Int. J. Corros. Scale Inhib., 2018, 7, no.

1, 112–13x 112

Volatile corrosion inhibitors for ferrous and non-ferrous metals

and alloys: A review
F.A. Ansari,1 C. Verma,2,3 Y.S. Siddiqui,4 E.E. Ebenso2,3
and M.A. Quraishi5*
1
Department of Applied Chemistry, JETGI, Faculty of Engineering, Barabanki,
India-225203
2
Department of Chemistry, School of Mathematical & Physical Sciences, Faculty of
Agriculture, Science and Technology, North-West University (Mafikeng Campus), Private
Bag X2046, Mmabatho 2735, South Africa
3
Material Science Innovation & Modelling (MaSIM) Research Focus Area, Faculty
of Agriculture, Science and Technology, North-West University (Mafikeng Campus),
Private Bag X2046, Mmabatho 2735, South Africa
4
Assistant Professor, Department of Civil Engineering, JETGI, Faculty of Engineering,
Barabanki, IndiaIndia-225203
5
Center of Research Excellence in Corrosion, Research Institute, King Fahd University of
Petroleum and Minerals, Dhahran 31261, Saudi Arabia
E-mail: [email protected], [email protected]

Abstract
Volatile corrosion inhibitors (VCIs) or vapor phase inhibitors (VPIs) represent a class of
highly compounds that are employed to protect the corrosion or oxidation of ferrous and
non-ferrous metals and alloys where surface treatments are impractical. The VCIs release
slowly inside the sealed airspace and actively adsorb and prevent corrosion. Several VCIs
have been employed as effective inhibitors for several metals like iron, zinc, aluminum,
etc. and their alloys. Literature study revealed that VCIs protect metallic corrosion either
by forming a surface protective film on the metal surface or neutralizing the corrosive
surrounding reagents H2O, SO2, H2S and CO2, etc. Because of the high volatility, VCIs
easily vaporize and their vapors condense on the metallic surface as well as the volume
available in the crevices, pores and cracks thereby gives complete protection where they
used. The VCIs can be inserted into coatings, foams, adhesives, powders, sprays and
plastics. Several VCIs are known those act as effective inhibitors by themselves and few
other VCIs are also known those hydrolyzed products act as corrosion inhibitors. The
inhibition ability as well as quantity of the adsorbed VCIs on metallic surfaces can be
determined by several commonly employed techniques such as contact angle, radiotracer,
polarographic and electrocapilarity methods. Present review article describes the
assortment of previous works published on VCIs as corrosion inhibitors for ferrous and
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 113

non-ferrous metals and alloys. The present report also deals with salient features of VCIs
and mechanism of their action.

Keywords: VCIs, vapour pressure, corrosion inhibition, vapour phase inhibitors,

DICHAN, mechanism of VCIs action.
Received: December 19, 2018. Published: March xx, 2018 doi: 10.17675/2305-6894-2018-7-2-1

1. Introduction
1.1. Economic Importance
Corrosion is a worldwide problem to be addressed by educational and industrial divisions
because it unfavorably affecting the economy of developed as well as developing countries
[1–3]. According to NACE study conducted in 2002, the United States losses around US $
276 billion in 1998 because of the damage caused by corrosion. The cost of corrosion
further increased to around US $ 2.2 trillion in the year 2011 [3, 4]. Recently, the damage
due to corrosion (worldwide) exceeds greater than US $ 2.5 trillion that results into loss of
about 3.4% of world GDP. Similar to the most of the countries, GDP of India and South
Africa are also being greatly affected due to corrosion as it has been estimated that
economic damage of India and South Africa due to corrosion are Rs. 5,000,000 (US $
100 billion) and R130 billion (US $ 9.6 billion), respectively. Nowadays, several methods
of corrosion anticipation are being employed that can reduce the damage caused by
corrosion from US $ 375 billion (15%) to US $ 875 billion (35%) [4]. The damage of
corrosion is most pronounced during industrial cleaning processes such as acid descaling
and acid pickling of metallic ores to remove the corrosion products collected on the
metallic surfaces [5–7]. During these cleaning processes a huge amount of metallic
contents are lost because of corrosive nature of the cleaning media (acidic solutions) and
therefore during these processes use of corrosion inhibitors is extremely anticipated [8, 9].
Organic compounds are most frequently utilized inhibitors among the several accessible
methods of corrosion prevention such as like coating and painting, anodic and cathodic
protections, alloying and de-alloying etc. The criteria behind their commercial uses are
based on their easily availability, highly effectiveness and ease of application in addition to
their economic synthesis using commercially available raw starting chemicals [10–14].
Generally, these compounds strongly interact through their - and non-bonding electrons
with metallic surface and form protective surface film via coordination bonds. This
inhibitor film acts as barrier between surrounding environment and metal surface thereby
helps in corrosion protection [15–17]. The presence of functional groups (–NH2, –OCH3,
–OH, –NO2, –COOH, –CONH2, etc.), homo-atomic (>C=C<, –C≡C–) and hetero-
atomic (>C=O, >C=S, –C=N–, –N=O, –C≡N, etc.) multiple bond of carbocyclic and
heterocyclic rings facilitate the adsorption of organic inhibitors on metal surfaces [18–20].
Generally, in strongly acidic media most of the organic inhibitors exist in their cationic
(positive) form as their heteroatoms easily undergo protonation, while in the same
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 114

environment metallic surface exist in the negative forms due to adsorption of anionic
counter ions (e.g. Cl–, SO24 , NO3 ) on the surface [21, 22]. Therefore, during the first stage
of adsorption in acidic solutions, metal surface and inhibitor molecules interact by
electrostatic force of attractions i.e. physisorption process. However, during the later stage
of adsorption, these inhibitors interact via their non-bonding and -electrons and form
coordination bonds i.e. chemisorption [23].

1.2. Factors affecting corrosion

Corrosion is an inherent property of pure metals except silver, gold and platinum, and its
rate largely depends upon the nature of surrounding environments [21–23]. Obviously,
an increase in the surrounding temperature results into corresponding increase in
corrosion rate [21–23]. Although, presence of organic inhibitors in corrosive acidic
environment decreases corrosion rate, however nature of groups exerted most significant
role on the inhibition effect of these inhibitors. The electron releasing groups such as
amino (–NH2), hydroxyl (–OH) and methoxy (–OCH3) substituents increase the
inhibition performance of the organic inhibitors as they increase the electron density at
the active sites that favors metal–inhibitor interactions [24, 25]. In contrast, electron
withdrawing groups like carboxyl (–COOH), cyano (–CN), ester (–COOC2H5), nitro
(–NO2) substituents decrease inhibition performance because they withdraw the electron
density from the active sites that disprove the metal–inhibitor interactions [24, 25]. The
electron donating and/or withdrawing nature of groups can be measured by their
Hammett constant (σ) values. The negative value of Hammett constant (e.g. σ = –0.17 for
p-CH3) suggests that substituent under consideration is electron releasing in nature and
can favor the adsorption of organic inhibitor in which it is present. Conversely, a group
with positive Hammett constant value (e.g. σ = 0.78 for p-NO2) indicates that concern
substituent group is electron withdrawing in nature and disfavors the adsorption of
organic inhibitor molecules. It has been demonstrated that addition of alkyl substituents
in organic inhibitors/ compounds enhances their hydrophobic character that results into
their limited solubility in the polar solvents like water, HCl and NaOH etc. [26, 27]. It is
obvious that for proper metal–inhibitor interactions, the inhibitor molecules should be
properly dissolved and homogenized. The geometry of the inhibitor molecule on metallic
surfaces largely influence their inhibition property because an inhibitor with flat or
horizontal geometry on metal surface would shelter larger area as compared to the same
inhibitor with vertical or non-planar geometry [24, 25]. Sometimes, presence of bulky
alkyl substituents cause steric repulsion/hindrance which in turn affect the geometry of
inhibitor molecules on the metallic surfaces [26, 27]. In that cases non-substituted
inhibitor showed relatively better corrosion inhibition as compared to their alkyl or other
substituted groups. Beside the nature of group, concentration of the organic inhibitors
play very significant role towards the metallic corrosion inhibitors in the aggressive
media. The inhibition performance of organic inhibitors increases successively on
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 115

increasing their concentration till the maximum value is not attained. The concentration
at which organic compounds show their maximum inhibition efficiency are called as
optimum concentration. It has been postulated that below optimum concentration,
inhibitor molecules adsorb on the metallic surfaces by their flat orientations and therefore
surface coverage successively increases on increasing inhibitor concentration. However,
at or above optimum concentration where maximum surface coverage occurs further
increase in concentration causes increases in intermolecular force of repulsion among the
inhibitor molecules i.e. below optimum concentration intermolecular force of attraction
among metal surface and inhibitor molecules dominates over intermolecular force of
repulsion among them and just reverse occur above optimum concentration.
Presence of humidity in the surrounding environment along with organic, inorganic
salts as impurities enhances the probability and rate of corrosion because polar (water) and
ionic species increase the ionic conductivity of the corrosive medium [28–30]. Movement
of the corrosive medium also plays a potential role of the corrosiveness of the aggressive
solution. In the flowing case, metallic corrosion would be more severe because moving
electrolyte molecules continuously remove the rusts and scales accumulated on the surface
leading to exposure of new metallic surface for corrosion as compared to the static
conditions. Under static conditions, the nature of corrosion products can be estimated by
Pilling–Bedworth ratio which is presented by Md/nmD [31, 32]. In this formula, m and M
represent atomic mass and molecular mass of metal under consideration and corrosion
products (rusts), respectively, d and D denote the densities of metal under taken and
corrosion products, respectively and n signifies number of metallic atom in the formula of
corrosion product. For instance, in corrosion products Al 2O3, Fe2O3, and Fe3O4 n is equal
to 2, 2 and 3, respectively [32]. In the situation Md/nmD < 1, it is assumed that surface
volume of the corrosion products is smaller than the volume of metallic surface and
therefore surface film have some pores, cracks and some exposed area and would be non-
protective in nature. However, for situation Md/nmD > 1 it can be assumed that volume of
the corrosion products is greater than the volume of metallic surface therefore surface film
in this situation will uniformly cover metallic surface and will be protective in nature.

1.3. Methods of corrosion protection

Corrosion is an extremely destructive problem adversely affecting the economics of most of
the developing and developed countries therefore its prevention is highly anticipated
primarily during industrial acid cleaning and oil well acidification processes [24, 25].
Several methods of corrosion prevention have been developed depending upon the nature of
metallic species and surrounding environments [24, 25]. The methods of corrosion
protection can be broadly divided into three categories namely anodic protection, cathodic
protection and mixed type of protection, depending upon the mode of action of the
inhibitors. Anodic inhibitors also known as passivating inhibitors those inhibit corrosion by
retarding the anodic oxidation reaction through a process known as passivation. In the
passivation process these inhibitors retard metal corrosion by adsorption and formation of
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 116

surface oxide layer (passive) that results into large anodic displacement in the corrosion
potential (Ecorr) [33]. Several anodic inhibitors have been reported as chromate, nitrite and
nitrate those can form passive oxide layer on metallic surface in non-oxygenic environments
[33]. These passivating species are known as oxidizing anions. On the other hands, there are
few other passivating inhibitors such as phosphate, molybdate and tungstate are known those
can form passive layer in the presence of oxygenic environment only [33]. Cathodic
inhibitors are chemical compounds those decrease the cathodic corrosion reaction or
precipitates on the cathodic sites. The precipitation of the cathodic inhibitors results into
sudden increase in the surface impedance because precipitated cathodic inhibitors reduce the
rate of diffusion of chemical species responsible for corrosion. Based on their mode of
action, cathodic inhibitors may be cathodic precipitates, cathodic poison and oxygen
scavenger types [33]. It is well demonstrated that hydrazine and sodium sulfite consume the
surrounding oxygen molecules by chemically reacting with them and thereby slow down the
cathodic reaction. These two compounds act as oxygen scavengers [33, 34]. Presence of
antimony and arsenic retards the combination of hydrogen ions (H+) during the cathodic
hydrogen evolution reaction. The two metallic species act as cathodic poisons. Lastly,
sodium, magnesium and zinc precipitate in their oxide forms on the cathodic area and
thereby act as cathodic precipitates [33]. The organic compounds, inorganic metals and their
oxides and mixtures of the inorganic-organic compounds have been employed in the several
common corrosive media for almost every kind of metals and alloys [35]. Alloying and de-
alloying of the metallic species can improve their corrosion resistance behavior. The use of
organic compounds as inhibitors has gained the highest priority because these compounds
are relatively economic, effective and can be derived from commercially available starting
chemicals. Their high inhibition efficiency is based on the fact that they contain several
adsorption centers in the form of polar functional groups and multiple bonds [9, 35].
1.4. Corrosion inhibitors
Till today several types of inhibitors have been developed and used for effective inhibition
of metallic corrosion those can be divided into several classes or groups depending upon
their nature. Recently, use of plant extracts in the field of corrosion inhibition is among the
widely growing methods because of their green and sustainable nature [36–38]. The
phytochemicals present in the extracts offer strong metal–inhibitor interactions that come in
form of high inhibition efficiencies of these extracts. Moreover, these phytochemicals are
naturally synthesized using atmospheric carbon dioxide (CO2) and water in the presence of
sunlight without using any toxic chemicals or solvents that offers them as one of the greenest
chemicals to be used for various applications including the field of corrosion inhibition [36–
38]. Each plant extracts generally contain several phytochemicals those can effectively
adsorb on the metallic surface and inhibit their corrosion. Chemical medicines or drugs are
other commonly employed green inhibitors for metallic corrosion in various electrolytic
media [39–41]. Their biological and natural origin offers them a green and environmental
friendly chemical to be used for several purposes. Generally, drugs are chemically complex
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 117

molecules those possess several active sites in the form of heteroatoms and extensive
conjugation [39–41]. The extensive use of inorganic compounds as inhibitors as such or in
combination with organic compounds for solution phase as well as for coating has been
reported in literature. The presence of inorganic compounds in the solution enhances the
effectiveness of the organic inhibitors through the phenomenon of synergism [42]. Literature
survey shows that synthetic compounds have been employed most commonly but their
recent application now based on their several physiochemical properties like cost, lifespan,
effectiveness, ease of synthesis and applications, solubility in the test medium, temperature
and pH dependent stability etc. Most of the used synthetic inhibitors are toxic and hazardous
for living organisms and also to the surrounding environments because of their multistep
synthesis and use of conversional energy source for heating those are associated with huge
discharge of environmental malignant chemicals into the surrounding and reduced yield
owing to their association with several workups and purification processes. In view of this
recently organic inhibitors are being synthesized using the one step multi component
reactions (MCRs) which is generally connected with ease to handle and high reaction yield.
The reduction in the number of purification and workup steps because of their one step
nature, MCRs are also associated with high atom economy (high yield). The conventional
heating methods for activation of reactive molecules is an outdated protocol that offers very
slow heating of the reaction vessels and require several hours or even days for completion of
the reactions. The microwave and ultrasound irradiations are being frequently utilized as
energy (heating) source for various chemical transformations like esterification, hydrolysis,
condensation, cyclization, nitration, alkylation, acylation etc. because of their quick and
uniform heating throughout the reaction vessels. In summary, it can be say that ultrasound
and microwave in combination of MCRs is one of the best methods for the development of
the green synthetic inhibitors particularly solvent free condition or in green solvents like
water and ionic liquids.

1.5. An introduction to volatile corrosion inhibitors (VCIs)

1.5.1. Historical background
Volatile corrosion inhibitors (VCIs) are also known as vapour phase corrosion inhibitors
(VPCIs). The efficiency of VCIs depends on its adsorption ability on the metal’s surface,
the strength of this adsorption, and the temperature dependence of its vapor pressure.
However, the corrosion inhibition of numerous components of US military equipments by
dicyclohexylammonium nitrite (DICHAN) in 1940s is being considered as first work on
VCIs [43]. The majority of strong aliphatic and alicyclic base compounds were effective
vapor-phase inhibitors. It was found that compounds like cyclohexylamine,
hexamethyleneimine, piperidine, morpholirne [44], and benzylamine were found as
effective VCI’s for ferrous metals.
Ammonia and lower amines were used extensively for protection of metallic materials
in power industry during the 20s to 30s decades of 20th century [43–45]. Many formulations
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 118

were suggested which may protect ferrous as well as nonferrous metals i.e. Benzimidazole,
2-benzimidazolethiol, and 2-mercaptobenzotriazole were reported to be effective for Cu, Al,
Zn and their alloys. Thereafter, several VCIs have been developed and employed for
inhibition of ferrous and non-ferrous metallic corrosion in their vapour phase.

1.5.2. Vapor pressure (p0) and its measurement

The VCI molecules have strong tendency to escape in surrounding air because of their high
volatility nature thereby these molecules can adsorb on the metal surface (passivation) and
avoids the contact of corrosive surrounding [43–46]. The volatility or sublimation which
can be expressed in the term of saturated vapour pressure (p0) is one of the most
characteristics properties of the VCIs. Literature survey reveals that compounds with
values of saturated vapour pressure (p0) greater than in the range of 10–2–10–7 mmHg can
be used as VCIs [43, 45]. There are several VCIs that have ability to protect the metallic
surface either by themselves or their hydrolysis products have been reported in literature.
For instance, nitrite–hexamethylenetetramine and nitrile–carbamide become effective as
vapour phase inhibitors for metallic corrosion because of the formation of highly volatile
ammonium nitrite through hydrolysis reaction [43, 45].
(CH2)6N4 + 4H2O + 10NaNO2 = 4NH4NO2 + 6CH2O + 4NaOH (1)
CO(NH2)2 + 2H2O + 2NaNO2 = Na2CO3 + 2NH4NO2 (2)
Generally, vaporization of most of the VCIs in gas phase occurs without their decomposition
however, carbon dioxide and cyclohexylamine vaporization occur mainly either thermal or
hydrolytic dissociation [43, 45, 46]. A substantial attention has been paid to describe the
mechanism of vaporization/ sublimation with the particular emphasis of amines and
DICHAN which obviously depends upon interaction with the surrounding environment
[43, 45, 46]. Presence of moisture or humidity favors adsorption of VCI molecules on
metallic surface because of increased volatility (saturation vapour pressure; p0) of their
components through hydrolysis. However, the decrease in p0 with increase in humidity have
been observed have also been reported in few cases. Besides, humidity temperature is
another important factor that limits the volatility of the VCIs. Several methods have been
developed for measurement of p0 those can be classified into static, evaporation from open
surface, dynamic, boiling point measurement and their modified forms.
(i) Regnault dynamic method involves the heating of weighted amount of inhibitor at
the constant temperature under the flowing stream of oxygen free nitrogen followed by
measurement of weight loss. The vaporization rate of the VCI molecule at several studied
temperatures can be computed using following equation [43, 46, 47]:
Total volume of compound Total pressure
 (3)
Volume of vapor Vapor pressure
The value of vapor pressure can be obtained by plotting a graph between vapour
pressure and temperature.
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 119

(ii) Knudsen effusion method employs the measurement of the rate of gas effusion
through a small orifice. The value of vapour pressure can be determined using following
formula [46, 47]:
1

pt0  W   T 
2
(4)
KSt  M 
In the equation 4, ∆W represents the weight loss of compound, K is a constant, S is the
area of orifice, t is the time, T is the absolute temperature and M is the molecular weight of
the tested compound.
(iii) Torsion effusion method employed the measurement of recoil force established
when VCI molecules in gas form effuse from pores into a vacuum. When a compound is
kept in an effusion vessel suspended from a fiber and its vapour escapes in a horizontal
route from two strangely (eccentrically) placed pores, the fibber will be twisted through some
angles. The magnitude of the vapour pressure can be computed from the angle of
deflection using following relationship [46, 47]:
2 KB
pt0  (5)
f1d1a1  f 2d 2a2
In the above equation, p0 represents the vapour pressure, B is the steady angle of torque
produced by effusion at a constant temperature (T), d1 and d2 represent the distance
between pore 1 and pore 2 from the axis of origin, f1 and f2 represent the correction factors
and a1 and a2 are the area of the cavities. The K, f, a and d factors are difficult to measure
with adequate precision and therefore another modified equation has been proposed by
calibrating the measuring instrument with a compound with known vapour pressure at
several temperatures. In that case Equation 5 can be simplified as [46, 47]:
Pt = Kt B (6)
In the equation (6), Kt is constant and its calculated value can be employed to
determine the vapour pressure of other compounds under the same temperature range.
(iv) Boiling point determination method employs determination of boiling
temperature and/or pressure of the undertaken compounds when their p0 equal to external
pressure (P).
(v) Microbalance method involves the measurement of the weight loss using
microwave of the high accuracy at measured temperature after calibration with compounds
of the recognized vapour pressure.
A relationship between the physicochemical and electronic characteristics of various
metals and molecular parameters of inhibitors predicts performance and inhibition
efficiency of volatile corrosion inhibitor (VCI’s) of ferrous and nonferrous metals [48–52].
It was predicted that the unambiguous prediction of the inhibitive effects of compounds
and estimation of the adsorptivity of compounds on metals and, consequently, their
inhibitive properties from the general electronic characteristics of the compound and the
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 120

metal (ionization potential and electron work function) does not allow to a general
approach. The estimation of the inhibitive effect was based on the correlation between the
first adiabatic potentials of compounds and “resonance” potentials of metals and metal
oxides. It can be only used to predict possible forms of adsorption bonds between a
compound and a metal.

1.5.3. Effect of temperature on vapour pressure

Obviously, molecular structure and molecular weight (mass) exert significant effect on the p0
value (volatility) of the VCI molecules. It was demonstrated that increase in the molecular
mass generally decreased the volatility of the organic compound. However, it is recall that
composition and mechanism of the evaporation depends upon the external factors along with
the inherent properties of the VCI molecules. Among the external factors, temperature exerts
the most significant effect of the vapour pressure of the VCI molecules. The effect of
temperature can be best explain by Claussius–Clapeyron equation [46, 47, 53]:
Log (P) = A–B/T (7)
where, p is the usual vapour pressure, A and B are constants and T is the absolute
temperature. The value of latent heat of sublimation can be calculated using equation (7).
The calculated values of vapour pressure (p0) and talent heat of sublimation of the some
selected compounds are listed in Table 1. The inspection of results shown in Table it can
be observed that values of p0 are decreasing on increasing the value of talent heat for
nitrobenzoates and for amine benzoates. The decrease in the p0 values of these compounds
on increasing their latent heat is attributed to the corresponding increase in the
intermolecular force of attraction and the increase in the molecular weight that in turn
enhances the Van-der Waals force of attraction. Variation of vapour pressure (p0) with
latent heat of sublimation for DICHAN, cyclohexylamine benzoate and di-isopropylamine
nitrile are presented in Figure 1 [46, 47, 53].

Figure 1. Change in the vapour pressure with latent heat of sublimation of DICHAN,
cyclohexylamine benzoate and di-isopropylamine nitrile.
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 121

Table 1.

Test Material Inhibitor Test Environment Ref.

Mild steel,
copper, and 6-Amino-benzothiazole 100% humidity [80]
brass
Brass β-Amino alcohols 100% humidity [81]
Bis-piperidiniummethyl-urea Humid atmosphere [82]
Mild steel
Bis-piperidiniummethyl-urea (BPMU) and
Humid atmosphere [65]
mono-piperidiniummethyl-urea(MPMU)
Aggressive environments
Mild steel,
of SO2 and NaCl at high
copper, and Benzoic hydrazide stearate (BHS) [83]
relative humidity and
brass
high temperature.
Mild steel, Laurichydrazide (LH) with cinnamic acid
copper, brass, (LHC), succinic acid (LHS), [84]
100% RH
zinc, and Nitrobenzoic acid (LHNB), Phthalic acid
aluminum (LHP), and maleic acid (LHM)
Aluminium,
1-(2-Aminoethyl)-2-dec-9-enyl-2-
mild steel,
imidazoline salicylic acid, nitrobenzoic [85]
brass, and
acid, phthalic acid, and cinnamic acid
copper
100% relative humidity
Piperazine and its derivatives such as
at 40°C for 8 hours and
Mild steel phosphates, carbonates, benzoates, [86]
then for 16 hours under
cinnamate and maleate
the room temperature
1,3-bis-diethylamino-propan-2-ol as VPI [87]
Brass 100% RH
for steel component
Steel
Diethylamine phosphate 100% RH [88]
component
Thiomorpholin-4-methyl-phosphonic acid
Carbon steel and morpholin-4-methyl-phosphonic acid [89]
Morpholine and its derivatives
Amine carboxylate [90]
Dicyclohexylaminebenzotriazole (DCHA-
BTZ)
Mild steel Cl2 environment
octylpalmamide (OTP) [91]
octylcaprilamide (OTC)
octylstearamide (OTS)
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 122

Test Material Inhibitor Test Environment Ref.

Oleic hydrazide benzoate (OHB)oleic
NaCl environment [92]
hydrazide salicylate (OHS)
Dicyclohexylamine CO2 Environment [93]
Urea–amine High humidity [94]
Dicyclohexylamine nitrite [95]
Atmospheric amines [74]
Wood bark oil HCl Environment [96]
Thyme H2S gas environment [97]
Rape-cake extract [98]
Mild steel
Menthol NaCl & HCl [53, 99]
High humidity,
Copper and Hydrogen chloride and
DICHAN (dicyclohexylammonium nitrite) [100]
electronic items sulphide contaminated
environment
Triethylamine (TEA), Ethylamine (EA)
[50]
and N-Ethylaniline (NEA)
n-Caprylic acid (CA), n-Butyric acid (BA),
N,N-dimethyl propylene urea (DMPU) and
2-Amino Benzothiazole temperature of 40.0°C [101]
Mild steel
(ABT)
Diallylamine (DAA), 1-Benzylimidazole
temperature of 50.0°C [54]
(1-BIZ) and 5-Aminotetrazole (5-ATZ)
Vapour Phase
Thiocarbohydrazides and their salts [102]
environment

Altsybeeva et al. [54, 55] studied the mechanism of action of vapour phase corrosion
inhibitor in a model electrolyte solution and that testing of electrolytes provides no
accurate pattern of corrosion inhibition in the vapor phase. Further, it was also discussed
about the kinetics of VCIs from the surface of various metals, action mechanism and
higher inhibition efficiency upon electrostatic application.

1.5.4. Mechanism of VCIs action and Effect of pH

The inhibition of metallic corrosion by VCI molecules involves the two steps, first step
comprises the vaporization of the VCI molecules into surrounding atmosphere and second
step involves dissolution of vapour molecules into pre-adsorbed moisture film that
provides adequate corrosion protection. The tendency of the VCI molecules to enhance the
hydrophobic character of the moisture film on the metallic surface is one of the greatest
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 123

interest in the field of corrosion inhibition using this technique [48, 56]. Dissolution of the
VCI molecules takes place when the pH of the moisture is not very high (basic) or very
low (acidic). It has been reported that salts of weak volatile bases and acids can be best
suited as VCIs. Most of the VCI molecules show their best activity in the pH range of 5.5
to 8.5 [48, 49]. The VCI molecules can protect the metallic corrosion either by forming the
protective film over the metal surface that isolates and relief from corrosion or neutralizing
the corrosive agents present in the environment such as H 2O, S2O, CO2, SO2 etc. Literature
survey suggests that several methods such as contact angle, radiotracer and polarographic
methods to measure electro-capillarity curves have been employed to determine the ability
and quantity of the inhibitors adsorbed on the metallic surface. Figure 2 represents the
mechanism of corrosion protection by VCIs.

Figure 2. Mechanism of corrosion inhibition by VCI molecules.

1.5.5. Advantages and disadvantages of VCIs

The VCI molecules have ability of vaporize and condense on the metallic surfaces in order
to make them less prone to corrosion. The VCIs have several advantages: (i) they can be
inserted into adhesives, coatings, foams, powders, plastics and spray, (ii) they can be
employed into packaging to retard the corrosion of stored items, (iii) they easily vaporize
and their vapour moves quickly to cover the metallic surface and empty volume available
for them until the saturation is established i.e. VCIs start their work once they are exposed
to the environment, (iv) generally they fill all the surfaces including crevices, pores and
cracks where ordinary inhibitors cannot penetrate, (v) VCIs form very thin inhibitive film
that can be easily removed without affecting the properties of metallic surfaces and (vi)
they can be used as corrosion protectors during the transport of metals and components.
The VCI molecules can be used in several sectors such as in the military, nuclear and
petrochemical plants, automotive industries, cultural heritage conservators, surgical
equipments, electronic components manufacturers and producers of high precision
electronic materials because of their high tendency to adsorb on the metallic surface.
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 124

However, at the same time there are a few limitations of the VCIs such as sometime they
increase the corrosion rate of non-ferrous metals and alloys.

1.5.6. Methods of testing VPIs

1.5.6.1. Vapor pressure determination. At some temperatures and pressures, a solid or
liquid is in equilibrium with its vapor. This equilibrium pressure is called the vapor
pressure of the solid or liquid. Standard Knudsen methods were used to determine the
vapor pressure of various vapor phase corrosion inhibitors (VPCIs). The volatilization rate
of VPI’s is in the similar functional dependence upon temperature, so that more inhibitive
material is evaporated at higher temperatures. Criterion for the selection of a compound to
be used as a VPI is that it should not have very low or very high vapor pressure as to give
lasting protection [57–59].
1
W  2πRT  2
P  (8)
At  M 
Where, P = vapor pressure of the VPCI (mmHg), A = area of the orifice (m2), t = time of
exposure (sec.), W = weight loss of substance (kg), T = temperature (K), M = molecular
mass of the inhibitor (kg) and R = gas constant (8.314 J K – 1 mol – 1).
1.5.6.2. Weight loss test. All testing specimen were mechanically polished successively
with the help of emery papers grading 100, 200, 300, 400 and 600 μ and then thoroughly
cleaned with plenty of triple distilled water, ethanol and acetone. Specimen were dried with
hot air blower and stored in desiccators over silica gel. After recording initial weights of
specimen on analytical balance, they were kept in different isolated chambers of air
thermostat having fixed amount of VPCI at a constant temperature of 50°C for 24 hours of
exposure time. A uniform thin film of VPCI was adsorbed onto the metal coupons after 24
hours of exposure. Then these coupons were transferred to a digitally controlled humidity
chamber maintained at 85% humidity at a constant temperature of 50°C for 10 days [60].
The gravimetric evaluation cell is presented in Figure 3.

Figure 3. Gravimetric evaluation cell.

 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 125

1.5.6.3. Esckhe test. Eschke test was carried out on the pre weighed mechanically polished
specimens. Kraft papers of suitable size were dipped in the VPCI for 30 seconds and then
dried to adsorb uniform layer of the inhibitor on the Kraft papers. Then metal coupons
were wrapped in VPCI impregnated Kraft papers and then taken in the humidity chamber
maintained at 85% relative humidity maintained at a constant temperature of 50°C for first
12 hours and 50°C for next 12 hours, alternately for 10 days. This temperature cycle was
maintained in two sets because of formation and condensation of the vapours of VPCI on
mild steel surface regularly. After exposing the coupons for 10 days, the coupons were
treated in same manner as treated in weight loss test to remove corrosion products and then
corrosion rate (CR) and inhibition efficiency (IE) was calculated [61].
1.5.6.4. Salt Spray Method. After exposing the pre weighed mild steel coupons to VPCI in
air thermostat for 24 hours, they were transferred to salt spray chamber having 3.0%
sodium chloride solution maintained at constant temperature of 50°C for duration of 10
days along with blank specimens. After exposing the coupons for 10 days in NaCl spray,
coupons were treated in same manner as treated in weight loss test to remove corrosion
products and corrosion rate CR and inhibition efficiency (IE) was evaluated.
1.5.6.5. Sulfur Dioxide Test. SO2 test was carried out on the mild steel coupons of same
dimension as in weight loss test. SO2 gas was prepared by dissolving 0.04 g of sodium
thiosulphate in 30 mL aqueous solution of 1.0% NH4Cl and 1.0% Na2SO4 solution and
0.5 mL of 1.0 N H2SO4 was added to the flask. Initially pre weighed and mechanically
polished mild steel coupons were placed in air thermostat maintained at a constant
temperature of 50°C for duration of 10 days. Definite weight of VPCIs in a petri dish and
the flask, which is the source of SO2, were placed in the isolated chambers of air
thermostat containing mild steel coupons. The specimens exposed for 10 days were then
treated in same manner as treated in weight loss test to remove corrosion products and
there CR and IE was calculated [57].
1.5.6.6. Metallurgical Research Microscopy Technique. To investigate the corrosion
inhibition efficiency of VPCIs, micrographs of the corroded coupons treated with
investigated VPCI were subjected to porosity study and morphology of surface. Percentage
porosity (PP) and total objects (TO) shows the roughness of surface. On the other hand
maximum perimeter and maximum area object ratio (A/O) provide the information about
the size and depth of the pores on the surface of mild steel. A/O ratio is not very high as
compared to that of salt spray test.
1.5.6.7. Potentiodynamic polarization measurements. The polarization measurements were
determined by thin layer technique for different metals using the atmospheric corrosion
monitor cell. The potential vary from cathodic to anodic direction from the corrosion
potential and then the polarization measurements were carried out. The plot of E vs.
log Icorr was made from which corrosion potential (Ecorr), corrosion current density (Icorr),
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 126

anodic and cathodic Tafel slopes (βa & βc) values are calculated. The inhibition efficiency
for these systems is calculated using the following equation
0
I corr  I corr
i
IE %  0
(9)
I corr
0 i
where, I corr and I corr are the corrosion current density with and without inhibitor.
1.5.6.8. Electrochemical Impedance Spectroscopy. The method of impedance spectroscopy
is a powerful tool for investigation of electrical properties of materials and interfaces of
conducting electrodes. Relevant fields of application are the kinetics of charges in bulk or
interfacial regions, the charge transfer of ionic or mixed ionic–ionic conductors,
semiconducting electrodes, the corrosion inhibition of electrode processes, investigation of
coatings on metals, characterization of materials and solid electrolyte as well as solid-state
devices [62, 63].The VCI’s doesn’t amend the mechanism of dissolution of metal. Hence,
it’s purely depends on the charge transfer process. All experimental plots approximately
have a semi-circular shape. The impedance measurement shows that the inhibition of the
VCIs is characterized by increasing diameter of the arc which is acting the resistance.
The studies reveal that with the increase in inhibitor concentration there is an increase
in charge transfer resistance (Rct) value is ascertained to the formation of protective film on
the metal/solution interface. The charge transfer process mainly controls the corrosion
process. On the contrary, value of double layer capacitance (Cdl) decreases with increases
in the inhibitor concentration. The Cdl is an electrical capacitor between the charged metal
surface and the solution. This decrease in local dielectric constant and/or an increase in the
thickness of the double layer causes decrease in Cdl, hence it is suggested that inhibitor
molecules inhibit the iron corrosion by adsorption at the metal/acid interface
1
Cdl  (10)
2πf max Rct
where Cdl – double layer capacitance, Rct – charge transfer resistance, fmax – frequency.
Rct0  Rcti
IE %  (11)
Rct0

2. VCIs as corrosion inhibitors: literature survey

2.1. VCI as corrosion inhibitors for ferrous materials
Steel in the form of carbon and mild steel being used is a main construction material in
different industries because of its high mechanical strength and cost effective
characteristics. The temporary corrosion protection of these materials is essential when
they are transported from one place to other and during their storage. The role of VCIs to
protect metals from atmospheric corrosion are among the most efficient and cost-effective
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 127

method. The physicochemical aspects of VCI protective action are covered in a number of
reviews [64]
Literature study suggests that several methods of protection have been developed and
being incorporated for temporary protection of mild steel and carbon steel among them use
of VCIs is the most effective, profitable and popular method. The selection of VCIs as
corrosion inhibitors is primarily determined by their vapour pressure and nature of metallic
surface to be protected. Zhang et al. [65, 66] demonstrated the inhibition effect of two
VCIs namely, mono-piperidiniummethyl-urea (MPMU) and bis-piperidiniummethyl-urea
(BPMU) for mild steel and carbon steel corrosion. Weight loss method was employed to
measure the volatility of BPMU and MPMU. Electrochemical techniques were also
employed to study the inhibition characteristic of these tested VCIs. Adsorption of both
VCIs, BPMU and MPMU on mild steel surface was supported by X-ray photoelectron
spectroscopy (XPS) method. Results showed that BPMU forms coordinate bonds with Fe
atoms using its two nitrogen atoms, while MPMU coordinates with Fe atoms using its one
nitrogen atom. The electrochemical results were supported by semi-empirical DFT
approach which showed that energy band gap (∆E) is minimum in the case of BPMU
which results in its high inhibition efficiency as compared to the MPMU. Two tertiary
amines namely, 1,3-bis-diethylamino-propan-2-ol (DEAP) and 1,3-di-morpholin-4-
ylpropan-2-ol (DMP) were synthesized, characterized and evaluated as VCIs for carbon
steel employing chemical and electrochemical methods [67]. Results showed that DEAP
showed best inhibition efficiency of 95% at 2.5×10–2 M concentration. The adsorption of
both the VCIs followed Langmuir adsorption isotherm. Adsorption of DMP and DEAP
molecules on carbon steel surface is supported by FT-IR method. Inhibition performance
of both the VCIs enhanced on enhancing their concentrations as observed by
potentiodynamic polarization study. The corrosion inhibition of mild steel by a few
amines, azoles and carboxylates alone and their mixtures in acidic and basic media have
been studied by electrochemical (OCP and EIS) methods [68]. Results showed that all
studied compounds and their mixtures inhibit mild steel corrosion by passivating the
metallic surface and the extent of passivation mainly depends upon nature of pH. Kannan
and coworkers [69] demonstrated inhibition property of several VCIs namely,
octylsteramide (OTS), octylpalmamide (OTP), octylbenzamide (OTB) octylcaprylamide
(OTC) and Dicyclohexylaminebenzotriazole (DCHAB) on mild steel corrosion in H2S
medium. Inhibition efficiency of the tested VCI molecules have been evaluated using
weight, electrochemical and surface measurement methods. Results showed that adsorption
of the VCI molecules obeyed the Langmuir adsorption isotherm. The adsorption of VCIs
on metallic surface and surface morphologies of the inhibited and uninhibited metallic
specimens were studied by SEM-EDX methods. The inhibition effect of these inhibitors
has also been tested on mild steel in Cl 2 gas environment using chemical, electrochemical
and surface study methods and it was observed that OTS showed the best inhibition
efficiency out of tested VCIs [70]. Thyme Extract of Thymus vulgar L. has also been tested
as effective VCI for mild steel in sodium chloride solution using weight and polarization
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 128

methods [71]. Inhibition of the extract increases with concentration and its adsorption on
mild steel surface obeyed the Temkin adsorption isotherm. Results showed the volatile
plant extract showed maximum efficiency of 84.9% at 1000 ppm concentration. Estevao
and Nascimento demonstrated the influence of zeolite and diatomaceous earths (DE) on the
volatility rate and inhibition performance of the dicyclohexylammonium nitrobenzoate
(DICHANB) and phosphate (DICHAP) for 1006 carbon steel corrosion [72]. Results
showed that inhibition properties of both DICHANB and DICHAP did not enhanced by
diatomaceous earths (DE), however presence of the zeolite significantly enhances the
inhibition performance of tested VCIs. By considering the high inhibition efficiency of the
sodium nitrite, the inhibition property of the dicyclohexylammonium nitrite for packaged
steel materials was studied [73]. A variety of the experiments have been carried out and it
was observed that dicyclohexylammonium nitrite undergoes vaporization and condensation
on the metallic surface and therefore acts as efficient inhibitor. Similar to synthetic
corrosion inhibitors [74] several other VCIs have been investigated as corrosion inhibitors
for mild steel and carbon steel [75].

The trend and technology has allowed new methods for a range of VCI applications to
be reliably extended into new areas of applications. The corrosion protection in Oil & Gas,
Military, Automotive, Electronic, Electrical, and other industrial sectors see existing and
new technologies which increase efficiency and service life and decrease the total cost
[76–78].

2.1. VCI as corrosion inhibitors for non-ferrous materials

Use of vapor-phase corrosion inhibitors is one of the most effective methods for preventing
atmospheric corrosion during transport and storage. In an attempt to develop multimetal
vapor-phase corrosion inhibitors, five amino-benzothiazole derivatives were synthesized to
investigate their inhibiting action on corrosion of mild steel, copper, and brass at 100%
relative humidity by weight loss and potentiodynamic polarization methods. 6-Methoxy-
aminobenzothiazole cinnamate exhibited the best performance among all the studied
compounds by giving >90% inhibition efficiency for all the metals investigated. All the
inhibitors shifted corrosion potential of all metals significantly to the noble direction,
indicating that they are predominantly anodic inhibitors [79]. Some common VCIs that
have been tested as corrosion inhibitors for ferrous and non-ferrous metals and alloys are
presented in Table 1.

3. Conclusions
Present review paper describes the collection of the works that have been published on the
corrosion inhibition performance of volatile corrosion inhibitors for ferrous and non-
ferrous metals and alloys. Obviously, the salts of weak and volatile acids and bases those
have vapour pressure in between 10–2 to 10–7 mmHg act as effective VCIs for metals and
alloys. Various VCI molecules have been tested as effective inhibitors for ferrous and non-
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 129

ferrous metals and alloys. The VCI molecules inhibit metallic corrosion either by forming
a surface protective film on the metal surface or neutralizing the corrosive surrounding
reagents H2O, SO2, H2S and CO2 etc. The mechanism of corrosion inhibition by VCI
molecules has also been described. Because of the high volatility, VCIs easily vaporize and
their vapors condense on the metallic surface as well as the volume available in the
crevices, pores and cracks thereby gives complete protection where they used. They can
also be used in coatings, foams, adhesives, powders, sprays and plastics. The VCI
molecules can act as inhibitors either as such or their hydrolyzed products can also be act
as VCI molecules. The inhibition ability as well as quantity of the adsorbed VCIs on
metallic surfaces can be determined by several commonly employed techniques such as
contact angle, radiotracer, polarographic and electro-capillarity methods.

References
1. B. Wu, J.-L. Cao and L. Kang, “Influence of local corrosion on behavior of steel I-
beams subjected to end patch loading: Experiments”, J. Constr. Steel Res., 2017, 135,
150–161.
2. C. Verma, E.E. Ebenso and M. Quraishi, “Ionic liquids as green and sustainable
corrosion inhibitors for metals and alloys: An overview”, J. Mol. Liq., 2017, 233, 403–
414.
3. R.K. Gupta, M. Malviya, C. Verma and M. Quraishi, “Aminoazobenzene and
diaminoazobenzene functionalized graphene oxides as novel class of corrosion
inhibitors for mild steel: Experimental and DFT studies”, Mater. Chem. Phys., 2017,
198, 360–373.
4. R.K. Gupta, M. Malviya, C. Verma, N.K. Gupta and M. Quraishi, “Pyridine-based
functionalized graphene oxides as a new class of corrosion inhibitors for mild steel: an
experimental and DFT approach”, RSC Adv., 2017, 7, 39063–39074.
5. E. Naveen, B.V. Ramnath, C. Elanchezhian and S.M. Nazirudeen, “Influence of
organic corrosion inhibitors on pickling corrosion behaviour of sinter-forged C45 steel
and 2% Cu alloyed C45 steel”, J. Alloys Compd., 2017, 695, 3299–3309.
6. P. Dohare, K. Ansari, M. Quraishi and I. Obot, “Pyranpyrazole derivatives as novel
corrosion inhibitors for mild steel useful for industrial pickling process: experimental
and quantum chemical study”, J. Ind. Eng. Chem., 2017, 52, 197–210.
7. S.H. Zaferani, M. Sharifi, D. Zaarei and M.R. Shishesaz, “Application of eco-friendly
products as corrosion inhibitors for metals in acid pickling processes – A review”,
J. Environ. Chem. Eng., 2013, 1, 652–657.
8. A. Kumari, M.K. Jha, J.-C. Lee and R.P. Singh, “Clean process for recovery of metals
and recycling of acid from the leach liquor of PCBs”, J. Cleaner Prod., 2016, 112,
4826–4834.
9. N.K. Gupta, C. Verma, M. Quraishi and A. Mukherjee, “Schiff’s bases derived from L-
lysine and aromatic aldehydes as green corrosion inhibitors for mild steel:
Experimental and theoretical studies”, J. Mol. Liq., 2016, 215, 47–57.
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 130

10. S. Mo, H.Q. Luo and N.B. Li, “Study on the influences of two thiazole flavor
ingredients on Cu corrosion caused by chloride ion”, J. Colloid Interface Sci., 2017,
505, 929–939.
11. L. Guo, S. Kaya, I.B. Obot, X. Zheng and Y. Qiang, “Toward understanding the
anticorrosive mechanism of some thiourea derivatives for carbon steel corrosion: A
combined DFT and molecular dynamics investigation”, J. Colloid Interface Sci., 2017,
506, 478–485.
12. I. Obot, D. Macdonald and Z. Gasem, “Density functional theory (DFT) as a powerful
tool for designing new organic corrosion inhibitors. Part 1: an overview”, Corros. Sci.,
2015, 99, 1–30.
13. D. Winkler, M. Breedon, P. White, A. Hughes, E. Sapper and I. Cole, “Using high
throughput experimental data and in silico models to discover alternatives to toxic
chromate corrosion inhibitors”, Corros. Sci., 2016, 106, 229–235.
14. F. Liu, L. Zhang, X. Yan, X. Lu, Y. Gao and C. Zhao, “Effect of diesel on corrosion
inhibitors and application of bio-enzyme corrosion inhibitors in the laboratory cooling
water system”, Corros. Sci., 2015, 93, 293–300.
15. J. Haque, V. Srivastava, C. Verma and M. Quraishi, “Experimental and quantum
chemical analysis of 2-amino-3-((4-((S)-2-amino-2-carboxyethyl)-1H-imidazol-2-yl)
thio) propionic acid as new and green corrosion inhibitor for mild steel in 1 M
hydrochloric acid solution,” J. Mol. Liq., 2017, 225, 848–855.
16. A. Fateh, M. Aliofkhazraei and A. Rezvanian, “Review of corrosive environments for
copper and its corrosion inhibitors”, Arab. J. Chem., 2017, In Press.
17. C. Verma, L. Olasunkanmi, I. Obot, E.E. Ebenso and M. Quraishi, “5-Arylpyrimido-
[4,5-b]quinoline-diones as new and sustainable corrosion inhibitors for mild steel in
1 M HCl: a combined experimental and theoretical approach”, RSC Adv., 2016, 6,
15639–15654.
18. N. Anusuya, J. Saranya, P. Sounthari, A. Zarrouk and S. Chitra, “Corrosion inhibition
and adsorption behaviour of some bis-pyrimidine derivatives on mild steel in acidic
medium”, J. Mol. Liq., 2017, 225, 406–417.
19. C. Verma, L.O. Olasunkanmi, E.E. Ebenso, M. Quraishi and I. Obot, “Adsorption
behavior of glucosamine-based, pyrimidine-fused heterocycles as green corrosion
inhibitors for mild steel: experimental and theoretical studies”, J. Phys. Chem. C, 2016,
120, 11598–11611.
20. C.B. Verma, M. Quraishi and A. Singh, “2-Aminobenzene-1,3-dicarbonitriles as green
corrosion inhibitor for mild steel in 1 M HCl: Electrochemical, thermodynamic, surface
and quantum chemical investigation”, J. Taiwan Inst. Chem. Eng., 2015, 49, 229–239.
21. R. Kumar, R. Chopra and G. Singh, “Electrochemical, morphological and theoretical
insights of a new environmentally benign organic inhibitor for mild steel corrosion in
acidic media”, J. Mol. Liq., 2017, 241, 9–19.
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 131

22. C. Verma, M. Quraishi and A. Singh, “A thermodynamical, electrochemical,

theoretical and surface investigation of diheteroaryl thioethers as effective corrosion
inhibitors for mild steel in 1 M HCl”, J. Taiwan Inst. Chem. Eng., 2016, 58, 127–140.
23. A. Fouda, M. Ismail, G. EL-ewady and A. Abousalem, “Evaluation of 4-amidino-
phenyl-2,2′-bithiophene and its aza-analogue as novel corrosion inhibitors for CS in
acidic media: experimental and theoretical study”, J. Mol. Liq., 2017, 240, 372–388.
24. C. Verma, M. Quraishi, L. Olasunkanmi and E.E. Ebenso, “L-Proline-promoted
synthesis of 2-amino-4-arylquinoline-3-carbonitriles as sustainable corrosion inhibitors
for mild steel in 1 M HCl: experimental and computational studies”, RSC Adv., 2015, 5,
85417–85430.
25. C. Verma, L.O. Olasunkanmi, I. Obot, E.E. Ebenso and M. Quraishi, “2,4-Diamino-5-
(phenylthio)-5H-chromeno-[2,3-b]pyridine-3-carbonitriles as green and effective
corrosion inhibitors: gravimetric, electrochemical, surface morphology and theoretical
studies”, RSC Adv., 2016, 6, 53933–53948.
26. H.Z. Al-Sawaad, A.S. Al-Mubarak and A.M. Haddad, “The inhibition effects of
dimethylol-5-methyl hydantoin and its derivatives on carbon steel alloy”, J. Mater.
Environ. Sci., 2010, 1, 227–238.
27. H.Z. Al-Sawaad, “Kinetic study for the hydroxymethylation of the rubeonic acid in
alkaline medium and evaluation of Rubeonic and its derivatives as corrosion inhibitor
for carbon steel by theoretical study”, J. Mater. Environ. Sci., 2012, 3 248-261.
28. Y. Yang, L. Guo, H. Liu, Factors affecting corrosion behavior of SS316L as bipolar
plate material in PEMFC cathode environments, international journal of hydrogen
energy, 2012, 37, 13822-13828.
29. A. Bauer, T. Mehner, B. Awiszus, T. Lampke, Detection and Prediction of Corrosion-
Affecting Parameters in Cold Flat Rolling Processes, Procedia engineering, 2017, 184,
22-29.
30. Y.-P. Song, L.-Y. Song, G.-F. Zhao, Factors affecting corrosion and approaches for
improving durability of ocean reinforced concrete structures, Ocean Engineering, 2004,
31, 779-789.
31. B. Mazères, C. Desgranges, C. Toffolon-Masclet, D. Monceau, Experimental study and
numerical simulation of high temperature (1100–1250° C) oxidation of prior-oxidized
zirconium alloy, Corros. Sci., 2016, 103,10-19.
32. X. Yu, B. Jiang, H. Yang, Q. Yang, X. Xia, F. Pan, High temperature oxidation
behavior of Mg-Y-Sn, Mg-Y, Mg-Sn alloys and its effect on corrosion property, Appl.
Surf. Sci., 2015, 353, 1013-1022.
33. M. Finšgar, J. Jackson, Application of corrosion inhibitors for steels in acidic media for
the oil and gas industry: a review, Corros. Sci., 2014, 86, 17-41.
34. S.H. Zaferani, M.R. Shishesaz, Corrosion Inhibition of Carbon Steel in Acidic Solution
by Alizarin Yellow GG “AYGG”, J Pet Environ Biotechnol, 2014, 5: 188
doi:10.4172/2157-7463.1000188.
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 132

35. C. Verma, E.E. Ebenso, M. Quraishi, Corrosion inhibitors for ferrous and non-ferrous
metals and alloys in ionic sodium chloride solutions: A review, J. Mol. Liq., 2017, 248,
Pages 927-942.
36. P. Parthipan, J. Narenkumar, P. Elumalai, P.S. Preethi, A.U.R. Nanthini, A. Agrawal
and A. Rajasekar, “Neem extract as a green inhibitor for microbiologically influenced
corrosion of carbon steel API 5LX in a hypersaline environments”, J. Mol. Liq., 2017,
240, 121–127.
37. A. Ehsani, M. Mahjani, M. Hosseini, R. Safari, R. Moshrefi and H.M. Shiri, “Evaluation
of Thymus vulgaris plant extract as an eco-friendly corrosion inhibitor for stainless
steel 304 in acidic solution by means of electrochemical impedance spectroscopy,
electrochemical noise analysis and density functional theory”, J. Colloid Interface Sci.,
2017, 490, 444–451.
38. H.L.Y. Sin, A.A. Rahim, C.Y. Gan, B. Saad, M.I. Salleh and M. Umeda, “Aquilaria
subintergra leaves extracts as sustainable mild steel corrosion inhibitors in HCl”,
Measurement, 2017, 109, 334–345.
39. G. Gece, “Drugs: A review of promising novel corrosion inhibitors”, Corros. Sci.,
2011, 53, 3873–3898.
40. I. Rotaru, S. Varvara, L. Gaina and L.M. Muresan, “Antibacterial drugs as corrosion
inhibitors for bronze surfaces in acidic solutions”, Appl. Surf. Sci., 2014, 321, 188–196.
41. J.H. Al-Fahemi, M. Abdallah, E.A. Gad and B. Jahdaly, “Experimental and theoretical
approach studies for melatonin drug as safely corrosion inhibitors for carbon steel using
DFT”, J. Mol. Liq., 2016, 222, 1157–1163.
42. R. Hudson and C. Warning, “Influence of halide mixtures with organic compounds on
dissolution of and hydrogen absorption by low-C steel in H2SO4”, Corros. Sci., 1970,
10, 121–134.
43. D. Bastidas, E. Cano and E. Mora, “Volatile corrosion inhibitors: a review”, Anti-
Corros. Meth. Mater., 2005, 52, 71–77.
44. N. Andreev and Yu.I. Kuznetsov, “Volatile inhibitors of metal corrosion. I.
vaporization, Int. J. of Corr.and Scale Inhi.”, 2012, 1, 16–25.
45. N.N. Andreev and Yu.I. Kuznetsov, “Physicochemical aspects of the action of volatile
metal corrosion inhibitors”, Russ. Chem. Rev., 2005, 74, 685–695.
46. Yu.I. Kuznetsov, “Current state of the theory of metal corrosion inhibition”, Prot. of
Metals, 2002, 38, 103-111.
47. I. Rosenfeld, B. Persiantseva, P. Terentiev, “Mechanism of metal protection by volatile
inhibitors”, Corrosion, 1964, 20, 222t-234t.
48. A. I. Altsybeeva, V. V. Burlov, N. S. Fedorova, T. M. Kuzinova and G. F. Palatik,
“Volatile inhibitors of atmospheric corrosion of ferrous and nonferrous metals I.
Physical and chemical aspects of selection of starting reagents and synthetic routes”,
Int. J. Corros. Scale Inhib., 2012, 1,51–64.
49. A. I. Altsybeeva, V. V. Burlov, N. S. Fedorova, T. M. Kuzinova and G. F. Palatik,
“Volatile inhibitors of atmospheric corrosion of ferrous and nonferrous metals II.
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 133

Prediction of the efficiency of volatile inhibitors of atmospheric corrosion of steel (with

Schiff and Mannich bases as examples)”, Int. J. Corros. Scale Inhib., 2013, 2, 99–106.
50. N. N. Andreev and Yu. I. Kuznetsov, “Volatile inhibitors of metal corrosion II.
Interaction of systems being protected with the environment and corrosion prevention
conditions’’, Int. J. Corros. Scale Inhib., 2012, 1,146–153.
51. A.I. Altsybeeva, V.V. Burlov, N.S. Fedorova and T.M. Kuzinova., “Volatile inhibitors
of atmospheric corrosion of ferrous and nonferrous metals III. VNKh-L-408 inhibitor:
basics of production and application technology’’, Int. J. Corros. Scale Inhib., 2013, 2,
9–16.
52. N. N. Andreev and Yu. I. Kuznetsov, “Volatile inhibitors of atmospheric corrosion.
III. Principles and methods of efficiency estimation’’, Int. J. Corros. Scale Inhib.,
2013, 2, 39–52.
53. J. Bastidas, B. Chico, M. Alonso, E. Mora, “Corrosion of bronze by acetic and formic
acid vapours, sulphur dioxide and sodium chloride particles”, Materials and Corrosion,
1995, 46, 515-519.
54. A. I. Altsybeeva, V. V. Burlov, N. S. Fedorova and T. M. Kuzinova, “Volatile
inhibitors of atmospheric corrosion of ferrous and nonferrous metals. IV. Application
of the VNKh-L-408 inhibitor in an electrostatic field”, Int. J. Corros. Scale Inhib.,
2013, 2, 194–202.
55. A. I. Altsybeeva,1 V. V. Burlov,1 N. S. Fedorova1 and S. M. Reshetnikov, “Volatile
inhibitors of atmospheric corrosion of ferrous and nonferrous metals. V. Study of the
adsorption of inhibitors on steel from an aqueous electrolyte solution. Int. J. Corros.
Scale Inhib., 2013, 2, 277–286.
56. N.D. Tomashov, Theory of Corrosion and Protection of Metals, The Macmillan
Company, New York, 1966, 672.
57. V. Saini, H. Kumar, “Study of Amine as Vapour Phase Corrosion Inhibitors for Mild
Steel under different aggressive Atmospheric Conditions at high temperature”, Inter. J.
of Eng. and Innova. Tech., 2014, 3, 248-256.
58. M. A. Quraishi, D. Jamal, “Synthesis and evaluation of some organic vapour phase
corrosion inhibitors”, Int. J. of Chem. Tech., 2004, 11, 459-464.
59. S. Dogra, Physical Chemistry Through Problems, New Age International, 1984, 674.
60. P. Premkumar, K. Kannan, M. Natesan, “Evaluation of menthol as vapor phase
corrosion inhibitor for mild steel in NaCl environment”, Arab. J. for Sci. and Eng.,
2009, 34, 71-79.
61. V. Saini, H. Kumar, “DAA, 1-BIZ and 5-ATZ as vapour phase corrosion inhibitors for
mild steel under different aggressive atmospheric conditions at high temperature”,
Inter. Let. of Chem. Phys. and Astr., 2014, 36,174-192.
62. F. Mansfeld, “Use of electrochemical impedance spectroscopy for the study of
corrosion protection by polymer coatings”, J. of App. Electrochem., 1995, 25, 187-202.
63. U. Retter, H. Lohse, Electrochemical impedance spectroscopy, Electroanal.Methods,
Springer, 2010, 159-177.
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 134

64. N. N. Andreev, O. A. Goncharova and S. S. Vesely, “Volatile inhibitors of atmospheric

corrosion. IV. Evolution of vapor-phase protection in the light of patent literature”. Int.
J. Corros. Scale Inhib., 2013, 2 , 162-193.
65. D.-q. Zhang, Z.-x. An, Q.-y. Pan, L.-x. Gao, G.-d. Zhou, “Comparative study of bis-
piperidiniummethyl-urea and mono-piperidiniummethyl-urea as volatile corrosion
inhibitors for mild steel”, Corros. Sci., 2006, 48, 1437-1448.
66. D.-q. Zhang, Z.-x. An, Q.-y. Pan, L.-x. Gao, G.-d. Zhou, “Volatile corrosion inhibitor
film formation on carbon steel surface and its inhibition effect on the atmospheric
corrosion of carbon steel”, Appl. Surf. Sci., 2006, 253, 1343-1348.
67. G. Gao, C.H. Liang, H. Wang, “Synthesis of tertiary amines and their inhibitive
performance on carbon steel corrosion”, Corros. Sci., 2007, 49, 1833-1846.
68. U. Rammelt, S. Koehler, G. Reinhard, “Use of vapour phase corrosion inhibitors in
packages for protecting mild steel against corrosion”, Corros. Sci., 2009, 51, 921-925.
69. P. Kannan, P. Jithinraj, M. Natesan, “Multiphasic inhibition of mild steel corrosion in
H2S gas environment”, Arab. J. of Chem., 2018, 11, 388-404.
70. T.A. Söylev, M. Richardson, “Corrosion inhibitors for steel in concrete: State-of-the-
art report”, Cons. and Build. Mater., 2008, 22, 609-622.
71. P. Premkumar, K. Kannan, M. Natesan, “Thyme extract of Thymus vulgar L. as
volatile corrosion inhibitor for mild steel in NaCl environment”, Asian J. of Chem.,
2008, 20, 445-451.
72. L. Estevao, R. Nascimento, “Modifications in the volatilization rate of volatile
corrosion inhibitors by means of host–guest systems”, Corros. Sci., 2001, 43, 1133-
1153.
73. A. Wachter, T. Skei, N. Stillman, “Dicyclohexylammonium Nitrite, A volatile inhibitor
for corrosion preventive packaging”, Corrosion, 1951, 7, 284-294.
74 Z. Amjad, “Impact of iron oxide (rust) on the performance of calcium phosphate scale
inhibitors for industrial water systems”, Inter. J. of Corros. and Scale Inhib., 2014, 3,
177-189.
75.V. Vorobyova, M. Skiba, І. Kurmakova, O. Bondar, “Self-assembled monoterpenoid
phenol as vapor phase atmospheric corrosion inhibitor of carbon steel”, Inter. J. of
Corros. and Scale Inhi., 2017, 6, 485-503.
76. A. I. Altsybeeva,1 V. V. Burlov,1 N. S. Fedorova1 and S. M. Reshetnikov, “Volatile
inhibitors of atmospheric corrosion of ferrous and nonferrous metals. V. Study of the
adsorption of inhibitors on steel from an aqueous electrolyte solution”, Int. J. Corros.
Scale Inhib., 2013, 2, 277–286.
77. S. Koehler and G. Reinhard, “VCI containing package material – mode of
functioning”, Int. J. Corros. Scale Inhib., 2014, 3, 286-306.
78. E. Lyublinski, 1 P. Lynch, 1 I. Roytman1 and T. Yakubovskaya, “Application
experience and new approaches for volatile corrosion inhibitors”, Int. J. Corros. Scale
Inhib., 2015, 4, 176-192.
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 135

79. L.V. Ramanathan, Corrosão e seu controle, Uhlig, H. H., John Wiley & Sons, 1988,
264.
80. J. Rawat, M. Quraishi, “Influence of some 6-methoxy-aminobenzothiazole derivatives
on corrosion of ferrous and nonferrous metals under vapor-phase conditions”,
Corrosion, 2003, 59, 238-241.
81. G. Gao, C. Liang, “Some β-amino alcohols compounds as green volatile corrosion
inhibitors for brass”, Journal of The Electrochemical Society, 2007, 154, C144-C151.
82. D.Q. Zhang, L.X. Gao, G.D. Zhou, “Polyamine compound as a volatile corrosion
inhibitor for atmospheric corrosion of mild steel”, Mater. and Corros., 2007, 58 594-
598.
83. M. Quraishi, D. Jamal, “Inhibition of metals corrosion by a new vapour phase
corrosion inhibitor”, J of Metallurgy and Mat. Sci., 2005, 47, 45-50.
84. M. Quraishi, V. Bhardwaj, J. Rawat, “Prevention of metallic corrosion by lauric
hydrazide and its salts under vapor phase conditions”, J. of Am. Oil Chem’. Soc., 2002,
79, 603-609.
85. M. Quraishi, D. Jamal, V. Bhardwaj, “Development and testing of new volatile
corrosion inhibitors for multilmetal systems”, Mat. Performance, 2003, 42, 44-48.
86. M. Quraishi, F. Ansari, J. Rawat, “Investigation of piperazine and its derivatives as
vapor phase corrosion inhibitor for mild steel”, Open Electrochem. J., 2009, 1 , 32-36.
87. G. Gao, C.H. Liang, “1, 3-Bis-diethylamino-propan-2-ol as volatile corrosion inhibitor
for brass”, Corros. Sci., 2007, 49, 3479-3493.
88. A. Subramania, A.S. Priya, T. Vasudevan, “Diethylamine phosphate as VPI for steel
components”, Mater. Chem. and Phy., 2006, 100, 193-197.
89. H. Amar, T. Braisaz, D. Villemin, B. Moreau, “Thiomorpholin-4-ylmethyl-phosphonic
acid and morpholin-4-methyl-phosphonic acid as corrosion inhibitors for carbon steel
in natural seawater”, Mater. Chem. and Phys., 2008, 110, 1-6.
90. E. Vuorinen, W. Skinner, “Amine carboxylates as vapour phase corrosion inhibitors”,
Brit. Corros. J., 2002, 37, 159-160.
91. G. Sorell, “The role of chlorine in high temperature corrosion in waste-to-energy
plants”, Mater. at High Temp., 1997, 14, 207-220.
92. Sudheer, M. Quraishi, E.E. Ebenso, M. Natesan, “Inhibition of Atmospheric Corrosion
of Mild Steel by New Green Inhibitors under Vapour Phase Condition”, Inter. J. of
Electrochem. Sci., 2012, 7, 7463-7475.
93. D.-Q. Zhang, L.-X. Gao, G.-D. Zhou, “Self-assembled urea-amine compound as vapor
phase corrosion inhibitor for mild steel”, Surf. and Coat. Tech., 2010, 204, 1646-1650.
94. E. Cano, D. Bastidas, J. Simancas, J. Bastidas, “Dicyclohexylamine nitrite as volatile
corrosion inhibitor for steel in polluted environments”, Corrosion, 2005, 61, 473-479.
95. X. Ge, A.S. Wexler, S.L. Clegg, “Atmospheric amines–Part I. A review”, Atmos.
Environ., 2011, 45, 524-546.
 Int. J. Corros. Scale Inhib., 2018, 7, no. 1, 112–13x 136

96. N. Poongothai, P. Rajendran, M. Natesan, N. Palaniswamy, “Wood bark oils as vapour

phase corrosion inhibitors for metals in NaCl and SO2 environments”, Ind. J. of Chem.
Tech., 2005, 12, 641-647.
97. P. Premkumar, K. Kannan, M. Natesan, “Natural thyme volatile corrosion inhibitor for
mild steel in HCl environment”, J. of Metall. and Mat. Sci., 2008, 50, 227-234.
98. E. Chygyrynets, V. Vorobyova, “A study of rape-cake extract as eco-friendly vapor
phase corrosion inhibitor”, Chem. and Chemical Tech., 2014, 8, 235-242.
99. P. Premkumar, K. Kannan, M. Natesan, “Effect of menthol coated craft paper on
corrosion of copper in HCl environment”, Bull. of Mater. Sci., 2010, 33, 307-311.
100. M.E. Tarvin, B.A. Miksic, “Volatile corrosion inhibitors for protection of electronics”,
1989 Conference of National Association of Corrosion Engineers (NACE), Citeseer,
1989, pp. 9.
101. H. Kumar, V. Saini, V. Yadav, “Study of vapour phase corrosion inhibitors for mild
steel under different atmospheric conditions”, Int. J. Engg. & Innovative Tech, 2013, 3,
206-211.
102. F. Ansari, M. Quraishi, “Prevention of metallic corrosion by thiocarbohydrazides and
their salts in vapor phase environment”, Chem. Eng. Comm., 2010, 198, 61-72.

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