 19 – 28.
23. Obot, I. B., Umoren, S. A., Gasem, Z. M., Suleiman, R., Ali, B.
(2015). Theoretical prediction and electrochemical evaluation of
vinylimidazole and allylimidazole as corrosion inhibitors for mild
steel in 1M HCl, Journal of Industrial and Engineering Chemistry 21
(1): 1238 – 1339.
24. Solomon, M. M., Umoren, S. A. (2015). Performance evaluation of
poly (methacrylic acid) as corrosion inhibitor in the presence of iodide
ions for mild steel in H2SO4 solution, Journal of Adhesion Science
and Technology 29 (11): 1060 -1080.
25. Umoren, S. A., Solomon, M. M., Israel, A. U., Eduok, U. M., Jonah,
A. E. (2015). Comparative study of the corrosion inhibition efficacy
of polypropylene glycol and poly (methacrylic acid) for mild steel in
acid solution, Journal of Dispersion Science and Technology 36 (12):
1721 – 1735.
26. Solomon, M. M., Umoren, S. A. (2015). Enhanced corrosion
inhibition effect of polypropylene glycol in the presence of iodide
ions at mild steel/sulphuric acid interface, Journal of Environmental
Chemical Engineering 3 (2015) 1812–1826
27. Solomon, M. M., Umoren, S. A. (2015). Performance assessment of
poly (methacrylic acid)/silver nanoparticles composite as corrosion
inhibitor for aluminium in acidic environment, Journal of Adhesion
Science and Technology 29 (21): 2311 – 2333.
28. Obot, I. B., Madhankumar, A., Umoren, S. A., Gasem, Z. M. (2015).
Surface protection of mild steel using benzimidazole derivatives:
experimental and theoretical approach, Journal of Adhesion Science
and Technology 29 (19): 2130–2152
29. Umoren, S. A., Obot, I. B., Gasem, Z. M. (2015). Adsorption and
corrosion inhibition characteristics of strawberry fruit extract at
steel/acids interfaces: experimental and theoretical approaches. Ionics
21 (4): 1171 – 1186.
30. Odewunmi, N. A., Umoren, S. A., Gasem, Z. M., Ganiyu, S. A.,

Muhammad, Q. (2015). L-Citrulline: an active corrosion inhibitor
component of watermelon rind extract for mild steel in HCl medium,
Journal of Taiwan Institute of Chemical Engineers 51: 177 – 185.
31. Umoren, S. A., Obot, I. B., Madhankumar, A., Gasem, Z. M. (2015).
Performance evaluation of pectin as ecofriendly corrosion inhibitor
for X60 pipeline steel in acid medium: Experimental and theoretical
approaches, Carbohydrate Polymers 124: 280 – 291.
2014
32. Umoren, S. A., Pan, C., Li, Y., Wang, F. H. (2014). Elucidation of
mechanism of corrosion inhibition by polyacrylic acid and synergistic
action with iodide ions by in-situ AFM. Journal of Adhesion Science
and Technology 28 (1): 31 – 37.
33. Obot, I. B., Gasem, Z. M. Umoren, S. A. (2014). Molecular Level
understanding of the mechanism of Aloes leaves extract inhibition of
low carbon steel corrosion: A DFT approach. International Journal of
Electrochemical Science 9 (2): 510 – 522.
34. Obot, I. B., Gasem, Z. M., Umoren, S. A. (2014). Understanding the
mechanism of 2-mercaptobenzimidazole adsorption on Fe (110), Cu
(111) and Al (111) surfaces: DFT and Molecular dynamics
simulations approaches, International Journal of Electrochemical
Science 9(5): 2367 – 2378.
35. Umoren, S. A., Solomon, M. M., Eduok, U. M., Obot, I. B., Israel, A.
U., (2014). Inhibition of mild steel corrosion in H2SO4 solution by
coconut coir Dust extract obtained from different solvent systems and
synergistic effect of iodide ions: Ethanol and acetone extracts. Journal
of Environmental Chemical Engineering 2(2): 1048 – 1060.
36. Umoren, S. A., Obot, I. B., Gasem, Z. M. (2014). Green synthesis and
characterization of silver nanoparticles using red apple (Malus
domestica) fruit extract at room temperature. Journal of Materials and
Environmental Science 5(3): 906 – 914.
37. Umoren, S. A., Obot, I. B., Israel, A. U., Asuquo, P. O., Solomon, M.
M., Eduok, U. M., Udoh, A. P. (2014). Inhibition of mild steel
corrosion in acidic medium using coconut coir dust extracted from
water and methanol as solvents. Journal of Industrial and
Engineering Chemistry, 20 (5): 3612 – 3622.
38. Umoren, S. A., Obot, I. B (2014). Synergistic inhibition between 1-

octadecanethiol and iodide ions on X60 pipeline steel for corrosion
protection, Journal of Adhesion Science and Technology 28 (20):
2054 – 2064.
39. Umoren, S. A., Gasem, Z. M. (2014). Influence of molecular weight
on mild steel corrosion inhibition effect by polyvinyl alcohol in
hydrochloric acid solution. Journal of Dispersion Science and
Technology, 35 (8): 1181 – 1190.
40. Umoren, S. A., Solomon, M. M. (2014). Recent developments on the
use of polymers as corrosion inhibitors: A Review. Open Materials
Science Journal 8: 39 – 54.
41. Umoren, S. A., Eduok, U. M., Solomon, M. M. (2014). Effect of
polyvinylpyrrolidone ̶ polyethylene glycol blends on the corrosion
inhibition of aluminium in HCl solution, Pigment & Resin Technology
43 (5): 299 – 313.
Publication: Book Chapters
1. Umoren, S. A., Solomon, M. M. “Polymer Characterization: Polymer

Molecular Weight Determination” In: Polymer Science: Research
Advances, Practical Applications and Education Aspects (A. Méndez-
Vilas, A. Solano-Martin (Eds)), Formatex Research Centre, Badajoz,
Spain (To be published in summer 2016)
2. Obot, I. B., Eduok, U. M., Umoren, S. A. “Natural Polymer:
Corrosion Protection”; In “Encyclopedia of Polymeric Applications:
(Munmaya Mishra (Ed.)), (To be published by Taylor and Francis,
New York, USA)
3. Umoren, S. A., Solomon, M. M. “Polypropylene (PP)/Starch Based
Biocomposites and Bionanocomposites” In: Propylene Based
Composites and Bionanocomposites (P. M. Visakh, Matheus Poletto
(Eds), (To be published by Wiley and Sons, USA).
Chapter 3
USES OF ENVIRONMENTALLY FRIENDLY

CORROSION INHIBITORS IN AMINE-BASED
CO2 ABSORPTION PROCESSES
Amornvadee Veawab*, Sureshkumar Srinivasan

and Adisorn Aroonwilas
Energy Technology Laboratory, Faculty of Engineering
and Applied Science, University of Regina, Regina, SK, Canada
ABSTRACT
Corrosion is a severe operational problem in the carbon dioxide
(CO2) absorption process using aqueous solutions of amines, when
carbon steel is used for plant construction. Past experiences with these
plants have provided practitioners with a number of recommendations to
keep corrosion under acceptable levels. Among these, the application of
corrosion inhibitors is the most widespread because it is economical and
requires small or no process modifications to existing plants. Various
corrosion inhibitors have been developed, patented and commercialized
by many major chemical companies for uses in amine treating plants. The
patented organic inhibitors include thiourea and salicyclic acid, while
inorganic inhibitors are vanadium, antimony, copper, cobalt, tin and
sulfur compounds. The inorganic inhibitors are in practice more favored
*
Corresponding author: Amornvadee Veawab. Address: 3737 Wascana Parkway, Regina,
Saskatchewan, Canada S4S 0A2. Tel: 1-306-585-5665, fax: 1-306-585-4855, email:
veawab@uregina.ca.
60 A. Veawab, S. Srinivasan and A. Aroonwilas
than the organic compounds because of their superior inhibition

performance. Vanadium compounds, particularly sodium metavanadate
(NaVO3), are the most extensively and successfully used in amine
treating plants. Despite the successful use of the inorganic corrosion
inhibitors, concerns about impacts of their toxicity on human health and
the environment have increased in past decades.
To respond to the environmental concerns on the use and disposal of
harmful chemicals, a number of initiatives were taken around the world.
In Canada, usage of toxic substances is regulated by the Canadian
Environmental Protection Act (CEPA). Inorganic arsenic and cadmium
inhibitors are classified as carcinogenic and considered toxic. As a result,
their usage was banned. In the US, the Environmental Protection Agency
(EPA) regulates the usage of chemicals through Clean Water Act (CWA)
and Clean Air Act (CAA). In Europe, an environmental regulatory
mechanism OSPAR was established by fifteen Northeast Atlantic nations
to protect the marine environment which was later broadened to cover
land based sources and offshore industry. Based on the OSPAR
guidelines, most corrosion inhibitors that are used, tested and patented for
amine-based CO2 absorption processes are non-environmental friendly.
Hence, to respond to the environmental concerns and reduce the cost of
waste disposal as well as prepare for more stringent regulations for
chemical uses, application of effective and environmentally friendly
corrosion inhibitors is necessary.
The objective of this book chapter is to provide a review of corrosion
inhibitors and a progress towards use of environmentally friendly
corrosion inhibitors in the amine-based CO2 absorption process for acid
gas treatment and carbon capture. The chapter is divided into four
sections. Section 1 provides background information of the amine-based
CO2 absorption process, including process description and type of amine
used. Section 2 describes typical corrosion problems taking place in the
process and provides historical corrosion cases in actual plant operations.
Section 3 provides a compiled list of corrosion inhibitors that have been
patented, tested and applied in this plant operation, discusses the use of
environmentally friendly corrosion inhibitors and provides an update on
research related to environmentally friendly corrosion inhibitors in the
amine-based CO2 absorption process.
Keywords: corrosion, corrosion inhibitor, carbon capture, CO2 absorption, gas

treating
Uses of Environmentally Friendly Corrosion Inhibitors … 61
CARBON CAPTURE FROM INDUSTRIAL WASTE GAS

The Intergovernmental Panel for Climatic Change (IPCC) has reported
that between 1995 and 2006, eleven out of twelve years were the warmest in
the instrumental record of global surface temperature (IPCC1, 2007). Melting
of glaciers and continual increases in sea level are the direct effects of global
warming. This is mainly attributed to the increase in the atmospheric
concentrations of greenhouse gases (GHGs) in recent times, which is evident
from the fact that GHG emissions now are 70% higher than their values in the
1970s (IPCC1, 2007). Particularly, carbon dioxide (CO2) is the most
significant greenhouse gas as its emissions have increased by 80% in the same
time frame, and CO2 represented 77% of the total anthropogenic GHG
emissions in 2004 (IPCC1, 2007). Coal-fired power plants, natural gas
processing plants, and manufacturing industries such as cement, ammonia, and
steel plants are some of the major sources of CO2 emissions (IPCC2, 2005).
Among the above, coal-fired power plants assume specific importance as they
typically contribute to approximately 30% of the total CO2 emissions (Aaron
and Tsouris, 2005).
Carbon capture and storage (CCS) is a technology used to remove CO2
from industrial flue gas especially from power plants where it can effect a
gross reduction of CO2 emissions by approximately 85-95% (IPCC2, 2005).
The CO2 removal can be accomplished by a number of processes such as
membrane separation, adsorption onto solids, and absorption into liquids.
However, the latter is most commonly used for gas treating applications
(Astarita et al., 1983). The industrial separation of CO2 for natural gas
processing and ammonia manufacture by absorption into liquid is a mature
technology and has been successfully used for many decades. However,
adaptation of this technology for flue gas treatment began only in the 1980s
(Kittel et al., 2009). For example, IMC Global Inc (previously North American
chemicals), in Trona, US, features a CO2 capture unit that is used to sequester
CO2 from flue gas from a coal-fired power generation plant that started
operation in 1978 and is still functioning. Similarly, Indo-Gulf Corporation, a
fertilizer industry in India, features CO2 capture from flue gas of the ammonia
reformer unit that has been operational since 1988 capturing 150 tonnes
CO2/day. Bellingham Cogeneration facility, Massachusetts, US, produces food
grade CO2 by treating 300 tonnes/day of CO2 from flue gas emitted from an
electricity generation plant since 1991. Sumitomo Chemicals, Japan, treats flue
gas generated from onsite boilers and coal/oil boilers since 1994 with a
capacity of 150 tonnes CO2/day. As illustrated by the above examples of
successful and continuous adaptation of this technology for the past three
decades, it is clearly discernible that the flue gas treatment using absorption
into liquid is viewed as a promising technology.
In a typical CO2 absorption process as illustrated in Figure 1, a flue gas
stream containing CO2 enters the absorber from the bottom and interacts
counter-currently with down-flowing chemical solvent entering from the top.
CO2 reacts with the solvent and is absorbed, rendering the gas stream with
permissible levels of CO2, and the treated gas leaves the absorber top. The
CO2 loaded rich solvent leaving the bottom of the absorber passes through the
rich-lean heat exchanger where it is preheated and then enters the regenerator
from the top where, on application of heat in the form of steam, the solvent is
stripped of CO2, and the lean solvent is recycled back into the absorber after
being cooled down to the required operating temperature. A portion of lean
solvent is withdrawn at the reclaimer where it is heated and the vapour mixture
containing amine and CO2 are reintroduced into the regenerator. From the
bottom of the reclaimer, a sludge containing insoluble salts and other
chemicals are obtained and removed for waste handling. The vapor mixture
containing CO2 and water vapor leaves the regenerator and enters the overhead
condenser where most of the water vapor is condensed and recycled back to
the regenerator, and the concentrated CO2 leaves the overhead condenser
(Aroonwilas, 1996).
CO2
OVERHEAD CONDENSER
TREATED GAS
COOLER
REFLUX PUMP
ABSORBER REGENERATOR
RICH-LEAN HEAT
EXCHANGER STEAM
REBOILER
FLUE GAS
CONDENSATE
RECLAIMER
SLUDGE DISPOSAL
Figure 1. Process flow diagram for the amine-based CO2 absorption process.
A wide range of absorption solvents have been used for CO2 absorption
processes, among which, aqueous alkanolomine-based solvents are the most
widely used absorbents. Alkanolamines can be classified into three categories,
namely, primary, secondary, and tertiary amines. Monoethanolamine (MEA)
and diglycolamine (DGA) belong to the primary type whereas diethanolamine
(DEA) and diisopropanolamine (DIPA) are the secondary type.
Methyldiethanolamine (MDEA) and triethanolamine (TEA) are examples of
tertiary amines. In general, primary amines have high reaction rates with CO2,
followed by secondary amines and tertiary amines, respectively (Veawab,
2000). Since, for flue gas applications, CO2 partial pressures are low and the
gas flow rate is extremely high compared to natural gas processing, the
absorption rate has to be correspondingly faster. With this consideration, MEA
shows promise and could well be the first available solvent absorbent for this
application (Kittel et al., 2009; Kittel et al., 2010).
CORROSION AND ITS IMPACTS

A typical CO2 absorption process has a number of factors that can cause
operational difficulties, but corrosion is the chief influencing factor from an
economic perspective (Kohl and Nielson, 1997). Corrosion can greatly
influence both economics and safety associated with the CO2 absorption
process. The economic losses are caused by unplanned downtime, production
losses, and reduced equipment life or safety issues such as injury or death of
plant personnel (Dupart et al., 1993). A summary of plant experiences on
corrosion in the CO2 absorption process is given in Table 1.
From Table 1, it can be observed that the absorber bottom, regenerator,
heat exchanger, and associated piping and valves are the areas susceptible to
severe corrosion. Both general (uniform) and localized corrosion were
observed in the CO2 absorption plants. Localized corrosion such as erosion
corrosion due to the presence of foreign particles in the circulating solution
and pitting corrosion were reported to occur in addition to galvanic corrosion,
stress corrosion cracking (SCC), and intergranular corrosion. Acid gas flashing
on walls, high lean loading, high solution velocities, the presence of particulate
contaminants, coupling of dissimilar alloys, and improper metal stress
treatment are some of the reported causes of corrosion. Corrosion mitigation
measures include use of corrosion inhibitors, design measures to reduce acid
gas flashing, and replacement of carbon steel with corrosion resistant alloys in
the heat exchanger and regenerator areas (trays and valves) in some cases.
USE OF CORROSION INHIBITORS

There are many alternative approaches to mitigating corrosion in CO2
absorption plants, such as proper equipment and process design, use of
corrosion resistant materials, side stream removal of particulate matters from
amine solution, and use of corrosion inhibitors. Among these, the use of
corrosion inhibitors is considered the most economical, mainly because it
requires no major process modification (Kohl and Nielson, 1997; Dupart et al.,
1993; Veawab, 2000). From the plant experiences detailed in Table 1, it can be
seen that despite the usage of corrosion inhibitors, corrosion can still occur due
to certain design problems such as coupling of dissimilar metals and acid gas
flashing in selected areas (Dupart et al., 1993). Hence, corrosion inhibitors in
combination with one or all of the above approaches have to be deployed for
effective corrosion reduction. This chapter focuses mainly on use of corrosion
inhibitors.
A corrosion inhibitor is defined as a chemical substance that, when added
in small concentrations to the fluid phase of a corroding environment, are
capable of retarding corrosion by interacting either with the metal surface or
the environment (Sastri, 2001). A wide array of corrosion inhibitors were
tested and patented for gas treating applications over the past fifty years (Table
2), but the most effective ones are heavy metal based chemicals such as
arsenic and vanadium (Dupart et al., 1993). For a period of around two
decades, beginning in 1957, several heavy metal inhibitors such as lead-,
antimony-, bismuth-, arsenic-, vanadium-, and tin-based compounds were
tested and patented.
Disposal of toxic chemicals has resulted in significant damage to human
health and environment and, based on those experiences, environmental
awareness has been tremendous growth in the last few decades. As a result, a
number of initiatives were taken across the world. For instance, in the United
States, for a period of over 100 years, since the late 1800s, only 20
environmental laws were passed. However, in the few decades that followed,
over 120 environmental regulatory laws were set in place. Consequently, the
cost of compliance with those environmental regulations through waste
treatment, control, and disposal were high and has been estimated to be in the
range of 100-150 billion USD per year for the affected industries (Anastas and
Williamson, 1998; Doble and Kruthiventi, 2007). In Canada, usage of toxic
substances is regulated by the Canadian Environmental Protection Act
(CEPA). For example, inorganic arsenic and cadmium compounds are
classified as carcinogenic and considered toxic and were listed as CEPA 1999
Schedule-I compounds, and as a result, their usage was banned. In the US, the
Environmental Protection Agency (EPA) regulates the usage of chemicals
through the Clean Water Act (CWA) and Clean Air Act (CAA). In Europe, an
environmental regulatory mechanism OSPAR was established by fifteen
Northeast Atlantic nations by unifying their policies in the 1972 Oslo
convention against waste dumping to protect the marine environment. This
was later broadened to cover land-based pollutant sources and offshore
industries in the Paris Convention of 1974 (OSPAR, 2011). As per the
guidelines set by OSPAR for environmentally-friendly chemicals, for a
chemical to be listed in PLONOR (poses little or no risk), two out of three of
the following requirements has to be satisfied with its biodegradability being
superior to 20% in 28 days: a) Biodegradability (>60% in 28 days), b) Toxicity
(Lethal concentration (LC50) or Effective concentration (EC50) > 1 mg/L for
inorganic species, and LC50 or EC50 > 10 mg/L for organic species, where
LC50 or EC50 is the dose large enough to kill 50% of sample animals under
test); and c) Bioaccumulation (logpow < 3 where pow is the partition in octanol/
water).
Based on the above OSPAR guidelines, it can be observed from Table 3
that most corrosion inhibitors that are used, tested, and patented are non-
environmentally friendly. For instance, Antimony (III) oxide, arsenic oxide,
cobalt acetate, thiourea, aniline, pyridine, and vanadium compounds are toxic
and carcinogenic. Hence, there is a need to develop an environmentally-
friendly corrosion inhibitor that can replace the present highly toxic inhibitors
and also provide comparable inhibition efficiencies.
Many works have attempted to search for effective and environmentally
friendly corrosion inhibitors for absorption-based gas treating plants. New
corrosion inhibitors were relatively less toxic than previous ones. Davidson
and Friedli (1978) registered a patent for the claim of copper and sulfur-based
chemical compounds as corrosion inhibitors that were less toxic than heavy
metal corrosion inhibitors. Copper carbonate in combination or alone has been
suggested as a potential corrosion inhibitor since 1979 (Asperger et al., 1979;
Pearsce, 1984; Trevino, 1987; Soosaiprakasam and Veawab, 2009). Many
organic compounds such as pyridinium-based, piperazine-based, thiophenol-
and thiol-based, and amine and carboxylic acid-based compounds were also
reported with comparable inhibition efficiencies of around 90%. Inorganic
inhibitors were generally used in the concentration range of 20-2000 ppm
whereas organic inhibitors were in the range of 100-20000 ppm.
Table 1. Summary of plant experience on corrosion in absorption-based gas treating plants
Reference Plant type Solvent Acid gas Corrosion problem Cause of corrosion Corrosion
mitigation
Dingman et al. Sour gas treating MEA CO2  Rich-lean heat exchanger, solution  Flashing of acid gas from hot surface N/A
(1966) plant H2S letdown valve, piping downstream  High solution velocity
letdown valve, upper portion of  Change in direction of fluid flow
regenerator  Contamination with solids such as iron
 Erosion corrosion oxide, iron sulfide, mill scale and sand
Smith and Twenty-four Sour DEA CO2  Erosion corrosion at:  Contamination of foreign particles in N/A
Younger (1972) gas treating plants in H2s Rich lean heat exchanger circulating solution
western Canada Regenerator  High solution velocity (5.5 ft/s)
Reboiler-vapor line and letdown  Insufficient liquid level over tight tube
Rich solution piping spacing in reboiler and heat exchanger
 Stress corrosion cracking at:  Chloride ion evolved from gasket
Stainless steel heat exchanger material used between plates
Heisler and Natural gas treating MEA CO2  Tray type regenerator including wall  Cavity in vapor flash N/A
Weiss (1975) plant, Aderklaa, H2S internal, downcomer, circumferential
Austria joint, weld seam and joint, and tray
 Uniform, pitting, erosion
Schmeal et al. Sour gas treating Sulfinol CO2  Absorber below 5th tray  Acid gas flashing N/A
(1978) plant (DIPA + H2S  Pitting
sulfolane)
Asperger et al. Refinery MEA CO2  Mild steel/Reboiler outlet and cross N/A Corrosion
(1979) (17-19%) H2S exchange inhibitor
COS  General corrosion (1.89 and 2.43 mmpy) (Cu based)
Hall and Barron Ram river gas plant DEA N/A  Reboiler bundle N/A N/A
(1981)  Rich lean heat exchanger (upper most
tubes)
 Hot side of cooler
Gerus (1981) Natural gas treating N/A CO2  Pitting and erosion corrosion N/A N/A
plant H2S
Reference Plant type Solvent Acid Corrosion problem Cause of corrosion Corrosion mitigation
gas
Krawczyk Gas MEA (18%) CO2  Carbon steel  N/A  Corrosion inhibitor (Ammonium
et al. (1984) conditioning  Hot rich amine circuit thiocyanate)
 General corrosion (18.8 mmpy)
Krawczyk Natural gas MEA (30%) CO2  Carbon steel  N/A  Corrosion inhibitor (Ammonium
et al. (1984) purification  Hot lean circuit thiocyanate)
 General corrosion (1.52 mmpy)
Krawczyk Hydrogen MEA CO2  Carbon steel and Stainless steel  N/A  Corrosion inhibitor (Arsenic
et al. (1984) purification (16-27%)  General corrosion (1.78 and 0.38 based)
mmpy)
Dupart et Gas treatment Formulated CO2  Carbon steel  Pitting - Wet CO2 flashing  Piping material in flashing zone
al. (1993) (Fuel gas MDEA H2S  Liquid level control valve in absorber  Erosion - Cavitation by was replaced with 304 SS. Piping
production) bottom to flash drum line bubble collapse velocity was limited to 5 ft/s.
 Pitting and erosion corrosion  High velocity impingement
points
Dupart et Ammonia plant Formulated CO2  Absorber wall (Bottom)  Turbulent interaction  Farthest inlet distributor holes
al. (1993) (Synthesis gas MDEA  Erosion between the inlet gas and were closed
treatment) liquid surface which  Cleaned eroded areas and filled
prevents the formation of with metal impregnated epoxy
normal passivation layer
Dupart et Ammonia plant 25% MEA (with CO2  Carbon steel  Penetration of passive iron  Direct contact between the inlet
al. (1993) (Synthesis gas heavy metal  Absorber bottom (vapor area between carbonate film in vapor gas and susceptible areas was
treatment) corrosion liquid level and first tray), bottom region due to reaction with avoided by removing bottom five
inhibitor) three tray downcomers, Vapor region oxygen. trays, turning the inlet gas
between bottom five trays  Galvanic action between distributor upside down and
 Uniform/ galvanic corrosion resulting active area due to maintaining the liquid level over
 Corroded to max. allowance in previous action and passive it.
absorber bottom regions.
Dupart et Natural gas Formulated CO2  Regenerator at carbon steel tray and  CO2 flashing in heat  Replaced stripper internals with
al. (1993) treatment MDEA 304 stainless steel (SS) valve opening, exchanger due to excessive 316 SS trays and valves
heat exchanger tube at shell side, pressure drop  Replaced carbon steel with SS
booster pump impeller and case, 304  High lean CO2 loading due 316 in heat exchanger bundle
SS valve coupled with carbon steel to plugging by carbon and
deck insufficient stripping
Table 1. (Continued)
Reference Plant type Solvent Acid Corrosion problem Cause of corrosion Corrosion mitigation
gas
Dupart et al. Natural gas Formulated CO2  Pitting, erosion, galvanic  Carbon solids circulation  Installed a full flow
(1993) treatment MDEA mechanical filter at the
downstream of filters
Dupart et al. Natural gas Formulated CO2  General corrosion  Coupling of SS valves  Use sufficient reflux ratio
(1993) treatment MDEA  (0.89 mmpy) with carbon steel decks for the stripper
Dupart et al. Ammonia plant Formulated CO2  304 SS/intergranular  Sensitization of stainless  Correct weld procedure to
(1993) MDEA  Heat affected shell steel from fabrication maintain corrosion
(longitudinal/circumferential techniques or metallurgy resistance of 304 SS and
welds) used in vessel affected welds repaired
Litschewski Treating H2S from MEA (with H2S  Regenerator areas between 304 SS  Excessive vibration from  N/A
(1996) FCC unit corrosion trays and carbon steel wall, reboiler disengaging gases and
inhibitor) bundle non-flooded top tubes
 Non-stress relieved pipe weld
 Galvanic and SCC
Dehart et al. CO2 recovery MEA (30%) CO2  Striper, bottom of absorber  Carbonic acid attack  N/A
(1999) plant  Uniform, galvanic corrosion accelerated by O2,
reduction of copper ion to
metal
Rodriguez Natural gas DEA-MDEA CO2  Carbon steel  N/A  Corrosion inhibitor
and Edwards processing, UPR blend (40%) H2S  Rich amine line (from Heat (Sulfur based-Non toxic)
(1999) gas plant complex, (Trace) exchanger)
TX  General corrosion (1.27-1.52
mmpy)
Rampin Refinery MEA CO2  Regenerator, amine exchanger  Presence of mixed phases  N/A
(2000)  Erosion and general corrosion
Sutopo and Liquified natural MDEA CO2  Absorber, regenerator, Erosion  N/A  N/A
Safruddin. gas unit
(2000)
Table 2. Summary of corrosion inhibitors in gas treating plants
Reference Plant type Solvent Material Inhibitor type Inhibitor Inhibitor Inhibition
dosage efficiency
Fischer (1957) Union Natural gas 10-30% MEA Mild steel Heavy metal, Mixture of lead naphthenate with linseed 0.05-0.5% N/A
Oil Company treatment Organometallic oil and two commercially available
products Armeen and Ninol
Fischer (1959) Union Natural gas 25% MEA Mild steel Heavy metal Mixture of tartaric acid, Antimony 0.05-0.5% N/A
oil Company treatment Organometallic trichloride, sodium hydroxine and alkyl
pyridines or quinolines
Negra et al. (1963) Synthesis gas Hot potassium carbonate Mild steel Heavy metal, Trivalent oxides of Arsenic, Antimony and 0.1-0.5% Corrosion rate of -
Chemical Construction production Inorganic Bismuth 11 mpy
Corporation
Mago and West, (1974)Ammonia plant - 15% MEA, 30% MEA and Mild steel Heavy metal, Vanadium - Antimony compounds (e.g., 0.05-0.1% 90-95%
Union Carbide Hydrogen 15% HEED [N-(2- Inorganic Sodium meta vanadate - Antimony
Corporation purification hydroxyethyl) ethylene tartrate)
diamine]
Mago and West (1975) Ammonia plant - 15% MEA, 30% MEA and Mild steel Organic Nitroterephthalic acid mixed with sodium 0.01 to >90% and 87% on
Union Carbide Hydrogen 15% HEED 4-nitro benzoate 2% heat transfer plate
Corporation purification
Mago (1976) Lab scale acid Hot potassium carbonate Mild steel Heavy metal, a) Vanadium compounds 0.01-2% a) -400%
Union Carbide gas treatment (with 5% bicarbonate) (Cold Inorganic b) Antimony compounds (aggravated
Corporation rolled) c) Combination of above corrosion)
b) -70%
(aggravated
corrosion)
c) 84-90%
Mago and West (1976) Ammonia plant - 30% MEA, 30% 1:1 Mild steel Heavy metal, Stannous tartarate 0.01-2% 80-95%
Union Carbide Hydrogen MEA:HEED Inorganic
Corporation purification
Davidson et al. (1978) Natural or 30% MEA Mild steel Inorganic Reaction product of copper and sulfur 0.002-2% N/A
Dow Chemical synthesis gas yielding compounds with
Company treatment (pilot monoethanolamine
plant)
Asperger and Clouse Natural or 30% MEA Mild steel Organic Tetradecyl polyalkylpyridinium bromide 100 ppm 91%
(1978) Dow chemical synthesis gas with polyethylene polyamine
company treatment
Table 2. (Continued)
Reference Plant type Solvent Material Inhibitor type Inhibitor Inhibitor dosage Inhibition efficiency
Clouse and Lab scale 30% MEA Mild steel Organic + Tetradecyl polyalkylpyridinium bromide 50 ppm (with 10-50 96%
Asperger (1978) Acid gas Inorganic with thio urea and cobalt acetate ppm cobalt acetate)
Dow Chemical treatment
Company
Clouse and Lab scale 30% MEA Mild steel Organic Tetradecyl polyalkylpyridinium with a) 50 ppm a) 77%
Asperger (1978) Acid gas Thio urea b) 91%
Dow Chemical treatment b) Thiocyanate or c) 92%
Company c) Thionicotinamide
Asperger et al. Refinery off- 30% DEA Mild steel Inorganic Copper carbonate mixed with sulfur 500 ppm CuCO3 with 55%
(1979) gas stripping 100 ppm sulfur
Nieh (1983) Texaco Lab scale 50% MEA Mild steel Heavy metal Sodium metavanadate with cobalt nitrate 100 ppm Corrosion rate of <1 mpy
Inc Acid gas solution
treatment
Nieh (1983) Texaco Lab scale 50% MEA Mild steel Heavy metal Mixture of Ammonium metavanadate with 100 ppm (with 0.4% a) <1 mpy (100 ppm)
Inc acid gas a) N-amino ethylethanolamine of amine compound) b) <1 mpy (200 ppm)
treatment b) ethylene diamine c) <1 mpy (300 ppm)
c) propylene diamine d) 3 mpy
d) N-hydroxy ethyl piperazine (300 ppm)
e) N-aminoethyl piperazine e) <1 mpy (300 ppm)
f) methylamino bispropylamine f) 11 mpy (300 ppm)
Krawczyk et al. General acid 25-30% Mild steel, Teflon Inorganic Mixture of Thio nitrogen compound with 200 ppm 90% (Ni salt)
(1984) gas treatment MEA coated steel trace quantities of Cobalt or Nickel salts 89% (Co salt)
Dow Chemical
Company
Pearsce (1984) Dow General acid 80% MEA Mild steel Inorganic Combination of Copper carbonate with 50-2000 ppm 99%
Chemical Company gas treatment dihydroxyethyl glycine, alkali metal
thiocyanate, ammonium permanganate and
Nickel or bismuth oxide
Dupart et al. (1984) Natural and 30% MEA Mild steel, Inorganic Combination of Ammonium thiocyanate, >50 ppm of 93.6%
Dow Chemical synthesis gas Stainless steel 304, Bismuth citrate and Nickel sulfate thiocyanate (with
Company treatment 316 and Monel Bismuth citrate 1-100
ppm)
Reference Plant type Solvent Material Inhibitor Inhibitor Inhibitor dosage Inhibition efficiency
type
Jones and Alkire (1985) Natural and synthesis 20-60% DEA Mild steel Organic- Dodecylbenzyl chloride with 2000 ppm (with 35 93.1% (max)
Standard Oil Company gas treatment Inorganic alkylpyridine still bottoms and Nickel ppm Ni compound)
acetate
Henson et al. (1986) Refinery gas 30% MEA Carbon steel Organic- Mixture of Aminoethyl piperazine- 5000 ppm As close as 100%
Dow Chemical conditioning Inorganic Formaldehyde-thiourea polymer and
Company Nickel sulfate
Trevino (1987) Hylsa Gas processing 25-30% MEA Carbon steel Inorganic Mixture of cupric oxide and Zinc sulfate 1-500 ppm Copper 80% (at regenerator top)
with bronze pieces (to maintain Copper 100-500 ppm Zinc and 90% (at absorber
and Zinc concentration) bottom)
Sekine et al. (1992) General acid gas 23% hot Mild steel Organic Combination of following a) 10 ppm 92-95% (max) for
University of Tokyo treatment potassium and Stainless a) 2-Aminothiophenol (ATP) b) 100 ppm Stainless steel
carbonate steel b) 1-Hydroxyethylidene bisphosphonic 3%
acid (HEDP) and
c) Diethanolamine (DEA)
Minevski and General acid gas 18% MEA Mild steel Organic 1,6 Hexanedithiol with cyclohexanethiol 25-100 ppm (with 90% (max) in CO2
Labmbousy (1998) Betz treatment (with heat or decanethiol or dodecane thiol less than 1% by environment and 75% in
Dearborn Inc stable salts weight of thiol) H2S environment
Minevski (2000) General acid gas 18% MEA Mild steel Organic Combination of Thiomorpholine with 500-2000 ppm 92% (max)
BetzDearborn Inc treatment (with heat Phthalic acid
stable salts)
Veawab et al. (2001) Industrial gas 3M MEA Carbon steel Organic a) Amine-based a) 1000 ppm a) 75%
University of Regina treatment b) Sulfoxide based b) 1000 ppm b) over 75%
c) Carboxylic acid based c) 5000 ppm c) 98%
Veldman and Trahan Natural gas plant and 50% MDEA Mild steel Heavy Sodium molybdate in the presence of 3.5% >99%
(2001) Coastal Refinery Hydrogen solution and Stainless metal hydroquinone, ethylketoxime and
Chemical Co treatment steel diethylhydroxyl amine
Chang and Minevski General acid gas 25% MEA and Carbon steel Organic Polythia ether compounds 10-20 ppm 96% for DEA and 99%
(2008) treatment 30% DEA for MEA
GE Betz Inc
Soosaiprakasam and General acid gas MEA (5M, 7M Carbon steel Inorganic Copper carbonate 250 ppm >80%
Veawab (2009) treatment and 9M)
University of Regina
Table 3. Ecological information of patented corrosion inhibitors
Inhibitor LD50 LD50 (fish) EC50 Biodegradability Bioaccumulation Ecological effect Regulatory and
(oral rat) mg/L (water Toxicological information
mg/kg flea) mg/L
Aniline 951 65.6 (96 h) 5 (48 h) Biotic/Aerobic 75% BCF: 13.6 for Oryzias - Highly toxic. Carcinogenic
(fathead readily biodegradable latipes
minnow)
Antimony (III) 525 9 (96 h) 10.1 (48 - - Toxic to aquatic organisms and -
chloride (fathead h) may cause long term adverse
minnow) effect s in aquatic environment
Antimony (III) 34600 >1000 1000 (48 - - - Very toxic material causing
oxide (96 h) (zebra h) other toxic effects.
fish) Carcinogenic
Ammonium 750 - - - - Very toxic to aquatic life with Toxic material causing
thiocyanate long lasting effects immediate and serious effects
Arsenic (III) 14.6 >1 (96 h) 8.23 (24 - Bioconcentration factor - Very toxic material causing
oxide (rainbow h) (BCF): 236 for Lepomis immediate and serious toxic
trout) cyanellus effects. Carcinogenic
Bismuth (III) 5000 - - - - - Toxic material causing other
oxide toxic effects
Cobalt (II) 503 - - - - - Very toxic material causing
acetate other toxic effects.
Carcinogenic
Cobalt (II) 691 - - - - Very toxic to aquatic life Toxic material causing
nitrate (hexa immediate and serious
hydrate) effects. Carcinogenic
Copper (II) 1350 - - - - - Toxic material causing other
carbonate toxic effects
Inhibitor LD50 (oral LD50 (fish) EC50 Biodegradability Bioaccumulation Ecological effect Regulatory and
rat) mg/kg mg/L (water Toxicological information
flea) mg/L
Copper (II) oxide 470 25.4 (96 h) 0.011- - - Very toxic to aquatic Toxic material causing
(rainbow trout) 0.039 (48 life with long lasting immediate and serious
h) effects effects.
Nickel (II) acetate 350 - - - - - Toxic material causing
(tetra hydrate) immediate and serious
effects. Carcinogenic
Pyridine 891 93.8 (96 h) - - Harmful to aquatic life Toxic material causing
(Fath ad other toxic effects.
minnow) Carcinogenic
Pyridine-2- 750 - - - - Not WHMIS Not WHMIS controlled
carboxylic acid controlled
Sodium 98 - - - - - Toxic material causing
metavanadate immediate and serious
effects
Thio urea 1750 10 (96 h) 5.6-18 (48 Biotic/Aerobic <1% not - - Toxic material causing
(zebra fish) h) readily biodegradable other toxic effects.
Carcinogenic
Vanadium 10 1) 1.8 (96 h) 0.94 (48 h) - - Dangerous for Highly toxic.
pentoxide (fathead environment Carcinogenic
minnow)
2) 5.2 (96 h)
(rainbow trout)
In general, it was observed that organic inhibitors are much more

environmentally friendly than inorganic inhibitors (Veawab et al., 2001).
Asperger and Clouse (1978) patented two organic corrosion inhibitors based
on polyalkyl pyridinium. Minevsky and Lambousy (1998) reported a corrosion
inhibitor based on organic thiol and dithiols. Minevsky (2000) also reported a
thiomorpholine-based corrosion inhibitor. Similarly, Veawab et al. (2001)
reported eight organic inhibitors based on carboxylic acid, sulfoxide, and
amines that are less toxic than the conventional vanadium-based inhibitors and
comparably efficient. All these suggest that searching for a potential corrosion
inhibitor that is environmentally friendly as well as efficient compared to
conventional corrosion inhibitors has been a continuous process, but no
compound yet has emerged as a satisfactory candidate for replacement of
conventional corrosion inhibitors.
CONCLUSION
Environmental impact is one of the considerations for selecting, designing
and operating chemical proceses. Discharges of vapour, liquid and solid
wastes are of great concerns for amine-based CO2 absorption processes
particularly that are used for carbon capture. Most effective corrosion
inhibitors currently used are inorganic heavy metals that pose adverse impacts
on health and the environment. Their usage will soon be restricted due to more
stringent environmental regulations. Environmentally friendly corrosion
inhibitors will, in the near future, be much needed to replace current inhibitors.
Due to the shift towards use of environmentally-friendly inhibitors, it is
inevitable to search and/or develop the corrosion inhibitors that are as effective
as the currently used inhibitors, compatible with chemical constituents existing
in process solutions, and at least less toxic and have faster biodegradation rate
and lower bioaccumulation rate compared to the absorption solvents used in
the process.
ACKNOWLEDGMENTS
Financial support from the Natural Sciences and Engineering Research
Council of Canada (NSERC) is gratefully acknowledged.
Towards Use of Environmentally Friendly Corrosion Inhibitors … 75
REFERENCES
Aaron, D. and Tsouris, C. (2005). Separation of CO2 from flue gas: a review.
Separation Science and Technology, 40, 321-348.
Anastas, P. T. and Williamson. T. C. (1998). Green chemistry: Frontiers in
benign chemical syntheses and processes. New York: Oxford University
Press.
Aroonwilas, A. (1996). High efficiency structured packing for CO2 absorption
using 2-Amino-2-methyl-2-propanol (AMP). M.A.Sc. Thesis, University
of Regina, Regina, Saskatchewan, Canada.
Asperger, R. G. and Clouse, R. C. (1978). Quarternary salt-polyamine
inhibitor for sour gas conditioning solutions. US Patent 4100099.
Asperger, R. G., Krawczyk, L. S. and Oakes, B. D. (1979). Method and
composition for inhibiting the corrosion of ferrous metals. US Patent
4143119.
Astarita, G., Savage. D. W. and Bisio. A. (1983). Gas treating with chemical
solvents. New York: John Wiley.
Chang, Z. and Minevski, L. (2008). Polythiaether compounds and their use as
corrosion inhibitors. US Patent 7335794 B2.
Clouse, R. C. and Asperger, R. G. (1978). Cobalt-containing inhibitor for sour
gas conditioning solutions. US Patent 4100100.
Clouse, R. C. and Asperger, R. G. (1978). Inhibitors for gas conditioning
solutions. US Patent 4102804.
Davidson, J. R. and Friedli, H. R. (1978). Method and composition for
inhibiting the corrosion of metals. US Patent 4071470.
DeHart, T. R., Hansen, D. A., Mariz, C. L. and McCullough, J. G. (1999).
Solving corrosion problems at the Nea Bellingham Massachusetts carbon
dioxide recovery plant. Corrosion 99, NACE, paper no. 264.
Dingman, J. C., Allen, D. L. and Moore, T. F. (1966). Minimize corrosion in
MEA units. Hydrocarbon Processing, 285-290.
Doble, M. and Kruthiventi. A. K. (2007). Green Chemistry and Engineering.
MA: Academic Press.
Dupart, M. S., Bacon, T. R. and Edwards, D. J. (1993). Understanding
corrosion in alkanolamine gas treating plants, Part 1 and 2. Hydrocarbon
Processing, 93, 75-80.
Dupart, M. S., Oakes, B. D. and Cringle, D. C. (1984) Method and
composition for reducing corrosion in the removal of acidic gases from
gaseous mixtures. US Patent 4446119.
Fischer, P. W. (1957). Corrosion prevention in gas recovery systems. US

Patent 2776870.
Fischer, P. W. (1959). Method of gas purification utilizing an amin solution
and an anti-corrosion agent. US Patent 2869978.
Gerus, B. R. D. (1981). Detection and mitigation of weight loss corrosion in
sour gas gathering systems. In: H2S corrosion in oil and gas production, A
Compilation of classic papers (pp. 888-903). Texas: NACE.
Hall, W. D. and Barron, J. G., (1981). Solving gas treating problems -A
different approach. Proceedings of the 31st Gas Conditioning Conference.
(pp. C1-C13). University of Oklahoma.
Heisler, L. and Weiss, I. H. (1975). Operating experience at Aderklaa with
alkanolamine gas treating plants for sour natural gas sweetening,
Proceedings of the 25th Gas Conditioning Conference. (p. H1-H22).
University of Oklahoma.
Hensen, E. R., Tipton, T. M. and Courtwright, J. G. (1986). Corrosoin
inhibitors for alkanolamines. US Patent 4595723.
IPCC1 (2007), IPCC Fourth Assessment Report (AR4), Climate Change 2007:
Synthesis Report, retrieved from www.ipcc.ch on February 2016.
IPCC2 (2005), IPCC special report on CO2 capture and storage, retrieved from
www.ipcc-wg3.de on February 2016.
Jones, L. W. and Alkire, J. D. (1985). Corrosion inhibitors for amine gas
sweetening systems. US Patent 4541946.
Kittel, J., Fleury, E., Vuillemin, B., Gonzalez, S., Ropital, F. and Oltra, R.
(2010). Corrosion in alkanolamine used for acid gas removal: From
natural gas processing to CO2 capture. Materials and Corrosion, 63(3),
223-230.
Kittel, J., Idem, R., Gelowitz, D., Tontiwachwuthikul, P., Parrain, G. and
Bonneau, A. (2009). Corrosion in MEA units for CO2 capture: pilot plant
studies. Energy Procedia, 1, 791-797.
Krawczyk, L. S., Martin, C. W. and Pearce, R. L. (1984). Inhibitors for acid
Litschewski, M. J. (1996). More experiences with corrosion and fouling in a
refinery amine system. Corrosion 96; NACE, paper no. 391.
Mago, B. F. and West, C. W. (1974). Antimony-Vanadium corrosion
inhibitors for alkanolamine gas treating system. US Patent 3808140.
Mago, B. F. and West, C. W. (1975). Nitrosubstituted Aromatic acid corrosion
inhibitors for alkanolamine gas treating system. US Patent 3896044.
Mago, B. F. (1976). Corrosion inhibition of aqueous potassium carbonate gas
treating systems. US Patent 3951844.
Towards Use of Environmentally Friendly Corrosion Inhibitors … 77
Mago, B. F. and West, C. W. (1976). Corrosion Inhibitors for alkanolamines

gas treating system. US Patent 3959170.
Minevski, L. V. (2000). Corrosion inhibitor for alkanolamine units. US Patent
6036888.
Minevski, L. V. and Lambousy, A. L. (1998). Corrosion inhibitor for
alkanolamine units. US Patent 5843299.
Negra, J. S. and McCloskey, J. W. (1963). Corrosion inhibiting. US Patent
3087778.
Nieh, E. C. Y. (1983). Vanadium-Cobalt corrosion inhibitor system for sour
Nieh, E. C. Y. (1983). Vanadium-amine corrosion inhibitor system for sour
OSPAR (2011) retrieved from www.ospar.org on March 2016.
Pearce, R. L. (1984). Process for removal of carbon dioxide from industrial
gases. US Patent 4440731.
Rampin, P. (2000). Amine units: results of a survey on structural reliability.
Proceedings of International Conference on Corrosion in refinery,
petrochemical and power generation plants. May 18-19, Venezia.
Rodriguez, E. F. and Edwards, M. A. (1999). The use of organic inhibitor to
control corrosion in alkanolamine units processing gas containing CO2.
Corrosion 99, NACE, paper no. 260.
Sastri, V. S. (2001). Corrosion Inhibitors: Principles and Applications. West
Sussex, England: John Wiley and Sons Ltd.
Schmeal, W. R., MacNab, A. J. and Rhodes, P. R. (1978). Corrosion in
amine/sour gas treating contactors. Chemical Engineering Progress,
74(3), 37-42.
Sekine, I., Shimode, T., Yuasa. M. and Takaoka. K. (1992). Corrosion
inhibition of structural steels in the carbon dioxide absorption process by
organic inhibitor composed of 2-aminothiophenol, (1-hydroxyethylidene)
bis(phosphonic acid), and diethanolamine. Ind. Eng. Chem. Res., 31(1),
434-439.
Smith, R. F. and Younger, A. H. (1972). Operating experiences of Canadian
diethanolamine plants. Proceedings of the 22nd Gas Conditioning
Conference. (pp. E1-E17). University of Oklahoma.
Soosaiprakasam, I. R. and Veawab, A. (2009). Corrosion inhibition
performance of copper carbonate in MEA-CO2 capture unit. Energy
Procedia, 1(1), 225-229.
Sutopo and Safruddin. R. (2000). Twenty years of experience in controlling

corrosion in amine unit, Badak LNG plant. Corrosion 2000. NACE, paper
no. 497.
Treviňo, J. A. V. (1987). Corrosion inhibitor for CO2 absorption process using
alkanolamines. US Patent 4714597.
Veawab, A. (2000). Corrosion and corrosion control in CO2 absorption
process using aqueous amine solutions, Ph.D. Thesis, University of
Regina, Saskatchewan, Canada.
Veawab, A., Tontiwachwuthikul, P. and Chakma, A. (2001). Investigation of
low-toxic corrosion inhibitors for CO2 separation process using aqueous
MEA solvent. Ind. Eng. Chem. Res., 40(22), 4771-4777.
Veldman, R. R. and Trahan, D. O. (2001). Gas treating solution corrosion
inhibitor. US Patent 6299836 B1.
Chapter 4
THE EFFECTIVENESS OF COPAIBA OIL

LOADED INTO A MICROEMULSION SYSTEM
AS A GREEN CORROSION INHIBITOR
Denise P. Emerenciano1, Ana Carla C. Andrade2,

Melyssa L. de Medeiros3, Maria de Fátima V. de Moura1
and Maria Aparecida M. Maciel1,3,
1
Institute of Chemistry, Center of Exact Sciences and Earth,
Federal University of Rio Grande do Norte, Natal, RN, Brazil
2
Department of Computing Engineering and Automation,
Center of Exact Sciences and Earth,
3
University Potiguar Laureate International Universities, Natal, RN, Brazil
ABSTRACT
Corrosion inhibitors have been applied onto steel structures and their
alloys for protection in industry. In this sense, natural inhibitors become
an important alternative to sustainable technological development. As an
advantage, natural corrosion inhibitors reduce the toxic effects observed

Corresponding author: Maria Aparecida M. Maciel. Institute of Chemistry, Center of Exact
Sciences and Earth, Federal University of Rio Grande do Norte, 59072-970, Natal, RN,
Brazil. University Potiguar Laureate International Universities, Campus Salgado Filho,
59075-000, Natal, RN, Brazil. Email: mammacial@hotmail. com.
80 D. P. Emerenciano, A. C. C. Andrade, M. L. de Medeiros et al.
for synthetic organic compounds, and depending on their formulation

could range from lower toxicity to nontoxic commercial products.
Additionally, green inhibitors are attractive in function of the low cost
procedures, inhibition performances are closely related to plant extracts,
fractions, oil, and even, isolated compounds. In this present work a
commercial copaiba oil sample (CO) belonging to the vegetal species
Copaifera L., was loaded into a O/W self-microemulsion system
(SMEDDS colloidal-type) composed with CO (1.0% as oil phase),
Tween® 80 (10.0% as surfactant) and water (89.0%), affording the green
sample SME-CO. The SME-CO formulation was applied as a natural
corrosion inhibitor measured at different concentrations (ranging from 5
ppm to 150 ppm), in a saline corrosive medium (3.5% of sodium
chloride). The best SME-CO corrosion inhibition efficiencies (77.15%)
was observed at 100 ppm by electrochemical method of linear
polarization curves with Tafel extrapolation, and obeys Langmuir model
isotherm. The greatest inhibitory effect of the tested green sample (SME-
CO) could be correlated with the SMEDDS adsorption phenomena on the
metal surface (steel AISI 1018), being herein considered as a eco-friendly
corrosion inhibitor. In the other hand, CO-corrosion efficiency could be
correlated with the synergistic effect of its phytocompounds of which
diterpenes and sesquiterpenes with different functional groups are
adsorbed on the metal surface, forming a stable plant source-metal
complex, reducing metal damage.
Keywords: Copaiba oil, Copaifera L., O/W type self-microemulsion,

SMEDDS-colloidal copaiba-based system, corrosion green inhibitor
INTRODUCTION
Corrosion is an unavoidable phenomena correlated with physical,
chemical or electrochemical damages which could act in combination with
mechanical strain in a progressive deterioration of materials [1]. In this sense,
prevention and reduction of corrosive effects represent the main goals of the
biotechnologic development. Nowadays, corrosion inhibitors applied to metals
and alloys have been studied aiming at eco-friendly development of processes
and methods for cathodic and anodic metal protection, metallic and non-
metallic protective coatings. For lower chemicals toxicity, application of green
corrosion inhibitors represent improvement of the protective films processes
acting on anodic and cathodic areas, controlling the triggering of
electrochemical reactions [1-5]. For this propose, plant extracts and its
derivatives have been showing to possess higher corrosion inhibition
The Effectiveness of Copaiba Oil … 81
efficiency becoming an important renewable source for a wide range of

inhibitors. Among them Embilica officianilis, Terminalia chebula, Terminalia
belivia, Sapindus trifolianus, Accacia conicianna, Azadirachta indica,
Vernonia amygdalina, Cocos nucifera, Anacardium occidentale and Croton
cajucara, naming a few [3-9]. The corrosion efficiency of plant extracts, their
fractions, oil, and even, isolated compounds has been correlated with
synergistic effect of different functional groups strongly adsorbed on the metal
surface, into a stable plant-metal complex protection [4, 7, 9].
Copaiba oil produced at Amazon and Central-West regions of Brazil as
well as around the world is a natural resinous oil exuded from the trunk of
Copaifera species. In Brazil, it is popularly known as “copaibeira” or “pau
d’oil,” and the most assessed Copaifera species to obtain copaiba oil are C.
reticulate (with 70% of production), C. guyanensis (10%), and C. multijuga
(10%). Additionally, C. langsdorffii Desf. is particularly important since it is
distributed throughout the country (from Amazon to Santa Catarina, in the
Northeast and Midwest) and has four different varieties (C. langsdorfii var.
grandifolia, C. langsdorfii var. grandiflora, C. langsdorfii var. slack and C.
langsdorfii var. glabra). Copaiba oleoresin is a transparent liquid whose color
ranges from yellow to light brown and in biological terms, it is a product of
excretion or detoxification of the plant organism, and acts as a plant defence
against animals, fungi and bacteria, but also many often affect specimens who
feed on them [10-13].
Nowadays, copaiba oil represents approximately 95% of the entire
oleoresin production country wide, being considerate as social and economic
significance to several communities that still depend on its extraction for their
livelihoods. According to the most recent silviculture data published by the
Brazilian Institute of Geography and Statistics (IBGE), the search for this raw
material still growing. In 2001, copaiba oil extraction corresponded to 414
tons and in 2003, it was 463 tons. Currently, annual production around 500
tons/year [11-13].
Copaiba oil chemical composition as well as its color and viscosity vary
according to the species. For example, if the same tree is exploited in different
periods of the year may produce modification on oil quality, oil yield and
density. Seasonal effect was observed to C. multijuga who showed variations
in the chemical composition of the collected oils at different times from
summer to winter [11-13]. Despite these variations, the substances detected
were basically the same, on different concentrations. Since the composition
variation can be associated with abiotic factors (such as insects and fungi),
light and soil nutrients, for many authors the phytocomponents variability
could be also attribute to different botanical Copaifera species, or even,

specimens of different ages and growing in different places, misidentification
of species, or in the case of commercial oils, problems of counterfeiting/
adulteration by mixing other lesser value oil-types.
Concerning to Copaifera chemical composition, it is known that
diterpenes and sesquiterpenes are the biomarkers of copaiba oil samples. In the
successful chromatographic profile (HRGC-FID and HRGC-MS analyses) of
copaiba oilresin (after suffering esterification) it is possible to identify two
well defined elution groups, one of them with lower molecular compound
weight, is atributed to sesquiterpene type compound and the second group is
characteristic identified as diterpene compounds. Sesquiterpene composition
could be divided into oxygenated and hydrocarbon groups [10, 14, 15].
Since the bioavailability of this natural oil is linked to seasonal variation,
collects dependent on the extractivism and low solubility, whose difficult its in
natura industrial utilization, in the present work, a polar self-microemulsion
system (O/W SMEDDS-type system, so called SME-CO) loading copaiba oil
(CO), at lower concentrations, was prepared in the presence of a biodegradable
surfactant, enabling its biotechnologic improvement as a green corrosion
inhibitor.
EXPERIMENTAL
Inhibitor Preparation
A commercial sample of copaiba oil (Copaifera L.) was loaded into a

O/W microemulsion system (SME-CO) composed with CO (1.0% as oil
phase), Tween® 80 (10.0% as surfactant) and doubly-distilled water (89.0%).
The procedure used to obtain the Winsor IV (WIV) region in the ternary phase
diagram was based on determination of the maximum solubility of the active
matter (surfactant) in aqueous and oil phases, by means of mass titrations,
being in accordance with a previously described methodology [16]. The
formed eco-friendly O/W colloidal-type formulation was confirmed to be a
self-microemulsion system (SME) due to its isotropic increasing aspect after
gradient dilution in water (30 mL of water/1 mL of SME).
Characteristically, a self-microemulsifying system is designed as
SMEDDS-colloidal vehicle for active compounds. The present SMEDDS
copaiba oil (CO) based system (named SME-CO) was characterized by
refractive index, droplet diameter, rheological behavior and surface tension.
The obtained SME-CO droplet diameter (8.6 nm) was measured in triplicate
based on CO-refractive index [1.463 (error: 0.005), refractometer (Brix)
analog at a temperature of 25°] with beam of light wavelength 659 nm and 90°
of incidence angle. The SME-CO rheological behavior by viscosity analyses
was evaluated using a rheometer at 25°C, with variation of shear rate ranging
from 1 to 370 s-1. The surface tension test was performed with 30.0 mL of the
SME-CO sample, through an apparatus tension meter, whose method consist
in measuring the maximum bubble pressure using two capillaries at different
diameters of orifices, in which an inert gas (N2) was pumped on a given
constant pressure (200 kPa). Whereing, the greater capillary measure the effect
of depth of immersion and the smallest measure the surface tension. For each
measurement, the tested sample (SME-CO) was diluted in doubly-distilled
water (adding volumes of 10 mL), varying water content until the surface
tension become near to γ water 72.1 mN m-1 (at 25°C). The surface tension
graph showed the intersection point of straight lines corresponding to
concentration of the micellar aggregates.
Corrosion Inhibition Efficiency of the SMEDDS Copaiba Oil-

Based System
The efficiency of the colloidal SMEDDS-CO sample (SME-CO) applied

as corrosion inhibition on steel AISI 1018, in saline medium, was evaluated by
potentiodynamic technique using AUTOLAB potentiostat coupled with GPES
version 4.9 software aiming to obtain Tafel curves and corrosion parameters.
An electrochemical cell with a reference electrode (Ag/AgCl), a platinum
auxiliary electrode, and a working electrode (steel AISI 1018) were applied at
different concentrations of SME-CO sample (5.0 ppm to 150.0 ppm).
Polarization curves were recorded at a scanning rate of 0.05 V min-1 varying
potential from the observed open circuit potential after 15 min. of immersion.
The corrosion parameters were obtained by extrapolating of the Tafel curves
which were used to calculate corrosion inhibition efficiency (IE) according to
the following equation:
𝐼𝐶𝑜𝑟𝑟 −𝐼𝑐𝑜𝑟𝑟(𝑖𝑛ℎ𝑖𝑏𝑖𝑡𝑜𝑟)
𝐼𝐸 (%) = (1)
𝐼𝑐𝑜𝑟𝑟
where Icorr and Icorr(inhibitor) correspond to the corrosion current density of the
steel coupons in the absence or presence of the colloidal SME-CO system.
In order to evaluate the adsorption phenomena of these tested sample on

the metal surface, Langmuir and Frumkin adsorption isotherms were applied,
using the following equations:
C 1
Langmuir: 𝜃
=𝐾 +C (2)
𝑎𝑑𝑠
θ
Frumkin: log [ (1−𝜃)𝐶 ] = log K ads + gθ (3)
The surface coverage (θ) was calculated from the rates of corrosion
inhibition obtained by polarization curves data, “C” represents the inhibitor
concentration in ppm, “Kads” is the adsorption equilibrium constant, and “g” is
the degree of lateral interaction among the adsorbed molecules.
RESULTS AND DISCUSSION

Ternary phase diagram (Figure 1) of the colloidal tested system (SME-
CO) was conducted by mass titration of oil phase in which the masses of the
surfactant and aqueous phase (previously quantified) recorded the phases of
transition points. The micellar aggregates were characterized as a O/W
colloidal microemulsion system (SMEDDS-type system) due to its isotropic
increasing aspect after several water dilutions. For corrosive analyzes, SME-
CO was diluted on saline corrosive medium (3.5% of sodium chloride) from
which no colloidal phase change was observed. Refractive index data 1.463
(error: 0.005) of copaiba oil (CO) was required for droplet size analysis of
SME-CO finding a droplet diameter (8.6 nm) in the microemulsion diameter
range (5.0 nm-100.0 nm) [17].
Concentration of the micellar aggregates (cmc) was obtained from surface
tension analysis by using 30.0 mL of SME-CO. The graph of surface tension
(mN m-1) versus SME-CO concentration (g mL-1) was obtained with surface
tension near to γ water 72.1 mN m-1, at 25°C (Figure 2). The intersection point
of two lines gives the specific cmc (0.0070 g mL-1), from which value below
this data form scattered monomers.
Rheological behavior was evaluated from the graph generated by data
from shear tension versus shear rate (1.0 to 370.0 s-1) resulting in the linear
behavior of the tested sample with r2 = 0.9995 (Figure 3). According to the
obtained data 2.0 mPa.s (2.0 cP) the fluid under consideration (SME-CO) was
classified as Newtonian. In fact, a Newtonian fluid flower was correlated to a

parameter of proportionality between the tension and rate shear, whose
viscosity is influenced by temperature and pressure variations [18].
Figure 1. Ternary phase diagram of the colloidal SME-CO system.
70
y = -1435.6x + 68.821
Surface Tension (mN/m)
R² = 0.8106
65
60
y = -87.429x + 59.741
R² = 0.9356
55
50
0 0.02 0.04 0.06 0.08 0.1 0.12
Surfactant Concentration (g/mL)
Figure 2. SME-CO surface tension measured at aqueous medium.

0.8
0.7
0.6
Shear Tension (Pa)
0.5
0.4
0.3
0.2 y = 0.002x
0.1 R² = 0.9995
0
0 50 100 150 200 250 300 350 400
Shear Rate (1/s)
Figure 3. SME-CO viscosity parameter.
Figure 4 shows the behavior of SME-CO polarization curves by the

measurement of its electrical current versus potential front. The find observed
by electric current reduction through a given system, is in accordance with
corrosion inhibition phenomena [19]. The protective film efficiency depend
upon SME-CO concentration as well as its contact effectiveness into metal
surface. The Tafel curves obtained for SME-CO showed corrosion potentials
dislocating to more positive values (anodic protection) by comparing it with
the without inhibitor curve. Meanwhile, anodic behavior occurred gradually
depending upon SME-CO increase concentration. Anodic or cathodic
corrosion inhibitors retard the corrosion processes by reductive oxidation
property in the metal at different medium, acting over physical or chemical
interaction between inhibitor and metal surface, by forming a protective film
on metal areas reducing the speed of the electrochemical reactions [2].
Current densities were measured from the extrapolation of Tafel curves
until the potential of corrosion. This method involve determination of Tafel
slope βa (anodic beta) and βc (beta cathodic), as well as Ecorr (corrosion
potential) and the Icorr (corrosion current) through a polarization curve. Table 1
shows the kinetic parameters obtained from slopes of Tafel curves and then,
SME-CO corrosion potential.
-3
-0.35 -0.45 -0.55 -0.65 -0.75 -0.85
-3.5
-4
-4.5
-5
Log i (A)
-5.5
-6
3.5 % sodium chloride
5 ppm
-6.5
10 ppm
20 ppm
-7
60 ppm
30 ppm
-7.5
80 ppm
100 ppm
-8
E (V) vs Ag/AgCl 150 ppm
Figure 4. Anodic and cathodic polarization curves for carbon steel AISI 1018 in 3.5%
of sodium chloride corrosive medium, in different concentrations of SME-CO.
The SME-CO corrosion inhibition efficiencies was calculated from the

values of currents (Icorr) and depending upon its concentrations, as shown in
Table 1. The best efficiency (77.15%) was correlated to 100 ppm of SME-CO.
That potential can be due to copaiba oil antioxidant property attributed to ist
phytocompounds such as sesquiterpenes and diterpenes [10]. Concerning to
the non-ionic surfactant Tween® 80 it has higher viscosity, higher solubility
and stability in different medium [20] justifying its use in the colloidal SME-
CO system.
Table 1. Kinetic parameters obtained from polarization curves for steel

AISI 1018, at saline solution containing the tested SME-CO green
inhibitor
Concentration bc ba Ecorr Icorr IE Corrosion rate

(ppm) (mV/dec) (mV/dec) (V/Ag/AgCl) (A/cm2) (%) (mg cm-2 h-1)
5 198 99 -0.708 5.17 x 10-6 23.38 1.49 x 10-9
10 105 205 -0.708 5.36 x 10-6 20.45 1.55 x 10-9
20 96 165 -0.665 4.81 x 10-6 28.69 1.39 x 10-9
30 99 168 -0.720 3.65 x 10-6 45.90 1.05 x 10-9
60 95 185 -0.648 4.70 x 10-6 30.38 1.36 x 10-9
80 76 303 -0.581 4.39 x 10-6 34.90 1.27 x 10-9
100 125 125 -0.773 1.54 x 10-6 77.15 4.50 x 10-8
150 90 234 -0.622 2.87 x 10-6 57.42 8.30 x 10-8
Substances that feature strongly polar groups such as heterocyclic nitrogen

and sulfur compounds, anionic and cationic surfactants, promote electronic
effects and shows significant adsorption on metal surfaces, resulting into good
protection. In this context, it was observed that the adsorption of SME-CO on
carbon steel surface obeys Langmuir adsorption isotherm (Figure 5, A). This
isotherm is based on three suppositions: (1) the adsorption can not go beyond a
monolayer coating, (2) all the adsorption sites are equivalent to each other and
the surface is perfectly flat on a microscopic scale (uniform), (3) the molecule
ability to be adsorbed on a determined site is independent of the occupation of
near sites, so, there is no interaction between adsorbed molecules [9]. Frumkin
isotherm is a model that optimized the Lagmuir isotherm. From that (Figure 5,
B) the adsorbed surface density was correlated to the concentration of SME-
CO chemical species investigated in the saline solution.
Since vegetal biomass are a rich source of organic complex mixtures they
generally act as efficient inhibitors on metal corrosion. Heteroatom type
compounds containing nitrogen, oxygen, phosphorus and/or sulphur as well as
those compounds with aromatic rings or conjugated double bonds in their
molecular structures, have been shown to improve the adsorption and
corrosion inhibition processes [21]. Concerning to copaiba oil chemical
composition the main oxygenate sesquiterpenes are an oxide compound
(named caryophyllene oxide) and alcohol compounds (named α-cadinol and β-
cadinol) as well as non-oxygenate phytocomponents with unsaturated
hydrocarbons chemical structures such as β-caryophyllene, β-elemene, α- and
β-selinene, β-bisabolene, among others [10, 14, 15].
300
200
C/θ
100
y = 1.5574x + 39.285
R² = 0.7576
0
0 30 60 90 120 150
C (ppm)
a
0.05
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
log(θ/1-θ)/ C
-0.05
-0.1
-0.15
y = 0.2118x - 0.1246
R² = 0.6552
-0.2
θ
b
Figure 5. Isotherms for carbon steel AISI 1018 at 25°C in saline solutions (3.5% of
sodium chloride) and SME-CO green inhibitor. (A) Langmuir, (B) Frumkin.
Table 2. Adsorption parameters for SME-CO green inhibitor on carbon

steel AISI 1018 in 3.5% of sodium chloride
Isotherm ΔGads Kads Adsorption type Process

Langmuir -0.766 kJ mol-1 0.0245 Physical Spontaneous
Frumkin -9.531 kJ mol-1 0.833 Physical Spontaneous
The variation of Gibbs free energy, ∆𝐺 0 𝑎𝑑𝑠 , according to the following

equation, is the difference between free energies of reaction products molars in
their standart-states and those of the reagents in their standard-states.
∆G0 ads = −R. T. ln(55.5. K ads ) (4)
where: "∆G0 𝑎𝑑𝑠 " is the variation in Gibbs free energy, “R” is the gas constant
(8.3145 J K-1 mol-1), “T” is the temperature (Kelvin); “55.5” is a constant used
for aqueous solutions and “Kads” is the adsorption equilibrium constant.
The analysis of the isotherms (Figure 5) showed that the experimental
results presented better adjustment the Langmuir isotherm, with factors of
correlation (R2) 0.758. From this isotherm, adsorption constants were obtained
(Kads) and Gibbs free energy of adsorption process (ΔGads), represented in
Table 2.
Adequacy isotherm implies that in a specific concentration of the tested

inhibitor, monolayer formation occurs occupying sites on metal surface. From
Langmuir isotherm the adsorption process was spontaneous, at constant
temperature and pressure, by negative value for ΔGads (-0.766 kJ mol-1) which
classify adsorption as typically physics, because the observed value was less
than |25.2| kJ mol-1 [9], being in agreement with the molecular monolayer
adsorption on metallic surface.
CONCLUSION
The inhibitor SME-CO was formulated based on a O/W colloidal
SMEDDS-type system with copaiba oil loaded in the presence of the
surfactant Tween® 80, affording a eco-friendly self-microemulsion
formulation, feasible for evaluation as green anticorrosive agent. A
electrochemical method of polarization with extrapolation of Tafel was
applied on carbon steel AISI 1018, in saline medium (3.5% of sodium
chloride). SME-CO at different concentrations (5 ppm-150 ppm) presented
maximum effectiveness of inhibition (77.15%) at a concentration of 100 ppm.
SME-CO adsorption on carbon steel surface obeys Langmuir isotherm. The
adsorption and CO-inhibition eficience was correlated to copaiba oil chemical
composition in which sesquiterpenes with oxygenate and unsaturated
hydrocarbons chemical structures are the main components. In accordance to
those results the biodegradable tested system (SME-CO) was herein
considered to be applied as natural corrosion inhibitor with commercial value
focused on lower concentrations of copaiba oil, and its commercial
importance, extractivism and environment protection.
ACKNOWLEDGMENTS
The authors are grateful to CAPES (Coordenação de Aperfeiçoamento de
Pessoal de Nível Superior) and the PPGQ-UFRN program for financial
support.
REFERENCES
[1] Gentil, V., (2011). Corrosion. LTC, Rio de Janeiro, Brazil, 6th Edition.
[2] Malik, M. A., Hashim, M. A., Nabi, F., AL-Thabaiti, S. A., Khan, Z.,
(2011). Anti-corrosion Ability of Surfactants: A Review. Int. J.
Electrochem. Sci. 6, 1927-1948.
[3] Raja, P. B., Sethuraman, M. G., (2008). Natural products as corrosion
inhibitor for metals in corrosive media-A review. Mater. Lett. 62, 113-
116.
[4] Felipe, M. B. M. C., Silva, D. R., Martinez-Huitle, C. A., Medeiros, S.
R. B., Maciel, M. A. M., (2013). Effectiveness of Croton cajucara Benth
on corrosion inhibition of carbon steel in saline medium. Mater. Corros.
64, 6, 530-534.
[5] Felipe, M. B. M. C., Maciel, M. A. M., Medeiros, S. R. B., Silva, D. R.,
(2013). General aspects of corrosion and plant inhibitors. Rev. Virtual
Quim. 5, 4, 746-758.
[6] Abiola, O. K., Oforka, N. C., Ebenso, E. E., Nwinuka, N. M., (2007).
Eco-friendly corrosion inhibitors: The inhibitive action of Delonix Regia
extract for the corrosion of aluminium in acidic media. Anti. Corros.
Method. M. 54, 4, 219-224.
[7] Moura, E. C. M., Souza, A. D. N., Rossi, C. G. F. T., Silva, D. R.,
Maciel, M. A. M., Echevarria, A., Bellieny, M. S. S., (2013). Evaluation
of anticorrosive effectiveness of thiosemicarbazones solubilized in a
microemulsion system. Quim. Nova. 36, 1, 59-62.
[8] Abiola, O. K., James, A. O., (2010). The effects of Aloe vera extract on
corrosion and kinetics of corrosion process of zinc in HCl solution.
Corros. Sci. 52, 2, 661-664.
[9] Anjos, G. C., Almeida, C. C., Melo, D. M. A., Martinez-Huitle, C. A.,
Rossi, C. G. F. T., Maciel, M. A. M., (2013). Effectiveness of
Anacardium occidentale on a microemulsion system in the carbon steel
corrosion inhibition. Rev. Virtual Quim. 5, 4, 760-769.
[10] Veiga Junior, V., Pinto, A. C., (2002). The Copaifera L. genus. Quim.
Nova. 25, 2, 273-286.
[11] Zuanazzi, J. A. S., Mayorga, P., (2010). Phytoproducts and economic
development. Quim. Nova. 33, 6, 1421-1428.
[12] Leite, A. C., (2001). Recommendations for the sustainable management
of copaiba oil. UFAC/SEFE, Rio Branco.
[13] Ferreira, L. A., Braz, E. M., (2001). Evaluation of potential for

commercial extraction of oleoresin of copaiba. The New York Botanical
Garden, New York and UFAC.
[14] Veiga Junior, V. F., Pinto, A. C., Calixto, J. B., Zunino, L., Patitucci, M.
L., (2001). Phytochemical and anti-oedematogenic studies of
commercial copaiba oils available in Brazil. Phytother. Res. 15, 476-
480.
[15] Leandro, L. M., Vargas, F. S., Barbosa, P. C. S., Neves, J. K. O., Silva,
J. A., Veiga Junior, V. F., (2012). Chemistry and biological activities of
terpenoids from Copaiba (Copaifera spp.) oleoresins. Molecules. 17, 4,
3866-3889.
[16] Dantas, T. N. C., Ferreira, M. E., Scatena Jr, H., Dantas Neto, A. A.,
Gurgel, A., (2002). Micellization and adsorption thermodynamics of
novel ionic surfactants at fluid interfaces. Colloid Surface A. 207, 243-
252.
[17] Rossi, C. G. F. T., Scatena Jr, H., Maciel, M. A. M., Dantas, T. N. C.,
(2007). Comparative effectiveness microemulsions of diphenylcarbazide
and saponified coconut oil in the carbon steel corrosion inhibition
process. Quim. Nova. 30, 5, 1128-1132.
[18] Machado, J. C. V., (2002). Rheology and Fluid Flow - Emphasis on Oil
Industry, Editora Interciência, Rio de Janeiro, Brazil.
[19] Elachouri, M., Hajji, M. S., Salem, M., Kertit, S., Aride, J., Coudert, R.,
Essassi, E. M., (1996). Some nonionic surfactants as inhibitors of the
corrosion of iron in acid chloride solutions. Corros. Sci. 52, 2, 103-108.
[20] Spring, S., Howard Jr., E., (1954). Solubilization by potassium laurate
solutions containing lauric acid. J. Colloid Interface Sci. 9, 5, 371-381.
[21] Deng, S., Li, X., (2012). Inhibition by Ginkgo leaves extract of the
corrosion of steel in HCl and H2SO4 solutions. Corros. Sci. 55, 407-415.
BIOGRAPHICAL SKETCH
Name: Maria Aparecida Medeiros Maciel
Affiliation: Institute of Chemistry, Center of Exact Sciences and Earth,
Federal University of Rio Grande do Norte, 59072-970, Natal, RN, Brazil.
University Potiguar Laureate International Universities, Campus Salgado
Filho, 59075-000, Natal, RN, Brazil.
Education: Ph. D.
Address:
Rua Alfredo Dias de Figueiredo, No. 1249/Casa E-16

Ponta Negra, Natal/RN, Brazil, 59092-570
Cellular Phone: 00558488047880
Home Phone: 00558432341778
Personal E-mail: mammaciel@hotmail.com.
Business E-mail:
maria.maciel@unp.br
mammaciel@quimica.ufrn.br
maria.maciel@pq.cnpq.br.
Research and Professional Experience: Research Scientist and Educator.

Achievements include development of bioctive natural products including
trans-dehydrocrotonin isolated from an Amazon plant (Croton cajucara
Benth); research in large biochemical; research in large biotecnology; research
in green chemistry applied to corrosion inhibition.
Maciel, Maria Aparecida Medeiros, research scientist, educator; b.
Pesqueira, Pernambuco, Brazil, Oct. 4, 1960; d. José Medeiros Ventura and
Paulina Maciel Medeiros; m. Ralph Oliveira Barata, Dec. 23, 1988; 1 child,
Julia Oliveira Maciel; Post Ph. D. (PRODOC-CAPES), U. Fed. RN (UFRN),
2006, Natal, Brazil; Post Ph. D. (PDS-CNPq), U. Fed. RN (UFRN), 2008,
Natal, Brazil; Ph. D., U. Fed. RJ (UFRJ), 1997, Rio de Janeiro, Brazil; MSc,
U. Fed. Rural RJ (UFRRJ), 1991, Rio de Janeiro, Brazil; Cert. in Chemistry,
U. Católica Pernambuco (PUC), 1986, Recife, Brazil. Vis. rsch. U. Calif. San
Diego, (UCSD), 1989, Califórnia, US; Vis. Rsch. U. Fed. Para (UFPA), 1993-
1995, Belém, Brazil; Collaborator rschr. U. Fed. Ceara (UFC), 1993-2010;
Collab. rschr. U. Fed. Rural RJ (UFRRJ), 1993-; Collab. Rschr. U. Est.
Londrina (UEL), Londrina, Brazil; 1994-2012; Collab. rschr. U. Fed. RJ
(UFRJ), 1998-2010; Prof. U. Castelo Branco (UCB), Rio de Janeiro, Brazil,
1998-2001; Collab. rschr. U. Fed. RN (UFRN), 2002-; Vis. Prof. Post
Graduate Program in Chemistry UFRN, 2002-2012; Collab. rschr. U. Fed.
Pernambuco (UFPE), 2002-; Vis. Prof. Graduate Program U. Fed. RN
(REUNI/UFRN), 2010-2012; Research Scientist of Post Graduate Program in
Chemistry of U. Fed. RN; Prof. Distance Learning Graduate Program U. Fed.
RN (e-learning/SEDIS-UFRN), 2010-; Prof. Post Graduate Program in
Biotechnology of the University Potiguar Laureate International Universities,
Natal, Brazil; 2012-; Prof. Post Graduate Program in Biotechnology Renorbio
(UFRN), 2013-; Research Scientist Fellow: Soc. Brasileira de Química

(assoc.). Green Party. Roman Catholic.
Honors: Who’s Who in the World (2010); Top 100 Scientist (2014).

Anjos, G. C.; Almeida, C. C.; Melo, D. M. A.; Martinez-Huitle, C. A.; Rossi,
C. G. F. T.; MAciel, M. A. M. Effectiveness of Anacardium occidentale
on a microemulsion system in the carbon steel corrosion inhibition.
Revista Virtual de Química. v. 5, n. 5, p. 760-769, 2013.
Chaves, O. A.; Soares, B. A.; Maciel, M. A. M.; Sant’Anna, C. M. R.; Netto-
Ferreira, J. C.; Cesarin-Sobrinho, D.; Ferreira, A. B. B. A study of the
interaction between trans-dehydrocrotonin, a bioactive natural 19-nor-
clerodane, and serum albumin. Journal of the Brazilian Chemical Society
(in press), 2016.
Emerenciano, D. P.; Cruz, A. M. F.; Pereira, J. D. S.; Moura, M. F. V.; Maciel,
M. A. M. Determination of antioxidant property and minerals contained in
the leaves of Azadirachta indica A. Juss. Revista Fitos
(Farmanguinhos/FIOCRUZ), v. 8, p. 147-156, 2013.
Emerenciano, D. P.; MacieL, M. A. M.; Xavier Junior, F. H.; Moura, M. F. V.
Phytochemical and Pharmacological Aspects of Meliaceae and
Azadirachta Indica A. Juss. International Journal of Latest Research in
Science and Technology, v. 4, p. 128-135, 2015.
Felipe, M. B. M. C.; Silva, D. R.; Martinez-Huitle, C. A.; De Medeiros, S. R.
B.; Maciel, M. A. M. Effectiveness of Croton cajucara Benth on
corrosion inhibition of carbon steel in saline medium. Materials and
Corrosion. v. 64, n. 6 p. 530-534, 2013.
Felipe, M. B. M. C.; Maciel, M. A. M.; Medeiros, S. R. B.; Silva, D. R.
General aspects of corrosion and plant inhibitor. Revista Virtual de
Química. v. 5, n. 5, p. 746-758, 2013.
Goulart, C. M.; Esteves-Souza, A.; Martinez-Huitle, C. A.; Rodirgues, C. J.,
F.; Maciel, M. A. M.; Echevarria, A. Experimental and theoretical
evaluation of semicarbazones and thiosemicarbazones as organic
corrosion inhibitors. Corrosion Science, v. 67, p. 281-291, 2013.
Lapenda, T. L. S.; Morais, W. A.; Almeida, F. J. F.; Ferraz, M. S.; Lira, M. C.
B.; Santos, N. P. S.; Maciel, M. A. M.; Santos-Magalhães, N. S.
Encapsulation of trans-dehydrocrotonin in liposomes: An enhancement of
the antitumor activity. Journal of Biomedical Nanotechnology, v. 9, n. 3,
p. 499-510, 2013.
Lima, G. S.; Castro-Pinto, D. B.; Machado, G. C.; Maciel, M. A. M;

Echevarria, A. Antileishmanial activity and trypanothione reductase
effects of terpenes from Croton cajucara Benth (Euphorbiaceae)
Amazonian species. Phytomedicine. v. 22, p. 1133-1137, 2015.
Moura, E. C. M.; Souza, A. D. N.; Rossi, C. G. F. T.; Da Silva, D. R.; Maciel,
M. A. M. Evaluation of anticorrosive effectiveness of thiosemicarbazones
solubilized in a microemulsion system. Química Nova, v. 36, n. 1, p. 59-
62, 2013.
Moura, E. C. M.; Rossi, C. G. F. T.; Silva, D. R.; Maciel, M. A. M. Corrosion:
a basic theoretical approach. Revista de Ciências Exatas da UFRRJ. v. 32,
n. 1, 2013.
Rodrigues, C. J. F.; Maciel, M. A. M.; Lima, K. M. Sorbitans as corrosion
inhibitors. Revista Virtual de Química. v. 5, n. 5, p. 912-920, 2013.
Rossi, C. G. F. T.; Moura, E. C. M., Maciel, M. A. M. Isotherms approach for
analysis of corrosion inhibitors effectiveness. Revista de Ciências Exatas,
RJ, EDUR, v. 32, n. 1, p. 66-76, 2013.
Santos, J. S.; Maciel, M. A. M; Silva, A. O. Biofuels: general aspects,
technological development and economic viability. International Journal
of Latest Research in Science and Technology. v. 4, n. 4, p. 8-17, 2015.
Silva, M. S.; Castro Dantas, T. N.; Rodrigues, G.; Barros Neto, E. L.; Dantas
Neto, A. A., Maciel, M. A. M. Oil epoxidation approach for Passiflora
edulis sims f. flavicarpa degener. International Journal of Latest Research
in Science and Technology. v. 4, n. 3, p. 46-52, 2015.
Silva, M. S.; De Barros Neto, E. L.; Dantas Neto, A. A.; Maciel, M. A. M; De
Castro Dantas, T. N. Synthetic eposidation of Moringa oleifera Lam with
performic acid generated in situ. Biointerface Research in Applied
Chemistry. v. 6, n. 2, p. 1080-1086, 2016.
Soares, B. A.; Firme, C. L.; Maciel, M. A. M.; Kaiser, C. R.; Schilling, E.;
Bortoluzzi, A. J. Experimental and NMR theoretical methodology applied
to geometric analysis of the bioactive clerodane trans-dehydrocrotonin.
Journal of the Brazilian Chemical Society, v. 25, n. 4, p. 629-638, 2014.
Soares, B. A.; Maciel, M. A. M.; Castro, R. N.; Kaiser, C. R.; Firme, C. L.
Synthesis, NMR data and theoretical study of semi-synthetic derivatives
from trans-dehydrocrotonin. Journal of Molecular Structure. v. 1108, p.
533-541, 2016.
Book Chapter
Maciel, M. A. M.; Gomes, F. E. S.; Soares, B. A.; Grynberg, N. F.;
Echevarria, A.; Cólus, I. M. S.; Kaiser, C.; Morais, W. A.; Magalhães, N.
S. S. Biological effectiveness and recent advancing of natural products on

the discovery of anticancer agents. In: Bioactive Phytochemicals:
Perspectives for Modern Medicine, v. 2, chapter 12, p. 239-293. Nova
Delhi: Daya Pulishing House, 2014.
Maciel, M. A. M.; Almeida, C. C.; Felipe, M. B. M. C.; Moura, L. S. A.;
Medeiros, M. L.; Medeiros, S. R. B.; Silva, D. R. Effectiveness of an
alkaloid fraction on carbon steel corrosion inhibition evaluated by green
chemistry biotechnological approach. In: Nanobiotechnology, chapter 4, p.
95-112. One Central Press (UK), 2014.
Patent
Dantas, T. N. C.; Emerenciano, D. P.; Maciel, M. A. M.; Rossi, C. G. F. T.;
Moura, M. F. V. Self-nanoemulsifier systems using vegetal oil from seeds
of Azadirachta indica A. Juss as green corrosion inhibitor. Brazil. Patent:
Privilege Innovation. Registration number: BR1020140228756 A2.
September 1, 2014. Registration Institution: INPI - Instituto Nacional da
Propriedade Industrial.
Macedo, R. G. M. A.; Tonholo, J.; Santos, A. R.; Maciel, M. A. M.; Rossi, C.
G. F. T. Corrosion inhibitory composition using heterocyclic organic
compounds loaded into a microemulsion containing saponified coconut
oil as surfactant. Brazil. Patent: Privilege Innovation. Registration
number: WO2014040159 A1. Marc 20, 2014. Application number
PCT/BR2013/000409. Registration Institution: INPI - Instituto Nacional
da Propriedade Industrial.
Maciel, M. A. M.; Andrade, A. C. C.; Emerenciano, D. P.; Moura, M. F. V.;
Medeiros, M. L. Self-microemulsion system containing copaiba oil for
application as a green corrosion inhibitory. Brazil. Patent: Privilege
Innovation. Registration number: BR1020140314598. December 2, 2014,
Registration Institution: INPI - Instituto Nacional da Propriedade
Industrial.
Maciel, M. A. M.; Medeiros, M. L.; Araujo Filho, I.; Rego, A. C. M.;
Emerenciano, D. P.; Veiga Junior, V. F. Preparation and evaluation of a
copaiba oil bioformulation to treat skin diseases. Brazil. Patent: Privilege
Innovation. Registration number: BR1020140331328, December 19,
2014, Registration Institution: INPI - Instituto Nacional da Propriedade
Industrial.
Maciel, M. A. M.; Medeiros, M. L.; Araujo Filho, I.; Rossi, C. G. F. T.;
Salgueiro, C. C. M.; Veiga Junior, V. F. Nanoformulaion containing
natural bioactives for wound healing. Brazil. Patent: Privilege Innovation.
Registration number: BR1020140331336 A2. December 19, 2014.

Industrial.
Maciel, M. A. M.; Sátiro, D. S. P.; Ramalho, H. M. M.; Rocha, H. A, O.
Bioformulation of a leave fraction from Croton cajucara BENTH for
application in the digestive and immunomodulatory therapy. Brazil.
Patent: Privilege Innovation. Registration number: BR1020150147031.
May 25, 2015. Registration Institution: INPI – Instituto Nacional de
Propriedade Intelectual.
Maciel, M. A. M.; Sátiro, D. S. P.; Pereira, J. D. S.; Rossi, C. G. F. T.; Rocha,
H. A. O. Bioformulation of an alkaloidal fraction obtained from Croton
cajucara BENTH for application in the immunomodulatory therapy.
Brazil. Patent: Privilege Innovation. Registration number:
BR1020150147040. Brazil. Patent: Privilege Innovation. Registration
number: BR1020150147031. May 25, 2015. Registration Institution: INPI
– Instituto Nacional de Propriedade Intelectual.
Maciel, M. A. M.; Sátiro, D. S. P.; Araújo Filho I.; Rossi, C. G. F. T.; Rocha,
H. A. O. Bioformulation of a hydroalcoholic extract from Croton cajucara
BENTH in a self-microemulsion system for application in the
immunomodulatory therapy. Brazil. Patent: Privilege Innovation.
Registration number: BR1020150147058. May 25, 2015. Registration
Institution: INPI – Instituto Nacional de Propriedade Intelectual.
Medeiros, M. L.; Maciel, M. A. M.; Carvalho, R. A.; Araujo Filho, I.; Rego,
A. C. M.; Marques, M. M.; Soares, C. D.; Veiga Junior, V. F. SMEDDS
copaiba oil based system for dental applications. Brazil. Patent: Privilege
Innovation. Registration number: BR1020150132310. May 18, 2015.
Industrial.
Maciel, M. A. M.; Magalhães-Padilha, D. M.; Freitas E Silva, K. R.; De
Figueiredo, J. R.; Vanderlinde, F. A. Bioavailability of the hydroalcoholic
extract obtained from the bark of Croton cajucara BENTH in a SMEDDS
system for medicinal uses. Brazil. Patent: Privilege Innovation.
BR1020150147198. June 3, 2015. Registration number: INPI – Instituto
Nacional de Propriedade Intelectual.
Maciel, M. A. M.; Silva Neto, P. F.; Sátiro, D. S. P.; Pereira, J. D. S.
Bioavailability of the hydroalcoholic extract obtained from the bark of
Croton cajucara BENTH in a polar coloidal system for hypoglycemic
application. Brazil. Patent: Privilege Innovation. Registration number:
BR1020150307900. December 9, 2015. Registration Institution: INPI –

Instituto Nacional de Propriedade Intelectual.
Maciel, M.A.M.; Emerenciano, D.P.; Rego, A.C.M.; Carvalho, R.A.; Sampaio,
T.B.M.; Araujo Filho, I.; Rocha, H.A.O.; Marques, M.M. Nanostructure
formulations based on the hydroalcoholic extracts of noni fruit (Morinda
citrifolia Linn) for dental applications. Brazil. Patent: Privilege
Innovation. Registration number: BR1020150315600. December 16,
2015. Registration Institution:INPI - Instituto Nacional da Propriedade
Industrial.
Maciel, M.A.M.; Emerenciano, D.P.; Moura, M.F.V.; Marques, M.L.M.;
Rocha, H.A.O. Development of a self- microemulsion system using oil
from seeds of Azadirachta indica A. Juss. for pest control. Brazil. Patent:
Privilege Innovation. Registration number: BR1020160021251. January
29, 2016. Registration Institution: INPI - Instituto Nacional da
Maciel, M. A. M.; Maciel A. S. S.; De Araujo, L. B. A.; Xavier Júnior, F. H.;
Marques, M. L. M.; Rocha, H. A. O. Farmaconutrients formulations based
on Anacardium occidentale L. for antioxidant, nutraceutical, and
immunomodulatory applications. Brazil. Patent: Privilege Innovation.
Registration number: BR1020160041139. February 25, 2016. Brazil.
Patent: Privilege Innovation. Registration Institution: INPI - Instituto
Nacional da Propriedade Industrial.
Maciel, M. A. M.; Maciel, A. S. S.; Medeiros, M. I. T.; De Araujo, L. B. A.;
De Medeiros, D. L.; Xavier Júnior, F. H.; Vanderlinde, F. A. Development
of analgesic nanostructure formulations based on Anacardium occidentale
LINN. Brazil. Patent: Privilege Innovation. Registration number:
BR1020160066875. March 26, 2016. Registration Institution: INPI -
Instituto Nacional da Propriedade Industrial.
Maciel, M. A. M.; Almeida, C. C.; Rossi, C. G. F. T.; Melo, D. M. A.;
Martinez-Huitle, C. A. Methanol extract from Ixora coccinea Linn as
green corrosion inhibitor. Brazil. Patent: Privilege Innovation.
Registration number: BR1020160016096. January 25, 2016. Registration
Institution: INPI - Instituto Nacional da Propriedade Industrial.
Maciel, M. A. M.; Conceição dos Anjos, G.; Silva, D.R.; Dantas, T. N. C.;
Felipe, M. B. M. C.; Melo, D. M. A. Colloidal formulation based on
saponified coconut oil (Cocos nucifera L.) as surfactant for loading a polar
extract from Phyllanthus amarus Schum. and Thonn as green corrosion
inhibitor. Brazil. Patent: Privilege Innovation. Registration number:
BR10201402287, February 21, 2016. Registration Institution: INPI -

Padilha, D. M.M.; Maciel, M. A. M.; Silva, K. R. F. E.; Emerenciano, D. P.;
Figueiredo, J. R. Hydroalcoholic extract of Croton cajucara BENTH
loaded on microemulsion as ovarian follicles growth medium. Brazil.
June 3, 2015. Registration Institution:INPI - Instituto Nacional da
Teixeira, E. R. F.; Maciel, M. A. M.; Castro Dantas, T., N.; De Carvalho, R.
A.; Soares, C. D.; Marques, M. M. Development of a drug delivery system
based on Syzigium aromaticum for dental applications. Brazil. Patent:
Privilege Innovation. BR1020150203845. August 24, 2015. Registration
number: INPI – Instituto Nacional de Propriedade Intelectual.
Name: Denise Porfirio Emerenciano

Federal University of Rio Grande do Norte.
Education: Ph. D. student.
Address: Rua Coronel Trajano, 57, Centro, São José de Mipibu, 59162-
000, Rio Grande do Norte, Brazil.
Personal E-mail: deniseemerenciano@yahoo.com.br
Research and Professional Experience: Research development on
analytical chemistry, electrochemical and phytochemistry. Degree in
chemistry.
Honors: Academic Merit, Federal University of Rio Grande do Norte,
2011.

Emerenciano, D. P.; Maciel, M. A. M.; Xavier Junior, F. H.; Moura, M. F. V.
Emerenciano, D. P.; Cruz, A. M. F.; Pereira, J. D. S.; Moura, M. F. V.;

MACIEL, M. A. M. Determination of antioxidant property and minerals
contained in the leaves of Azadirachta indica A. Juss. Revista Fitos
Innovation. Registration number: BR1020140314598 A2. December 2,
Industrial.
Industrial.
Industrial.
Name: Ana Carla Costa Andrade

Affiliation: Department of Computer Engineering and Automation,
Technology Center, Federal University of Rio Grande do Norte.
Education: Ph. D. student

Address: 318 Presidente Costa e Silva St., 59032-300, Alecrim, Natal,
Brazil.
Personal E-mail: ana.carla@gmail.com; acca.engpet@gmail.com
Research and Professional Experience: Degree in Computer Engineering
and Petroleum Engineering.

Andrade, A. C. C.; Maitelli, C. W. S. P. Simulation of single-phase of flow
viscous fluids in centrifugal pumps oil industry. Petro and Química
Magazine, n. 348, p. 50-53, 2013.
Andrade, A. C. C.; Maitelli, A. L.; Maitelli, C. W. S. P. Verifying the
influence of modifying the geometry parameters in a typical pump’s
impeller from an ESP system. ESSS Conference and Ansys Users Meeting,
2014.
Andrade, A. C. C.; Maitelli, A. L. Optimization method using flexible
polyhedral. Automation Symposium, 2014.
Araujo, I. B. Q.; Araujo Junior, M. E. U.; Andrade, A. C. C.; Lopes, K. R.;
Maitelli, A. L. Fault detection in residential storage and water distribution
systems through the use of maps self-organyzed. Automation Symposium,
2014.
Industrial.
Name: Melyssa Lima de Medeiros

Affiliation: University Potiguar Laureate International Universities
Education: Post Graduate Program in Biotechnology, University Potiguar
Laureate International Universities, Campus Salgado Filho, 59075-000, Natal,
RN, Brazil.
Graduate in Physiotherapy, University Potiguar Laureate International
Universities, Campus Salgado Filho, 59075-000, Natal, RN, Brazil.
Address: Av. Antonio Basílio, 3784, Apt. 16. Lagoa Nova, 59.056-500,
Natal, RN, Brazil.
Personal E-mail: medeiros.melyssa@gmail.com
Business E-mail: melyssamedeiros@unp.br
Research and Professional Experience: Teacher of the Physiotherapy

course at the University Potiguar Laureate International. Ph. D. student.
Professional Appointments: Research development for treatment of skin
diseases. Achievements include wound healing treatment and Laser therapy.

Maciel, M. A. M.; Almeida, C. C. A.; Felipe, M. B. M. C.; Moura, L. S. A.
M.; Medeiros, M. L.; Medeiros, S. R. B.; Silva, D. R. Effectiveness of an
alkaloid fraction on carbon steel corrosion inhibition evaluated in a green
chemistry biotechnological research. In: Waqar Ahmed; David Andrew.
(Org.). Nanobiotechnology. 1 ed. Manchester: One Central Press, 2014, v.
1, p. 99-117.
Industrial.
Industrial.
Industrial.
Industrial.
Meyer, P. F.; Soares, I. J. P.; Silva, R. M. V.; Medeiros, M. L.; Fortuny, E. P.
Evaluation and treatment of respiratory therapy on post-operative plastic
surgery. Revista Terapia Manual, v. 11, p. 444-450, 2013.
Silva, R. M. V.; Barichello, P. A.; Medeiros, M. L.; Mendonça, W. C. M.;

Dantas, J. S. C.; Ronzio, O. A.; Meyer, P. F.; Galadari, H. Effect of
Capacitive Radiofrequency on the Fibrosis of Patients with Cellulite.
Dermatology Research and Practice, v. 2013, p. 1-6, 2013.
Silva, R. M. V.; Meyer, P. F.; Souza, J. F.; Félix, J. L. O.; Delgado, E. B. S.;
Queiroz, L. D.; Medeiros, M. L. Effects of bioactive lipolytic gels on
phonophoresis in the abdominal adiposity. O Mundo da Saúde (Online), v.
38, p. 369-374, 2014.
Name: Maria de Fátima Vitória de Moura

Education: Ph. D.
Address: Rua Dolfo Gordo, 744, Cidade da Esperança, Natal, RN, Brazil.
Personal E-mail: mfvmoura.q@gmail.com
Business E-mail: mfvmoura@ufrnet.br
Research and Professional Experience:
Graduated in Pharmacy from the Federal University of Rio Grande do
Norte (1986), master’s degree in Chemistry from the Federal University of Rio
Grande do Norte (1994) and Ph. D. in Chemistry (Analytical Chemistry) at the
University of São Paulo (1998). Currently Associate Professor III of the
Federal University of Rio Grande do Norte. Experience in Analytical
Chemistry: Thermal Analysis (TG, DTA and DSC), Molecular Absorption
Spectroscopy (UV-VIS and IR), Atomic Absorption Spectroscopy (AAS) and
Chromatography (GC and HPLC), with emphasis on analysis food and
medicines.
Professional Appointments: Analytical Chemistry teacher in the
Universidade Federal do Rio Grande do Norte.
Cabral, A. M.; Moura, M. F. V.; Silva, D.R. Original method for identification
of abamectin and ivermectin in pharmaceutical formulations used in
producing animals, using liquid chromatography coupled to ultra
efficiency photodiodes: Risk assessment of pesticide residues in dairy
products. Science open posters, v. 1, p. 1, 2014.

Emerenciano, D. P.; Maciel, M. A. M.; Xavier Junior, F. H.; Moura, M. F. V.
Emerenciano, D. P.; Cruz, A. M. F.; Pereira, J. D. S.; Moura, M. F. V.;
MACIEL, M. A. M. Determination of antioxidant property and minerals
contained in the leaves of Azadirachta indica A. Juss. Revista Fitos
Industrial.
Chapter 5
CORROSION MECHANISM AND INHIBITORS

FOR AL BASED PARTICULATE METAL
MATRIX COMPOSITE (APMMCS)
Ajay Singh Verma*, Sumankant and N. M. Suri

Production & Industrial Engineering Department
PEC University of Technology Chandigarh, India
ABSTRACT
Corrosion in metals is gradual degradation by oxidation in hostile
environment. APMMCs are the materials which developed by combining
two distinguish parts namely matrix and reinforcement phases fabricated
by different casting techniques. Corrosion in APMMCs happens due to
pitting initiation at the interface of the fabricated APMMCs and crevices
on the surface of the fabricated APMMCs. Corrosion mechanism in
APMMCs is due to galvanic reaction between the matrix phase and its
reinforcement phase. Formation of new compounds at the interface of the
APMMCs is also a reason of selective corrosion. Pitting action occurs in
APMMCs as localize corrosion. Potential gradient elevate the oxidation
of metal in hostile environment results in pitting phenomenon. Generally
APMMCs are more susceptible to corrosion as compare to its base alloys
*
Corresponding author: Research Scholar, Production and Industrial engineering department,
PEC University of Technology, Chandigarh; Email: aashifun27@gmail.com,
+919466001914.
106 Ajay Singh Verma, Sumankant and N.M. Suri
but superior in strength in terms of mechanical properties. Cognition

behind this is reinforcement is hurdle for preserve the passive film which
is on the surface of aluminum. Aluminum having strong thin passive film
on the surface which brakes, it recovers itself. In APMMCs
reinforcements shatter the oxide film, allowing pitting and crevice
corrosion. Hence, inhibition of corrosion becomes necessary to protect
the APMMCs from the hostile environment and to increase the life of
fabricated APMMCs. Polymer coating, anodizing, surface modification
and chemical passivity are the inhibitor process for the fabricated
APMMCs. Among these inhibitors anodizing is the best method to protect
APMMCs from corrosion in hostile environment. This chapter addresses
the mechanism of corrosion for APMMCs. Different methods of
inhibition to corrosion for APMMCs are also discussed.
Keywords: Aluminum Particulate Metal Matrix Composite (APMMCs),

corrosion and corrosion Inhibitors
INTRODUCTION
Corrosion is an electrochemical phenomenon in which metals and alloys
converted into its oxides, hydroxides and aqueous salts. This electrochemical
reaction splits into two or more partially oxidation and reduction reaction. It
may also be defined as the deterioration of metal surface and its properties by
electrochemical or chemical reaction with its hostile environment.
Mechanism
In metals the corrosion takes place due to electrochemical reactions. This

reaction associated with charge transfer rather than mass transfer. Electrons
are set free by the anodic reaction and absorbed by the cathodic reaction at the
same time as illustrated in (1) – (3) and figure 1.
𝑀𝑒
→ 𝑀𝑒 2+ + 2𝑒 {𝐴𝑛𝑜𝑑𝑖𝑐 𝑃𝑟𝑜𝑐𝑒𝑠𝑠} (1)
𝑀𝑒𝑡𝑎𝑙 𝑀𝑒𝑡𝑎𝑙 𝑖𝑜𝑛 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠
𝐻2 ↑
2𝐻 + 2𝑒
+ → ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛 𝑔𝑎𝑠𝑠 {𝐶𝑎𝑡ℎ𝑜𝑑𝑖𝑐 𝑃𝑟𝑜𝑐𝑒𝑠𝑠} (2)
𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 𝑖𝑜𝑛 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛
𝑒𝑠𝑐𝑎𝑝𝑒
The overall reaction is a spontaneous reaction

Corrosion Mechanism and Inhibitors … 107
𝑀𝑒 + 2𝐻 + → 𝑀𝑒 2+ + 𝐻2 (3)
Figure 1. a) Systematic diagram of electrochemical process b) Corrosion mechanism of

metal.
CORROSION IN METAL MATRIX COMPOSITE

Metals and their alloys are susceptible to corrosion in neutral, basic and
acidic solutions. Aluminum is one of the major matrixes for metal matrix
composite is also susceptible to corrosion. Figure 2 illustrates the types of
corrosion in aluminum alloys and its composites.
Figure 2. Types of corrosion in aluminum based metal matrix composite.

Aluminum based particulate metal matrix composites (APMMCs) are

generally susceptible to corrosion in various hostile environments, due to
either selective corrosion, galvanic reaction between the base matrix and
reinforcement phase, creation of pathway for corrosion by fissures, formation
of new compound at the interface, or to defects at the interface [1]. APMMC is
very week in resistant to corrosion as compare to its base matrix because
reinforcement creates discontinuity in the protecting film and promotes local
corrosion sites at the interface. In fact the reinforcement phase creates hurdle
for protecting the passive film.
Aluminum alloys have natural strong thin passive film on the surface i.e.
protecting from pitting initiation. If this passive film breaks, aluminum alloy
itself recovers and generate this film. In APMMCs this passive film breaks,
allowing pitting and crevice corrosion of underlying substrate. Increase in
reinforcement phase further leads to discontinuity in the film and increases the
number of site for corrosion initiation and crevice; hence, reinforcement phase
makes the barrier for recovery of strong oxide film at the surface of aluminum.
The reinforcements like SiC, Al2O3, TiC, B4C, Zr etc. have different
mechanisms of corrosion due to the chemical composition, shape and size,
amount of the reinforcement. Hence, to overcome this problem, corrosion
inhibitors for APMMCs are required. Some methods as shown in figure 3 are
available for corrosion inhibitors like surface modification, polymer coatings,
anodizing and chemical passivity; however, these methods for PMMCs are not
as effective as for Al alloys [2, 3]. Among all of the corrosion protection
methods, the anodizing is the best method for protecting the APMMCs.
Corrosion Inhibitors in Metal Matrix Composite
Figure 3. Types of Corrosion Inhibitors for APMMCs.
ANODIZING OR MICRO-ARC OXIDATION (MAO)

Micro-arc oxidation (MAO) or Plasma Electrolytic Oxidation (PEO) is a
surface treatment process for producing oxide layer on metals. This process is
alike as anodizing. In this process an oxide layer is formed by mean of
combine effect of electrochemical oxidation with a higher potential treatment

in an alkaline electrolyte. The oxide film or coating is generated due to
chemical conversion of the substrate metal into its oxide. A systematic
diagram shows the complete process of MAO.
The advantage of this process is to obtain wear and corrosion resistant
surface as compare to its metal matrix. It is usually suitable for the surface
oxidation and coloring of Al, Mg, Nb, Ti, Zr and their alloys.
MAO coating is widely used surface treatment process for Mg, SiC and
Cu base aluminum alloys as shown in figure 5 [9-13]. Aluminum based
particulate type MMCs are more prone to corrosion due to its reinforcement
phase. The behavior of corrosion is depends on type of reinforcement use to
fabricate the APMMCs. Surface preparation is required to MAO coating on
APMMCs.
Its application on APMMCs foams has not been systematically
investigated because the behavior of the coating on APMMCs is not similar
like its base matrix coating. A thick and strong bond coating is required on the
surface of APMMCs.
Figure 4. Systematic diagram of MAO process [4-8].

Figure 5. Micrographs of MAO film on 2024/SiC: (a) and (c) scanning of Al line, (b)
and (d) scaning of SiC line (I) substrate of 2024/SiC (II) Inner layer film (III) outer
layer film [6].
Advantages of MAO Coating
1. It can be used where the alloys like high silicon and copper based
aluminum alloys difficult to anodize with traditional anodizing
process.
2. Higher thickness of coating (up to 300 microns) is achieved.
3. Pre and Post surface treatments are not required.
4. Decorative attractiveness of colors of the coatings.
5. Inexpensive electrolyte and environment friendly.
Applications
Worldwide use of MAO coating to enhance the corrosion, thermal and

wear resistance properties of industrial elements which is used in the
automobile, aerospace, textile and biomedical industries. It also used in
mechanics, transportation, building and chemical industries for the physical

appearance of the product. Some examples are illustrated further in figure 6.
Figure 6. a) Al locater pins, b) Mobile phone shell, c) Al appliance, d) Engine piston,

e)Vehicle wheel hub, f) Al alloy iron, g) Textile parts [4-8].
POLYMER COATING
Polymers are the molecules that contain atoms, typically tens of thousands
to millions. All polymer coatings are permeable to chloride and sodium ions,
water and gasses depending on the feature of the polymer coating and medium
of coating applied to APMMCs. Polymer coating like epoxy resin (Hysol G7-
4102) acts as an inhibitor for the SiC, graphite and Li based APMMCs [14].
Presently TiO2 doped polypyrrole nano coating (PPy-TiO2) is using for
aluminum and its alloy [15]. These coatings make the bar between the
substrate material and the environment. Types of polymer coating applied on
the surface of AMMCs are depending on the environmental requirements.
Coatings must have the following feature for superior corrosion resistance
[16].
1) High resistance to the electrons flow of electrons

2) Adequate thickness (lesser thickness fail to corrosion resistant)
3) Higher degree of adhesion to the substrate
4) Minimum level of porosity in coating (lesser the discontinuity)
5) Low diffusion rate of Cl- and H2O ions.
Applications
Use in automobile industries, structural industries, aluminum doors and

windows.
CHEMICAL PASSIVITY
Chemical passivation is the process to create a shield on the surface of the
material. It acts as a micro coating, created by chemical reaction with the base
material. Mechanism of passivation is to govern the increase of the thickness
of shield layer i.e., oxide layer over time. Aluminum and aluminum based
PMMCs are require inhibiting from corrosion. Aluminum have self healing
oxide layer on the surface which brakes and recover itself which creates a self
barrier to corrosion. However, Chromate conversion coating a type of
chemical passivity is a corrosion inhibitor for APMMCs. Chromate is not
environment friendly due to toxic in nature. It is also known as rare earth
metal ions such as Ce3+, La3+, Nd3+, Y3+, Pr3+. Cerium conversion is also a type
of chemical passivity for APMMCs to protect from corrosion as shown in
figure 7 [17, 18 - 20].
Figure 7. Cerium conversion films surface morphologies on Al/(Al2O3 + TiB2)

composite immersed in CeCl3 and H2O2 solutions [20].
Hydrated cerium oxide film formed by cerium salt at cathodic sites on the
surface of alloy therefore it inhibits the corrosion. This film acts as a cathodic
inhibitor at cathodic site of alloy surface by suppressing kinetics of the oxygen
reduction [21]. A hydrogen peroxide or sodium per chlorate is required to the
cerium chloride bath to accelerate the formation of cerium oxide/hydroxide
film [22].
Applications
Use to passivate aluminum and APMMCs, cadmium, silver, tin, steel,

copper, zinc and magnesium alloys [23].
REFERENCES
[1] Georgatis, E., Lekatou, A., Karantzalis, A. K., Petropoulos, H.,
Katsamakis, S., Poulia, A., 2013. Development of a cast Al-Mg2Si-Si In
Situ composite: Microstructure, heat treatment and mechanical
properties. Journal of Materials Engineering and Performance. 22, 729–
741.
[2] Mansfeld, F., Jeanjaquet, S. L., 1986. Evaluation of corrosion protection
measures for metal matrix composites. Corrosion Science. 26, 727.
[3] Lin, S., Greene, H., Shih, H., Mansfeld, F., 1992. Corrosion protection
of Al/SiC composites by anodizing. Corrosion. 48, 61.
[4] Jin, F. Y., Tong, H. H., Shen, L. R., Wang, K., Chu, P. K., 2006. Micro-
structural and Dielectric Properties of Porous TiO2 Films Synthesized on
Titanium Alloys by Micro-Arc Discharge Oxidization. Materials
Chemistry and Physics. 100 (1), 31-33.
[5] Jin, F. Y., Chu, P. K., Xu, G. D., Zhao, J., Tang, D. L., Tong, H. H.,
2006. Structure and Mechanical Properties of Magnesium Alloy Treated
by Micro-Arc Discharge Oxidation Using Direct-Current and High-
Frequency Bipolar Pulsing Modes. Materials Science and Engineering
A, 435-436 (1)- 2, 123-126.
[6] Jin, F. Y., Chu, P. K., Tong, H. H., Zhao, J., 2006. Improvement of
Surface Porosity and Properties of Alumina Films by Incorporation of Fe
Micrograins in Micro-Arc Oxidation. Applied Surface Science. 253 (2),
863-868.
[7] Wei, C. B., Tian, X. B., Yang, S. Q., Wang, X. B., R. Fu, K. Y., Chu, P.
K., 2007. Anode Current Effects in Plasma Electrolytic Oxidation.
Surface and Coatings Technology. 201 (9-11), 5021-5024.
[8] Qiu, T., Wu, X. L., Jin, F. Y., Huang, A. P., Chu, P. K., 2007. Self-
Assembled Growth of MgO Nanosheet Arrays via a Micro-Arc
Oxidation Technique. Applied Surface Science. 253 (8), 3987-3990.
[9] Xue, W., Wu, X., Li, X., Tian, H., 2006. Anti-corrosion film on
2024/SiC aluminum matrix composite fabricated by microarc oxidation
in silicate electrolyte, Journal of Alloys and Compounds. 425, 302–306.
[10] Mısırlı, C., Şahin M., Sozer U., Effect of Micro Arc Oxidation Coatings
on the Properties of Aluminum Alloys. Aluminum Alloys - New Trends
in Fabrication and Applications, Intech. 2012, pp 107-120.
[11] Jin, F., Chu, P. K., Tong, H., Zhao, J., 2006. Improvement of Surface
Porosity and Properties of Alumina Films by Incorporation of Fe
Micrograins in Micro-Arc Oxidation. Applied Surface Science. 253,
863–868.
[12] Liu, Y. J., Xu, J. Y., Lin, W., Gao, C., Zhang, J. C., Chen, X. H., 2013.
Effects of Different Electrolyte Systems on the Formation of Micro-Arc
Oxidation Ceramic Coatings of 6061 Aluminum Alloy. Review of
Advanced Material Science. 33, 126-130.
[13] N. V. Vyazovikina, Protect. Met., 35, 448 (1999).
[14] Lin, S., Shih, H., Mansfeld, F., 1992. Corrosion Protection of Aluminum
Alloys and Metal Matrix Composites by Polymer Coatings. Corrosion
Science. 33 (9), 1331-1349.
[15] Mert, B. D., 2016. Corrosion protection of aluminum by
electrochemically synthesized composite organic coating. Corrosion
Science. 103, 88-94.
[16] Ahamd Z., Principles of Corrosion Engineering and Corrosion Control.
Butterworth-Heinemann; 2006.
[17] Chen, Mansefeld, F., 1997. Corrosion protection of an Al6092/SiCp
metal matrix composite. Corrosion Science. 39 (6), 1075-1082.
[18] Aziz, I., Qi, Z., Min, X., 2009. Corrosion inhibition of SiCp/5A06
aluminum metal matrix composite by Cerium conversion treatment,
Chinese Journal of Aeronautics. 22, 670-676.
[19] Ahmad, Z., Aleem, A., 2009. The effect of inhibitors on the
susceptibility of Al6013/SiC interface to localized corrosion, Journal of
Materials Engineering and performance. 18, 129-136.
[20] Tjong, S. C., Huo, H. W., 2009. Corrosion protection of In Situ Al-based
composite by Cerium conversion treatment, Journal of Materials
Engineering and Performance. 18, 88-94.
[21] Arnott, D. R., Hinton, B. R. W., Ryan, N. E., 1989. Cationic-film-
forming inhibitors for the protection of the AA 7075 aluminum alloy
against corrosion in aqueous chloride solution, Corrosion. 45, 12–18.
[22] Wilson, L., Hinton, B. R. W., 1988. A method of forming a corrosion
resistant coating, Patent Int WO 88/06639.
[23] Buschow, K. H. Jürgen; Cahn, Robert W.; Flemings, Merton C.;
Ilschner, Bernhard; Kramer, Edward J.; Mahajan, Subhash, 2001.
Encyclopedia of Materials - Science and Technology. 1265, Elsevier,
Oxford, UK.
Chapter 6
ELECTROCHEMICAL STUDY OF 1,3,4-

TRIAZOLIUM-2-THIOL AS A CORROSION
INHIBITOR OF MILD STEEL
IN SALINE MEDIUM
Jardel D. Cunha1, Cátia G. F. T. Rossi2,

Djalma R. Silva2, Ewerton R. F. Teixeira2,
Aurea Echevarria3 and Maria Aparecida M. Maciel2,4,
1
Institute of Chemistry, Center of Exact Sciences and Earth,
2
Department of Environmental and Technological Sciences,
Rural Federal University of Semi Arid, Mossoró, RN, Brazil
3
Department of Chemistry,
Rural Federal University of Rio de Janeiro,
Seropédica, RJ, Brazil
4
University Potiguar Laureate International Universities,
Natal, RN, Brazil

Corresponding author: Maria Aparecida M. Maciel. Department of Environmental and
Technological Sciences, Rural Federal University of Semi Arid, 59625-900, Mossoró, RN,
Brazil. University Potiguar Laureate International Universities, Campus Salgado Filho,
59075-000, Natal, RN, Brazil. Email: mammacial@hotmail. com.
118 Jardel D. Cunha, Cátia G. F. T. Rossi, Djalma R. Silva et al.
ABSTRACT
The mesoionic compound 1,3,4-triazolium-2-thiol (MI) was
solubilized in an oil-in-water microemulsion (OCS-ME) containing
saponified coconut oil (OCS) as surfactant, butan-1-ol as cosurfactant,
kerosene as oil phase and saline solution as aqueous medium. The MI-
loaded system (OCS-ME-MI) was evaluated as corrosion inhibitor at
lower concentrations (ranging from 12.5 ppm to 100 ppm) using the
electrochemical and gravimetric methods, Linear Polarization Resistance
(LPR) and Mass Loss (ML), respectively. The corrosion inhibition of
OCS-ME-MI was evidenced on the AISI 1018 steel, in saline solution
(NaCl 1%) showing higher inhibitory effect, such as 92.60%, at 75 ppm
of OCS-ME-MI sample by LPR technique, and 92.68% at 75 ppm of
OCS-ME-MI sample by ML technique. According to the electrochemical
method applied, linear polarization curves with Tafel extrapolation, OCS-
ME-MI obeys Frumkin adsorptions isotherm.
Keywords: 1,3,4-triazolium-2-thiol, microemulsion, corrosion inhibitor, linear

polarization resistance, mass loss
INTRODUCTION
Particular attention may be paid to several studies involving corrosive
processes aiming to identify and characterize aggressive environment
responsible for the chemical, electrochemical and electrolytic reactions
developed on very important industrial metallic materials. Currently, corrosion
control is one of the biggest challenges in the environmental industry
technology, and the knowledge of corrosion reactive processes is based on
energy considerations which justify the spontaneity of the corrosion
phenomena. Corrosion in metallic surfaces causes strong material loss, which
has been generating much concern regarding the mitigation of corrosion
damage. Several protective measures are taken to control or prevent corrosion,
one of them is applying corrosion inhibitors, which form protective films
against the action of corrosion agents under different materials [1-5].
The use of inhibitors is one of the best methods to protect metals against
corrosion phenomena. Since mild steels are basically composed of metallic
atoms, the choice of a corrosion inhibitor comes especially from its electron
donation ability. In this sense, heterocyclic organic compounds containing
nitrogen, oxygen sulfur, and phosphorous among others, have been often
Electrochemical Study of 1,3,4-Triazolium-2-Thiol … 119
reported for their corrosion inhibition effectiveness. Most corrosion inhibitors

are synthetic organic compounds having heteroatoms in their aromatic or long
carbon chain. These organic compounds can adsorb on the metal surface,
block the active sites on the surface and thereby reduce the corrosion rate and
are commonly added in small amounts to pickling acids, acid stimulation
fluids, cooling waters, oil and gas production streams, either continuously or
intermittently to control corrosion [6-12].
Microemulsion systems have been studied as corrosion inhibitors, taking
advantage of their ability to dissolve active matter, with highly relevant
adsorption capacity correlated to the very low interfacial tensions and large
interfacial areas established at the contacting microregions. The mechanism of
microemulsion spontaneous formation involves as enhanced reduction in the
interfacial tension between water and oil. Specifically, colloidal type systems
(microemulsion) are formed by using: surfactant, and cosurfactant (if
necessary), oil and water. These components are arranged to reach
thermodynamic equilibrium [13-18].
Microemulsions are formed from an apparent spontaneous solubilization
of two immiscible liquids (water, oil) in the presence of a surfactant and, if
necessary, a cosurfactant. They are characteristically dispersed media
(dispersed microdroplets), monophasic, thermodynamically stable, transparent
or translucent systems, with lower interfacial tension and with the capability to
combine great amounts of two liquids in a single homogeneous phase.
Surfactant is an amphiphilic molecule-type whose structure has two opposite
polarity areas: a polar group (hydrophilic) and a non-polar (hydrophobic). The
presence of these two different areas in the same molecule enables its
adsorptions in air-water, oil-water, and solid-water interfaces. Due to its
chemical composition, the microemulsion systems (MES) present great
structural diversity, being formed by dispersed and dynamics microdroplets,
with a particle diameter ranging from 5 to 100 nm. They present a
mononuclear layer of amphiphilic molecules involving the microdroplets as a
membrane, and when the system is water-rich (o/w) they are the oil-in-water
type system, with “direct” microdroplets. In the other hand, water-in-oil (w/o)
represent the oil-rich type system, with “inverse” microdroplets [13-18].
The effectiveness of microemulsions (ME) containing saponified coconut
oil (OCS) as semissynthetic surfactant prepared with OCS, butan-1-ol
(cosurfactant), kerosene and saline solutions aiming at loaded
diphenylcarbazide (DC) were applied as corrosion inhibitors on AISI 1020
mild steel. The formed colloidal systems OCS-ME and OCS-ME-DC were
evaluated using an electrochemical method of polarization resistance and
showed highest inhibitory effects (77% for OCS-ME and 92% for OCS-ME-
DC) at lower concentrations (0.5% of samples). The surfactant OCS (dissolved
in H2O) showed lower efficiency (63% at concentrations ranging from 0.20%
to 0.25%). The greatest inhibitory effect of DC-ME was correlated with the
chemical structure of DC as well as its o/w colloidal type vehicle system,
which is very important for adsorption phenomena [18].
On using the OCS-ME system for loading thiosemicarbazones such as 4-
N-cinnamoyl-thiosemicarbazone (CTSC), 4-N-(2’methoxycinnamoyl)-
thiosemicarbazone (MCTSC), and 4-N-(4’-hydroxy-3’-methoxybenzoyl)-
thiosemicarbazone (HMBTSC) it was also possible to evaluate their
effectiveness on AISI 1020 mild steel, on saline medium (NaCl 0.5%).
Whereas the corrosion inhibition of the formed systems OCS-ME-CTSC,
OCS-ME-MCTSC, and OCS-ME-HMBTSC measured using a galvanostatic
method, showed great inhibitory effects (85.7%, 84.0%, 83.3%, respectively).
The surfactant OCS (dissolved in H2O) and the target OCS-ME system
showed lower efficacies (71.0% and 74.0% respectively) [17].
In this present study the heterocycle compound 1,3,4-triazolium-2-thiol
(MI) a mesoionic type chemical specimen was solubilized into this OCS-ME
system affording the target sample OCS-ME-MI aiming at evaluated its
corrosion inhibitor importance using the electrochemical Linear Polarization
Resistance (LPR) and Mass Loss (ML) methods.
EXPERIMENTAL
Inhibitor Preparation
The mesoionic compound 1,3,4-triazolium-2-thiol (MI) was synthesized

via anhydroacylation conditions as previously described [19, 20] and then
dissolved into a o/w microemulsion (ME) composed with CS/S =1 {20.0% of
surfactant [(S), saponified coconut oil (named OCS)] and 20.0% of butan-1-ol
as cosurfactant (CS)}, 5.0% of oil phase (kerosene) and 55% of saline solution
(NaCl 1%, as aqueous medium), affording a microemulsion system, so called
OCS-ME. The procedure used to obtain the Winsor IV (WIV) region in the
ternary phase diagram was based on determination of the maximum solubility
of the active matter (surfactant) in aqueous and oil phases, by means of mass
titrations, being in accordance with a previously described methodology,
which was chosen by its high stability and power for solubilizing organic
compounds [15-18, 21].
The solubility effectiveness of the tested sample (MI) loaded into OCS-
ME system was evaluated by the minimum and maximum solubility method
[21, 22]. Quantification was performed by spectrophotometer (Thermo
Electron Corporation/Nicolet Evolution 100) in the visible region using
wavelength (λ) between 400 to 800 nm for determining the λmax. Relationship
between a specific concentration of MI sample dissolved in 1 mL of methanol
versus absorbance of the tested coloidal sample (OCS-ME-MI) were used to
obtain the calibration curve (λmax was noted during each experiment). By using
known masses of MI, the maximum solubility was 0.0035 g/mL of 1,3,4-
triazolium-2-thiol in 1 mL of the vehicle OCS-ME system. To quantify the
solubility, a surplus of MI (0.0106 g) was added in a glass vial with 3 mL of
OCS-ME. The vials were sealed and the sample was vortexed for 10 minutes,
followed by stirring in ultrasound for 10 minutes at room temperature. After
equilibration, sample was filtered, diluted as required with the distilled water.
The resulting solution was analyzed by the UV-spectrophotometer method in
the λmax. The ideal solubilized amount of 1,3,4-triazolium-2-thiol into the
colloidal system (OCS-ME) was obtained using the linear regression equation.
The calibration curve was constructed based on the relationship between
concentration versus absorbance of the standard sample (MI dissolved in 1 mL
of methanol) in the λmax. The target 1,3,4-triazolium-2-thiol was completely
solubilized with maximum solubility at 0.0035 ± 0,0026 g/1 mL of OCS-ME,
corresponding to 40% of the initial concentration (0.0088 mg/mL). The total
amount of the tested sample used on the corrosion inhibition assays were
0.3914 g/110 mL of OCS-ME.
Corrosion Inhibition Assays
The efficiency 1,3,4-triazolium-2-thiol loaded into a microemulsion (so

called OCS-ME-MI) applied as corrosion inhibitior on AISI 1018 mild steel,
in saline medium, was evaluated by potentiodynamic technique using
AUTOLAB potentiostat coupled with GPES version 4.9 software aiming at to
obtain Tafel curves and corrosion parameters. Stern-Geary constant (B) was
obtained from the combination of Tafel-inclinations (ba = anodic and bc =
cathodic) [23]. An electrochemical cell (Figure 1a) with a reference electrode
(Ag/AgCl), a platinum auxiliary electrode, and a working electrode (AISI
1018 steel, chemical composition: Fe, 98.88; C, 0.18; Mn, 0.85; P, 0.04; S,
0.05, Figure 1b) were applied at different concentrations of OCS-ME-MI
sample (12.5 ppm to 100.0 ppm). Efficiency behaviour of OCS-ME-MI was
evaluated, in regular measurements (every 10 minutes), for an extended period

of 23 hours, using the Linear Polarization Resistance (LPR) method.
Electrodes presented the flow lines shown on Figure 2. Statgraphics®
Centurion XVI software was used for statistical comparison at a 95% level of
statistical significance for the LPR values. The criteria to evaluate the
corrosion inhibitors included: emulsion formation, film formation speed, film
persistence, and reduction of corrosion rates in 90% after 1h of injection.
a b
Figure 1. Electrochemical cell (a); Mass loss coupons and LPR shape and size (b).
Figure 2. LPR probe; coupon view and its two main generators in 0° (upstream) and
180° (downstream), adapted [23].
After the assay period (23 h) , the mass loss of the working electrodes was
measured, and the cleaning (acid cleaning) was performed in accordance to
ASTM G1-03. The average corrosion rate was calculated using Equation 1, in
which: W (mass loss, in grams), A (initial area of exposed samples, in mm2), T
(exposure time, in days) and D (material density, in g/cm3). Equation 2 was

used to calculate corrosion inhibition efficiency.
𝑊𝑥365𝑥1000
𝐶𝑜𝑟𝑟𝑜𝑠𝑖𝑜𝑛 𝑅𝑎𝑡𝑒 = 𝐴𝑥𝑇𝑥𝐷
(1)
(𝐶𝑅𝑤𝑖𝑡ℎ𝑜𝑢𝑡 𝐼𝑛ℎ𝑖𝑏𝑖𝑡𝑜𝑟 −𝐶𝑅𝑤𝑖𝑡ℎ 𝐼𝑛ℎ𝑖𝑏𝑖𝑡𝑜𝑟 )

𝐼𝑛ℎ𝑖𝑏𝑖𝑡𝑜𝑟 𝐸𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 = 𝐶𝑅𝑤𝑖𝑡ℎ𝑜𝑢𝑡 𝐼𝑛ℎ𝑖𝑏𝑖𝑡𝑜𝑟
𝑥100 (2)
In order to evaluate the adsorption phenomena of these tested sample on

the metal surface, adsorption isotherms were applied, using equations 3, 4, and
5. The surface coverage (θ) was calculated from the rates of corrosion
inhibition obtained by polarization curves data, “C” represent the inhibitor
concentration in ppm, “K” is the adsorption equilibrium constant, and “g” is
the degree of lateral interaction among the adsorbed molecules.
C 1
 C
Langmuir:  K (3)
  
Log    LogK  g
Frumkin:  1   .C  (4)
 
Log    LogK  g
Temkin: C  (5)
RESULTS AND DISCUSSION

The target 1,3,4-triazolium-2-thiol (Figure 3) at lower concentrations
(maximum of 0.5%) into the microemulsion OCS-ME, was loaded aiming at
strong adsorption by filming formation. A ternary phase diagram of the
colloidal OCS-ME system was conducted by a mass titration of oil phase in
which the masses of the surfactant and aqueous phase (previously quantified)
recorded the phases of transition points. The micellar aggregates were
characterized as a o/w colloidal self-microemulsion system due to its
increasingly isotropic aspect after several water dilutions. The stability of the
vehicle (OCS-ME microemulsion system) was confirmed by tensiometry
measurements which revealed that surface tension decreases at higher
surfactant concentration and viscosity varies with temperature increase.

According to the OCS-ME viscosity data a linear relationship between the
shear stress and rate was observed, suggesting a Newtonian flow feature [15-
18, 21].
In the sequencial analysis, OCS-ME-MI at low concentrations (12.5 ppm
to 100 ppm) was assayed as corrosion protector of AISI 1018 mild steel, in
saline medium. For corrosive assays, OCS-ME-MI was diluted on saline
corrosive medium (1% of sodium chloride) from which, no colloidal phase
change was observed.
Analyses of the findings on the OCS-ME-MI filming speed formation,
after ten minutes of the inhibitor addition (12.5, 25, 50, 75 and 100 ppm),
showed efficiency higher than 75% and a strong reduction (90%) in the
corrosion rates after one hour (Figure 4). The OCS-ME-MI films showed great
stability within the 24 hours of assay (Figures 5, 6, 7, 8, 9, and 10). No rupture
was observed, and this behaviour was ascertained by the lack of corrosion in
the working electrode (AISI 1018 steel) from an LPR probe, and also, in the
mass loss coupons. The presence of the mesoionic inhibitor promotes higher
adsorption on metal surfaces due to the existence of the heteroatoms on its
molecular structure as well as the aromatic rings, with higher electronic
distribution, affording strong adsorption phenomena on metal surfaces, thus
favoring the corrosion inhibitions. Compared to the previously published
OCS-ME-DC (diphenylcarbazide) [18] and OCS-ME-TSC
(thiosemicarbazone) [17] rich electronic systems, the tested OCS-ME-MI
sample improved the vehicle OCS-ME effectiveness, as a result of the higher
number of aromatic rings in the chemical structure of 1,3,4-triazolium-2-thiol
(MI). On the other hand, microemulsion system optimizes the solubilization of
water-insoluble organic material and increase the adsorption potential due to
the presence of surfactant, and the subsequent expansion of the surface
coverage.
Results of OCS-ME-MI inhibition efficiency obtained from mass loss
showed the sample 75 ppm concentration as the best one, since higher
concentrations were seen as unnecessary waste of chemical product, and the
lower ones were unable to promote protection for the metal in the saline-rich
solution under a carbon dioxide atmosphere. Mass loss results and the inhibitor
efficiency are found in the Table 1, and the Figure 11 shows the graph
efficiency versus each inhibitory concentration. The efficiency result from the
inhibitor concentration shown on Figure 11, follows the adsorption model
proposed by Frumkin.
Cl-
+
N N
SH
N
Figure 3. Chemical structure of the mesoionic compound 1,3,4-triazolium-2-thiol.
Figure 4. OCS-ME-MI film speed.
As far as aspect is concerned, the presence of corrosion located in the

tested sample was not detected. Uniform corrosion process was prevalent in
the OCS-ME-MI sample at the studied concentrations. Table 2 shows
comparison of corrosion rate and OCS-ME-MI inhibitor concentration
increases, a boost in the inhibitor efficiency can be seen through the
Polarization Linear Resistance (PLR) and mass loss (ML), as the applied
techniques.
Figure 5. Corrosion rate versus time at 12.5 ppm of OCS-ME-MI sample.
Figure 6. Corrosion rate versus time at 25 ppm of OCS-ME-MI sample.


Figure 10. Corrosion rate versus time at all OCS-ME-MI concentrations.

Table 1. Mass loss and corrosion rate for OCS-ME-MI system
Inhibitor C Mass Loss (g) Corrosion Rate Efficiency Corrosion

Content (mm/year) (%) morphology
Without 1 0.0059 0.3720 0.00 Uniform
inhibitor 2 0.0068 Uniform
3 0.0078 Uniform
Inhibitor C Mass Loss (g) Corrosion Rate Efficiency Corrosion
Content (mm/year) (%) morphology
12.5 ppm 1 0.0025* 0.1140 69.27 Uniform
2 0.0022 Uniform
3 0.0020 Uniform
25.0 ppm 1 0.0021* 0.0930 75.12 Uniform
2 0.0016 Uniform
3 0.0018 Uniform
50.0 ppm 1 0.0017 0.0910 75.61 Uniform
2 0.0017 Uniform
3 0.0016 Uniform
75.0 ppm 1 0.0010 0.0270 92.68 Uniform
2 0.0014 Uniform
3 0.0000* Uniform
100.0 ppm 1 0.0001 0.0054 98.54 Uniform
2 0.0001 Uniform
3 0.0003 Uniform
C=coupons, * Excluded coupon specimen due to higher mass loss than the others.
Table 2. OCS-ME-MI inhibitory efficiency through LPR and ML

methods
OCS-ME-MI (ppm) Corrosion rate Efficiency (%)

LPR ML LPR ML
0 0.419 0.372 0.00 0.00
12.5 0.091 0.144 78.28 69.27
25.0 0.027 0.093 93.55 75.12
50.0 0.103 0.091 75.41 75.61
75.0 0.031 0.027 92.60 92.68
100.0 0.047 0.005 88.78 98.54
Variables Control of the Corrosion Inhibition Assays
Dissolved oxygen and pH variable control in the cell system conditions

were done every 10 minutes, of the 23 h period of OCS-ME-MI analysis, form
which any sample microemulsion alteration leads to OCS-ME-MI film
disruption (Figure 12), pH initial values were between 6.5 and 7.0. Once
carbon dioxide (CO2) was injected into the solution, there was a reduction in
the pH value, which indicates the formation of carbonic acid. In the other
hand, the insertion of the inhibitor in the system conditions did not cause any
variance in the solution pH values. In fact, the presence of the semissynthetic
surfactant (saponified coconut oil, OCS) enhances the formation of a stable
and homogeneous protective film increasing the availability of the mesoionic
compound (MI), on metal surface.
During the 23 h period of OCS-ME-MI analysis, the dissolved oxygen
concentration showed values between zero (0.00 ppm) and 0.01 ppm (<10
ppb). Its lower concentration amount is the result of a continuous injection of
CO2.
When the mesoionic compound 1,3,4-triazolium-2-thiol (0,003 g/mL) was
dissolved into a o/w microemulsion (ME) composed with 15.0% of surfactant
(S), saponified coconut oil, OCS), 15.0% of butan-1-ol as cosurfactant (CS),
10.0% of kerosene (oil phase) and 60% of saline solution (NaCl 0.5%, as
aqueous medium) (Figure 13), a higher corrosion inhibitory effect as observed
(94%) at very lower concentrations (Tabel 3) of the tested sample. The
electrochemical method of linear polarization curves with Tafel extrapolation,
obeys Frumkin isotherm (Table 4, and Figure 14).
Figure 11. Mass loss corrosion efficiency of OCS-ME-MI versus inhibitor

concentration.
Figure 12. Variation of pH cell system conditions versus time.
Table 3. OCS-ME-MI contents versus NaCl (0.5%) volumes
VNaCl VOCS-ME-MI [OCS-ME-MI] [OCS-ME-MI] Mass (g) of OCS-

(mL) (mL) (%) (ppm) ME-MI
20 0 0 0 0
19 1 0.02 200 0.003
18 2 0.05 500 0.006
16 4 0.10 1000 0.012
14 06 0.15 1500 0.018
12 08 0.20 2000 0.024
10 10 0.25 2500 0.030
08 12 0.30 3000 0.036
06 14 0.35 3500 0.042
04 16 0.40 4000 0.048
02 18 0.45 4500 0.054
0 20 0.50 5000 0.060
1,3,4-triazolium-2-thiol (g/mL) dissolved in the modified OCS-ME.
Table 4. Adsorption constants (K) and lateral interaction (A) parameters

of the target sample OCS-ME-MI with 1,3,4-triazolium-2-thiol loaded in
the modified OCS-ME colloidal system
K A
Langmuir 6320
Frumkin 161000 4.39
Figure 13. Ternary phase diagram of the colloidal OCS-ME system.
Figure 14. Surface covered fraction obtained from electrochemical measurements and
corrosion efficiency data for OCS-ME-MI with CS/C = 1 (15% cosurfactant/15%
surfactant), 10.0% of oil phase, and 60% of aqueous saline medium.
CONCLUSION
The colloidal OCS-ME system containing saponified coconut oil, as
surfactant, effectively dissolved the heterocycle compound (1,3,4-triazolium-
2-thiol). The critical micelle concentration of this system occurs with low
concentrations of surfactant in pure distilled water and saline solution. The
OCS-ME-MI inhibitor efficiency enhances according to the concentration
rises; at 75 ppm maximum inhibition efficiencies were 92.60% and 92.68%
through LPR and ML techniques, respectively. The LPR electrochemical
method of polarization with extrapolation of Tafel was applied on mild steel
AISI 1018, in saline medium (1% of sodium chloride), and it showed Frumkin
as the optimum adsorption isotherm. Moreover, OCS-ME-MI at 100 ppm
showed effectiveness reduction (88.78%) by LPR analysis, but an increase in
the ML result (98.4%). In order to evaluate the adsorption phenomena of this
tested sample on the metal surface, facing some modified conditions of the
OCS-ME colloidal system by using lower amounts of surfactant, cosurfactant
and saline medium (NaCl 0.5%), the maximum LPR inhibition efficiency,
increased (94%), and obeys Frumkin isotherm. According to these findings,
this present electrochemical study validates the tested mesoionic compound,
1,3,4-triazolium-2-thiol, as an efficient corrosion inhibitor of mild steel.
ACKNOWLEDGMENTS
The authors are grateful to PPGQ-UFRN program for financial support.
REFERENCES
[1] Burstein, G. T., Liu, C., Souto, R. M., Vines, S. P., (2004). Origins of
pitting corrosion, Corros. Eng. Sci. Technol. 39, 1, 25-30.
[2] Fontana, M. G. and Greene, N. D., Corrosion Engineering, 3rd edition,
McGraw-Hill, New York, 1987.
[3] Bockris, J. O. M., Reddy, A. K. N., Modern Electrochemistry, vol. 2,
Plenum Publishing Corporation, New York, 1976.
[4] Soylev, T. A., Richardson, M. G., (2008). Corrosion inhibitors for steel
in concrete: state-of-the-art report. Constr. Build. Mater. 22, 1, 609-622.
[5] Lukovits, I., Kalman, E., Zucchi, F., (2001). Corrosion inhibitors-
correlation between electronic structure and efficiency, Corrosion Sci.
57, 3-8.
[6] D. Daoud, T. Douadi, H. Hamani, S. Chafaa, M. Al-Noaimi, (2015).
Corrosion inhibition of mild steel by two new S-heterocyclic compounds
in 1 M HCl: experimental and computational study, Corros. Sci. 94 21-

37.
[7] Rochdi, A., Kassou, O., Dkhireche, N., Touir, R., El Bakri, M., Ebn
Touhami, M., Sfaira, M., Mernari, B., Hammouti, B., (2014). Inhibitive
properties of 2,5-bis(nmethylphenyl)-1,3,4-oxadiazole and biocide on
corrosion, biocorrosion and scaling controls of brass in simulated
cooling water, Corros. Sci. 80 442-452.
[8] Solmaza, R., Altunbas, E., Kardas, G. z. (2011). Adsorption and
corrosion inhibition effect of 2-((5-mercapto-1,3,4-thiadiazol-2-
ylimino)methyl)phenol schiff base on mild steel. Mater. Chem. Phys.
125, 3, 796-801.
[9] Khaled, R. Y., Abdel-Gaber, A. M., Holail, H. M., (2016).
Electrochemical studies of the inhibition effect of 4,6-dichloro-2-
(methylthio) pyrimidine on the corrosion of AISI type 321 stainless steel
in 1.0 M Hydrochloric Acid. Int. J. Electrochem. Sci. 11, 1, 2790-2798.
[10] Fouda, A. S., Abdallah, M., Al-Ashrey, S. M., Abdel-Fattah, A. A.,
(2010). Some crown ethers as inhibitors for corrosion of stainless steel
type 430 in aqueous solutions, Desalination, 250,1, 538-543.
[11] Abiola, O. K., (2006). Adsorption of 3-(4-amino-2-methyl-5-pyrimidyl
methyl)-4-methyl thiazolium chloride on mild steel. Corros. Sci. 48, 1,
3078-3090.
[12] Goulart, C. M., Esteves-Souza, A., Martinez-Huitle, C. A., Rodrigues, C.
J. F., Maciel, M. A. M., Echevarria, A. (2013). Experimental and
theoretical evaluation of semicarbazones and thiosemicarbazones as
organic corrosion inhibitors, Corros. Sci. 67 281-291.
[13] Roberto, E. C., Wanderley Neto, A. O., Martinez-Huitle, C. A., Fonseca,
J. L. C., Dantas, T. N. C., Gurgel, A., (2013). The effect of type of self-
assembled system and pH on the efficiency of corrosion inhibition of
carbon-steel surfaces. Prog. Org. Coat. 76, 1308-1315.
[14] Moura, E. F., Wanderley Neto, A. O., Dantas, T. N. C., Scatena Júnior,
H., Gurgel, A., (2009). Applications of micelle and microemulsion
systems containing aminated surfactants synthesized from ricinoleic acid
as carbon steel corrosion inhibitors. Colloids and Surfaces A:
Physicochem. Eng. Aspects, 340, 199-207.
[15] Felipe, M. B. M. C., Silva, D. R., Martinez-Huitle, C. A., Medeiros, S.
R. B., Maciel, M. A. M., (2013). Effectiveness of Croton cajucara Benth
on corrosion inhibition of carbon steel in saline medium. Mater. Corros.
64, 6, 530-534.
[16] Anjos, G. C., Almeida, C. C., Melo, D. M. A., Martinez-Huitle, C. A.,

Rossi, C. G. F. T., Maciel, M. A. M., (2013). Effectiveness of
Anacardium occidentale Linn on a microemulsion system in the carbon
stell corrosion inhibition. Rev. Virtual Quim. 5, 4, 760-769.
[17] Moura, E. C. M., Souza, A. D. N., Rossi, C. G. F. T., Silva, D. R.,
Maciel, M. A. M., Echevarria, A., Bellieny, M. S. S., (2013). Evaluation
of anticorrosive effectiveness of thiosemicarbazones solubilized in a
microemulsion system. Quim. Nova. 36, 1, 59-62.
[18] Rossi, C. G. F. T., Scatena Jr, H., Maciel, M. A. M., Dantas, T. N. C.,
(2007). Comparative effectiveness microemulsions of diphenylcarbazide
and saponified coconut oil in the carbon steel corrosion inhibition
process. Quim. Nova. 30, 5, 1128-1132.
[19] Echevarria, A., Galembeck, S., Maciel, M. A. M., Miller, J, Montanari,
C. A., Rumjanek, V., Simas, A. M., Sandall, J. P. B. (1995). Reaction of
aroyl chlorides with 1,4-diphenylthiosemicarbazide: formation of Both
1,3,4-thiadiazólium-2-aminides and 1,3,4-triazolium-2-thiolate.
Heterocy. Commun. 1, 129.
[20] Maciel, M. A. M., Echevarria, A., Rumjanek, V., (1998). Isolation and
characterization of acyl-thiosemicarbazides as intermediates in
mesoionic compounds synthesis. Quim. Nova. 21, 5, 569-572.
[21] Maciel, M. A. M., Almeida, C. C., Felipe, M. B. M. C., Moura, L. S. A.,
Medeiros, M. L.; Medeiros, S. R. B., Silva, D. R. (2014). Effectiveness
of an alkaloid fraction on carbon steel corrosion inhibition evaluated by
green chemistry biotechnological approach. In: Nanobiotechnology. One
Central Press (UK), chapter 4, pp. 95-112.
[22] Xavier Junior, F. H, Gueutin, C., Morais, A. R. V., Alencar, E. N., Egito,
E. S. T., Vauthier, C., (2016). HPLC Method for the Dosage of
Paclitaxel in Copaiba Oil: Development, Validation, Application to the
Determination of the Solubility and Partition Coefficients.
Chromatographia, 79, 7, 405-412.
[23] Cunha, J. D., Silva, D. R. (2015). Application of the Linear Polarization
Resistance technique (LPR), for OCS microemulsion based system
evaluated as steel corrosion inhibitor in a medium of sodium chloride in
the presence of CO2. In: João Telésforo Nóbrega de Medeiros. (Org.).
TribLOOK: Um livro da Tribologia e Integridade Estrutural. 1 ed.
(v.B), Natal: EDUFRN, Editora da UFRN, pp. 243-254.
BIOGRAPHICAL SKETCH
Name: Maria Aparecida Medeiros Maciel
University Potiguar Laureate International Universities, Campus Salgado
Filho, 59075-000, Natal, RN, Brazil.
Education: Ph. D.
Personal E-mail: mammaciel@hotmail.com.
Business E-mail:
maria.maciel@unp.br
mammaciel@quimica.ufrn.br
maria.maciel@pq.cnpq.br.
Research and Professional Experience: Research Scientist and Educator.
Achievements include development of bioctive natural products including
trans-dehydrocrotonin isolated from an Amazon plant (Croton cajucara
Benth); research in large biochemical; research in large biotecnology; research
in green chemistry applied to corrosion inhibition.
Maciel, Maria Aparecida Medeiros, research scientist, educator; b.
Pesqueira, Pernambuco, Brazil, Oct. 4, 1960; d. José Medeiros Ventura and
Paulina Maciel Medeiros; m. Ralph Oliveira Barata, Dec.23, 1988; 1 child,
Julia Oliveira Maciel; Post Ph. D. (PRODOC-CAPES), U. Fed. RN (UFRN),
2006, Natal, Brazil; Post Ph. D. (PDS-CNPq), U. Fed. RN (UFRN), 2008,
Natal, Brazil; Ph. D., U. Fed. RJ (UFRJ), 1997, Rio de Janeiro, Brazil; MSc,
U. Fed. Rural RJ (UFRRJ), 1991, Rio de Janeiro, Brazil; Cert. in Chemistry,
U. Católica Pernambuco (PUC), 1986, Recife, Brazil. Vis. rsch. U. Calif. San
Diego, (UCSD), 1989, Califórnia, US; Vis. Rsch. U. Fed. Para (UFPA), 1993-
1995, Belém, Brazil; Collaborator rschr. U. Fed. Ceara (UFC), 1993-2010;
Collab. rschr. U. Fed. Rural RJ (UFRRJ), 1993-; Collab. Rschr. U. Est.
Londrina (UEL), Londrina, Brazil; 1994-2012; Collab. rschr. U. Fed. RJ
(UFRJ), 1998-2010; Prof. U. Castelo Branco (UCB), Rio de Janeiro, Brazil,
1998-2001; Collab. rschr. U. Fed. RN (UFRN), 2002-; Vis. Prof. Post
Graduate Program in Chemistry UFRN, 2002-2012; Collab. rschr. U. Fed.
Pernambuco (UFPE), 2002-; Vis. Prof. Graduate Program U. Fed. RN
(REUNI/UFRN), 2010-2012; Research Scientist of Post Graduate Program in
Chemistry of U. Fed. RN; Prof. Distance Learning Graduate Program U. Fed.
RN (e-learning/SEDIS-UFRN), 2010-; Prof. Post Graduate Program in
Biotechnology of the University Potiguar Laureate International Universities,
Natal, Brazil; 2012-; Prof. Post Graduate Program in Biotechnology Renorbio

(UFRN), 2013-; Research Scientist Fellow: Soc. Brasileira de Química
(assoc.). Green Party. Roman Catholic.
Honors: Who’s Who in the World (2010); Top 100 Scientist (2014).

C. G. F. T.; MAciel, M. A. M. Effectiveness of Anacardium occidentale
on a microemulsion system in the carbon steel corrosion inhibition.
Revista Virtual de Química. v. 5, n. 5, p. 760-769, 2013.
Chaves, O. A.; Soares, B. A.; Maciel, M. A. M.; Sant’Anna, C. M. R.; Netto-
Ferreira, J. C.; Cesarin-Sobrinho, D.; Ferreira, A. B. B. A study of the
interaction between trans-dehydrocrotonin, a bioactive natural 19-nor-
clerodane, and serum albumin. Journal of the Brazilian Chemical Society
(in press), 2016.
Emerenciano, D. P.; Cruz, A. M. F.; Pereira, J. D. S.; Moura, M. F. V.; Maciel,
M. A. M. Determination of antioxidant property and minerals contained in
the leaves of Azadirachta indica A. Juss. Revista Fitos
Emerenciano, D. P.; MacieL, M. A. M.; Xavier Junior, F. H.; Moura, M. F. V.
Corrosion. v. 64, n. 6 p. 530-534, 2013.
Química. v. 5, n. 5, p. 746-758, 2013.
Goulart, C. M.; Esteves-Souza, A.; Martinez-Huitle, C. A.; Rodirgues, C. J.,
F.; Maciel, M. A. M.; Echevarria, A. Experimental and theoretical
evaluation of semicarbazones and thiosemicarbazones as organic
corrosion inhibitors. Corrosion Science, v. 67, p. 281-291, 2013.
Lapenda, T. L. S.; Morais, W. A.; Almeida, F. J. F.; Ferraz, M. S.; Lira, M. C.
B.; Santos, N. P. S.; Maciel, M. A. M.; Santos-Magalhães, N. S.
Encapsulation of trans-dehydrocrotonin in liposomes: An enhancement of
the antitumor activity. Journal of Biomedical Nanotechnology, v. 9, n. 3,
p. 499-510, 2013.
Lima, G. S.; Castro-Pinto, D. B.; Machado, G. C.; Maciel, M. A. M;

effects of terpenes from Croton cajucara Benth (Euphorbiaceae)
Amazonian species. Phytomedicine. v. 22, p. 1133-1137, 2015.
Moura, E. C. M.; Souza, A. D. N.; Rossi, C. G. F. T.; Da Silva, D. R.; Maciel,
M. A. M. Evaluation of anticorrosive effectiveness of thiosemicarbazones
solubilized in a microemulsion system. Química Nova, v. 36, n. 1, p. 59-
62, 2013.
Moura, E. C. M.; Rossi, C. G. F. T.; Silva, D. R.; Maciel, M. A. M. Corrosion:
a basic theoretical approach. Revista de Ciências Exatas da UFRRJ. v. 32,
n. 1, 2013.
Rodrigues, C. J. F.; Maciel, M. A. M.; Lima, K. M. Sorbitans as corrosion
inhibitors. Revista Virtual de Química. v. 5, n. 5, p. 912-920, 2013.
RJ, EDUR, v. 32, n. 1, p. 66-76, 2013.
Santos, J. S.; Maciel, M. A. M; Silva, A. O. Biofuels: general aspects,
technological development and economic viability. International Journal
of Latest Research in Science and Technology. v. 4, n. 4, p. 8-17, 2015.
Silva, M. S.; Castro Dantas, T. N.; Rodrigues, G.; Barros Neto, E. L.; Dantas
Neto, A. A., Maciel, M. A. M. Oil epoxidation approach for Passiflora
edulis sims f. flavicarpa degener. International Journal of Latest Research
in Science and Technology. v. 4, n. 3, p. 46-52, 2015.
Silva, M. S.; De Barros Neto, E. L.; Dantas Neto, A. A.; Maciel, M. A. M; De
Castro Dantas, T. N. Synthetic eposidation of Moringa oleifera Lam with
performic acid generated in situ. Biointerface Research in Applied
Chemistry. v. 6, n. 2, p. 1080-1086, 2016.
Soares, B. A.; Firme, C. L.; Maciel, M. A. M.; Kaiser, C. R.; Schilling, E.;
Bortoluzzi, A. J. Experimental and NMR theoretical methodology applied
to geometric analysis of the bioactive clerodane trans-dehydrocrotonin.
Journal of the Brazilian Chemical Society, v. 25, n. 4, p. 629-638, 2014.
Soares, B. A.; Maciel, M. A. M.; Castro, R. N.; Kaiser, C. R.; Firme, C. L.
Synthesis, NMR data and theoretical study of semi-synthetic derivatives
from trans-dehydrocrotonin. Journal of Molecular Structure. v. 1108, p.
533-541, 2016.
Book Chapter

Patent

Industrial.

Industrial.
Industrial.
Maciel, M. A. M.; Sátiro, D. S. P.; Ramalho, H. M. M.; Rocha, H. A, O.
Bioformulation of a leave fraction from Croton cajucara BENTH for
application in the digestive and immunomodulatory therapy. Brazil.
May 25, 2015. Registration Institution: INPI – Instituto Nacional de
Propriedade Intelectual.
Industrial.
Maciel, M. A. M.; Magalhães-Padilha, D. M.; Freitas E Silva, K. R.; De
Figueiredo, J. R.; Vanderlinde, F. A. Bioavailability of the hydroalcoholic
extract obtained from the bark of Croton cajucara BENTH in a SMEDDS
system for medicinal uses. Brazil. Patent: Privilege Innovation.
BR1020150147198. June 3, 2015. Registration number: INPI – Instituto
Nacional de Propriedade Intelectual.
Maciel, M. A. M.; Silva Neto, P. F.; Sátiro, D. S. P.; Pereira, J. D. S.

Bioavailability of the hydroalcoholic extract obtained from the bark of
Croton cajucara BENTH in a polar coloidal system for hypoglycemic
application. Brazil. Patent: Privilege Innovation. Registration number:
BR1020150307900. December 9, 2015. Registration Institution: INPI –
Instituto Nacional de Propriedade Intelectual.
Industrial.
Maciel, M. A. M.; Maciel A. S. S.; De Araujo, L. B. A.; Xavier Júnior, F. H.;
Marques, M. L. M.; Rocha, H. A. O. Farmaconutrients formulations based
on Anacardium occidentale L. for antioxidant, nutraceutical, and
immunomodulatory applications. Brazil. Patent: Privilege Innovation.
Registration number: BR1020160041139. February 25, 2016. Brazil.
Patent: Privilege Innovation. Registration Institution: INPI - Instituto
Nacional da Propriedade Industrial.
Maciel, M. A. M.; Maciel, A. S. S.; Medeiros, M. I. T.; De Araujo, L. B. A.;
De Medeiros, D. L.; Xavier Júnior, F. H.; Vanderlinde, F. A. Development
of analgesic nanostructure formulations based on Anacardium occidentale
LINN. Brazil. Patent: Privilege Innovation. Registration number:
BR1020160066875. March 26, 2016. Registration Institution: INPI -
based on Syzigium aromaticum for dental applications. Brazil. Patent:
Privilege Innovation. BR1020150203845. August 24, 2015. Registration
number: INPI – Instituto Nacional de Propriedade Intelectual.
Name: Jardel Dantas da Cunha

Affiliation: Rural Federal University of Semi Arid
Education: Master and Doctor in Science and Petroleum Engineering from
the Federal University of Rio Grande do Norte (UFRN) in 2008 and 2013,
respectively. Graduated in Materials Engineering from the Federal University
of Rio Grande do Norte (UFRN) in 2004.
Address: Department of Environmental and Technological Sciences, Rural
Federal University of Semi Arid, Avenue Francisco Mota, 572, Campus
Universitário, Costa e Silva, 59625-900, Mossoró-RN, Brazil.
Personal E-mail: jardeldantas@yahoo.com.br
Business E-mail: jardel.dantas@ufersa.edu.br
Research and Professional Experience: Experience in corrosion
monitoring area of ducts and equipment in oil and gas sector companies,
specifically, Brazilian Petroleum Corporation - PETROBRAS, for 6 years as
researcher (2004-2010).
Researcher in Materials Engineering area, with emphasis on corrosion
processes of pipelines and equipment. Currently, developing research in the
area of oil industry corrosive processes in different segments: Drilling,
completion and pipelines monitoring/maintenance.
Cunha, J. D.; Silva, D. R. Application of the Linear Polarization Resistance

technique (LPR), for OCS microemulsion based system evaluated as steel
corrosion inhibitor in a medium of sodium chloride in the presence of
CO2. In: TribLOOK: Um livro da Tribologia e Integridade Estrutural, v.
B, chapter 12, p. 243-254. Natal: EDUFRN, Editora da UFRN, 2015.
Silva, F. N.; Cunha, J. D.; Barbosa, A. F. F.; Silva, D. R. Evaluation of the
Colunm Fouling Production in Wells Producing Oil and Gas: Study Case.
Periódico Tchê Química, v. 11, p. 64-70, 2014.
Silva, F. N.; Cunha, J. D.; Silva, D. R. Preliminary Inspection of Corrosive,
Erosive and Cavitative Wear of Low Carbon Steel Coupons in a
Multiphasic Aqueous Flow with NaCl, CO2 and SiO2. In: TribLOOK: Um
livro da Tribologia e Integridade Estrutural, v. B, chapter 11, p. 221-241.
Natal: EDUFRN, Editora da UFRN, 2015.
Name: Cátia Guaraciara Fernandes Teixeira Rossi

Affiliation: Faculdade Natalense de Ensino e Cultura (Fanec), Av. Coronel
Estevan, 1055 (Praça Pedro II) - Bairro do Alecrim - Natal/RN, CEP 59030-
400,Campus Neves.
Education: Degree in Chemistry (University Federal of Rio Grande do
Norte), master’s degree in Chemistry (University Federal of Rio Grande do
Norte) and a PhD in Chemistry (University Federal of Rio Grande do Norte)
Address: R. Arenópolis, q.2, C. 3, Ponta Negra, 59091-160, Natal-Rn
Personal E-mail: catia_gua@yahoo.com.br
Business E-mail: www.suafaculdade.com.br/fanec/index.asp
Research and Professional Experience: Corrosion Science; Medicinal
Chemistry, synthesis of amines, animated surfactants, microemulsion systems,
solubilization of heavy oils and oil sludge, enhanced oil recovery.
Professor of Organic Chemistry, General Chemistry, Analytical
Chemistry, Instrumental Chemistry, Pharmacognosy.

C. G. F. T.; Maciel, M. A. M. Effectiveness of Anacardium occidentale on
a microemulsion system in the carbon steel corrosion inhibition. Revista
Virtual de Química, v. 5, p. 760-769, 2013.
Dantas, T. N. C.; Viana, F. F.; Rossi, C. G. F. T.; Dantas, N.; Moura, M. C. P.

A. Aged oil sludge solubilization using new microemulsion systems:
Design of experiments. Journal of Molecular Liquids (Print). v. 211, p.
44-50, 2015.
Moura, E. C. M.; Souza, A. D. N.; Rossi, C. G. F. T.; Silva, D. R.; Maciel, M.
A. M. Evaluation of anticorrosive effectiveness of thiosemicarbazones
solubilized in a microemulsion system. Química Nova (Online), v. 35, p.
59-62, 2013.
RJ, EDUR, v. 32, n. 1, p. 66-76, 2013.
Book Chapter
Cardozo, J. C.; Rossi, C. G. F. T.; Sousa, R. A.; Silva, D. R. A vegetal system

as green corrosion inhibitor on mild steel. In: Giovanni Seabra, v. II,
chapter 1, p. 2639-2650. Ituiutaba: Barlavento, 2016. ISBN:
9788568066256.
Patent


Industrial.
Name: Ewerton Richard Fernandes Teixeira

Affiliation: Chemistry Institute Federal University of Rio Grande do Norte
Education: Degree in Chemistry (University Federal of Rio Grande do
Norte), master’s degree in Chemistry (University Federal of Rio Grande do
Norte) and PhD in Chemistry (University Federal of Rio Grande do Norte).
Address: R. Guanabara 135. Neópolis, 59080-730, Natal-RN
Personal E-mail: ewerton_richard@hotmail.com
Business E-mail: ewerton_richard@hotmail.com
Research and Professional Experience: Surfactants; microemulsion
systems; enhanced oil recovery; corrosion; green chemistry; medicinal
chemistry.

based on Syzigium aromaticum for dental applications. Patent: Privilege
Innovation. BR1020150203845. August 24, 2015. Registration number:

INPI – Instituto Nacional de Propriedade Intelectual.
Name: Djalma Ribeiro da Silva

Affiliation: Chemistry Institute Federal University of Rio Grande do Norte
Education: PhD in Materials Science and Engineering from UFRN
Address: Institute Chemistry, Federal University of Rio Grande do Norte,
59078-970 Natal, Brazil.
Personal E-mail: djalmarib@gmail.com
Business E-mail: djalma@ccet.ufrn.br
Research and Professional Experience: Researcher and Professor about
materials engineering fild, with emphasis on corrosion processes of pipelines
and equipment. Currently, developing research in the area of oil industry
corrosive processes in different segments: Drilling, completion and pipelines
monitoring/maintenance. Additionally, nalytical Chemistry; Thermal and
Molecular Absorption Analysis, Electrochemical studies; Effluent treatment
by electrochemical technology.
Araújo, E. G.; Santos, J.; Silva, A.; DJalma R.; Salazar, Ricardo; Martínez-
Huitle, Carlos A. Cysteic acid-modified glassy carbon electrode for
monitoring oxalic ccid (OA) concentration during its electrochemical
oxidation at Ti/Pt Anode. Electroanalysis, v. 26, p. 748-755, 2014.
Brito, C. N.; Silva, D. R.; Garcia-Segura, S.; Moura, D. C.; Martínez-Huitle,
C. A. Indirect Electrochemical Oxidation of Reactive Blue 19 Dye as a
Model Organic Substrate: Role of anode material and oxidants
electrochemically generated. Journal of the Electrochemical Society, v.
163, p. E62-E69, 2015.
Costa, P. R. F.; Silva, D. R.; Martínez-Huitle, C. A.; Garcia-Segura, S. Fuel
station effluent treatment by electrochemical technology. Journal of
Electroanalytical Chemistry, v. 763, p. 97-103, 2016.
Corrosion. v. 64, n. 6 p. 530-534, 2013.
Química. v. 5, n. 5, p. 746-758, 2013.
Ferreira, M. B.; Rocha, J. H. B.; Silva, D. R.; Moura, D. C.; Araújo, D. M.;
Martinez-Huitle, C. A. Application of oxidation process to the degradation
of the Novacron Blue dye using single and dual flow cells. Journal of
Solid State Electrochemistry (Print), v. 20, p. 1-9, 2016.
Figueredo, K. S. L.; Martínez-Huitle, C. A.; Teixeira, A. B. R.; Pinho, A. L.
S.; Vivacqua, C. A.; Silva, D. R. Study of produced water using
hydrochemistry and multivariate statistics in different production zones of
mature fields in the Potiguar Basin - Brazil. Journal of Petroleum Science
and Engineering, v. 116, p. 109-114, 2014.
Moura, D. C.; Cerro-Lopez, M.; Marco, Q. A.; Silva, D. R.; Martinez Huitle,
C. A. Large disk electrodes of Ti/TiO2-Nanotubes/PbO2 for environmental
applications. RSC Advances: an international journal to further the
chemical sciences, v. 5, p. 31454-31459, 2015.
Moura, D. C.; Quiroz, M. A.; Silva, D. R.; Salazar, R.; Martínez-Huitle, C. A.
Electrochemical degradation of Acid Blue 113 dye using TiO2-nanotubes
decorated with PbO2 as anode. Environmental Nanotechnology,
Monitoring and Management, v. 5, p. 13-20, 2015.
Ramalho, A. M. Z.; Sobrinho, H. L. A.; Anjos, R. B.; Dantas, T. N. C.;
SILVA, D.R. Study of contamination by benzene due diesel and gasoline
leaks at a gas station in Natal/Brazil. International Journal of Engineering
and Technology, v. 14, p. 49-54, 2014.
Santos, A. J.; Lima, M. D.; Silva, D. R.; Garcia-Segura, S.; Martínez-Huitle,
C. A. Influence of the water hardness on the performance of electro-
Fenton approach: Decolorization and mineralization of Eriochrome Black
T. Electrochimica Acta, v. 208, p. 156-163, 2016.
Santos, E. V.; Sena, S. F. M.; Silva, D. R.; Ferro, S; Battisti, A.; Martínez-
Huitle, C. A. Scale-up of electrochemical oxidation system for treatment
of produced water generated by Brazilian petrochemical industry.
Environmental Science and Pollution Research International, v. 21, p.
8466-8475, 2014.
Book Chapter
Cunha, J. D.; Silva, D. R. Application of the Linear Polarization Resistance

technique (LPR), for OCS microemulsion based system evaluated as steel
corrosion inhibitor in a medium of sodium chloride in the presence of
CO2. In: TribLOOK: Um livro da Tribologia e Integridade Estrutural, v.
B, chapter 12, p. 243-254. Natal: EDUFRN, Editora da UFRN, 2015.

Silva, F. N.; Cunha, J. D.; Silva, D. R. Preliminary Inspection of Corrosive,
Erosive and Cavitative Wear of low carbon steel coupons in a multiphasic
aqueous flow with NaCl, CO2 and SiO2. In: TribLOOK: Um livro da
Tribologia e Integridade Estrutural, v. B, chapter 11, p. 221-241. Natal:
EDUFRN, Editora da UFRN, 2015.
Patent
Name: Aurea Echevarria

Affiliation: Departamento de Química, Universidade Federal Rural do Rio
de Janeiro.
Education: Degree in Chemistry (Universidade Estadual de Campinas –
UNICAMP), master’s degree in Chemistry (Universidade Estadual de
Campinas – UNICAMP) and a PhD in Chemistry (Universidade de São Paulo
– USP).
Address: BR 465, km 07, Seropédica-Rio de Janeiro, Brazil
Personal E-mail: echevarr@hotmail.com
Business E-mail: echevarr@ufrrj.br
Research and Professional Experience: Organic Chemistry; Corrosion
Science; Medicinal Chemistry
Professional Appointments: Professor of Organic Chemistry
Albuquerque, M. A.; Goulart, C. M.; Amorim, Oliveira, A. P.; Oliveira, M. C.

C.; Echevarria, A. New Thiosemicarbazone and Vegetal Extract
Formulations with Potential Anti-corrosion Activity. Revista Virtual de
Química, v. 5, p. 734-745, 2013.
Albuquerque, M. A.; Oliveira, M. C. C.; Echevarria, A. Evaluation of the

Anti-corrosion Activity of Formulations with Crude Extract through
Gravimetric and Electrochemical Techniques. Revista Virtual de Química,
v. 7, p. 1841-1853, 2015.
Amorim, A. P. O.; Oliveira, M. C. C.; Amorim, T; Echevarria, A. Antioxidant,
Iron Chelating and Tyrosinase Inhibitory Activities of Extracts from
Talinumtri angulare Leach Stem. Antioxidants, v. 2, p. 90-99, 2013.
Andrade Pires, A. R.; Jabor Gozzi, G.; Rodrigues Noleto, G.; Echevarria, A.;
Moretto Reis, C.; Merlin Rocha, M. E.; Regina Martinez, G.; Correia
Cadena, S. M. S. Antioxidant effect of 1,3,4-thiadiazolium mesoionic
derivatives on isolated mitochondria. European Journal of Pharmacology,
v. 770, p. 78-84, 2016.
Brandt, A. P.; Pires, A. R. A.; Rocha, M. E. M.; Noleto, Guilhermina, R.;
Acco, A.; Souza, C. E. A.; Echevarria, A.; Canuto, A. V. S.; Cadena, S.
M. S. C. Sydnone SYD-1 affects the metabolic functions of isolated rat
hepatocytes. Chemico-Biological Interactions, v. 218, p. 107-114, 2014.
Campos, M.; Pinto, D. C.; Ribeiro, G. A.; Pinho, M. M. B.; Gomes, L. H. F.;
Bellieny, M. S. S.; Goulart, C. M.; Echevarria, A.; Leon, L. L. P-
glycoprotein efflux pump plays an important role in Trypanosoma cruzi
drug resistance. Parasitology Research, p. 2341-2351, 2013.
Canuto, A. V. S.; Echevarria, A. HNMR for quantifying sulfide trapping
efficiency by using 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane. Magnetic
Resonance in Chemistry, v. 52, p. 353-357, 2014.
Carmo, D. F. M.; Amaral, A. C. F.; Machado, M; Lopes, D.; Echevarria, A;
Rosario, V. E.; Silva, J. R. A. S. Evaluation of Antiplasmodial activity of
extracts and constituents from Ampelozizyphus amazonicus.
Pharmacognosy Magazine, v. 11, p. S244-S250, 2015.
De Melos, J. L. R.; Torres-Santos, E. C.; Faiões, V. S.; DE Nigris Del Cistia,
C.; Sant’Anna, C. M. R.; Rodrigues-Santos, C. E.; Echevarria, A. Novel
3,4-methylenedioxyde-6-X-benzaldehyde-thiosemicarbazones: synthesis
and antileishmanial effects against Leishmania amazonensis. European
Journal of Medicinal Chemistry, v. 103, p. 409-417, 2015.
Galuppo, L. F.; Lívero, F. A. R; Martins, G. G.; Cardoso, C. C.; Beltrame, O.
C.; Klassen, L. M. B.; CanutO, A. V. S.; Echevarria, A.; Telles, J. E. Q.;
Klassen, G.; Acco, A. Sydnone 1: A Mesoionic Compound with Anti-
tumoural and Hematological Effects In Vivo. Basic and Clinical
Pharmacology and Toxicology, v. 117, p. 1-10, 2016.
Goulart, C. M.; Esteves-Souza, A.; Martinez-Huitle, C. A.; Rodrigues, C. J. F.;
Maciel, M. A. M; Echevarria, A. Experimental and Theoretical Evaluation
of Semicarbazones and Thiosemicarbazones as Organic Corrosion

Inhibitors. Corrosion Science, v. 67, p. 281-291, 2013.
Gozzi, G. J.; Pires, A. R. A.; Martinez, G. R.; Rocha, M. E. M.; Noleto, G. R.;
Echevarria, A.; Canuto, A. V.; Cadena, S. M. S. C. The antioxidant effect
of the mesoionic compound SYD-1 in mitochondria. Chemico-Biological
Interactions, v. 205, p. 181-187, 2013.
Gozzi, G. J.; Pires, A. R. A.; Valdameri G; Rocha, M. E. M.; Martinez, G. R.;
Noleto, G. R.; Acco, A.; Souza, C E A; Echevarria, A.; Reis, C. M.;
Pietro, A.; Cadena, S. Selective Cytotoxicity of 1,3,4-Thiadiazolium
Mesoionic Derivatives on Hepatocarcinoma Cells (HepG2). Plos One, v.
10, p. e0130046-e0130063, 2015.
Lopes, G.; Silva, T. M. S.; Echevarria, A. Toxicity from Crude Extracts and
Glycoalkaloid Fractions of Solanumspp against Artemiasalina and
Biomphalariaglabrata. Revista Virtual de Química, v. 8, p. 141-156,
2016.
Lima, G. S.; Castro-Pinto, D. B.; Machado, G. C.; Maciel, M. A.M.;
effects of terpenes from the Amazonian species Croton cajucara Benth
(Euphorbiaceae). Phytomedicine, v. 22, p. 1133-1137, 2015.
Moura, E. C. M.; Souza, A. D. N.; Rossi, C. G. F. T; Silva, D. R.; Maciel, M.
A. M.; Echevarria, A.; Bellieny, M. S. S. Evaluation of anticorrosive
effectiveness of thiosemicarbazones solubilized in a microemulsion
system. Química Nova, v. 36, p. 59-62, 2013.
Paiva, R. O.; Kneipp, L. F.; Goular, C. M.; Albuquerque, M. A.; Echevarria,
A. Antifungal activities of thiosemicarbazones and semicarbazones
against mycotoxigenic fungi. Ciência e Agrotecnologia, v. 38, p. 531-537,
2014.
Paiva, R. O.; Kneipp, L. F.; Reis, C. M.; Echevarria, A. Mesoionic compounds
with antifungal activity against Fusarium verticillioides. BMC
Microbiology, v. 15, p. 1-8, 2015.
Rodrigues-Santos, C.; Echevarria, A.; S.; Bitencourt, T.; Nascimento, M.;
Bauerfeldt, G. Quantitative Structure-Property Relationship (QSPR)
Models for a Local Quantum Descriptor: Investigation of the 4- and 3-
Substituted-Cinnamic Acid Esterification. Molecules, v. 20, p. 17493-
17510, 2015.
Santos, C. E. R.; Leon, L. L.; Bortoluzzi, A. J.; Canto-Cavalheiro, M.;
Machado, G. M. C; Echevarria, A. Synthesis, antileishmanial activity and
structure-activity relationship of 1-N-X-phenyl-3-N-Y-phenyl-
benzamidines. European Journalof Medicinal Chemistry, v. 67, p. 166-

174, 2013.
Santos-Frauche, C; Albuquerque, M. A.; Oliveira, M. C. C.; Echevarria, A.
The Corrosion and the Anticorrosion Agents. Revista Virtual de Química,
v. 6, p. 239-309, 2014.
Soares-Bezerra, R. J.; Leon, L. L.; Echevarria, A.; Reis, C. M.; Gomes-Silva,
L.; Agostinho, C. G.; Fernandes, R. A.; Canto-Cavalheiro, M. M.;
Genestra, M. S. In vitro evaluation of 4-phenyl-5-(4-X-phenyl)-1,3,4-
thiadiazolium-2-phenylaminide chlorides and 3[N-4-X-phenyl]-1,2,3-
oxadiazolium-5-olate derivatives on nitric oxide synthase and arginase
activities of Leishmania amazonensis. Experimental Parasitology, v. 135,
p. 50-54, 2013.
Book Chapter

Melos, J. L. R.; Echevarria, A. Enzyme systems Trypanosomatids as Potential
Targets Chemotherapy. In: Doenças Negligenciadas, v. 1, p. 52-67. RVq-
FAPERJ, 2013.
Santos-Frauche, C; Albuquerque, M. A.; Oliveira, M. C. C.; Echevarria, A.
Corrosion and Anti-corrosion Agents. In: Advances in Petroleum
Engineering. I: Refining, v. 1, chapter XX, p. 769-791. New Delhi
Publishing House, 2015.
INDEX
adsorption isotherms, 84, 123
# aerospace, 110
AFM, 57
1,3,4-triazolium-2-thiol, vii, xi, 118,
aggregation, 31
120, 121, 123, 124, 125, 130, 131,
albumin, 94, 137
133, 135
algae, 10
21st century, 29
alkaloids, 10
aluminium, 11, 39, 44, 45, 48, 49, 50,
A 54, 55, 56, 58, 91
Aluminum Particulate Metal Matrix
abstraction, 54 Composite (APMMCs), 106, 108
acetic acid, 6 amine, vii, ix, 6, 59, 60, 62, 63, 64, 65,
acetone, 50, 57 67, 68, 70, 71, 74, 76, 77, 78, 143
acid, vii, ix, 4, 5, 6, 8, 10, 11, 13, 15, 16, amino, 6, 14, 34, 46, 54, 70, 134
28, 30, 33, 34, 35, 38, 39, 40, 41, 43, ammonia, 61
44, 45, 46, 47, 48, 49, 53, 55, 56, 57, ammonium, 70
58, 59, 60, 63, 64, 65, 66, 68, 69, 70, analgesic, 98, 141
71, 73, 74, 76, 77, 92, 95, 119, 122, aniline, 16, 30, 34, 45, 46, 65
130, 134, 138, 146 Anodizing, 108
acidic, 9, 11, 13, 17, 44, 45, 46, 47, 49, antimony, ix, 59, 64
50, 55, 56, 57, 75, 91, 107 antioxidant, 87, 94, 98, 100, 104, 137,
acrylic acid, 33, 35 141, 150
activated carbon, 54 antitumor, 94, 137
active compound, 82 aquatic life, 72, 73
additives, 2, 3, 10, 46, 51 aqueous solutions, ix, 59, 89, 134
adhesion, 47, 111 aromatic rings, 88, 124
adhesion properties, 47 arsenic, ix, 60, 64, 65
adiposity, 103 assessment, viii, 2, 7, 17, 18, 19, 49, 56,
adsorption, vii, viii, x, 1, 6, 7, 8, 12, 13, 103
14, 16, 17, 28, 29, 32, 33, 35, 39, 41, atoms, 8, 12, 14, 15, 32, 111, 118
44, 46, 47, 51, 54, 57, 61, 80, 84, 88,
89, 90, 92, 119, 120, 123, 124, 133
154 Index
casting, xi, 105

B cathodic process, 15
cationic surfactants, 88
background information, x, 60
cellulose, 44, 47
bacteria, 10, 81
cerium, 34, 42, 43, 44, 45, 113
base, vii, xi, 7, 25, 34, 35, 41, 43, 46,
chemical(s), vii, ix, xi, 1, 2, 3, 5, 6, 7, 8,
105, 108, 109, 112, 134
9, 10, 11, 12, 20, 22, 27, 28, 29, 41,
benzene, 8, 12, 13, 147
49, 59, 60, 61, 62, 64, 65, 69, 74, 75,
bicarbonate, 69
80, 81, 82, 86, 88, 90, 106, 108, 109,
bioaccumulation, 74
111, 112, 118, 119, 120, 121, 124,
bioavailability, 82
147
biodegradability, 65
chemical deposition, 3
biodegradation, 10, 74
chemical interaction, 86
biological activities, 92
Chemical Passivity, 112
bismuth, 64, 70
chemical properties, 49
blends, 45, 50, 58
chemical structures, 88, 90
boilers, vii, 1, 61
chemisorption, 8, 11, 15, 16
bonding, 8, 12
chitosan, 34, 35, 39, 40, 41, 43, 46, 47
bonds, 15, 41, 88
chromatography, 103
brass, 15, 134
circulation, 11, 68
Brazil, 79, 81, 91, 92, 93, 96, 97, 98, 99,
Clean Air Act, ix, 60, 65
100, 101, 102, 103, 104, 117, 136,
Clean Water Act (CWA), ix, 60, 65
139, 140, 141, 142, 144, 145, 146,
cleaning, 18, 28, 122
147, 148
CO2 absorption, vii, ix, 60, 62, 63, 64,
by ex-situ, ix, 28
74, 75, 78
coal, 61
C coatings, viii, 27, 44, 47, 51, 80, 108,
110, 111
cadmium, ix, 60, 64, 113 cobalt, ix, 59, 65, 70
calcium, 5, 9, 44 coconut oil, xi, 92, 96, 98, 118, 119,
calcium carbonate, 9 120, 130, 132, 135, 139, 141, 144,
calibration, 121 148
capillary, 83 commercial, x, 2, 5, 11, 21, 39, 42, 80,
carbon, vii, ix, 4, 5, 6, 10, 15, 33, 34, 39, 82, 90, 92
47, 48, 54, 55, 57, 59, 60, 61, 63, 67, compatibility, 38
68, 74, 75, 77, 87, 88, 89, 90, 91, 92, complexity, 11
94, 96, 102, 119, 124, 130, 134, 135, compliance, 64
137, 139, 143, 146, 147, 148 Composite(s), v, vii, ix, 28, 29, 30, 33,
carbon capture, vii, x, 60, 74 34, 36, 37, 38, 39, 40, 42, 43, 45, 46,
carbon dioxide (CO2), v, vii, ix, 54, 59, 47, 48, 49, 51, 55, 105, 107, 113
60, 61, 62, 63, 64, 66, 67, 68, 71, 74, composites, vii, ix, 28, 30, 33, 34, 36,
75, 76, 77, 78, 124, 130, 135, 143, 37, 38, 39, 42, 43, 45, 46, 47, 48, 49,
147, 148 51, 55, 107, 108, 113
carboxylic acid, 65, 73, 74
carboxymethyl cellulose, 47
Index 155
composition, viii, 2, 6, 9, 17, 20, 21, 75, covalent bond, 8

81, 82, 88, 90, 96, 108, 119, 121, 139, crude oil, 42, 50
144 CWA, ix, 60, 65
compounds, ix, x, xi, 5, 6, 7, 8, 10, 12,
13, 15, 16, 29, 32, 59, 64, 65, 69, 71,
75, 80, 81, 82, 88, 96, 105, 119, 120, D
133, 135, 139, 144, 150
concentration, 4, 6, 10, 11, 13, 14, 15, DEA, 63, 66, 68, 70, 71
16, 20, 21, 28, 33, 34, 35, 39, 43, 65, decomposition, 38
71, 83, 84, 86, 88, 90, 121, 123, 124, defects, 47, 108
125, 130, 133, 146 defence, 81
conditioning, 67, 71, 75, 76, 77 degradation, xi, 10, 21, 105, 146, 147
constituents, ix, 28, 29, 38, 74, 149 degradation mechanism, 10, 21
construction, ix, 59 deposition, 3, 6, 9
consumption, 28, 50 deposits, 6
contamination, 3, 147 depth, 83
convention, 65 derivatives, 3, 15, 47, 56, 80, 95, 138,
conventional composite, 38 149, 151
COOH, 16 desorption, 38
cooling, vii, 1, 2, 3, 4, 6, 9, 10, 11, 15, detection, 101
21, 119, 134 detoxification, 81
cooling water systems, vii, 1, 2, 3, 7, 9, DFT, 57
11, 21 diffusion, 112
Copaiba oil, 80, 81 direct adsorption, vii, 1
Copaifera L., x, 80, 82, 91 discontinuity, 108, 111
copolymer, 44, 46 diseases, 96, 100, 102, 139
copper, vii, ix, 1, 4, 11, 12, 13, 15, 21, dispersion, 30
59, 65, 68, 69, 77, 110, 113 displacement, 35
correlation, 89, 133 dissolved oxygen, 130
corrosion and corrosion Inhibitors, 106 distilled water, 82, 83, 121, 133
corrosion green inhibitor, 80 distribution, 30, 101, 124
Corrosion Inhibitor(s), i, iii, v, vii, viii, diversity, 119
ix, x, xi, 1, 2, 3, 4, 5, 6, 7, 9, 10, 11, DOI, 45, 48
12, 14, 15, 16, 17, 19, 21, 22, 27, 28, dosage, 4, 6, 69, 70, 71
29, 31, 32, 33, 34, 35, 38, 39, 40, 41, double bonds, 88
42, 43, 45, 46, 47, 49, 50, 51, 54, 55, drug delivery, 99, 142, 145
56, 57, 58, 59, 60, 63, 64, 65, 67, 68, drug resistance, 149
69, 72, 74, 75, 76, 77, 78, 79, 80, 82, DSC, 103
86, 90, 91, 94, 95, 96, 98, 99, 100, durability, 13, 29
101, 102, 103, 104, 108, 112, 118,
119, 120, 122, 130, 133, 134, 135, E
137, 138, 139, 141, 142, 143, 144,
145, 147, 148, 149 economic development, 91
Corrosion Inhibitors in Metal Matrix economic losses, 63
Composite, 108 ecosystem, 29
156 Index
electric current, 86 films, 3, 6, 21, 25, 36, 47, 80, 112, 118,
electricity, 61 124
electrode surface, 8 financial, 43, 90, 133
electrodes, 122, 147 financial support, 90, 133
electrolyte, 39, 109, 110, 114 flavonoids, 10
electron, 8, 11, 12, 33, 41, 118 flexibility, 38
electron pairs, 12 flue gas, 61, 62, 63, 75
electronic structure, 133 fluid, 64, 66, 84, 92
electronic systems, 124 follicles, 99, 100, 142
electrons, 8, 14, 29, 41, 111 formation, ix, 4, 8, 10, 13, 15, 17, 28, 33,
energy, 33, 89, 118 42, 67, 90, 108, 113, 119, 122, 123,
engineering, vii, 1, 11, 20, 105, 146 124, 130, 135
environment, vii, viii, ix, xi, 1, 3, 6, 7, fungi, 10, 81, 150
10, 11, 13, 16, 18, 21, 27, 28, 33, 35,
38, 39, 41, 43, 45, 49, 56, 60, 64, 71,
72, 73, 74, 90, 105, 106, 110, 111, G
112, 118
environmental awareness, 64 gas treating, 60, 61, 64, 65, 66, 69, 75,
environmental conditions, 21 76, 77
Environmental Protection Act, ix, 60, 64 GDP, viii, 27
Environmental Protection Agency (EPA) geography, 29
, ix, 32, 60, 65 geometry, 101
environmental regulations, 64, 74 glucose, 44
environments, 9, 25, 28, 32, 39, 43, 51, glycine, 70
108 glycol, 17, 30, 33, 34, 39, 40, 45, 46, 48,
equilibrium, 9, 84, 89, 119, 123 49, 50, 53, 54, 55, 56, 58
erosion, 63, 66, 67, 68 GNP, viii, 27
ethylene, 6, 39, 40, 55, 69, 70 graph, 83, 84, 124
ethylene glycol, 39, 40, 55 graphite, 111
evaporation, 3 green chemistry, 2, 93, 96, 102, 135,
examinations, 17 136, 139, 145, 147
exposure, 13, 16, 18, 34, 35, 43, 123 greenhouse gases (GHG), 61
exposure time, 16, 18, 34, 35, 123 growth, 64, 99, 100, 142
extraction, 10, 81, 92 guidelines, ix, 60, 65
extracts, x, 10, 11, 21, 50, 57, 80, 98,
100, 141, 149 H
exudate, 17
hardness, 4, 6, 9, 147
healing, 96, 102, 112, 140, 144
F
health, ix, 49, 60, 64, 74
fabrication, 30, 68, 114 heat transfer, 69
fatty acids, 54 heavy metals, 49, 74
Federal Government, 53 heavy oil, 143
film formation, 33, 122 hepatocytes, 149
film thickness, 25 histidine, 34, 35
Index 157
human, ix, 60, 64 135, 137, 139, 141, 142, 143, 144,
hydrocarbons, 88, 90 145, 146, 147, 148
hydrogen, 19, 113 inhibitor efficiency, 19, 21, 124, 125,
hydrogen peroxide, 113 133
hydrolysis, 55 inhibitor molecules, 6, 9, 11, 13, 14, 16,
hydrophilicity, 42 17, 33, 35, 38, 39, 41
hydroquinone, 71 initiation, xi, 105, 108
hydroxide, 4, 113 insertion, 15, 130
hydroxyl, 4, 6 in-situ, ix, 17, 18, 28, 30, 33, 39, 45, 49,
57
interface, vii, ix, xi, 1, 3, 8, 13, 14, 28,
I 29, 33, 56, 105, 108, 114
interfacial layer, 33
ICS, 32 interference, viii, 2
identification, 17, 103 ions, vii, 1, 3, 4, 5, 13, 15, 16, 18, 42, 44,
illumination, 13 48, 49, 50, 54, 55, 56, 57, 58, 111,
immersion, 35, 36, 83 112
immunomodulatory, 97, 98, 140, 141, iron, 3, 14, 15, 16, 42, 44, 66, 67, 92,
145 111
incidence, 83 isotherms, 84, 89, 123
independent variable, 20, 21 Israel, 45, 48, 49, 50, 54, 55, 56, 57
industry(ies), ix, x, 2, 28, 29, 30, 51, 60, issues, viii, 2, 42, 63
61, 64, 79, 101, 110, 112, 118, 142,
146, 147
inhibition, vii, viii, ix, x, xi, 4, 5, 6, 7, 8, K
9, 10, 13, 14, 15, 16, 17, 18, 19, 20,
28, 32, 33, 34, 35, 36, 37, 38, 39, 42, kerosene, xi, 118, 119, 120, 130
43, 44, 45, 46, 47, 48, 49, 50, 54, 55, kinetic parameters, 86
56, 57, 58, 60, 65, 76, 77, 80, 83, 84, kinetic studies, 46
86, 87, 88, 90, 91, 92, 93, 94, 96, 102, kinetics, 44, 91, 113
106, 114, 118, 119, 120, 121, 123,
124, 133, 134, 135, 136, 137, 139,
143, 146, 147 L
inhibition efficiency, 5, 6, 7, 9, 10, 13,
15, 16, 17, 19, 20, 32, 33, 34, 35, 36, leaks, 147
37, 38, 39, 44, 50, 55, 81, 83, 123, learning, 93, 136
124, 133 leucine, 34, 35, 46
inhibitor, vii, x, xi, 1, 3, 4, 5, 6, 7, 8, 9, light, 10, 81, 83
10, 11, 13, 14, 15, 16, 17, 19, 20, 21, lignin, 17
22, 28, 29, 32, 33, 34, 35, 38, 39, 41, linear polarization resistance, 18, 118
42, 43, 45, 46, 49, 54, 55, 56, 57, 60, liposomes, 94, 137
64, 65, 66, 67, 68, 74, 75, 77, 78, 80, liquid chromatography, 103
82, 83, 84, 86, 87, 89, 90, 91, 94, 96, liquids, 61, 119
98, 99, 103, 106, 111, 112, 113, 118, low temperatures, 38
120, 123, 124, 125, 129, 130, 133, LSI, 9
LTC, 91
158 Index
Luo, 24, 25 modifications, ix, 59

molecular structure, 12, 88, 124
molecular weight, 16, 58
M molecules, 6, 7, 8, 11, 13, 14, 16, 17, 21,
29, 33, 35, 38, 39, 41, 84, 88, 111,
macromolecules, 16, 32 119, 123
magnesium alloys, 113 monolayer, vii, 1, 39, 40, 88, 90
marine environment, ix, 60, 65 monomers, 84
mass, 82, 84, 106, 118, 120, 122, 123, morphology, 129
124, 125, 129 multivariate statistics, 147
mass loss, 118, 122, 124, 125, 129
materials, viii, xi, 9, 16, 27, 29, 47, 48,
64, 80, 105, 118, 146 N
matrix, viii, xi, 2, 9, 28, 29, 30, 42, 105,
107, 108, 109, 113, 114 NaCl, xi, 15, 32, 34, 35, 39, 40, 45, 54,
measurements, viii, 2, 4, 15, 17, 18, 19, 118, 120, 130, 131, 133, 143, 148
33, 49, 55, 83, 86, 122, 123, 132 nanocomposites, vii, ix, 28, 30, 38, 40,
mechanical properties, xi, 105, 113 42, 43, 45
Mechanism, v, 39, 105, 106, 112 nanoparticles, 30, 39, 42, 45, 47, 48, 49,
media, vii, viii, ix, 2, 7, 28, 38, 44, 45, 51, 53, 55, 56, 57
46, 47, 54, 55, 91, 119 natural gas, 61, 63, 68, 76
membranes, 47 natural polymers, 16
MES, 119 neutral, 9, 40, 107
metal complexes, 6 NH2, 14, 16
metal ion(s), vii, 1, 3, 5, 15, 16, 18, 19, nickel, 4, 25
46, 112 nicotinic acid, 8
metal nanoparticles, 42 Nigeria, 49, 50, 52, 53
metallurgy, 68 nitrates, 3, 29
metals, vii, xi, 1, 11, 13, 28, 29, 32, 33, nitric oxide synthase, 151
34, 36, 38, 40, 42, 49, 64, 74, 75, 80, nitrogen, 7, 8, 11, 12, 70, 88, 118
91, 105, 106, 108, 118 NMR, 95, 138
methacrylic acid, 30, 39, 40, 45, 48, 49, nonionic surfactants, 92
55, 56 non-polar, 119
methanol, 50, 57, 121 North America, 30, 61
methodology, 20, 82, 95, 120, 138 nucleation, 4
microemulsion, vii, x, xi, 80, 82, 84, 90, nutraceutical, 98, 141
91, 94, 95, 96, 97, 98, 99, 100, 101, nutrients, 49, 81
102, 104, 118, 119, 120, 121, 123,
124, 129, 130, 134, 135, 137, 138,
139, 140, 141, 142, 143, 144, 145, O
147, 150
microorganisms, 10 O/W type self-microemulsion, 80
microscope, 33 OCS, xi, 118, 119, 120, 121, 123, 124,
mineralization, 147 125, 126, 127, 128, 129, 130, 131,
mitochondria, 149, 150 132, 135, 143, 147
MMCs, 109
Index 159
oil, vii, x, xi, 1, 2, 28, 29, 42, 50, 51, 54, polyamine, 69, 75
61, 69, 76, 80, 81, 82, 84, 87, 88, 90, Polymer Coating, 111, 114
91, 92, 96, 97, 98, 99, 100, 101, 102, polymer composites, vii, ix, 28, 30, 33,
103, 104, 118, 119, 120, 123, 130, 42, 43, 47
132, 135, 139, 140, 141, 142, 143, polymer materials, viii, 28, 29
144, 145, 146, 148 polymer matrix, viii, 28, 29, 30, 42
oil samples, 82 polymer nanocomposites, 38, 45
operations, x, 60 polymer synthesis, 48
optimization, 20, 21, 22, 54 Polymer(s), vii, viii, 5, 6, 14, 16, 28, 29,
organic compounds, ix, x, 7, 10, 11, 13, 30, 32, 33, 38, 42, 43, 45, 46, 47, 48,
29, 60, 65, 80, 96, 118, 120, 139, 144 50, 51, 54, 58, 71, 108, 111
organic inhibitors, vii, ix, 1, 2, 3, 7, 8, 9, polymeric materials, 16
10, 11, 21, 39, 59, 65, 74 polymerization, 33, 45
oxidation, xi, 86, 105, 106, 108, 109, polymers, viii, 5, 16, 28, 29, 32, 38, 42,
114, 146, 147 45, 50, 54, 58
oxygen, 7, 19, 67, 88, 113, 118, 129, 130 polypropylene, 30, 39, 45, 48, 49, 53,
54, 56
polyvinyl alcohol, 35, 46, 55, 58
P porosity, 111
potassium, 44, 69, 71, 76, 92
PAA, 33 power generation, 29, 61, 77
parallel, 15 power plants, 61
partition, 65 preparation, 45, 46, 48, 53, 55, 109
passivation, 67, 112 prevention, 6, 9, 76, 80
PCT, 96, 139, 144 proportionality, 85
Petroleum, 27, 42, 51, 52, 101, 142, 147, propylene, 70
151 protection, vii, viii, x, 1, 9, 10, 12, 13,
pH, viii, 2, 3, 5, 6, 9, 10, 12, 13, 17, 20, 16, 20, 22, 27, 32, 35, 39, 42, 43, 46,
21, 129, 131, 134 47, 51, 56, 58, 79, 80, 86, 88, 90, 108,
pharmaceutical, 103 113, 114, 115, 124
phase diagram, 82, 84, 85, 120, 123, 132 protective coating, 80
phenol, 8, 134 purification, 67, 69, 76
phenolic compounds, 10 pyrimidine, 134
phosphates, vii, 1, 3, 4, 5, 29
phosphorous, 4, 7, 88, 118
physicochemical properties, 50 R
pipeline, 4, 54, 57, 58
plants, ix, 4, 10, 18, 59, 61, 63, 64, 65, reaction rate, 63
66, 69, 75, 76, 77 reactions, 19, 28, 39, 80, 86, 106, 118
platinum, 83, 121 reagents, 89
polar, 82, 88, 97, 98, 119, 141, 148 recommendations, iv, ix, 59
polarity, 119 recovery, 68, 75, 76, 108, 143, 145
polarizability, 8 refractive index, 82
polarization, x, xi, 11, 18, 19, 80, 84, 86, regression, 20, 121
87, 90, 118, 119, 123, 130, 133 regression analysis, 20
polyacrylamide, 34, 35, 44 regression equation, 121
160 Index
regulations, x, 60, 64, 74 species, x, 2, 4, 6, 10, 11, 17, 35, 39, 41,
reinforcement, xi, 105, 108, 109 44, 50, 55, 65, 80, 81, 88, 95, 138,
reliability, 77 150
repetitions, 32 specific adsorption, 35
residues, 103 spectroscopic techniques, 17
resins, 51, 54 spectroscopy, 17, 18
resistance, 18, 47, 68, 110, 111, 118, spontaneity, 118
119, 149 Spring, 92
risk, 3, 4, 9, 49, 65 stability, viii, 6, 8, 12, 14, 16, 28, 29, 31,
room temperature, 57, 121 35, 87, 120, 123, 124
routes, viii, 2, 7 stable complex, 3
statistics, 147
steel, vii, ix, x, xi, 1, 2, 3, 4, 5, 6, 9, 10,
S 14, 15, 16, 20, 21, 32, 33, 34, 35, 38,
39, 40, 41, 43, 44, 45, 46, 47, 48, 49,
safety, 63 50, 53, 54, 55, 56, 57, 58, 59, 61, 63,
salts, 3, 17, 62, 70, 71, 106 66, 67, 68, 69, 70, 71, 79, 83, 87, 88,
saturation, 9 89, 90, 91, 92, 94, 96, 102, 113, 118,
Saudi Arabia, 27, 51, 52 119, 120, 121,124, 133, 134, 135,
scaling, 4, 134 137, 139, 143, 144, 146, 147, 148
scope, 9 steel industry, 2
sea level, 61 stimulation, 119
sediment, 49, 50 storage, 61, 76, 101
self-repair, 47 stress, 63, 68, 124
serum, 94, 137 structure, 8, 12, 15, 46, 119, 120, 124,
serum albumin, 94, 137 125, 133, 150
silver, 30, 34, 39, 40, 45, 47, 48, 49, 53, substrate, vii, viii, ix, 3, 27, 28, 54, 108,
55, 56, 57, 113 109, 110, 111
simulation(s), 15, 57 sulfate, 4, 70, 71
SiO2, 143, 148 sulfur/sulphur, ix, 7, 8, 11,14, 59, 65, 69,
skin diseases, 96, 100, 102, 139 70, 88, 118
sludge, 62, 143 surface modification, xi, 106, 108
SMEDDS-colloidal copaiba-based surface properties, 38
system, 80 surface tension, 82, 84, 85, 123
sodium, ix, x, 3, 4, 5, 15, 16, 17, 44, 60, surface treatment, 108, 109, 110
69, 80, 84, 87, 89, 90, 111, 113, 124, surfactant, x, xi, 44, 46, 80, 82, 84, 87,
133, 135, 143, 147 88, 90, 92, 96, 98, 118, 119, 120, 123,
solubility, 3, 16, 32, 33, 82, 87, 120, 121 124, 130, 132, 134, 139, 141, 143,
solution, vii, xi, 1, 3, 8, 10, 13, 14, 15, 144, 148
16, 17, 18, 32, 33, 34, 39, 41, 42, 43, synergistic effect, viii, x, 4, 17, 28, 29,
44, 45, 47, 48, 49, 50, 53, 54, 55, 56, 49, 50, 55, 57, 80, 81
57, 58, 63, 64, 66, 70, 71, 76, 78, 87, synthesis, viii, ix, 2, 11, 28, 30, 42, 45,
88, 91, 115, 118, 120, 121, 124, 130, 48, 51, 54, 57, 69, 70, 71, 135, 143,
133 149
solvents, 50, 57, 63, 74, 75 synthetic polymers, 42
Index 161
T V
target, 120, 121, 123, 131 valve, 66, 67

techniques, viii, xi, 2, 4, 8, 15, 17, 68, vanadium, ix, 59, 64, 65, 74
105, 125, 133 vapor, 62, 66, 67
temperature, viii, 2, 10, 12, 13, 16, 20, variables, 20, 21
21, 29, 34, 37, 38, 39, 43, 51, 57, 61, variations, 81, 85
62, 83, 85, 89, 90, 121, 124 velocity, 66, 67
tension, 83, 84, 85, 119, 123 versatility, 3, 7
terpenes, 95, 138, 150 viscosity, 81, 83, 85, 86, 87, 124
theoretical approach, 56, 57, 95, 138
therapy, 97, 102, 140, 145
thermodynamic equilibrium, 119 W
thermodynamics, 92
thiophenol, 65 waste, x, 56, 60, 62, 64, 124
tin, ix, 59, 64, 113 waste disposal, x, 60
toxic effect, x, 72, 73, 80 waste treatment, 64
toxic substances, ix, 60, 64 wastewater, 6, 46
toxicity, ix, x, 21, 29, 60, 80 water, vii, x, xi, 1, 2, 3, 4, 5, 6, 7, 8, 9,
treatment, vii, x, 6, 18, 60, 61, 63, 64, 10, 11, 15, 16, 17, 18, 20, 21, 25, 33,
67, 68, 69, 70, 71, 102, 109, 113, 114, 34, 35, 41, 45, 46, 49, 50, 57, 62, 65,
115, 146, 147 72, 73, 80, 82, 83, 84, 101, 111, 118,
tricarboxylic acid, 4, 6 119, 121, 123, 124, 133, 134, 147
water chemistry, 18
water vapor, 62
U weak interaction, 8
weight loss, viii, 2, 4, 18, 76
ultrasound, 121 wound healing, 96, 102, 140, 144
uniform, 18, 63, 88
Union Carbide, 69
United States (USA), 50, 53, 58, 64 Z
urea, 70, 73
zinc, 3, 4, 91, 113
zinc sulfate, 4
ZnO, 39, 40, 47

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CHEMISTRY RESEARCH AND APPLICATIONS

Additional books in this series can be found on Nova’s website

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NOTICE TO THE READER

Library of Congress Cataloging-in-Publication Data

Published by Nova Science Publishers, Inc. † New York

Chapter 6 Electrochemical Study of 1,3,4-Triazolium-2-Thiol

This book discusses principles, mechanisms and applications of corrosion

application of organic inhibitors for protection of steel against corrosion. On

chemically distinct constituents on a minute-scale, having a distinct interface

environmental concerns and reduce the cost of waste disposal as well as

ORGANIC CORROSION INHIBITORS

Gözde Tansuğ1 and Tunç Tüken2,

organic inhibitors for protection of steel against corrosion. On the other

Keywords: organic inhibitors, corrosion, cooling water systems, green

2. INHIBITORS IN INDUSTRIAL APPLICATIONS

heat exchangers or hydrothermal plants, water hardness and ionic species

Figure 1. Structures of the mostly used commercial phosphate compounds.

Figure 2. Structures of the mostly used commercial phosphonic acids.

The good performance of phosphate compounds is simply related to their

success of corrosion inhibition. As a conclusion, the chelating performance

Going back to adsorptive interaction of organic inhibitors with the surface,

useful for characterizing the orientation, and binding properties of inhibitor

3.2. Organic Inhibitors in Cooling Water Systems

There is necessity for novel organic corrosion inhibitors to be employed in

LSI = pH - pHs (1)

zero, this is also frequently recommended by suppliers and also in the

3.3. Plant Extracts

Plant extracts are generally considered as green corrosion inhibitors and

comosum (CC) extract was investigated on Cu corrosion in 2 M HCl solution.

3.4. Molecular Designing and Synthesis

Designing an organic inhibitors molecule is challenging task because of

Figure 4. Functional groups of mostly used for designing corrosion inhibitors.

Following the physisorption of molecule on copper surface via

Cu(s) + BTAH(aq) → Cu:BTAH(ads) + H +(aq) (2)

Cu:BTAH(ads) → Cu(I)BTA(s) + H +(aq) + e (3)

Self-assembled monolayers (SAM) of a series of thiol compounds with

example 4-amino-4H-1,2,4-triazole-3-thiol exhibits 91.38%, in acidic chloride

Figure 5. The schematic illustration for 2-AEE adsorption on steel/0.1 M HCl

Also, methyl 3-((2-mercaptophenyl)imino)butanoate (MMPB) compound

dimethylaminophenyl)-1,3,4-oxadiazole in 1 M HCl acid solutions [64]. Also

strongly adsorbed DDTC molecules. Li et al. have reported the use of

3.5. Polymeric Inhibitors

Water soluble polymers have also been investigated as corrosion

4. ASSESMENT OF CORROSION INHIBITON

corrosive environment is also important for success of this method. In such

independent variables (pH, temperature, water composition etc.) of system. It

Figure 6. Efficiency versus pH and concentration (C) diagram.

As an example, 2-aminoethanethiol (2-AEE) was reported to have

arguments, residual and variance analysis, T and F tests, R2 value. It was

[44] Curkovic, H. O.; Stupnisek-Lisac, E.; Takenouti, H. Corros Sci. 2009,

APPLICATION OF POLYMER COMPOSITES

Saviour A. Umoren1,* and Moses M. Solomon2

inhibitors as replacement for the toxic inorganic and organic corrosion

Keywords: polymers, composites, nanocomposites, corrosion inhibitor

2. GLOBAL DEMAND OF CORROSION INHIBITORS

market is divided into organic and inorganic inhibitors. Geographically, the

3. POLYMER COMPOSITES AND NANOCOMPOSITES