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Green corrosion inhibitors for aluminium and its

Cite this: RSC Adv., 2017, 7, 27299
alloys: a review†
Open Access Article. Published on 23 May 2017. Downloaded on 28/05/2017 18:17:09.
Klodian Xhanari, ab Matjaž Finšgar, *a Maša Knez Hrnčič,a Uroš Maver, c
Željko Kneza and Bujar Seitib
This review summarises the research work published in the last two decades on the use of natural
compounds as corrosion inhibitors for aluminium and aluminium alloys in different solutions. Herein,
plant extracts, gums, drugs, and oils have been considered as green corrosion inhibitors. The advantages
Received 6th April 2017
Accepted 10th May 2017
and disadvantages of the methods used to obtain green corrosion inhibitors are presented. Additionally,
the inhibition effectiveness of these corrosion inhibitors, including the techniques used to evaluate them
DOI: 10.1039/c7ra03944a
and the respective inhibition mechanisms, are discussed. Finally, a critical evaluation is presented
rsc.li/rsc-advances together with the outlook as regards possible future improvements.
review article have been tested as corrosion inhibitors for

1. Introduction various types of aluminium alloys. However, in the majority of
Corrosion-related costs represent up to a few percent of the the cases the authors do not designate the alloy type. Moreover,
gross domestic product (GDP) of the most developed countries in some cases the chemical composition of the same alloy type,
in the world,1 which can sometimes be close to what is spent on, obtained by different providers, it is not the same. Therefore, in
for example, public education or healthcare. Due to this reason, Table S1 (in the ESI†) we present the chemical composition and
corrosion and its related phenomena have always been of great respective designation (as reported by the authors) for the
interest to the scientic community. tested aluminium alloys.
Aluminium is found in its ionic form in most kinds of In terms of corrosion, aluminium by itself is not resistant,
animal and plant tissues and in natural waters everywhere.2 It is however if an oxide layer is formed on the surface, it becomes
the third most prevalent element and the most abundant metal highly resistant to corrosive attack in various media. However,
in the earth's crust, representing approximately 8% of total when exposed to acidic, alkaline, and chloride-containing
mineral components.3 Dietary aluminium is ubiquitous but media, the oxide layer is damaged, exposing the aluminium
exists in such small quantities that it is not a signicant source materials to the attack of the corrosive environment.6,7
of concern in humans with normal elimination capacity.4 The Different methods can be employed to protect aluminium
most important feature of aluminium is its high strength to and its alloys. For closed systems or sometimes even under
weight ratio. Its high electrical and thermal conductivity, in owing conditions, it is convenient to employ corrosion
addition to its relatively low price, make aluminium very inhibitors. A corrosion inhibitor is a chemical compound that is
attractive in various applications.5 The mechanical properties of added to the corrosive medium in very small amounts (usually
pure aluminium can be signicantly improved by adding up to 1 wt%). These compounds then adsorb on the metallic
different elements forming alloys. Several alloy series have been surface and mitigate corrosion. The performance of corrosion
developed. The type and amount of the elements added inu- inhibitors is usually evaluated from the calculation of the
ence not only the mechanical properties, but also the corrosion inhibition effectiveness, i.e. a percentage calculation of the
resistance of aluminium alloys. The higher the purity of the corrosion rate relative to the medium without a corrosion
alloy, the less susceptible it is to pitting corrosion. Therefore, it inhibitor. Herein, the corrosion rate is usually related to weight
is of great importance to know the chemical composition of the loss (how much mass of the sample is lost aer the corrosion
aluminium alloy. The natural products summarised in this tests) and hydrogen evolution (the volume of released
hydrogen is measured). These two techniques were the most
a
frequently employed methods to evaluate corrosion inhibition
University of Maribor, Faculty of Chemistry and Chemical Engineering, Smetanova
ulica 17, 2000 Maribor, Slovenia. E-mail: matjaz.nsgar@um.si; Tel: +386 2 2294 447 effectiveness.
b
University of Tirana, Faculty of Natural Sciences, Boulevard “Zogu I”, 1001 Tirana, In order to increase the performance of a corrosion inhibitor,
Albania a mixture of surfactant(s), solvent(s), and intensier(s) is usually
c
University of Maribor, Faculty of Medicine, Taborska ulica 8, 2000 Maribor, Slovenia blended. This mixture is then called a corrosion inhibitor
† Electronic supplementary information (ESI) available. See DOI: formulation.8 A corrosion inhibitor is usually effective for
10.1039/c7ra03944a
This journal is © The Royal Society of Chemistry 2017 RSC Adv., 2017, 7, 27299–27330 | 27299
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a certain metallic material in a particular environment and even effective reactive oxygen scavengers. Polyphenol-based extracts
minor change can cause it to become ineffective. Even though seem to satisfy most of the demands of a composite anti-
some models (especially quantum chemical calculations) are corrosion/anti-biodeterioration product, in addition to having
lately being developed to forecast corrosion inhibition effec- the advantage of being less toxic than other plant extracts, e.g.
tiveness, for the moment, empirical tests are still the most alkaloid extracts. However, there is always the question of the
reliable methods in corrosion inhibition effectiveness research. stability of these extracts in the conditions tested as corrosion
This is due to the fact that the inhibition mechanisms of these inhibitors.1
compounds on metallic surfaces are frequently not well known. Gums and natural oils are two other groups of green corro-
Organic compounds are frequently used as corrosion sion inhibitors obtained from plants. In this review, drugs are
inhibitors. However, the toxicity of organic compounds considered to be green compounds as they are actually
combined with their low cost and availability, have made consumed by humans, however, as pointed out below, their
natural products an excellent alternative as possible corrosion consumed dosage is always questionable and therefore their
inhibitors. Furthermore, the care for the environment by using use as green corrosion inhibitors might be questionable as well.
sustainable resources abundant in nature is already of para- Several studies reported that the use of synergists, mainly KI
mount importance and will have an increasing impact on and other halides (KBr and KCl) in combination with these
society and the well-being of people. As a result, natural prod- green inhibitors, further enhances their corrosion inhibition
ucts will become even more important in the near future. As efficiency.9–17 The authors usually explain this phenomenon
shown herein, natural compounds have already been exten- with the fact that the cation of the inhibitor adsorbs on the
sively employed as useful substitutes for synthetic materials in metal surface where the halide ions are strongly adsorbed. The
different corrosion inhibition applications. The authors re- adsorbed ions are stabilized through electrostatic interaction
ported herein designate the employed inhibitors as green, eco- with the inhibitor molecules which leads to increase surface
friendly or environmentally acceptable. Several groups of coverage, and therefore higher corrosion inhibition efficiency.18
natural compounds have been investigated as possible corro- Given the complexity of the eld, there is still a “barrier”
sion inhibitors for aluminium materials. Fig. 1 shows the between research and application. Much more research should
distribution of the research work published in the last two be done regarding the analytical and micro-biological charac-
decades on these groups of products, which are presented in terisation assessments of natural products tested as new eco-
this review article. The majority of these studies have been friendly materials protecting products for both purposes,
focused on plant extracts. The main constituents of the plant practical and scientic, in order to achieve quality control
extracts have been reported to be a wide variety of organic thereof and the effectiveness of certain phytocompounds.19,20
compounds, including polyphenols, terpenes, carboxylic acids In the following text, we discuss the research work per-
and alkaloids. Therefore, most of these compounds contain P, formed on different types of green corrosion inhibitors for
N, S, O atoms and multiple bonds in their structure, which serve aluminium and its alloys. Detailed information on the type of
as bonding centres for their adsorption on the surface of the natural product and aluminium material tested, as well as the
aluminium materials. Some of these compounds have the testing conditions (the corrosive environment and tempera-
ability to inhibit microbial development as they can act as very ture), the inhibition effectiveness values (as reported by the
authors), and the techniques used to evaluate them, are pre-
sented in Tables 1–8.
Recently, we presented two extensive reviews covering the
use of organic compounds as corrosion inhibitors for
aluminium and its alloys in acidic6 as well as in chloride and
alkaline solutions.7 Both mentioned review articles summarise
the research work published on this topic aer the review of
Jayalakshmi and Muralidharan21 in 1997 (covering organic and
green corrosion inhibitors for aluminium and its alloys in
various solutions). Several attempts have been made before to
present the application of natural products as green corrosion
inhibitors.22–29 However, these reviews discussed either green
inhibitors for different metals (including aluminium and its
alloys)22–26,29 or only certain types of green inhibitors (for
example extracts) for aluminium materials.27,28 To the best of
our knowledge, such a comprehensive summary covering all
types of green corrosion inhibitors for aluminium and
aluminium alloys alone, as reported herein, has not been
published in the last two decades.
Fig. 1 Distribution of the research work performed in the last two
This review rst discusses the use of plant extracts, followed
decades on natural products as corrosion inhibitors for aluminium and by gums, oils, and drugs employed as green corrosion inhibitors
its alloys presented in this review. for aluminium and its alloys. Finally, the outlook as regards
27300 | RSC Adv., 2017, 7, 27299–27330 This journal is © The Royal Society of Chemistry 2017
Table 1 The inhibition effectiveness of different extracts (extracted with organic solvents) tested as corrosion inhibitors for aluminium and different aluminium alloys in various solutions. The
inhibition effectiveness values are reported as given in the article. In instances where different techniques were used for the determination of the inhibition effectiveness, the range from the
minimum to the maximum values reported in the article is reported below in this table
Review
Inhibitor
Material Inhibitor concentration Medium h (%) Test methods and conditions Reference
Al (composition NG) Capparis decidua fruit extract in ethyl alcohol 0.08–0.40a 0.5–5.0 N HCl 32.27–98.48 WL at room temperature 46
Al (composition NG) Capparis decidua stem bark extract in ethyl alcohol 0.08–0.40a 0.5–5.0 N HCl 25.42–95.52 WL at room temperature 46
Al (composition NG) Capparis decidua root bark extract in ethyl alcohol 0.08–0.40a 0.5–5.0 N HCl 27.74–94.79 WL at room temperature 46
Al (composition NG) Capparis decidua fruit extract in ethyl alcohol 0.08–0.40a 0.5–5.0 N H2SO4 23.10–81.76 WL at room temperature 46
Al (composition NG) Capparis decidua stem bark extract in ethyl alcohol 0.08–0.40a 0.5–5.0 N H2SO4 15.86–82.37 WL at room temperature 46
Al (composition NG) Capparis decidua root bark extract in ethyl alcohol 0.08–0.40a 0.5–5.0 N H2SO4 18.91–83.50 WL at room temperature 46
AA1060 Jasminum nudiorum Lindl. leaf extract in ethanol 0.1–1.0 g L1 1 M HCl 69.0–93.6 EIS at 20 C 50
AA1060 Jasminum nudiorum Lindl. leaf extract in ethanol 1.0 g L1 1 M HCl 72.6–93.1 WL at 20–35 C 50
AA5083 Lawsonia inermis extract in ethyl acetate 200 ppm Sea water 45.50 WL, PDP, and EIS 39
AA5083 Lawsonia inermis extract in methanol 200 ppm Sea water 43.74 WL, PDP, and EIS 39
This journal is © The Royal Society of Chemistry 2017

99.89% Rosemary leaf extract in ethanol 0.1–0.5 g L1 Biodiesel 62.7–97.3 WL and PDP at 25 C 43
>99.9% Coffee husk extract in methanol 100–500 ppm 0.5 M HCl 48.9–92.7 WL, PDP, EFM, and EIS at 25 C 61
>99.9% Coffee husk extract in methanol 100–500 ppm 0.5 M HCl 45.0–80.0 WL aer 1.5 h immersion at 45 C 61
AA1060 Ananas sativum leaf extract in ethanol 0.1–0.5 g L1 0.1 M HCl 75.86–96.09 WL at 30–60 C 51
AA1060 Ananas sativum leaf extract in ethanol 0.1–0.5 g L1 2 M HCl 81.13–93.10 HE at 30 C 51
99.8% Ficus carica leaf extract in methanol 10–100 mg L1 0.5 M HCl 58.65–91.34 WL at 30–60 C 52
AA1060 Treculia africana leaves macerated in ethanol 0.1–0.5 g L1 1 M HCl 31.64–74.17 WL and thermometric at 30–60 C 53
AA1060 Mango peel waste extract in ethanol 0.1–0.5 g L1 0.1 M HCl 23.65–75.33 WL and HE at 30 C 59
99.16% Dendrocalamus brandisii leaf extract in ethanol 0.1–1.0 g L1 1 M HCl 41.3–94.0 PDP and EIS at 20 C 47
99.16% Dendrocalamus brandisii leaf extract in ethanol 0.1–1.0 g L1 1 M H3PO4 14.9–56.3 PDP and EIS at 20 C 47
98.60% Coconut coir dust extract in acetone 0.1–0.5 g L1 1 M HCl 18.6–80.0 WL and HE at 30–60 C 40
NG Citrullus colocynthis leaf extract in methanol 0.12–0.60a 0.5–5.0 N H2SO4 54.35–79.45 WL aer 24 h immersion at 48
25 C and thermometric
NG Citrullus colocynthis seed extract in methanol 0.12–0.60a 0.5–5.0 N H2SO4 53.49–80.77 WL aer 24 h immersion at 48
NG Citrullus colocynthis leaf extract in methanol 0.12–0.60a 0.5–5.0 N HCl 53.78–90.01 WL aer 24 h immersion at 48
NG Citrullus colocynthis seed extract in methanol 0.12–0.60a 0.5–5.0 N HCl 53.56–89.11 WL aer 24 h immersion at 48
AA1050/1070 (99.0% Al) Chrysophyllum albidum fruit extract in ethanol 0.1–0.5 g L1 1.5 M H2SO4 7.20–40.52 WL aer 168 h immersion 58
at 30–60 C
AA1050/1070 (99.0% Al) Chrysophyllum albidum fruit extract in ethanol 0.1–0.5 g L1 1.5 M H2SO4 58.33–90.38 Thermometric 58
99.8% Sorghum bicolor leaf extract in ethanol 5–25 mL L1 2 M H2SO4 3.22–50.00 WL at 32–42 C 55
99.2% Black pepper seed extract in methanol 0.006–0.243 g L1 1 M HCl 35.45–99.66 WL aer 60 min immersion, 57
GSP, and EIS at 35 C
98.611% Cassia auriculata owers extract in ethanol 0.05–1.0 vol% 2 M HCl 15.73–97.27 PDP and EIS at 30 C 60
99.55% Phoenix dactylifera L. leaf extract in methanol 200–1000 ppm 0.5 M HCl 57.6–89.1 PDP, EIS, and EFM at 20 C 41
followed by butanol
NG Prosopis laevigata leaf extract in methanol 50–200 ppm 0.5 M H2SO4 2.7–93.6 WL, PDP, and EIS at 20–60 C 56
2S (99.05% Al) Cola acuminata leaf extract in ethanol 30 vol% 0.5 M H2SO4 12.05–54.31 WL aer 6–24 days immersion 45
at room temperature
2S (99.05% Al) Cola acuminata fruit extract in ethanol 30 vol% 0.5 M H2SO4 7.84–45.78 WL aer 12–21 days immersion 45
at room temperature
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using such an approach and the evaluation of the future
Reference
potential thereof is given.
45
45
45
45
49
49
49
49
49
49
2. Plant extracts as corrosion
inhibitors
WL aer 15–21 days immersion
WL at 25 C and thermometric

Test methods and conditions
Phytocompounds and herbal-based extracts have garnered

increasing interest in the eld of sustainable material-
at room temperature
at room temperature
at room temperature
at room temperature
protecting products. The evaluation of some plant extracts
and the correlation between the extract prole and the corro-
sion inhibitive effect should be focused on the total phenolic
WL at 25 C
WL at 25 C
WL at 25 C
content. Indeed, a good correlation was obtained between the
corrosion inhibition effectiveness of the plant extracts and their
total phenolic contents. The higher the total phenolic content,
the higher it is the inhibition effectiveness of the extracts. It can
be argued that the total phenolic content may act as a guide for
11.10–41.65
15.18–39.97
10.38–19.74
49.07–95.50
46.97–95.61
46.73–93.32
22.22–89.33
15.40–84.82
20.68–81.15
4.09–45.04
screening plant extracts for their inhibitive properties.30

h (%)
2.1 Extraction methods used to obtain plant extracts

Numerous publications on the isolation and fractionation of
different compounds such as plant extracts, essential oils, and
0.1–2 N H2SO4
0.1–2 N H2SO4
0.1–2 N H2SO4
0.1–4.0 N HCl
0.1–4.0 N HCl
0.1–4.0 N HCl
0.5 M H2SO4
0.5 M H2SO4
puried compounds have appeared over the past decades. The

1 M H2SO4
1 M H2SO4
Medium
decision on selecting the extraction method to prole the target

content of plant species is related to the chemical nature of the
substance, sample particle size, and also by the presence of
interfering substances.31 The method used must be carefully
chosen according to the aim of the research. The selection of
concentration
the extraction technique has an impact on the rate, yield, and

0.12–0.60%
0.12–0.60%
0.12–0.60%
0.12–0.60%
0.12–0.60%
0.12–0.60%
purity and is inuenced by the niche of the compound of

Inhibitor
30 vol%
60 vol%
60 vol%
60 vol%
interest and the degree of purity required.

The type of extraction solvent as well as the isolation
procedures may have a signicant impact on the extraction
yield of substances from plants material. Each extraction tech-
nique certainly has unique operating factors that affect the
concentration and antioxidant activity of the extract, and need
to be optimised. The extraction time, temperature, solvent-to-
Cola acuminata fruit extract in ethanol
feed ratio, number of repeated extractions of the sample, as

Cola acuminata leaf extract in ethanol
virens bark extract in methanol
virens bark extract in methanol

virens seed extract in methanol
virens seed extract in methanol

virens leaf extract in methanol
virens leaf extract in methanol
well as the choice of extraction solvents, are the main parame-

Nicotiana leaf extract in ethanol
ters controlling extraction kinetics. Solubility is highly affected

by the extraction time and temperature. At a higher extraction
Nicotiana extract in ethanol
temperature, the viscosity and surface tension of solvents

decrease, which accelerates the mass transfer rate.32 An addi-
tional parameter controlling the extraction kinetics is the
material pretreatment, which affects the moisture content,
sample matrix, particle size, and distribution.
Inhibitor
Conventional liquid–liquid and solid–liquid extraction

Ficus
Ficus
Ficus
Ficus
Ficus
Ficus
NG – not given. a No units given.
techniques are still commonplace due to their simplicity, effi-

ciency, and wide-ranging applicability. However, these tradi-
tional methods have their own advantages and limitations.
Solvent-based extraction results in a higher yield. The main
drawbacks of this technique are related to the use of conven-
(Contd. )
tional solvents such as alcohols (methanol, ethanol, iso-

2S (99.05% Al)
2S (99.05% Al)
2S (99.05% Al)
2S (99.05% Al)
propanol), acetone, diethyl ether, and ethyl acetate, oen mixed

with different proportions of water for sample preparation,
Material
Table 1
separation, and detection, and the identication are of both

NG
NG
NG
NG
NG
NG
environmental and economic concern. Additional purication
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steps either by membrane or ultraltration are required to meet tuned by selection of proper solvent and/or operating condi-
regulation requirements. Exposure to a higher temperature for tions. Studies on the nature of corrosion inhibitors demonstrate
a prolonged period of time may lead to a rapid degradation of that polar as well as non-polar compounds show corrosion
active compounds. Long extraction time is yet another problem inhibition effectiveness. In addition, the extraction procedures
facing the conventional extraction procedure.33 listed above are benecial from the economic point of view. As
Modern extraction techniques are centred on reduced- reported in this review polyphenols are among the main
solvent methods, sorption-based methods, environmental components of the green corrosion inhibitors tested. The
applications, and on both solid and liquid samples.34 highest yields of polyphenols are usually achieved with ethanol
Supercritical uid extraction (SFE), pressurised-liquid and methanol and their mixtures with water, although other
extraction (PLE), microwave-assisted extraction (MAE), solid- solvents have been widely used for extraction of polyphenols
phase extraction (SPE), and solid-phase microextraction from plants, as ethyl acetate or acetone.
(SPME) offer important advantages over organic solvent tech- Given the complexity of the eld, it may be concluded that, in
nology, such as ecological friendliness and ease of product practice, there is still a “barrier” between research and appli-
fractionation. These methods became interesting due to their cation. Much more research should be done regarding analyt-
simplicity, shorter extraction times, and the lower release of ical and micro-biological characterisation assessments on
toxic pollutants by reducing organic solvent consumption. The vegetal extracts tested as new eco-friendly material-protecting
most important advantage of SFE is the selective extraction of products for both purposes, practical and scientic, in order
components or the fractionation of the total extracts.35 This is to achieve the quality control of vegetal extracts and the effec-
possible with the use of different gases for isolation/ tiveness of certain phytocompounds.19,20
fractionation of the components and/or by changing the In the following text, we discuss in more details the research
process parameters. Sub- and supercritical uids are widely work published in the last two decades on plant extracts as
accepted as non-carcinogenic, non-toxic, non-mutagenic, non- corrosion inhibitors for aluminium and its alloys in various
ammable, and thermodynamically stable solvents. A super- corrosive environments. Information on the extraction tech-
critical uid is any substance at a temperature and pressure nique as well as the main components of the extracts (as re-
above its critical point, where distinct liquid and gas phases do ported by the authors in the given corrosion inhibition
not exist. They represent a suitable substitute for organic research, or in other studies not strictly related to corrosion
solvents which close to the critical point show a unique feature, research), is also given. The extracts have been divided into four
i.e. small changes in pressure or temperature result in large groups, based on the solvents used for the extraction. The main
changes in density, allowing their many properties to be “ne- ndings (as described above) regarding the use of plant extracts
tuned”. In the pressure-temperature phase diagram (Fig. 2), the as corrosion inhibitors for aluminium materials are presented
boiling curve separates the gas and liquid region and ends in in Tables 1–4.
the critical point, where the liquid and gas phases disappear
and only a single supercritical phase is present.
On the other hand, the main feature of the extraction 2.2 The corrosion inhibition of plant extracts obtained by
procedures described above is their suitability for isolation of means of organic solvents
both, polar and non-polar compounds and selectivity is ne- Organic solvents are commonly used to extract phenolic
compounds from agricultural tissue. Pretreatment of raw
material with hexane to remove lipids is commonly the rst step
of conventional organic solvent extraction, as ground plant
material may be extracted in a Soxhlet apparatus. Polyphenols
contain multiple phenolic functionalities with diverse chemical
structures and properties. Since it is generally known that the
yield of chemical extraction depends on the type of solvent with
varying polarities, extraction time, and temperature, the mass-
to-solvent ratio, and the chemical composition and physical
characteristics of the samples, much attention is devoted to the
choice of the most suitable organic solvent. Methanol, ethanol,
acetone, ethyl acetate, and their combinations are known for
their high efficiency in the extraction of phenolics from plant
materials, oen with different proportions of water. In partic-
ular, methanol has been proved to be a selective solvent for the
extraction of lower molecular weight polyphenols. High
molecular weight avanols are usually efficiently extracted with
aqueous acetone.36–38
Fig. 2 p–T diagram of a pure substance and separation processes. Tc Ethanol is known to be safe for human consumption and is
and pc are the critical temperature and pressure, while Ttp and ptp are employed for the extraction of anthocyanin-rich phenolic
the triple point temperature and pressure, respectively. species from plant tissues. Ethyl acetate or ethanol are usually
Table 2 The inhibition effectiveness of different aqueous extracts tested as corrosion inhibitors for aluminium and different aluminium alloys in various solutions. The inhibition effectiveness
values are reported as given in the article. In instances where different techniques were used for the determination of the inhibition effectiveness, the range from the minimum to the maximum
values reported in the article is reported below in this table
Inhibitor Test methods and

RSC Advances
Material Inhibitor concentration Medium h (%) conditions Reference
AA7075 Ambrosia maritima L. extract reuxed in distilled water 0.006–0.100 g L1 0.5 M NaCl 30.4–62.5 PDP at 30 C 77
AA7075 Lupinus sp. L extract reuxed in distilled water 0.0005–0.300 g L1 0.5 M NaCl 5.4–82.1 PDP at 30 C 77
AA7075 Cymbopogon proximus extract reuxed in distilled water 0.001–0.250 g L1 0.5 M NaCl 16.1–61.1 PDP at 30 C 77
AA7075 Ambrosia maritima L. extract reuxed in distilled water 0.005–0.070 g L1 0.5 M NaCl 30.9–64.3 EIS at 30 C 77
AA7075 Lupinus sp. L extract reuxed in distilled water 0.0005–0.260 g L1 0.5 M NaCl 13.6–83.6 EIS at 30 C 77
AA7075 Cymbopogon proximus extract reuxed in distilled water 0.005–0.250 g L1 0.5 M NaCl 32.9–62.8 EIS at 30 C 77
27304 | RSC Adv., 2017, 7, 27299–27330

99.61% Carcinia indica seed extract, using reux in distilled water 100–500 ppm 0.5 M H3PO4 41.34–85.59 PDP and EIS at 30–50 C 76
32177 (97.025% Al) Cantaloupe (Cucumis melo) pulp extract 2.0–50.0 vol% 1 M HCl 15.01–92.75 WL and HE at 27 C 63
32177 (97.025% Al) Cantaloupe (Cucumis melo) pulp extract 4.0–50.0 vol% 1 M NaOH 5.69–69.95 WL and HE at 27 C 63
32177 (97.025% Al) Cantaloupe (Cucumis melo) seed extract 2.0–40.0 vol% 1 M HCl 10.97–71.60 WL and HE at 27 C 63
in double-distilled water
32177 (97.025% Al) Cantaloupe (Cucumis melo) seed extract 2.0–30.0 vol% 1 M NaOH 2.82–33.68 WL and HE at 27 C 63
in double-distilled water
98.06% Neolamarkia cadamba bark extract 0.2–0.6 g L1 1 M NaOH 64.6–87.1 WL aer 3 h 64
immersion at 30 C
98.06% Neolamarkia cadamba bark extract 0.6 g L1 1 M NaOH 78.5–87.1 WL aer 3 h 64
immersion at 30–60 C
98.06% Neolamarkia cadamba bark extract 0.2–0.6 g L1 1 M NaOH 68.0–90.62 Tafel extrapolation, Rp, 64
and EIS at 35 C
>99.9% Senna auriculata leaf extract in water 300–900 ppm 1 N NaOH 52.2–76.2 WL aer 2 h immersion, 65
HE, polarisation,
and EIS at 30 C
>99.9% Senna auriculata leaf extract in water 900 ppm 1 N NaOH 72.0–76.2 WL aer 2–10 h 65
immersion at 30 C
>99.9% Senna auriculata leaf extract in water 900 ppm 1 N NaOH 69.6–76.2 WL aer 2 h immersion 65
at 30–60 C
99.99% Saffron leaf extract in triple-distilled water 600 ppm 2 M HCl 78.5–84.6 WL, Tafel extrapolation, 74
and Rp at 25 C
AA1060 Bacopa monnieri stem extract in double-distilled water 30–400 mg L1 0.5 M NaOH 61–96 PDP and WL aer 1 h 66
immersion at 35 C
AA7075 Phoenix dactylifera L. (date palm) fruit juice 100–2000 ppm 3.5% NaCl 30–72 PDP and EIS 78
dissolved in double-distilled water
NG Solanum trilobatum leaf extract in distilled water 0.3–1.5 g L1 1 M NaOH 77.82–93.90 WL, HE, Tafel 67
extrapolation, and
EIS at 30 C
NG Solanum trilobatum leaf extract in distilled water 0.3–1.5 g L1 1 M NaOH 63.2–89.6 WL at 40–60 C 67
98.63% Olive seed extract in water 1–10 vol% 1 M HCl 48.56–98.86 WL and HE at 30 C 80
NG Vitex negunda leaf extract in distilled water 0.3–1.5 g L1 1 M NaOH 38.6–79.7 WL, Tafel extrapolation, 68
and EIS at 30–60 C
AA1060 (98.5%) Vigna unguiculata husk extract in distilled water 0.1–0.5 g L1 0.5 M NaOH 38.65–79.63 WL at 30–60 C 69
AA1060 (98.5%) Vigna unguiculata husk extract in distilled water 0.1–0.5 g L1 0.5 M H2SO4 20.42–66.24 WL at 30–60 C 69
95.30% Aloe leaf extract in water 4–60 vol% 0.5 M HCl 15.00–88.42 Polarisation and 16
EIS at 30 C
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Table 2 (Contd. )
Review

95.30% Aloe leaf extract in water + 0.01 M NaI 4–60 vol% 0.5 M HCl 12.5–80.9 Polarisation and 16
EIS at 30 C
95.30% Aloe leaf extract in water + 1 104 to 5 102 M NaI 48 vol% 0.5 M HCl 44.94–83.55 Polarisation and 16
EIS at 30 C
AA1060 Trachyspermum copticum seed extract 300–500 ppm 0.5 M NaOH 68.54–94.00 WL, PDP, and 70
in double-distilled water EIS at 35 C
99.687% Damsissa extract in water 0.05–1.20 g L1 0.1 M Na2CO3 63.3–91.7 PDP at 30 C 79
99.687% Corchours itorius extract in water 0.05–1.50 g L1 0.1 M Na2CO3 53.2–90.7 PDP at 30 C 79
99.687% Damsissa extract in water 0.10–1.00 g L1 0.1 M Na2CO3 3.3–90.1 EIS at 30 C 79
99.687% Corchours itorius extract in water 0.10–1.50 g L1 0.1 M Na2CO3 10.9–89.1 EIS at 30 C 79

99.68% Lupine seed extract, using the reux in distilled water 0.372–4.464 g L1 2 M NaOH 32.55–87.10b PDP and EIS 17
95% Hibiscus rosa-sinensis owers extract in water 2–8 mL NaOH (pH ¼ 12) 24.0–40.0 WL aer 1 day immersion 71
95% Hibiscus rosa-sinensis owers extract in water + 50 ppm Zn2+ 2–8 mL NaOH (pH ¼ 12) 23.0–98.0 WL aer 1 day immersion 71
95% Hibiscus rosa-sinensis owers extract in water + 50 ppm Zn2+ 8 mL NaOH (pH ¼ 12) 29–98 WL aer 1–11 71
days immersion
95% Hibiscus rosa-sinensis owers extract in water + 50 ppm 8 mL NaOH (pH ¼ 12) 44–98 WL aer 1 day immersion 71
Zn2+ + 50–250 ppm sodium dodecyl sulphate
95% Hibiscus rosa-sinensis owers extract in water + 50 ppm 8 mL NaOH (pH ¼ 12) 36–98 WL aer 1 day immersion 71
Zn2+ + 50–250 ppm N-cetyl-N,N,N-trimethylammonium bromide
95% Hibiscus rosa-sinensis owers extract in water + 50 ppm Zn2+ 8 mL NaOH (pH ¼ 12) 9.31–29.51a Rp, PDP, and EIS 71
98.8% Date palm leaf extract in water 0.20–0.60 g L1 1 M HCl 40.2–87.8 WL at 20–50 C 75
97.4% Adathoda vasica leaf extract in water 200–1000 ppm 1 M NaOH 65.8–81.5 WL aer 2 h 72
immersion at 30 C
97.4% Adathoda vasica leaf extract in water 800 ppm 1 M NaOH 66.2–81.7 WL aer 2–24 h 72
immersion,
PDP and EIS at 30 C
97.4% Adathoda vasica leaf extract in water 800 ppm 1 M NaOH 71.4–81.5 WL at 30–70 C 72
a
NG – not given. h was calculated on the basis of the values of the corrosion rate, the corrosion current, the corrosion current density, or the resistance of the blank solution and inhibited samples.
b
h was calculated on the basis of the sum (Roxide + Rp + Rinhibitor) of the blank solution and of the inhibited samples.
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applied to obtain avonoids. Sequential solvent extraction is polyavonols, thiols, anthocyanins, and tannins are the main
being used increasingly oen; the material is rst extracted with components of the extract. Advantageously, the extraction
dichloromethane. This step comprises the isolation of avonoid procedure does not affect the content of the target compounds
aglycones and other components of lower polarity. A serious since it requires only moderate operating temperatures. A
drawback of dichloromethane is its toxicity. In the subsequent signicant decrease in the inhibition effectiveness of the extract
step, avonoid glycosides and polar constituents are extracted was reported in H3PO4 compared to HCl solution. The inhibi-
using a suitable alcohol.37,38 tion effectiveness of the extract increased with increasing
As seen in Table 1, methanol and ethanol were widely used immersion time up to 2 h for both acids and then gradually
as solvents in the performed studies. However, other organic decreased for longer immersion times. The concentration of the
solvents, such as ethyl acetate,39 acetone,40 and methanol fol- acids was found to inuence the inhibition effectiveness of the
lowed by butanol,41 have also been employed. The extracts ob- extract. The later increased at low acid concentrations (0.5–1.0
tained were used to protect mostly pure aluminium and 1xxx M), but signicantly decreased for higher concentrations (1.0–
series aluminium alloys in acidic solutions. Only a few studies 3.0 M).
reported the inhibition effectiveness of the extracts in chloride- The extracts tested as corrosion inhibitors were obtained
containing solutions,39,42 or even in biodiesel.43 The inhibition from different parts of the plants, including leaves,41,43,45,47–57
effectiveness of all studied extracts increased with increasing stem and root bark,42,46,49 fruits45,46,54,58 and fruit peel,59
concentration, independently of their type, corrosive environ- seeds,48,49,57 owers,60 husks,61 and nuts.44 Wan Nik et al.39 gave
ment, or material. However, Nnaji et al.44 investigated the no clear indication as to which part of Lawsonia inermis was
inhibition effectiveness of cashew nut (Anacardium occidentale) selected to prepare the extract. The distribution of active
testa extract in acetone as a corrosion inhibitor for AA1060 compounds in different parts of plants, such as such as leaves,
aluminium alloy in 0.1, 0.5, and 2.0 M HCl solutions at 30– stems, roots, and fruit, shows qualitative and quantitative
50 C. It was reported that the inhibition effectiveness increased variations. Oen different parts of the same plant contain
with increasing extract concentration in 0.5 and 2.0 M HCl completely different compounds.62 Several studies have been
solutions, while in 0.1 M HCl solution a decrease in the inhi- performed evaluating the inhibition effectiveness of different
bition effectiveness was observed with increasing extract parts of the same plant extracted with the same
concentration. Moreover, Loto and Popoola45 studied the inhi- solvent.45,46,48,49,54 Capparis decidua fruit extract in ethyl alcohol
bition effectiveness of the ethanol extracts of cola acuminate showed higher inhibition effectiveness in both HCl and H2SO4
leaves and fruit and Nicotiana leaves as corrosion inhibitors for solutions compared to stem bark and root bark extracts from
2S aluminium alloys in 0.5 and 1 M H2SO4 solution at room the same plant.46 No signicant change in the inhibition
temperature. The authors reported no clear trend in the inhi- effectiveness was reported between the stem bark and root bark
bition effectiveness at the different concentrations tested. In in HCl solution, while in H2SO4 solution the root bark extract
some cases certain concentrations even promoted corrosion. protected aluminium better. Ficus virens extracts of seeds,
Arora et al.,46 Li and Deng,47 Chauhan et al.,48 and Jain et al.49 leaves, and bark in methanol showed no signicant difference
investigated the inhibition effectiveness of extracts as a func- in the h values in HCl solution, while in H2SO4 solution the
tion of the corrosive environment. Arora et al.46 tested the inhibition effectiveness followed the order bark extract > leaf
extracts of Capparis decidua fruits, stem bark, and root bark in extract > seed extract.49 Kumar and Mathur54 investigated the
ethyl alcohol as inhibitor in the corrosion of aluminium in 0.5– ethanolic extracts of the leaves, latex, and fruit of Calotropis
5.0 N HCl and 0.5–5.0 N H2SO4 solutions, at room temperature. procera and Calotropis gigantea as corrosion inhibitors for
The authors reported a higher inhibition effectiveness of all 98.79% aluminium in 0.5–5.0 N H2SO4 solutions. However, the
types of extract in HCl compared to H2SO4 solution. data showed only non-signicant differences in the h values of
The same conclusion was reported also by Chauhan et al.,48 the three types of extracts. The same behaviour was reported by
who evaluated the inhibition effectiveness of Citrullus colocyn- Chauhan et al.48 regarding Citrullus colocynthis leaf and seed
this leaf and seed extracts in methanol as corrosion inhibitors extracts in methanol. Furthermore, no clear distinction as to the
for aluminium in 0.5–5.0 N H2SO4 and 0.5–5.0 N HCl solutions inhibition performance of ethanolic extracts of Cola acuminate
at 25 C. The inhibition effectiveness increased with increasing leaves and fruits was reported by Loto and Popoola.45
concentration of both acids. The inhibition effectiveness of the tested extracts was
Jain et al.49 studied the inhibition effectiveness of Ficus virens investigated in a temperature range from 20 C to
seed, leaf, and bark extracts in methanol as corrosion inhibitors 60 C.40–42,44,47,50–53,55,56,58,59,61 In the majority of the above-
for aluminium in 0.1–4.0 N HCl and 0.1–4.0 N H2SO4 solutions mentioned studies it was reported that the inhibition effec-
at 25 C. The authors showed that the extracts protected tiveness of the respective extracts decreased with increasing
aluminium better in HCl than in H2SO4 solutions. A methoxy temperature, apart from the works of Ating et al.51 and Umoren
derivative of alstonine (11-mithoxy tetrahydroalstonine) named et al.40 Ating et al.51 studied the inhibition effectiveness of the
aricine is reported as the main component of Ficus virens. extract of Ananas sativum leaves in ethanol as an inhibitor for
The inhibition effectiveness of Dendrocalumus brandisii leaf AA1060 aluminium alloy in 0.1 M and 2.0 M HCl solutions at
extract in ethanol as a corrosion inhibitor for 99.16% 30–60 C. Umoren et al.40 tested the inhibition effectiveness of
aluminium alloy in 1 M HCl and 1 M H3PO4 solutions at 20 C coconut (Cocos nucifera) coir dust extract in acetone as a corro-
was evaluated by Li and Deng.47 The authors reported that sion inhibitor for Al 3SR (98.60% aluminium) aluminium alloy
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in 1 M HCl solution at 30 and 60 C. According to the authors, studied the inhibition effectiveness of Phoenix dactylifera L. leaf
coconut coir dust extract contains a mixture of alkaloids, extract in methanol followed by butanol as a corrosion inhibitor
avonoids, and organic acids, without identifying any for 99.55% aluminium and 92.482% Al–Si alloy at 20–60 C and,
compound in particular. based on the PDP measurements, reported that the extract acted
The change in the inhibition effectiveness with temperature as a mixed-type inhibitor, with predominant action on the
was found to be dependent on the corrosion environment in the cathodic corrosion reaction. The main components of the
case of Dendrocalamus brandisii leaf extract in ethanol.47 The extract were reported to be gallic acid, protocatechuic acid,
authors reported that the inhibition effectiveness of the extract caffeic acid, b-carotene, and lutein. The extract protects Al–Si
decreased with increasing temperature in HCl solutions, while alloy better compared to aluminium.
remained almost constant in H3PO4 solutions. Only Deyab43 reported that rosemary (Rosmarinus officinalis)
PDP measurements revealed different behaviour of the leaf extract in ethanol acted as a mixed-type inhibitor, with
extracts in terms of inuencing the anodic, cathodic, or both a predominant effect on the anodic corrosion reaction of
corrosion reactions of the corrosion couple. Deng and Li50 99.89% aluminium in biodiesel at 25 C.
studied the inhibition effectiveness of the ethanol extract of In general, when explaining the inhibition action of the
Jasminum nudiorum Lindl. leaf in the corrosion of AA1060 extracts, the authors refer to their ability to adsorb on the
aluminium alloy in 1 M HCl solution at 20–35 C and concluded aluminium material surface through the adsorption centres
that the extract acted as a cathodic-type inhibitor. The same contained in the constituents of these extracts. In most of the
behaviour was reported for Prosopis laevigata leaf extract in cases they do not specify which compound or compounds are
methanol56 used as a corrosion inhibitor for aluminium in responsible for the adsorption. This is the case in the works of
0.5 M H2SO4 solution at 30 C. Based on the PDP measure- Yiase et al.55 and Madufor et al.58 and Ukpe et al.59 Yiase et al.55
ments, Li and Deng47 concluded that Dendrocalumus brandisii reported on the inhibition effectiveness of Sorghum bicolor leaf
leaf extract acted as a cathodic-type inhibitor in HCl solutions, extract in ethanol as a corrosion inhibitor for 99.8% aluminium
but as a mixed-type inhibitor in H3PO4 solutions. Prosopine and in 2 M H2SO4 solution at 32–42 C. Madufor et al.58 studied the
prosopinine were reported to be the main constituents of the inhibition effectiveness of Chrysophyllum albidum fruit extract
extract. in ethanol as a corrosion inhibitor for AA1050/1070 (99.0% Al)
Singh et al.42 used Berberine (5,6-dihydro-9,10-dimethox- aluminium alloy in 1.5 M H2SO4 solution, at 30–60 C. Ukpe
ybenzo[g]-1,3-benzodioxolo[5,6-a]quinolizinium), a compound et al.59 reported on the inhibition effectiveness of mango
obtained from the extraction of dried Coptis chinensis roots in (Mangifera) fruit peel waste extract in ethanol as a corrosion
ethanol, as an inhibitor in the corrosion of AA7075 aluminium inhibitor for AA1060 aluminium alloy (98.5% purity) in 0.1 M
in 3.5% NaCl solution at 25–60 C, and, based on the PDP HCl solution at 30–60 C. Based on the thermodynamic calcu-
measurements, concluded that the extract acted as a mixed-type lations, as well as the change in the inhibition effectiveness with
inhibitor. Mixed-type inhibition was reported also for Cassia temperature, the authors discussed the possible adsorption
auriculata ower extract in alcohol60 and coffee (Coffea) husk mechanism for the extracts on the aluminium material surface.
extract in methanol.61 Cassia auriculata ower extract in All three authors above 55,58,59 suggested that the extracts phys-
alcohol60 was tested as a corrosion inhibitor for 97.704% isorbed on the aluminium materials.
aluminium alloy in 2 M HCl solution at 30 C. It was reported Nnaji et al.44 reported that quercetin, azaleatin, catechin,
that luteolin-7-o-glucoside is the main component of the epicatechin, cyaniding, and dephinidin are among the main
extract. The main drawback is the extraction procedure, which components of cashew nut (Anacardium occidentale) testa
is rather complicated and involves isolation steps using extract in acetone. Based on the quantum chemical parameters,
different organic solvents. Coffee (Coffea) husk extract in the authors suggested that the extract adsorbed on the
methanol61 was used as a corrosion inhibitor for aluminium aluminium surface through the aromatic C]C, C]O, and O–H
with purity higher than 99.9% in 0.5 M HCl solution at 25 and sites contained in the protonated forms of the extract compo-
45 C. The authors reported that the main components in coffee nents. Physisorption was the proposed mechanism for the
husk are cellulose, hemicellulose, pectin, lignin, caffeine, adsorption of cashew nut testa extract on the alloy surface.
tannin, and polyphenol. Physisorption seems to be the common mechanism sug-
Several authors reported that the respective extracts acted as gested by authors in general. Onen et al.52 suggested phys-
mixed-type inhibitors, but with a predominant action on either isorption as the possible mechanism for the adsorption of Ficus
the cathodic or anodic corrosion reaction. In fact, Wan Nik carica leaf extract in methanol on the surface of 99.8%
et al.39 studied the inhibition effectiveness of Lawsonia inermis aluminium immersed in 0.5 M HCl solution at 30–60 C. Eji-
extracts in ethyl acetate and in methanol as corrosion inhibitors keme et al.53 reported that the main components found in
for AA5083 aluminium alloy in sea water (no composition given) Treculia africana leaf extract in 96% ethanol are alkaloids,
and concluded that the extracts acted as mixed-type inhibitors, avonoids, terpenes, and proteins. These components phys-
with a predominant effect on the cathodic reaction. The same isorbed on the alloy surface to inhibit the corrosion of AA1060
conclusion was reached by Divya et al.,57 who evaluated the aluminium alloy in 1 M HCl solution at 30 and 60 C. Phys-
inhibition effectiveness of black pepper (Piper nigrum) seed isorption was also suggested for rosemary leaf extract in
extract in methanol as a corrosion inhibitor for 99.2% ethanol,43 Dendrocalumus brandisii leaf extract in ethanol,47 and
aluminium in 1 M HCl solution at 35 C. Next, Shalabi et al.41 Jasminum nudiorum Lindl. leaf extract in ethanol,50 while
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Fouda et al.61 concluded that the inhibition is due to adsorption reported that the pulp extract is more effective compared to the
on the aluminium surface through electrostatic interactions for seed extracts in both alkaline and acidic solutions.
coffee husk extract in methanol. A few studies report a chemi- Leaves,16,67,68,72,74,75 seeds,17,63,70,73,76,80 pulp and fruit juice,63,78
sorption mechanism for the tested extracts40,51,56 and only Divya bark and stem,64,66 and husk and owers69,71 were the plant parts
et al.57 suggested that the main constituent of black pepper seed used to prepare the extracts. No indication of what parts of the
extract in methanol, piperine, followed by E-caryophyllene and plants were used to prepare extracts was given in the works of
9-octadecynoic acid, adsorbed through a mixed-type mecha- Fetouh et al.77 and Abd-El-Nabey et al.79 Although the general
nism (both physisorption and chemisorption) on the trend in all the published works is that the inhibition effec-
aluminium surface. tiveness increased with increasing extract concentration, there
In addition, in a few studies the inhibition action of the are a few exceptions.72,74,77 Fetouh et al.77 evaluated the inhibi-
extracts was attributed to the formation of a surface layer as tion effectiveness of the aqueous extracts of Ambrosia
a result of the adsorption of the extracts' components on the maritima L. (damsissa), Lupinus sp. L (lupine), and Cymbopogon
aluminium materials. This surface layer protected the materials proximus (halfa-bar) as corrosion inhibitors of AA7075-T6
from further attack from the corrosive environment.39,42,57 Singh aluminium alloy in 0.5 M NaCl solution at 30 C. The main
et al.42 attributed the decrease in inhibition effectiveness with active compounds in Damsissa extract are ambrosin and dam-
increasing temperature to the dissolution of this protective sin. Lupanine, multiorine, and sparteine were the main
surface layer. components of the Lupine extract. The most abundant
Lower extraction temperatures and the omission of large components in the halfa-bar extract are proximadiol, 5a-
amounts of organic solvents will certainly contribute to a higher hydroxy-b-eudesmol, 5a-hydroperoxy-b-eudesmol, and 1b-
yield of phenolic compounds in the nal product. Some hydroxy-b-eudesmol. The inhibition effectiveness of all three
authors43–47,50,52,56,61 report easy, economically feasible extraction extracts increased with increasing concentration, up to a certain
procedures carried out at low temperatures with a low concentration, and then decreased with a further increase in the
consumption of chemicals. Modern extraction techniques extract concentration. The authors reported that the highest
certainly represent a green solution to obtain extracts of high inhibition effectiveness was obtained for lupine extract, while
quality. Despite the high extraction temperatures and use of the lowest inhibition effectiveness for halfa-bar extract. Next,
organic solvents, Arora et al.46 reported a high inhibitive effec- Soror74 studied the inhibition effectiveness of the aqueous
tiveness for the ethanolic extracts of Capparis decidua. The main extract of saffron (Crocus sativus) leaves as a corrosion inhibitor
drawback of the extraction procedure is probably its duration, for 99.99% aluminium in 2 M HCl solution at 25 C. It was re-
which takes several days. Additionally, further purication steps ported that the main components of the saffron extract are
are required to remove solvent residues from the obtained safranal, crocin, zeaxanthin, picrocrocin, crocetin, and decyl
extracts. glucoside. The inhibition effectiveness increased with
increasing saffron leaf extract concentration up to 600 ppm and
then decreased for higher concentrations. Finally, Prabha
2.3 The corrosion inhibition of aqueous plant extracts et al.72 tested the aqueous extracts of Adathoda vasica leaves as
A considerable number of studies have investigated the inhi- corrosion inhibitors in the corrosion of 97.4% aluminium in 1 N
bition effectiveness of different parts of plants extracted with NaOH solution at 30–70 C. The inhibition effectiveness
water (Table 2). Aluminium materials similar to what was re- increased with an increase in the extract up to 800 ppm. No
ported for the extracts obtained with organic solvents were improvement in the inhibition effectiveness was observed for
studied for these extracts, mainly for pure aluminium and 1xxx concentrations higher than 800 ppm. Apart from aqueous
and 7xxx series aluminium alloys. However, there is a clear extracts of this plant, the presence of phenols, tannins, alka-
distinction in the corrosive environments tested. The aqueous loids, anthraquinones, saponins, avanoids, aminoacids, and
extracts were tested in various corrosion environments, mainly reducing sugars was found to be relatively high also for ethanol
alkaline,17,63–73 but also acidic16,63,69,74–76 and salts.77–79 Two and petroleum ether extracts.62
studies discussed the possible effect of the corrosive environ- The synergistic effect of some ions or molecules on the
ment on the inhibition effectiveness of the extract. Umoren inhibition effectiveness of the extracts was also reported,16,17,71
et al.69 tested the aqueous extract of Vigna unguiculata husk as meaning that the corrosion inhibition performance is higher
an inhibitor in the corrosion of AA1060 aluminium alloy in for the mixture than for the individual components alone. Al-
0.5 M H2SO4 and 0.5 M NaOH solutions at 30 and 60 C. The Turkustani et al.16 added NaI to the aqueous extract of Aloe
extract showed higher inhibition effectiveness in NaOH than in vera leaves and then studied its inhibition effectiveness in the
H2SO4 solution. Emran et al.63 tested the inhibition effective- corrosion of 95.30% aluminium in 0.25–1.50 M HCl solution at
ness of cantaloupe (Cucumis melo) pulp extract obtained with 30 C. The results showed a further increase in the inhibition
a blender and cantaloupe (Cucumis melo) seed extract in double- effectiveness of the extract when 0.01 M NaI was added.
distilled water, as corrosion inhibitors for 32177 aluminium However, when changing the iodide concentration from 1
alloy (97.025% Al) in 1 M HCl and 1 M NaOH solutions at 27 C. 104 to 5 102 M in the presence of 48 vol% aloe leaf extract,
The extracts protected the aluminium alloy better in HCl than in rst an increase in the inhibition effectiveness was observed (up
NaOH solution. In the same study the authors extracted two to 2.5 102 M) and then for higher iodide concentrations the
different parts of the cantaloupe plant, i.e. pulp and seeds. They inhibition effectiveness decreased. In addition to the well-
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known iodide ions, it was reported that metals can also inu- inhibition effectiveness of Trachyspermum copticum seed extract
ence the performance of the tested extracts. In fact, Rajendran in double-distilled water as a corrosion inhibitor for AA1060
et al.71 tested the aqueous extract of Hibiscus rosa-sinensis aluminium alloy in 0.5 M NaOH solution at 35 C. PDP
owers, with and without the addition of Zn2+, as a corrosion measurements showed that the extract acted as a mixed-type
inhibitor for 95% aluminium in NaOH solution of pH ¼ 12. In inhibitor. The same was reported by Sirajunnisa et al.65
the presence of 50 ppm of Zn2+, the authors reported an regarding the aqueous extract of Senna auriculata leaves tested
improvement in the inhibition effectiveness. However, the data as a corrosion inhibitor for aluminium with purity higher than
showed that this is not the case for low volumes of extract added 99.9% in 1 N NaOH solution at 30–60 C. Other extracts acted
(2 and 4 mL added). Moreover, the addition of 25 ppm of Zn2+ also as mixed-type inhibitors.16,17,64,66,67,72,73,76,79 Geetha et al.68
dramatically decreased the inhibition effectiveness (promoting found that the aqueous extract of Vitex negundo leaves acted as
corrosion). The authors explained this with the possible a mixed-type inhibitor, but with a predominant effect on the
precipitation of the complex formed between Zn2+ and the anodic reaction in the corrosion of aluminium in 1 M NaOH
active principle present in the extract. The performance of the solution at 30–60 C. The aqueous extracts of saffron leaves were
system 8 mL of extract + 50 ppm of Zn2+ was also tested with the found to act as a cathodic-type inhibitor.74 The same was re-
addition of sodium dodecyl sulphate (SDS) and N-cetyl-N,N,N- ported by Fetouh et al.77 for the aqueous extracts of Ambrosia
trimethylammonium bromide (CTAB) aer 1 day of immersion. maritima L., Lupinus sp. L, and Cymbopogon proximus. However,
It was reported that the inhibition effectiveness decreased and as mentioned above, Abd-El-Nabey et al.79 reported that the
reached a minimum (for 150 ppm SDS added) and then aqueous extract of damsissa (Ambrosia maritima L.) acted as
increased again in the case of SDS. The authors reported that a mixed-type inhibitor. Moreover, Gerengi78 reported that the
the inhibition effectiveness rst increased with the increase in aqueous extract of Phoenix dactylifera fruit juice acted as a weak
the CTAB concentration (up to 200 ppm) and then decreased. cathodic-type inhibitor in the corrosion of AA7075 aluminium
Abdel-Abdel-Gaber et al.17 studied the synergistic effect of cetyl alloy in 3.5% NaCl solution.
trimethyl ammonium bromide and the aqueous extract of Based on the change of inhibition effectiveness with the
lupine seed as an inhibitor in the corrosion of 99.68% temperature described above, as well as on the thermodynamic
aluminium in 2 M NaOH solution. The authors reported that calculations, several authors discussed the possible mechanism
there is no signicant synergistic effect between the lupine seed for their respective extracts. Geetha et al.68 suggested that the
extract and cetyl trimethyl ammonium bromide. The authors aqueous extract of Vitex negundo leaves physisorbed on the
reported that CTAB was used to alter the wettability, acting as aluminium surface immersed in 1 M NaOH solution at 30–
a foaming agent as well as reducing the surface tension to 60 C. Next, Al-Haj-Ali et al.75 suggested that phytochemical
ensure the stability of the lupine seed extract. compounds contained in the aqueous extract of date palm
The inuence of temperature on the inhibition effectiveness (Phoenix dactylifera) leaves are responsible for the physisorption
of aqueous extracts was studied from 20 to 70 C.64–69,73,75,76,80 of the extract on 98.8% aluminium surface immersed in 1 M
Singh et al.66 prepared extracts of Bacopa monnieri stem and HCl solution, at 20–50 C. Physisorption was suggested as the
evaluated the inhibition effectiveness of the extract in the mechanism responsible for the adsorption of other extracts on
corrosion of AA1060 aluminium alloy in 0.5 M NaOH solution at the surface of aluminium materials.16,65,67,75,78
35–55 C. The authors reported that the inhibition effectiveness The aqueous extract of olive (Olea europaea) seeds was re-
of the extract decreased with increasing temperature. Geetha ported to chemisorb on 98.63% aluminium alloy in 1 M HCl
et al.67 reached the same conclusion when studying the inhibi- solution at 30 C.80 It was reported by Prabhu and Rao76 that
tion effectiveness of the aqueous extract of Solanum trilobatum garcinol, isogarcinol, and curcumin are the main active
leaves as a corrosion inhibitor in the corrosion of aluminium in components of the aqueous extract of Garcinia indica seeds.76
1 M NaOH solution at 30–60 C. A decrease in the inhibition The authors suggested that the extract physisorbed on the
effectiveness with increasing temperature was reported in the surface of 99.61% aluminium immersed in 0.5 M H3PO4 solu-
case of aqueous extract of Piper longum seeds tested as an tion at 30–50 C. The same mechanism was also suggested for
inhibitor in the corrosion of AA1060 aluminium alloy in 1 M aqueous extracts of Vigna unguiculata husk.69 A mixed-type
NaOH solution,73 as well for the aqueous extract of Neolamarkia (physisorption and chemisorption) adsorption mechanism
cadamba bark as a corrosion inhibitor for 98.06% aluminium was suggested by Fetouh et al.77 The authors concluded that the
alloy in 1 M NaOH solution at 30–60 C.64 The same inuence of extracts initially physisorbed on the aluminium surface and
temperature on the inhibition effectiveness of the extracts was then chemisorption occurred through coordinate bond forma-
also reported by Sirajunnisa et al.,65 Geetha et al.,68 and Al-Haj- tion between the p-valence orbitals of the aluminium and the
Ali et al.75 The opposite behaviour, i.e. an increase in inhibition oxygen and nitrogen atoms or OH groups present in the struc-
effectiveness with increasing temperature, was reported for ture of the main components of these extracts.
aqueous extracts of Garcinia indica seed,76 Vigna unguiculata The inhibitive action of the studied aqueous extracts has
husk,69 and olive seeds.80 been attributed in general to the formation of a protective
Polarisation measurements were conducted in several monolayer on the aluminium/solution interface.64,66,71,73,74,76
studies and the authors reported on the inhibitor types of the According to Prabhu and Rao,76 this layer is formed on the
respective extracts. In the vast majority, the extracts acted as aluminium surface as a result of chelate complex formation
mixed-type inhibitors. Singh and Quraishi70 investigated the with aluminium ions, which then precipitates on the areas
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where the oxide lm is destroyed. Complex formation was also inhibitor for AA1060 aluminium alloy in 2 M HCl and 2 M KOH
reported for the aqueous extract of Hibiscus rosa-sinensis solutions at 30 and 60 C. The authors reported that the inhi-
owers.71 Soror74 suggested that the inhibition action of the bition effectiveness of Gongronema latifolium leaves in HCl was
aqueous extract of saffron leaves is due to the formation of higher than Gongronema latifolium leaves in KOH. The extract of
a compact barrier lm though adsorption on the metal surface, Euphorbia hirta leaves in HCl and NaOH was tested as an
displacing the water molecules. Moreover, they suggested the inhibitor in the corrosion of AA3003 aluminium alloy in 0.5 M
formation of a coordinative covalent bond between the lone pair HCl and 0.25 M NaOH solutions at 30 and 60 C.93 The alkaline
electrons present in the oxygen atoms of the inhibitor molecule extract was reported to be more effective. The alkaline extract of
and the metal. Euphorbia hirta leaves was also reported as a corrosion inhibitor
Abd-El-Nabey et al.79 concluded that the anodic dissolution for AA3003 aluminium alloy in 0.25 M NaOH solution at 30 and
of aluminium is controlled by the diffusion of AlO2 from the 60 C, in addition to Dialum guineense leaf extract in NaOH.87
surface of the metal to bulk solution. The authors studied the In two studies Loto et al.106,107 tested the inhibition effec-
effect of the aqueous extracts of damsissa and Corchours itorius tiveness of Camellia sinensis leaf extracts in HCl and H2SO4 as
on the corrosion of 99.687% aluminium in 0.1 M Na2CO3 a corrosion inhibitor for 99% aluminium alloy in 0.5 M HCl
solution. They reported that the main components in the solution and 0.8 M H2SO4 solution, respectively. The inhibition
damsissa extract are ambrosin, damsin, and coumarin, while effectiveness increased with increasing extract concentration
for Corchours itorius extract the main components are beta and with increasing exposure time in the HCl solution. The
carotene, and vitamins A, B-1, B-2, C, and E. authors reported a decrease in the inhibition effectiveness with
Chaubey et al.,64 Al-Turkustani and Emran80 and Emran increasing extract concentration in H2SO4 solution.
et al.63 reported efficient extraction of inhibitive compounds The inhibition effectiveness increased with increasing
under moderate conditions with water as the solvent of choice. extract concentration, with the exception of Euphorbia hirta leaf
This technique enables efficient extraction of inhibitive extracts in HCl and NaOH93 and Camellia sinensis leaf extract in
compounds under moderate conditions. Further purication is H2SO4,107 mentioned above. Loto et al.107 reported a decrease in
performed simply by ltering the obtained extract to obtain inhibition effectiveness with increasing concentration of the
a homogenous solution. As mentioned above, high tempera- extract, while no signicant change was reported by Nnanna
tures are a serious drawback of the conventional procedures, et al.93
due to possible degradation of thermally unstable compounds. The possible synergistic effect of potassium iodide and
The loss of some components and the degradation of some thiocyanate with the tested extracts was also explored. Obot and
unsaturated compounds by thermal effects or by hydrolysis can Obi-Egbedi9 added 5 mM KI to the extract of ginseng (Panax
be generated by these conventional extraction techniques. Sir- ginseng) root in HCl used as a corrosion inhibitor for AA1060
ajunnisa et al.65 reported high temperatures during sample aluminium alloy at 30–60 C. A further increase in the inhibi-
preparation and subsequent heating of the ltrates in a water tion effectiveness was observed with the addition of KI and was
bath to fully evaporate the moisture content to obtain the dried more pronounced at higher temperatures. A synergistic
compound, which may affect the inhibiting action of Senna increase in the inhibition effectiveness of Thymus algeriensis
auriculata leaf extract. Umoren et al.81 discussed that leaf and seed extracts in HCl extract was reported upon the
compounds are subjected to degradation or undergo undesir- addition of KI.11 The mixture was tested as a corrosion inhibitor
able oxidation by exposure to high processing temperature. for AA2024 aluminium alloy in 1 M HCl solution at 25–65 C.
The inhibition effectiveness of Ipomoea invulcrata leaf extract in
HCl, tested as a corrosion inhibitor for AA1060 aluminium alloy
2.4 The corrosion inhibition of plant extracts obtained with (98.8% purity) in 1 M HCl solution at 30–60 C was further
solvents used as a corrosive environment increased with the addition of KI.10 The authors reported that
The plant extracts tested in the research works described below KSCN showed an antagonistic effect when added to the extract
were prepared using the same solvents as the corrosive envi- at high temperatures.
ronment in which the aluminium materials were immersed. The corrosion inhibition of numerous aluminium materials
The work of Berković et al.82 included an additional step in the was reported, including pure aluminium82,86,90–93,97,105 and
extract preparation procedure. The authors rst dissolved rutin 1xxx,9,10,85,94,99,103 2xxx,11,102 3xxx,87,88 and 8xxx98,100,104 series
and quercetin in NaOH solution, from which a solution of each aluminium alloys. The corrosion of 3SR aluminium alloy
in 3% NaCl was prepared. These solutions were then tested as (98.60% Al) in 2 M NaOH solution was investigated in the
inhibitors in the corrosion of 99.95% aluminium in 3% NaCl presence of Gossypium hirsutum L. leaf and seed extracts in
solution. Apart from this study,82 all other research work was NaOH83 and Phyllanthus amarus leaf extract.84 Other aluminium
published on the inhibition of aluminium materials in alkaline alloys were also tested.106,107 Leaves,10,11,83–85,87–89,91,93,97–104,106,107
(NaOH and KOH)83–96 and acidic (HCl and H2SO4)9–11,85,93,97–107 seeds,11,86,102 peel,90 root,9 and petals105 were the parts of the
solutions (Table 3). plants from which extracts were prepared. Extracts in HCl of
Two research groups investigated the inuence of the Mentha pulegium102 and Thymus algeriensis11 were prepared from
corrosive environment on the inhibition effectiveness of the the aerial parts (leaves and seeds) of the respective plants.
respective extracts.85,93 Oguzie et al.85 tested the extract of Gon- Abiola et al.83 investigated the inuence of the plant part on
gronema latifolium leaves in HCl and KOH as a corrosion the inhibition effectiveness of the extract. Gossypium hirsutum L.
Table 3 The inhibition effectiveness of different extracts (extracted with the same solvent as the corrosive environment) tested as corrosion inhibitors for aluminium and different aluminium
alloys in various solutions. The inhibition effectiveness values are reported as given in the article. In instances where different techniques were used for the determination of the inhibition
effectiveness, the range from the minimum to the maximum values reported in the article is reported below in this table
Review
Inhibitor
3SR (98.60% Al) Phyllanthus amarus leaf extract in NaOH 5–20 vol% 2 M NaOH 66.0–76.0 WL aer 6 h immersion at 30 C 84
AA1060 Ginseng root digested in HCl 10–50 vol% 1 M HCl 41.0–93.1 WL aer 4 h immersion at 30–60 C 9
AA1060 Ginseng root digested in HCl + 5 mM KI 10–50 vol% 1 M HCl 46.6–96.0 WL aer 4 h immersion at 30–60 C 9
AA1060 Gongronema latifolium leaf extract in HCl 10 vol% 2 M HCl 56.28–96.45a HE at 30 C 85
AA1060 Gongronema latifolium leaf extract in HCl 50 vol% 2 M HCl 94.95–97.51a HE at 60 C 85
AA1060 Gongronema latifolium leaf extract in KOH 10 vol% 2 M KOH 74.45–90.85a HE at 30 C 85
AA1060 Gongronema latifolium leaf extract in KOH 50 vol% 2 M KOH 56.30–89.14a HE at 60 C 85
99.95% Rutin in NaOH 104 M 3% NaCl 61–67 PSP and Rp 82
99.95% Rutin in NaOH 105 M 3% NaCl 90–96 PSP and Rp 82
99.95% Quercetin in NaOH 104 M 3% NaCl 50–65 PSP and Rp 82

99.95% Quercetin in NaOH 105 M 3% NaCl 54–94 PSP and Rp 82
99.6% Solanum melongena L. leaf extract in H2SO4 0.6 g L1 0.5 M H2SO4 16.26–31.38 WL aer 24–144 h immersion 97
99.6% Solanum melongena L. leaf extract in H2SO4 0.1–0.7 g L1 0.5 M H2SO4 17.66–31.76 WL aer 24 h immersion 97
AA3003 Euphorbia hirta leaf extract in NaOH 0.1–0.3 g L1 0.25 M NaOH 69.4–87.5 WL aer 4 h immersion at 30–60 C 87
AA3003 Dialum guineense leaf extract in NaOH 0.1–0.3 g L1 0.25 M NaOH 75.2–87.5 WL aer 4 h immersion at 30–60 C 87
AA8011 Newbouldia leavis leaf extract in H2SO4 0.1–0.4 g L1 0.5 M H2SO4 50.20–92.47 WL at 30–60 C 98
AA3003 Palisota hirsute leaf extract in KOH 0.1–0.5 g L1 0.25 M KOH 71.26–86.21 WL at 30 C 88
NG Ziziphus jujuba leaf extract in NaOH 300–900 ppm 1 N NaOH 53.2–76.4 WL aer 2 h immersion, HE, Tafel 89
extrapolation, and EIS at 30 C
NG Ziziphus jujuba leaf extract in NaOH 900 ppm 1 N NaOH 72.1–76.4 WL aer 2–10 h immersion at 30 C 89
NG Ziziphus jujuba leaf extract in NaOH 900 ppm 1 N NaOH 69.8–76.4 WL aer 2 h immersion at 30–60 C 89
99.76% Pisum sativum peel extract in NaOH 1.5 g L1 1 M NaOH 91.40–94.15 EIS, PDP, and Rp at 30 C 90
99.76% Solanum tuberosum peel extract in NaOH 1.5 g L1 1 M NaOH 83.60–89.50 EIS, PDP, and Rp at 30 C 90
99.76% Citrus reticulate peel extract in NaOH 1.5 g L1 1 M NaOH 72.48–74.40 EIS, PDP, and Rp at 30 C 90
99.96% Plumbago europaea leaf extract in NaOH 4.0–20.0 ppm 1 M NaOH 88.69–96.76 WL at 25–50 C 91
99.96% Lupinus varius L. extract in NaOH 20–100 vol% 1 M NaOH 26.69–93.73 WL aer 1 h immersion at 25–50 C 92
AA8011 Moringa oleifera leaf extract in HCl 0.5 g L1 0.5 M HCl 94 WL at room temperature 100
AA2024 Mentha pulegium leaf and seed extract in HCl 0.5–2.5 g L1 1 M HCl 30.09–59.22 WL at 25 C 102
AA2024 Mentha pulegium leaf and seed extract in HCl 0.5–1.5 g L1 1 M HCl 40.01–60.90 EIS at 25 C 102
AA2024 Mentha pulegium leaf and seed extract in HCl 1.5 g L1 1 M HCl 63–88 WL at 25–45 C 102
AA1060 Chromolaena odorata L. leaf extract in HCl 10–50 vol% 2 M HCl 57.97–95.12 HE and thermometric at 30–60 C 103
98.611% Euphorbia hirta leaf extract in HCl 0.10–0.30 g L1 0.5 M HCl 80.10–88.20 WL at 30–60 C 93
98.611% Euphorbia hirta leaf extract in NaOH 0.10–0.30 g L1 0.25 M NaOH 78.77–85.91 WL at 30–60 C 93
AA1060 Ipomoea invulcrata leaf extract in HCl 10–50 vol% 1 M HCl 45.8–82.1 WL at 30–60 C 10
AA1060 Ipomoea invulcrata leaf extract in HCl + 0.005 M KI 10–50 vol% 1 M HCl 52.3–89.1 WL at 30–60 C 10
AA1060 Ipomoea invulcrata leaf extract in HCl + 0.005 M KSCN 10–50 vol% 1 M HCl 34.0–82.1 WL at 30–60 C 10
AA3003 Aspilia africana leaf extract in HCl 700 mg L1 0.4 M HCl 93.42b EIS aer 1 h immersion at 30 C 104
AA2024 Thymus algeriensis leaf and seed extract in HCl 0.25–1.00 g L1 1 M HCl 36.7–78.7 WL aer 2 h immersion at 25 C 11
AA2024 Thymus algeriensis leaf and seed extract in HCl 0.75 g L1 1 M HCl 77.3–80.9 WL aer 2 h immersion at 25–65 C 11
AA2024 Thymus algeriensis leaf and seed extract in HCl 0.25–0.75 g L1 1 M HCl 61.0–83.0 EIS at 25 C 11
AA2024 Thymus algeriensis leaf and seed extract in 0.75 g L1 1 M HCl 78.7–93.1 WL aer 2 h immersion at 25 C 11
HCl + 0.5–3.0 mM KI
Pure Hibiscus sabdariffa petal extract in H2SO4 200–2000 ppm 0.5 M H2SO4 4–95 PDP and EIS at 25 C 105
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leaf and seed extracts, prepared by using the reux in NaOH
NG – not given. a h was calculated on the basis of the values of the corrosion rate, the corrosion current, the corrosion current density, or the resistance of the blank solution and inhibited samples.
Reference
solution, was tested in the corrosion of 3SR aluminium alloy
105
(98.60% aluminium) in 2 M NaOH solution. The authors re-
95
96
96
96
96
96
96
ported that the seed extract was slightly more effective than the
WL aer 120 min and PSP at 25–50 C leaf extract.

This group of extracts was tested at temperatures varying
from 25 to 60 C.9–11,87,89,91–93,95,96,98,100,102–105 The inhibition effec-
tiveness of the majority of the extracts decreased with
increasing temperature. Nnanna et al.87 investigated the extracts

PDP and EIS at 25–60 C
of Euphorbia hirta and Dialum guineense leaves in NaOH as

PDP and EIS at 27 C
PDP and EIS at 27 C
PDP and EIS at 27 C
corrosion inhibitors of AA3003 aluminium alloy in 0.25 M
NaOH solution at 30 and 60 C. The major constituents of
WL at 30–60 C
WL at 30–60 C
WL at 30–60 C
Euphorbia hirta were reported to be triterpenoids, alkaloids,

tannins, glycosides, sterols, essential oil, avones, and phenols.
Dialum guineense contains mainly saponins, tannins, alkaloids,
avonoids, and essential oil. The authors reported that the
inhibition effectiveness decreased with increasing temperature
for both extracts. The same conclusion was reported for
91.26–98.41
Euphorbia hirta leaf extract in NaOH in another study by

65.0–85.3
60.5–77.5
59.4–75.2
85.4–86.5
79.1–81.2
72.0–79.1
Nnanna et al.93 It was found by Sirajunnisa et al.89 that the

20–94
h (%)
inhibition effectiveness of Ziziphus jujuba leaf extract in NaOH,

tested as an inhibitor in the corrosion of aluminium in 1 N
h was calculated on the basis of the sum (Roxide + Rp + Rinhibitor) of the blank solution and of the inhibited samples.
NaOH solution, decreased with increasing temperature. Irshe-

dat et al.92 reported that the inhibition effectiveness of Lupinus
0.5 M H2SO4
1 M NaOH
1 M NaOH
1 M NaOH
1 M NaOH
1 M NaOH
1 M NaOH
1 M NaOH
varius L. extract in NaOH as a corrosion inhibitor for 99.96%

Medium
aluminium in 1 M NaOH solution at 25–50 C decreased with

increasing temperature. A decrease in the inhibition effective-
ness with increasing temperature was also reported by Nnanna
et al.98 for Newbouldia leavis leaf extract in H2SO4, tested as an
concentration
inhibitor in the corrosion of AA8011 aluminium alloy in 0.5 M

0.2–1.0 vol%
H2SO4 solution at 30 and 60 C. The same behaviour was re-

2000 ppm
Inhibitor
0.6 g L1
0.6 g L1
0.6 g L1
0.6 g L1
0.6 g L1
0.6 g L1
ported by Khadraoui et al.102 regarding the inhibition effec-

tiveness of Mentha pulegium leaf and seed extract in HCl used as
a corrosion inhibitor for AA2024 aluminium alloy in 1 M HCl
solution at 25–45 C. Obot and Obi-Egbedi103 reported
a decrease in the inhibition effectiveness of Chromolaena odor-
Sinapis alba dry powder extract reuxed in NaOH
ata L. leaf extract in HCl, tested as a corrosion inhibitor for

AA1060 aluminium alloy in 2 M HCl solution, when increasing
Terminalia arjuna stem bark extract in NaOH
Terminalia arjuna stem bark extract in NaOH

Mangifera indica stem bark extract in NaOH
Mangifera indica stem bark extract in NaOH

Moringa oleifera stem bark extract in NaOH
Moringa oleifera stem bark extract in NaOH
the temperature from 30 to 60 C. Chaubey et al.,96 Obot and

Hibiscus sabdariffa petal extract in H2SO4
Obi-Egbedi,9 Nnanna and Owate,100 Obot et al.,10 and Molina-

Ocampo et al.105 reached the same conclusion regarding the
inuence of temperature on the inhibition effectiveness of the
respective extracts. Different behaviour was reported by Batai-
neh et al.,91 who concluded that the inhibition effectiveness of
Plumbago europaea leaf extract in NaOH used as an inhibitor in
the corrosion of 99.96% aluminium in 1 M NaOH solution at
20–50 C increased with increasing temperature. Similarly,
Mejeha et al.104 concluded that the inhibition effectiveness of
Inhibitor
Aspilia africana leaf extract in HCl tested as a corrosion inhib-

itor for AA3003 aluminium alloy in 0.4 M and 0.5 M HCl solu-
tions at 30 and 60 C, increased with increasing temperature. A
slight increase in the inhibition effectiveness with increasing
(Contd. )
temperature was reported by Bataineh et al.95 for Sinapis alba

dry powder extract reuxed in NaOH tested as a corrosion
inhibitor for 99.999% aluminium in 1 M NaOH solution at 25–
99.999%
Material
98.06%
98.06%
98.06%
98.06%
98.06%
98.06%
Table 3
50 C. Only Khadraoui et al.11 reported no signicant change in

Pure
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inhibition effectiveness with increasing temperature for Thymus in HCl, which are responsible for its inhibition action. The
algeriensis leaf and seed extract in HCl. authors suggested physisorption at low temperatures and
Polarisation measurements have been performed in a few chemisorption at high temperatures. Finally, Nnanna et al.88
studies and the inhibitor type for the respective extracts has tested the extract of Palisota hirsute leaves in KOH as an
been reported.89,90,95,104,105 Chaubey et al.90 studied the inhibition inhibitor in the corrosion of AA3003 aluminium alloy in 0.25 M
effectiveness of Pisum sativum, Solanum tuberosum, and Citrus KOH solution at 30 C. Thermodynamic calculations suggested
reticulate peel extracts in NaOH in the corrosion of 99.76% that the adsorption of the extract was of a mixed nature (phys-
aluminium alloy in 1 M NaOH solution at 30 C. The inhibition isorption and chemisorption). A mixed adsorption mechanism
effectiveness of the extracts decreased in the order Pisum sat- was also suggested for Euphorbia hirta leaf extract in NaOH.87
ivum > Solanum tuberosum > Citrus reticulate. PDP measure- The authors attribute the inhibition action of these extracts
ments showed that all three extracts acted as mixed-type to the ability of their components to adsorb on the surface of the
inhibitors. Hibiscus sabdariffa petal extract in H2SO4 was re- aluminium materials. However, in the best of cases they
ported to act as a mixed-type inhibitor in the corrosion of pure mention only the class of compounds responsible for the
aluminium in 0.5 M H2SO4 solution at 25–60 C.105 Moreover, it adsorption and very rarely are the compounds identied.
was reported that the extracts of Ziziphus jujuba leaves in Irshedat et al.92 attributed the inhibition action of Lupinus
NaOH,89 Sinapis alba dry powder in NaOH,95 as well as stem bark varius L. extract in NaOH to its phytochemical constituents
extracts in NaOH of Moringa oleifera, Terminalia arjuna, and (alkaloids, tannins, oligosaccharides, polysaccharides, gluco-
Mangifera indica96 also acted as mixed-type inhibitors. PDP proteins, volatile monoterpenes, and related oxygenated
measurements showed that Aspilia africana leaf extract in HCl sesquiterpenes) that contain oxygen and nitrogen atoms,
acted as a cathodic-type inhibitor.104 serving as adsorption centres. Ipomoea invulcrata leaf extract in
Based on the thermodynamic calculations, authors have HCl10 and in NaOH94 adsorbed due to the presence of the
suggested the adsorption mechanism of the studied heteroatoms and aromatic rings with p-bonds in the molecule
extracts.9,10,85–89,91–95,97–107 Nwosu and Osarolube86 studied the of the main constituent, which serve as adsorption centres. The
extract of Xylopia aethiopica seeds in KOH as a corrosion authors reported that the main constituent of this plant is D-
inhibitor for 98.47% aluminium in 0.75 M KOH solution at lysergic acid amide and also it contains small amounts of other
room temperature. The authors reported that the optimal alkaloids, such as chanoclavine, elymoclavine, ergometrine,
inhibition effectiveness was 84.53%, but this is not supported and D-isolysergic acid amide.
by the results presented. According to the authors, the extract The presence of certain groups or a particular bonding of
protected aluminium by physisorption on its surface. Similarly, these components with the surface of aluminium materials was
Mejeha et al.97 suggested physisorption as the possible mecha- also reported. Nnanna and Owate100 evaluated the inhibition
nism for the adsorption of Solanum melongena L. leaf extract in effectiveness of the leaf extract of Moringa oleifera in HCl, as
H2SO4, tested as an inhibitor in the corrosion of AA1060 a corrosion inhibitor for AA8011 aluminium alloy in 0.5 M HCl
aluminium alloy in 0.5 M H2SO4 solution. Physisorption was solution at 30 and 60 C. The authors attributed the inhibition
also suggested for other extracts as the possible mechanism for action of the extract to the presence of the C]O functional
their adsorption on the surface of the aluminium mate- group. Omotosho and Ajayi101 attributed the inhibition action of
rials.9,10,89,91–95,98,100,103,105–107 Chemisorption was suggested by Vernonia amygdalina leaf extract in HCl to the formation of
Oluseyi et al.99 as the possible adsorption mechanism for Ver- a covalent bond between the phytochemical constituents of the
nonia amygdalina leaf extract in HCl on the AA1100 aluminium extract and the aluminium alloy. Molina-Ocampo et al.105
alloy surface, immersed in 0.5 M HCl solution at 40 C. Omo- attributed the inhibition action of Hibiscus sabdariffa petal
tosho and Ajayi101 investigated the inhibition effectiveness of extract in H2SO4 to adsorption on the aluminium surface
Vernonia amygdalina leaf extract in HCl as a corrosion inhibitor through the lone pairs and p-orbitals of the heteroatoms
for 99% aluminium alloy in 2 M HCl solution. Based on the present in the structure of the avonoid compounds present in
thermodynamic calculations, the authors suggested chemi- the extract.
sorption as the possible adsorption mechanism for Vernonia In addition, a few authors reported a protective layer (lm)
amygdalina extract on the aluminium alloy surface. The same formation as the result of adsorption.82,95,96,100 This protective
adsorption mechanism was suggested for Mentha pulegium leaf layer in the case of stem bark extracts in NaOH of Moringa
and seed extract in HCl.102 The studies of Oguzie et al.85 and oleifera, Terminalia arjuna, and Mangifera indica96 was formed
Mejeha et al.104 reported an inuence of either the corrosive through the adsorption of their main components, 4-(alpha-l-
environment or temperature on the adsorption mechanism of rhamnopyranosyloxy)-benzylglucosinolate, ellagic acid, and
the tested extracts. Oguzie et al.,85 based on the variation of the mangiferin, respectively. Berković et al.82 reported that the
inhibition effectiveness with temperature, suggested chemi- protective layer (lm) formed by the adsorption of rutin and
sorption in the case of Gongronema latifolium leaf extract in HCl quercetin was stable at lower concentrations (104 and 105 M),
tested in 2 M HCl solution and physisorption in the case of 2 M while at higher concentrations (higher pH) the lm dissolved
KOH solution. However, they reported on the possibility of due to the amphoteric nature of aluminium, promoting
chemisorption in 2 M KOH at higher extract concentrations. corrosion.
Mejeha et al.104 reported the presence of three B vitamins, i.e. The majority of the authors reported quick and simple
thiamine, riboavin, and niacin, in Aspilia africana leaf extract extraction procedures to obtain extracts with a high inhibitive
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effect. A simple extraction procedure was utilised in the work of foods, nevertheless, the optimal procedure is usually unique to
Abiola et al.84 to isolate these compounds from the plant of different plant matrices.110,111
Phyllanthus amarus. The authors reported that Phyllanthus In the following paragraphs we discuss studies published on
amarus extract contains several phytochemicals, in particular the corrosion inhibition of aluminium and its alloys by plant
two lignans, i.e. phyllathin and hypophyllathin, which contain extracts that are extracted by either several solvents of different
several adsorption centres. These kind of extraction procedures types,112–114 or by a mixture of two solvents.115–117 As seen in
are uncomplicated and require a signicantly lower amount of Table 4, an acetone/water (1 : 1) mixture was used to prepare
organic solvents compared to other methods, a relatively short extracts of red onion (Allium cepa L.) skin,115 breadfruit (Arto-
time for crude sample preparation, and above all, a high yield of carpus altilis) peel,116 and garlic (Allium sativum) skin,117 which
the target compounds is reported as having been attained. were then tested as corrosion inhibitors for 98.76% aluminium
These procedures may be applied to prepare a relatively large in 2 M H2SO4 solution at 30–50 C (ref. 115) for commercial
amount of extract using either a plant's stem, leaf, or root, aluminium in 0.5 M H2SO4 solution116 and for 97.58%
which are otherwise usually discarded. Each step in the aluminium alloy in 0.5 M HCl solution,117 respectively. Ethanol,
extraction procedure requires specic attention regarding the ethyl acetate, HCl, and water were employed to extract different
operating parameters and furthermore this increases operating parts of various plants. Several studies reported on the possible
costs and inuences the duration of the process. Compared to inuence of the solvent used on the inhibition effectiveness of
previous isolation methods, which included multiple steps the respective extract. Alinnor and Ejikeme112 used HCl,
using various organic solvents with a time intensive separation ethanol, and distilled water to prepare extracts of Ocimum gra-
process,108 the method reported by Obot and Obi-Egbedi9 is tissimum leaves and tested the extracts as corrosion inhibitors
simple and found to produce a much higher yield of active for AA1060 aluminium alloy in 1 M HCl solution at 30 and 60 C.
compounds as compared to the method of Pyo et al.108 The The authors showed that the inhibition effectiveness followed
development of “modern” sample-preparation techniques with the order extract in distilled water > extract in ethanol > extract
signicant advantages over conventional methods for the in HCl.
extraction and analysis of plants is likely to play an important Abiola et al.113 prepared extracts of Delonix regia leaves and
role in the overall effort to ensure and provide high-quality plant seeds in hydrochloric acid and ethanol and tested the extracts
extracts. Khadraoui et al.102 reported that different methods as inhibitors in the corrosion of 99.16% aluminium in 2 M HCl
were investigated for selectively preparing extracts of Mentha solution at 30 C. The authors concluded that the acid extracts
pulegium leaves and seeds and the extracts were subsequently were more effective than the ethanolic extracts.
evaluated to compare the efficiency of the SFE with the hydro- Aqueous extract of Juglans regia L. leaves showed a higher
distillation process. In comparison to the hydrodistillation inhibition effectiveness compared with ethyl acetate extract in
method, SFE yields a lower number of constituents of interest. protecting 99.8% aluminium immersed in 1 M HCl solution, at
The authors assume that all of these components are present in room temperature.114 Several solvents (water, methanol,
the SC-CO2 extracts, but at lower concentration than those ob- ethanol, and 50% aqueous solutions of methanol and ethanol)
tained by hydrodistillation.109 Modern extraction techniques were utilised to prepare extracts from walnut green husk,
feature mild operating conditions, resulting in a higher placing a specic emphasis on the extraction yield and antiox-
concentration of active compounds present in the extract. idant properties of the compounds present in total extracts. The
Nnanna et al.93 highlights that it may be safely assumed that highest extraction yield was obtained with water, although
lower extraction temperatures would yield a higher content of aqueous extracts showed the lowest antioxidant properties. The
phytochemical components, which include tannins, alkaloids, highest total phenol content and antioxidant activities,
and essential oil in the extract. The inhibitive properties of measured by reducing power and diphenylpicrylhydrazyl
tannins have been attributed to the reaction of the polyphenolic assays, were obtained with 50% aqueous ethanol.
fraction of tannin moieties by hindering both cathodic and Leaves,112–114 seeds,113 skin, and peel115–117 were used to
anodic electrode processes due to the high number of bonds in prepare the extracts. Abiola et al.113 found an inuence of the
the extracts. plant part used to prepare the extract on the inhibition effec-
tiveness of Delonix regia. The authors reported that the inhibi-
tion effectiveness followed the order acid seed extract > acid leaf
extract > ethanol seed extract > ethanol leaf extract.
2.5 Corrosion inhibition of plant extracts obtained with All the extracts were tested in an acidic environment, mainly
mixed solvents in HCl solution. In all these studies it was reported that inhi-
Differences in the structure of phenolic compounds also bition effectiveness increased with increasing extract concen-
determine their solubility in solvents of different polarity. tration. Pure aluminium and 1xxx series aluminium alloy were
Therefore, different solvent compositions may have a signi- the only tested materials.
cant impact on their relative capacity to extract the total The inhibition effectiveness of these extracts has been
phenolic and total avonoid components of a plant's leaves, investigated from room temperature up to 60 C.112,115,116 In all
trunk, and stems. There are some reports concerning the opti- three studies the authors reported that the inhibition effec-
misation of the extraction conditions of the phenolic tiveness decreased with increasing temperature. However,
compound content and antioxidant activities of some plant Alinnor and Ejikeme112 reported a signicant decrease in
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different aluminium alloys in acidic solutions. The inhibition effectiveness values are reported as given in the article. In instances where different techniques were used for the determination of inhibition effectiveness with increasing temperature for Oci-
The inhibition effectiveness of different extracts (extracted either with solvents of different natures or with a mixture of two solvents) tested as corrosion inhibitors for aluminium and
Reference
mum gratissimum leaf extracts in HCl, ethanol, and distilled
112
112
112
113
113
113
113
113
114
114
114
114
115
116
water, while only a slight decrease was observed when
increasing the temperature for breadfruit (Artocarpus altilis)
peel extract.116
WL aer 2–8 h immersion at room temperature

WL aer 2–8 h immersion at room temperature
The vast majority of the studies evaluated the inhibition
effectiveness of the extracts using chemical techniques (WL and
HE). Only Akin et al.,114 based on the PDP measurements,
concluded that Juglans regia L. leaf extracts in water and ethyl
PDP and EIS at room temperature

PDP and EIS at room temperature
acetate reduced the anodic and cathodic currents of the corro-
HE aer 60–120 min immersion

sion couple.
HE aer 30 min immersion

Based on the thermodynamic calculations, the authors sug-

gested physisorption as the possible mechanism for the
adsorption of the respective extracts on the surface of
aluminium materials.112,113,116,117 Red onion (Allium cepa L) skin
WL at 30–60 C
WL at 30–60 C
WL at 30–60 C
WL at 30–50 C
WL at 30–50 C
extract in acetone/water (1 : 1 v/v) mixture115 was reported to
physisorb through its main component, quercetin.
the inhibition effectiveness, the range from the minimum to the maximum values reported in the article is reported below in this table
3. Drugs as corrosion inhibitors for

aluminium and its alloys
15.11–95.65
38.30–88.78
20.54–77.13
55.65–95.02
4.83–90.72
7.81–93.74
84.8–95.0
62.3–90.3
50.1–68.4
44.3–66.1
0.00–85.8
55.5–85.3
As pointed out above, drugs were previously considered as

41–84
23–75
h (%)
corrosion inhibitors, especially in relation to the corrosion

inhibition of steel.22 However, studies describing drugs as
corrosion inhibitors for aluminium and its alloys are rather
0.5 M H2SO4
2 M H2SO4
rare, although such research might become attractive in the

1 M HCl
1 M HCl
1 M HCl
2 M HCl
2 M HCl
2 M HCl
2 M HCl
2 M HCl
1 M HCl
1 M HCl
1 M HCl
1 M HCl
Medium
near future. Fig. 3 summarises the structures of all the drugs

reported as corrosion inhibitors herein. Until now, antibacterial
and antifungal drugs were among the most studied compounds
as corrosion inhibitors for aluminium and its alloys in various
0.0025–0.0145 g L1
solutions.12,13,118–123 However, a few studies were also performed

0.02–0.14 mg mL1
0.02–0.14 mg mL1
0.02–0.14 mg mL1
0.02–0.14 mg mL1
0.05–0.25 g dm3
on the possible application of antihypertensive and antiemetic

20–100 mg L1
20–100 mg L1
20–100 mg L1
concentration
0.1–0.6 g L1
0.1–0.6 g L1
0.1–0.6 g L1
0.1–0.6 g L1
0.1–0.6 g L1
drugs as corrosion inhibitors.124,125 All the studied drugs were

tested as corrosion inhibitors in acidic solutions.
Inhibitor
The WL technique has been widely used to evaluate the

inhibition performance of these compounds. Polarisation
techniques were also employed in several of the included
studies12,118,123,124 and in all cases the authors concluded that the
Ocimum gratissium leaf extract in distilled water
respective drugs used acted as mixed-type inhibitors. In all the

Delonix regia seed extract in absolute ethanol
Delonix regia leaf extract in absolute ethanol
Juglans regia L. leaf extract in ethyl acetate
Juglans regia L. leaf extract in ethyl acetate
research work published on the use of drugs as corrosion

Ocimum gratissium leaf extract in ethanol
inhibitors it was reported that inhibition effectiveness

Ocimum gratissium leaf extract in HCl
increased proportionally with drug concentration, but

Juglans regia L. leaf extract in water
Juglans regia L. leaf extract in water
Red onion skin extract in acetone/
Breadfruit peel extract in acetone/

Delonix regia seed extract in HCl
Delonix regia seed extract in HCl
decreased with increasing temperature. Based on the thermo-

Delonix regia leaf extract in HCl
dynamic calculations, the authors suggested mainly phys-

isorption as the possible adsorption mechanism for all the
studied drugs,12,13,119,120,122,123 apart from the work of Bhat and
water (1 : 1) mixture
water (1 : 1) mixture
Alva,124 who suggested a mixed-type adsorption (physisorption

and chemisorption) for meclizine hydrochloride. However,
these authors also reported the predominance of physisorption
Inhibitor
in the total mechanism.

Gece prepared a comprehensive review article relating drugs
NG – not given.
from different pharmacotherapeutic groups, that have

completely different biologic mechanism of action, as corrosion
inhibitors for various materials.22 However, it has to be taken
Material
AA1060
AA1060
AA1060
99.16%
99.16%
99.16%
99.16%
99.16%
98.76%
Table 4
99.8%
99.8%
99.8%
99.8%
into account that the pharmacodynamic, and hence the phar-

NG
macologic action the drugs cause to the body, has in its essence
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Fig. 3 Structures of the drugs tested.
nothing to do with the mechanism of their potential corrosion their description, related to their corrosion inhibition potential.
inhibition. Furthermore, these drug-based corrosion inhibition Namely, by doing these, a researcher with a background related
candidates can be better grouped together by general molecular to biological sciences, can then easily search for their potential
features (like the presence of heterocycles in their structure, or dual use in practice. This is especially true in relation to medical
reactive centres like O, N and/or S atoms containing lone pairs implants (e.g. metal based hip prostheses), where either anti-
of electrons, which can aid their adsorption onto metal microbial drugs (like antifungals and antibiotics) or anti-
surfaces), rather than by their biologic activity. Here we can inammatory drugs, can signicantly contribute to both, the
again build on the conclusions by Gece, who found essentially corrosion inhibition during their prolonged exposure to the
the same,22 namely that the features related to the bare chem- harsh biologic environment of the body, while at the same time
ical structure (backbone) of these is far more important, than easing the uptake of the implant by the body, by either pre-
their features, giving them their potential to be used as drugs venting infections or diminishing the possibility of an immune
for various purposes. Nevertheless, reviewing (or grouping) response that could even lead to the implants rejection.
drugs by their pharmacotherapeutic groups it is logical also in
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In each of the following paragraphs, we briey describe the penicillins, their corrosion inhibition potential lies most likely
general use of these drugs in medical applications. The main in the possible delocalization of p electrons, which can enhance
ndings (as described above) regarding the use of drugs as their adsorption to metal surfaces.22
corrosion inhibitors for aluminium materials are presented in Fouda et al.12 investigated the use of ve antibacterial
Table 5, followed by a more detailed description of the work. compounds from the group of penicillins, i.e. ucloxacillin (also
known by the name oxacillin), dicloxacillin, cloxacillin, and
cephalosporins of the rst-generation, i.e. cephalexin, and
3.1 Antibacterial drugs cefadroxil, as inhibitors in the corrosion of AA6063 aluminium
Antimicrobial agents are some of the most widely used thera- alloy in 0.5 M H3PO4 solution at 30 C. The authors reported
peutic drugs worldwide. The terms antimicrobial, antibiotic, that cloxacillin and cefadroxil performed better compared to the
and anti-infective encompass a wide variety of pharmaceutical other compounds in the penicillin and rst-generation cepha-
agents that include antibacterial, antifungal, antiviral, and losporins groups. A further increase in inhibition effectiveness
antiparasitic drugs. Of these, antibacterial agents are by far the was reported upon the addition of KI.
most commonly used and thus are a focus of this article, 3.1.3 Aminoglycosides. Aminoglycosides are antibacterial
although similar principles apply to the agents from the other drugs that inhibit bacterial protein synthesis by binding
groups as well.126 The combination of antibacterial drugs and specically to the bacterial 30S ribosomal subunit, causing
metals seems straightforward, since there are many applications a misreading of mRNA and leaving the bacterium unable to
of metals and alloys where antibacterial activity is desired.127–130 synthesise proteins important for growth.135 Their name origi-
3.1.1 Penicillins. Penicillins are among the rst effective nates from the amino-modied glycoside in their structure. The
antibacterial drugs used in modern medicine.131 The lead drugs used in ref. 118 include gentamicin and kanamycin
compound was of natural origin (derived from Penicillium (mostly referred to as kanamycin A), which belong to the
fungi), and was subsequently modied to yield several novel deoxystreptamin-containing aminogylocides, and amikacin,
semisynthetic drugs with different spectra of activity and which is usually used as a last-resort medication against
effectiveness against a variety of bacterial infections.131 Peni- multidrug-resistant bacteria. Although the main structure of the
cillins act by inhibiting the formation of cross-links in the aminoglycosides is not based on the b-lactam ring structure,
bacterial cell wall, which weakens it to such an extent that the some similarity with the above described antibiotics can be
osmotic pressure in the interior of the bacteria becomes seen. Some aminoglycosides also include heterocycles in their
increasingly uncompensated, causing cell death.132 Since their structures. These are single saccharide O-containing mono-
biological target is an enzyme involved in the bacterial cell wall mers, which can work as binding centers in a similar manner as
synthesis, their corrosion inhibition activity is more likely the above mentioned antibiotics.
related only to their base chemical structure, probably due to Abdallah and Jahdaly118 evaluated the inhibition effective-
the heteroatoms present in their so called b-lactam heterocycle ness of three antibacterial drugs from the group of amino-
lead structure. glycosides, i.e. gentamicin, kanamycin, and amikacin as
To the best of our knowledge, there are only two studies that corrosion inhibitors for 99.99% aluminium in 1 M HCl solution
evaluated the corrosion inhibition potential of penicillins for at 30 C. The inhibition effectiveness followed the order ami-
the protection of aluminium,12,133 namely two b-lactamase kacin > kanamycin > gentamicin. The authors attributed this
resistant penicillins, i.e. cloxacillin and dicloxacillin, and two order to the change in molecular weight and the number of
compounds from the so-called aminopenicillins group, i.e. heteroatoms present in these compounds. According to the
amoxicillin and ampicillin, which are two of the most authors, these drugs adsorbed on the aluminium surface
commonly used antibiotics at the moment (Fig. 3). through the oxygen atoms in the heterocyclic rings as well as the
Abdallah133 reported on the use of four antibacterial drugs amino groups. Coordination bonds might be formed between
from the group of penicillins, i.e. ampicillin, cloxacillin, u- the unshared electron pairs of the oxygen and nitrogen atoms
cloxacilin, and amoxicillin as inhibitors in the corrosion of and the empty p-orbitals of aluminium.
99.99% aluminium in 2 M HCl solution. The authors attributed
the increase in the inhibition effectiveness of these compounds
to the increase in the electron donor characteristics of the 3.2 Antifungals
substituted groups, following the order amoxicillin > ampicillin Drugs for systemic antifungal treatment (some are also used for
> cloxacillin > ucloxacillin. the treatment of topical infections) include amphotericin B
3.1.2 Cephalosporins. Cephalosporins were discovered in (and its lipid formulations), various azole derivatives, echino-
the middle of the last century as extracts from the fungus candins, and ucytosine.136 In the following articles, antifungal
Cephalosporium acremonium.134 With a similar spectrum of drugs from the subgroup of “azoles” (a commonly used term in
activity against bacteria as penicillins, they are oen the second medicine for this type of antifungal, which all exhibit the same
line of treatment, when penicillins cannot be used or when their mechanism of action, regardless of the type of non-carbon
oen low solubility in aqueous media is not a limitation. Since atoms in the heterocycle), were the only ones applied. The
they possess a structure similar to penicillins, they are also respective drugs from this group of antifungals inhibit the
prone to degradation by b-lactamase, a common bacterial fungal enzyme called lanosterol 14 a-demethylase, which
strategy to gain resistance to antibacterial drugs.132 Similar to converts lanosterol to ergosterol.137 Ergosterol is an important
Table 5 The inhibition effectiveness of different drugs tested as corrosion inhibitors for aluminium and different aluminium alloys in acidic solutions. The inhibition effectiveness values are
reported as given in the article. In instances where different techniques were used for the determination of the inhibition effectiveness, the range from the minimum to the maximum values
reported in the article is reported below in this table
RSC Advances
Material Inhibitor Inhibitor concentration Medium h (%) Test methods and conditions Reference
99.99% Ampicillin 200–1000 ppm 2 M HCl 62.22–87.97 WL, HE, and Tafel extrapolation at 25 C 133
99.99% Cloxacillin 200–1000 ppm 2 M HCl 56.34–87.41 WL, HE, and Tafel extrapolation at 25 C 133
99.99% Flucloxacilin 200–1000 ppm 2 M HCl 52.13–86.82 WL, HE, and Tafel extrapolation at 25 C 133
99.99% Amoxycillin 200–1000 ppm 2 M HCl 63.96–90.00 WL, HE, and Tafel extrapolation at 25 C 133
99.99% Ampicillin 1000 ppm 2 M HCl 70.96–85.00 WL at 25–65 C 133
27318 | RSC Adv., 2017, 7, 27299–27330

99.99% Cloxacillin 1000 ppm 2 M HCl 68.54–80.00 WL at 25–65 C 133
99.99% Flucloxacilin 1000 ppm 2 M HCl 59.67–77.50 WL at 25–65 C 133
99.99% Amoxycillin 1000 ppm 2 M HCl 73.38–90.00 WL at 25–65 C 133
Pure Enalapril maleate 50–1000 ppm 0.01 M HCl 57.70–80.33 PSP at 25 C 125
Pure Atenolol 50–1000 ppm 0.01 M HCl 46.34–67.69 PSP at 25 C 125
Pure Etilefrine hydrochloride 50–1000 ppm 0.01 M HCl 39.80–59.64 PSP at 25 C 125
AA6063 Enalapril maleate 50–1000 ppm 0.01 M HCl 69.72–81.10 PSP at 25 C 125
AA6063 Atenolol 50–1000 ppm 0.01 M HCl 55.43–74.36 PSP at 25 C 125
AA6063 Etilefrine hydrochloride 50–1000 ppm 0.01 M HCl 47.61–66.97 PSP at 25 C 125
AA20556 Enalapril maleate 50–1000 ppm 0.01 M HCl 82.96–91.11 PSP at 25 C 125
AA20556 Atenolol 50–1000 ppm 0.01 M HCl 51.11–76.60 PSP at 25 C 125
AA20556 Etilefrine hydrochloride 50–1000 ppm 0.01 M HCl 48.15–84.15 PSP at 25 C 125
AlSi11MgSr Enalapril maleate 50–1000 ppm 0.01 M HCl 89.40–93.70 PSP at 25 C 125
AlSi11MgSr Atenolol 50–1000 ppm 0.01 M HCl 73.50–82.00 PSP at 25 C 125
AlSi11MgSr Etilefrine hydrochloride 50–250 ppm 0.01 M HCl 64.00–80.16 PSP at 25 C 125
AA6063 Floxacillin 1 106 to 11 106 M 0.5 M H3PO4 28.0–49.5 WL and GSP at 30–35 C 12
AA6063 Dicloxacillin 1 106 to 11 106 M 0.5 M H3PO4 31.7–53.8 WL at 30–35 C 12
AA6063 Cloxacillin 1 106 to 11 106 M 0.5 M H3PO4 38.3–61.5 WL at 30–35 C 12
AA6063 Cephalexin 1200–2200 ppm 0.5 M H3PO4 28.8–48.9 WL at 30–35 C 12
AA6063 Cefadroxil 1200–2200 ppm 0.5 M H3PO4 48.6–72.5 WL at 30–35 C 12
AA6063 Floxacillin + 102 M KI 1 106 to 11 106 M 0.5 M H3PO4 53.3–67.6 WL at 30 C 12
AA6063 Dicloxacillin + 102 M KI 1 106 to 11 106 M 0.5 M H3PO4 62.6–76.9 WL at 30 C 12
AA6063 Cloxacillin + 102 M KI 1 106 to 11 106 M 0.5 M H3PO4 67.6–82.4 WL at 30 C 12
AA6063 Cephalexin + 102 M KI 1200–2200 ppm 0.5 M H3PO4 54.9–70.3 WL at 30 C 12
AA6063 Cefadroxil + 102 M KI 1200–2200 ppm 0.5 M H3PO4 80.2–91.2 WL at 30 C 12
AA1060 Clotrimazole 2 105 to 1 104 M 0.1 M HCl 36.0–88.0 WL at 30–50 C 119
AA1060 Fluconazole 2 105 to 1 104 M 0.1 M HCl 19.0–82.0 WL at 30 C 119
AA1060 Fluconazole 2 105 to 1 104 M 0.1 M HCl 19.6–82.4 WL at 30–50 C 120
96.9–97.8% Meclizine hydrochloride 5–500 ppm 1 M HCl 41.69–95.40 WL, PDP, and AC impedance at 30 C 124
AA1060 Nizoral 2–10 105 M 2 M HCl 45.36–65.85 Thermometric 13
AA1060 Nizoral + 0.005 M KI 2–10 105 M 2 M HCl 49.35–69.40 Thermometric 13
99.99% Gentamicin 200–1000 ppm 1 M HCl 76.55–91.09 WL, HE, GSP, and EIS at 30 C 118
99.99% Kanamycin 200–1000 ppm 1 M HCl 80.36–92.36 WL, HE, GSP, and EIS at 30 C 118
99.99% Amikacin 200–1000 ppm 1 M HCl 83.61–93.68 WL, HE, GSP, and EIS at 30 C 118
96.9–97.8% Miconazole nitrate 5–500 ppm 1 M HCl 43.3–98.1 WL, EIS, and PDP at 30 C at 30 C 123
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component of the fungal membrane and its depletion leads to study,125 three drugs acting on the cardiovascular system were
the disruption of the membrane structure (e.g. nutrient trans- employed. They belong to the group of antihypertensive drugs,
port, uidity, etc.), which results in the inhibition of fungal which are among the most prescribed group of drugs in the
growth.138 Studies investigating the use of antifungals as world. The antihypertensive drugs used in the work of Abdallah
corrosion inhibitors report the use of two different type of et al.125 come from different pharmacodynamic groups (they act
azoles, namely the imidazoles (clotrimazole, ketoconazole, and on different physiological processes in the body). Namely,
miconazole) and the newer triazole (uconazole). The azole type enalapril inhibits the angiotensin converting enzyme, while
compounds, in a chemical sense, are well known as effective atenolol is a selective b1 receptor antagonist (this subgroup of
corrosion inhibitors for different metallic materials in various antihypertensive drugs is commonly referred to as b-blockers).
corrosive solutions.6,8,139–141 The third drug used in125 is an antihypotensive (working in the
Since the main target of these drugs is again an enzyme opposite manner as the rst two drugs), and is clinically used in
involved in the synthesis of an essential microbe structural the treatment of orthostatic hypotension regardless of the
element, it seems that the biologic and corrosion inhibitions origin thereof.
activities are not related. Nevertheless, it has to be stated, that the The main “heterocycle/heteroatom” theory can be partially
target enzyme in the case of the below mentioned antifungals, is used in the case of enalapril and meclizine, which both include
an iron including protein. This could point to a potential relation N-containg heterocycles in their structures. In the case of ate-
between their biologic and corrosion inhibitions activities. nolol and etilefrine this is not the case, nevertheless, also both
Further studies are necessary to see if the actual drug target site of these drugs include functional groups, capable of p electron
(and hence the molecule orientation) has any correlation with its delocalization (aromatic ring in etilefrine; the aromatic ring and
alignment and adsorption to the metal surface. Furthermore, the the amide group in atenolol), which may be responsible for the
enzyme contains iron, which raises the question if a similar adsorption.
consideration can be also used in the case of aluminium. In terms of corrosion research, Abdallah et al.125 concluded
Obot et al.119 evaluated the performance of two antifungal that three drugs acting on the cardiovascular system i.e. ena-
drugs, i.e. clotrimazole and uconazole, as corrosion inhibitors lapril maleate, atenolol, and etilefrine hydrochloride, act as
for AA1060 aluminium alloy in 0.1 M HCl at 30 and 50 C. inhibitors of the general and pitting corrosion of pure
Clotrimazole was more effective than uconazole in protecting aluminium and three aluminium alloys, i.e. AA6063, AA20556,
the aluminium alloy in 0.1 M HCl solution. The authors and AlSi11MgBr in 0.01 M HCl solution at 25 C. The authors
attributed this behaviour to the fact that clotrimazole has the reported that pure aluminium was less susceptible to corrosion
highest HOMO energy (E(HOMO)) and the lowest difference of compared to the three alloys. The inhibition effectiveness of the
E(LUMO) E(HOMO). In a previous publication, Obot and Obi- drugs increased with their concentration up to 250 ppm. At
Egbedi120 reported that the adsorption of uconazole was higher concentration values the inhibition effectiveness
mainly due to an increase in the adsorption enthalpy rather decreased and the authors attributed that to a steric hindrance
than a reduction in the adsorption entropy. Fluconazole can effect. However, in the case of AA20556 alloy, when higher than
adsorb not only as a cationic species on the aluminium alloy 250 ppm of etilefrine hydrochloride was added, the inhibition
surface, but it can also adsorb as a molecular species using effectiveness rst decreased and then increased again. The
oxygen, nitrogen, and benzylic carbons as its active centres. The authors attributed the inhibitive action of these drugs to the
same conclusion is also presented by Obot et al.121 Obot et al.122 formation of insoluble complex adsorbed on the metal surface.
reported that the inhibition action of clotrimazole on the In the second article, Ishwara Bhat and Alva124 reported on
corrosion of 98.8% aluminium under the same conditions the use of antiemetic drugs as corrosion inhibitors. The authors
(0.1 M HCl solution at 30 and 50 C) is due to physisorption studied the inhibition effectiveness of meclizine hydrochloride
through the active centres found mainly in the imidazole ring. as a corrosion inhibitor for 96.9–97.8% aluminium alloy in 1 M
Bhat and Alva123 evaluated the inhibition effectiveness of HCl solution at 30–60 C.
miconazole nitrate as a corrosion inhibitor for 96.9–97.8%
aluminium in 1 M HCl solution at 30 C. The authors reported
that this drug is protonated in acid solutions, probably at the 4. Gums as corrosion inhibitors
nitrogen atoms of the imidazole ring, forming in this way
a cationic inhibitor species. Plant-derived gums consist of a mixture of long-chain poly-
Obot and Obi-Egbedi13 studied the inhibition effectiveness of saccharide compounds, which are formed either naturally as
the antifungal drug nizoral (ketoconazole) as a corrosion a result of the disintegration of plant tissue (gummosis), injury
inhibitor for AA1060 aluminium alloy in 2 M HCl solution. A to the bark or stem, or due to microbial attack (fungi and
further increase in inhibition effectiveness was reported upon bacteria).142 In general, they do not dissolve in oils and organic
the addition of KI. solvents. However, in contact with water, some of the gums are
easily soluble, while others either adsorb water and swell up or
disperse in water, giving a viscous solution or jelly. When
3.3 Other drugs hydrolised, these gums give simple monosaccharides (galac-
There are two additional studies reporting the use of other tose, mannose arabinose) and glucuronic acid.26,142 The
drugs as corrosion inhibitors for aluminium.124,125 In the rst majority of gums are obtained from the stem, and only a few of
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them from other parts (roots, leaves, seeds) of plants mainly effective. The authors described that Raphia hookeri exudate
from the Leguminosae and Sterculiaceae families. gum consists of D-mannopyranose and D-galactopyranose
Apart from their well-known applications in the pharma- joined together. A further increase in the inhibition effective-
ceutical142–144 and food industries,145,146 gums are used as ness was reported by the authors upon the addition of potas-
corrosion inhibitors for different metals in various corrosive sium halides (KI, KCl, and KBr). The synergistic effect of the
environments.26 These gums contain polysaccharide halides was found to decrease in the order I > Br > Cl. The
compounds rich in nitrogen and oxygen atoms, which serve as authors attributed the order to the inuence of the radii and
adsorption centres and therefore can act as corrosion inhibi- electronegativity of the halide ions on the adsorption process.
tors. Furthermore, gum-metal complexes are formed that act as In another study, Umoren et al.148 compared the inhibition
a barrier layer and isolate the metal surface from the corrosive effectiveness of Raphia hookeri and Pachylobus edulis exudate
environment.26 In addition, gums have low toxicity, are biode- gums in the corrosion of AA1060 aluminium alloy (98.5%
purity) in 0.1 M and 2 M HCl solutions at 30–60 C. The results
gradable, and environmentally friendly. Several gums have been

tested as corrosion inhibitors for aluminium and its alloys in showed that Raphia hookeri is a better inhibitor than Pachylobus
various solutions.14,15,147–157 Xanthan, Commiphora pedunculata, edulis.
and arabic gums were used without further purica- Umoren et al.15 reported on the inhibition effectiveness of
tion.15,147,149,155,156 Two different methods158,159 were used to gum arabic as a corrosion inhibitor for AA1060 aluminium alloy
purify the other gums in the above studies. Purication of the in 1 M and 2 M NaOH solutions at 30 and 40 C. The authors
gums through dissolution in 95% ethanol158 was employed for attributed the inhibition ability of this gum to the adsorption on
Raphia hookeri,14 Pachylobus edulis,148 and Dacroydes edulis.154 the aluminium alloy surface of the main constituents, i.e.
Eddy et al.159 puried the gum by rst dissolving it in cold oligosaccharides, polysaccharides, glucoproteins, and arabino-
distilled water and then the solution was centrifuged, forming glactan. Umoren155 investigated the inhibition effectiveness of
a dense gel. The supernatant was acidied to acidic pH with gum arabic as a corrosion inhibitor for the same aluminium
diluted hydrochloric acid. Then, 80% ethanol was slowly added alloy and temperatures in lower concentrations of NaOH (i.e.
and the precipitated gum was obtained by centrifugation. 0.1 M NaOH) solutions. The same trend in the change of inhi-
Finally, the gum was washed with alcohol, followed by ether, bition effectiveness with gum concentration and temperature
and then dried before use. The same procedure was employed compared to the previous work15 was reported by the author.
by Eddy et al.150,152,153,157 and Ameh151 to purify the gums used in The inhibition effectiveness of gum arabic increased further
their respective studies. upon the addition of 0.5 M KI. Gum arabic was also tested by
The main ndings (as described above) regarding the use of Umoren156 as a corrosion inhibitor for the same aluminium
gums as corrosion inhibitors for aluminium materials are pre- alloy immersed in 0.1 M H2SO4 solution at 30–60 C. The
sented in Table 6. In all these studies only classical techniques inhibition effectiveness decreased with increasing temperature,
(WL, HE, and thermometric) were employed to evaluate the contrary to what was reported regarding alkaline solutions.15,155
inhibition effectiveness of the tested gums (no electrochemical Ameh and Eddy149 studied the inhibition effectiveness of
analysis was reported). Pure aluminium147,150–153 and 1xxx series Commiphora pedunculata exudate gum as a corrosion inhibitor
aluminium alloy15,148,154–156 are among the most tested materials. for AA3001 aluminium alloy in 0.1 M HCl solution at 30 and
It was reported in all studies that the inhibition effectiveness of 60 C. Next, Ameh151 evaluated the inhibition effectiveness of
the studied gums increased with increasing concentration. An Commiphora kestingii gum exudate as a corrosion inhibitor for
increase in temperature resulted in an increase in the inhibition 96.65% aluminium alloy in 0.1 M H2SO4 solution at 30 and
effectiveness in the studies of Arukalam et al.,147 Ameh,151 Eddy 60 C. The author reported that this gum contained a signicant
et al.,150,157 Umoren et al.,15 and Umoren,155 while the opposite amount of sucrose, octadecanoic acid, alpha camphorenal,
was observed in other studies.14,148,149,153,154,156 A more irregular nerolidolisobutyrate, diisopropenyl-1-methyl-1-vinyl cyclo-
trend in the change in inhibition effectiveness with increasing hexane, and abetic acid. Based on the change in inhibition
temperature was reported by Eddy et al.152 for Ficus tricopoda effectiveness with temperature, the authors suggested chemi-
gum. The authors reported a decrease in the inhibition effec- sorption as the possible adsorption mechanism for Commi-
tiveness with an increase in temperature for concentrations up phora kestingii gum exudate. The same mechanism was
to 0.3 g L1 gum added, while for higher gum concentrations previously suggested by Umoren et al.15 for the adsorption of
the inhibition effectiveness increased with increasing gum arabic on AA1060 aluminium alloy surface in NaOH
temperature. solution.
Arukalam et al.147 reported on the inhibition effectiveness of Eddy et al.152 studied the inhibition effectiveness of Ficus
xanthan gum in the corrosion of 98.08% aluminium alloy in tricopoda gum as a corrosion inhibitor for 96.65% aluminium
0.5 M HCl solution at 28–60 C. The authors concluded that the alloy in 0.1 M H2SO4 solution at 30 and 60 C. Camphene,
inhibition process is due to the ability of the protonated and sucrose, 2-methylene cholestan-3-ol, and 7-hexadecenal are
molecular species to adsorb on the cathodic and anodic sites of among the constituents of this gum, as reported by the authors.
the corroding metal surface. The authors reported that the adsorption of the Ficus tricopoda
Umoren and Ebenso14 tested Raphia hookeri exudate gum as gum was endothermic up to 0.3 g L1, but exothermic for higher
a corrosion inhibitor for aluminium (no composition given) in gum concentrations. Next, the same group153 investigated the
0.1 M and 2 M HCl solutions at 30–60 C and suggested that it is inhibition effectiveness of Ficus thonningii gum as a corrosion
Review
Table 6 The inhibition effectiveness of different gums tested as corrosion inhibitors for aluminium and different aluminium alloys in acidic solutions. The inhibition effectiveness values are
Inhibitor
98.08% Xanthan gum 1–5 g L1 0.5 M HCl 6.05–48.55a WL aer 1–5 days immersion at 28 C 147
98.08% Xanthan gum 1–5 g L1 0.5 M HCl 15.91–72.30 WL at 40–60 C 147
NG Raphia hookeri exudate gum 0.5 g L1 0.1 M HCl 46.1–56.3 WL at 30–60 C 14
NG Raphia hookeri exudate gum + 0.06 M KCl 0.5 g L1 0.1 M HCl 40.7–60.5 WL at 30–60 C 14
NG Raphia hookeri exudate gum + 0.06 M KBr 0.5 g L1 0.1 M HCl 50.6–62.2 WL at 30–60 C 14

NG Raphia hookeri exudate gum + 0.06 M KI 0.5 g L1 0.1 M HCl 53.2–70.5 WL at 30–60 C 14
NG Raphia hookeri exudate gum 0.5 g L1 2 M HCl 37.0–65.4 HE at 30 C and thermometric 14
NG Raphia hookeri exudate gum 0.5 g L1 2 M HCl 25–34 WL at 40–60 C 14
NG Raphia hookeri exudate gum + 0.06 M KCl 0.5 g L1 2 M HCl 59.0–67.9 WL at 30 C and thermometric 14
NG Raphia hookeri exudate gum + 0.06 M KCl 0.5 g L1 2 M HCl 33–51 WL at 40–60 C 14
NG Raphia hookeri exudate gum + 0.06 M KBr 0.5 g L1 2 M HCl 65.0–74.6 WL at 30 C and thermometric 14
NG Raphia hookeri exudate gum + 0.06 M KBr 0.5 g L1 2 M HCl 37–54 WL at 40–60 C 14
NG Raphia hookeri exudate gum + 0.06 M KI 0.5 g L1 2 M HCl 68.0–89.5 WL at 30 C and thermometric 14
NG Raphia hookeri exudate gum + 0.06 M KI 0.5 g L1 2 M HCl 41–58 WL at 40 C 14
AA1060 Pachylobus edulis exudate gum 0.1–0.5 g L1 0.1 M HCl 8.70–41.00 WL at 30–60 C 148
AA1060 Raphia hookeri exudate gum 0.1–0.5 g L1 0.1 M HCl 34.40–56.30 WL at 30–60 C 148
AA1060 Pachylobus edulis exudate gum 0.1–0.5 g L1 2 M HCl 19.36–64.24 Thermometric 148
AA1060 Raphia hookeri exudate gum 0.1–0.5 g L1 2 M HCl 40.60–85.51 Thermometric 148
AA3001 (96.65% Al) Commiphora pedunculata gum 0.1–0.5 g L1 0.1 M HCl 41.80–64.22 WL at 30–60 C 149
AA3001 (96.65% Al) Commiphora pedunculata gum 0.1–0.5 g L1 0.1 M HCl 59.24–73.03 Thermometric 149
96.65% Ficus benjamina gum 0.1–0.5 g L1 0.1 M H2SO4 64.00–87.50 WL at 30–60 C 150
96.65% Commiphora kestingii gum exudate 0.1–0.5 g L1 0.1 M H2SO4 65.40–83.22 WL at 30–60 C 151
96.65% Ficus tricopoda gum 0.1–0.5 g L1 0.1 M H2SO4 67.51–85.80 WL at 30–60 C 152
96.65% Ficus thonningii gum 0.1–0.5 g L1 0.1 M H2SO4 59.00–70.00 WL at 30–60 C 153
AA1060 Dacroydes edulis exudate gum 0.1–0.5 g L1 2 M HCl 8.7–42.0 WL at 30–60 C 154
AA1060 Gum arabic 0.1–0.5 g L1 1 M NaOH 19.09–74.16 HE at 30–40 C 15
AA1060 Gum arabic 0.1–0.5 g L1 2 M NaOH 31.34–75.86 Thermometric 15
AA1060 Gum arabic 0.1–0.5 g L1 0.1 M H2SO4 52.42–79.69 WL at 30–60 C 156
AA1060 Gum arabic 0.1–0.5 g L1 2.0 M H2SO4 22.33–70.00 Thermometric 156
AA1060 Gum arabic 0.1–0.5 g L1 0.1 M NaOH 15.1–54.2 WL and HE at 30–40 C 155
AA1060 Gum arabic + 0.05 M KI 0.1–0.5 g L1 0.1 M NaOH 46.9–75.4 WL and HE at 30–40 C 155
96.65% Gloriosa superba exudate gum 0.1–0.5 g L1 0.1 M HCl 70.84–86.38 WL at 30–60 C 157
NG – not given. a h values recalculated from the given corrosion rate values.
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inhibitor for 96.65% aluminium alloy in 0.1 M H2SO4 solution material. Since safer and less harmful solvents that are easy to
at 30 and 60 C. Gas chromatography-mass spectrometry (GC- remove or recover are gaining in popularity, the extraction of
MS) measurements showed that 16-methyl-octadecanoic acid, essential oil components using SFE has received much atten-
abietic acid, n-hexadecanoic acid, and andrographolide are tion, particularly in the food, pharmaceutical, and cosmetic
among the main constituents of this gum. Finally, Eddy et al.150 industries, as a sustainable alternative to conventional
investigated the inhibition effectiveness of Ficus benjamina gum processes such as organic solvent extraction and steam
as a corrosion inhibitor for 96.65% aluminium alloy in 0.1 M distillation.62
H2SO4 solution at 30 and 60 C. The authors reported that The presence of the above-mentioned components
sucrose and D-glucose are the major constituents of the gum, combined with their low toxicity and high availability make
while several carboxylic acids (including hexadecanoic acid, essential oils suitable for use as corrosion inhibitors for
octadedecanoic acid, and 6,13-pentacenequinone) are present different metals in various environments.160–163 However, only
in smaller amounts. According to the authors, the inhibition a limited number of oils have been tested as corrosion inhibi-
action of Ficus benjamina gum is due to multiple-layer adsorp- tors for aluminium and its alloys.164–171 The majority of the
tion through its various components. Multiple-layer adsorption studies have been carried out in acidic solutions. Fayomi and
of the gum components was also proposed as the mechanism Popoola166 reported on the inhibition effectiveness of green
responsible for their inhibitive properties in the case of Com- roasted Elaeis guineensis oil in the corrosion of AA6063
miphora kestingii gum by Ameh151 and for gum arabic by aluminium alloy in 3.5% NaCl solution, while Lavandula
Umoren.155 angustifolia L. and Laurus nobilis L. oils inhibited the corrosion
Umoren et al.154 studied the inhibition effectiveness of of aluminium and AA5754 aluminium alloy, respectively, in 3%
Dacroydes edulis exudate gum as a corrosion inhibitor for NaCl solutions.169,170 Pure aluminium and the 5xxx and 6xxx
AA1060 aluminium alloy in 2 M HCl solution at 30–60 C. series aluminium alloys were the tested materials. The main
Although based on the thermodynamic calculations the authors ndings (as described above) regarding the use of natural oils as
suggested physisorption as the possible mechanism for this corrosion inhibitors for aluminium materials are presented in
gum, no specic indication of which of the gum components Table 7. As for the other natural compounds, the inhibition
adsorbed on the aluminium surface was given. The same effectiveness increased with increasing concentration of all the
mechanism (physisorption) was also suggested for Raphia studied oils.
hookeri gum,14,148 Pachylobus edulis gum,148 Commiphora pedun- Halambek et al.,167 Halambek and Berković,168 and Halam-
culata gum,149 Ficus benjamina gum,150 Ficus thonningii gum,153 bek et al.170 investigated the inuence of temperature on the
and gum arabic in acidic solution.156 inhibition effectiveness of three oils dissolved in 30 vol%
Eddy et al.157 reported on the inhibition effectiveness of ethanol. Halambek et al.167 reported on the inhibition effec-
Gloriosa superba exudate gum (pH z 2) as a corrosion inhibitor tiveness of Ocimum basilicum L. essential oil as a corrosion
for 96.65% aluminium alloy in 0.1 M HCl solution at 30 and inhibitor for 99.85% aluminium in 0.5 M HCl solution at 30–
60 C. GC-MS revealed that the main constituents of the Glori- 85 C. The upper temperature employed certainly contributes to
osa superba gum are 1-piperoylp, 1-penta-decarborxylic acid, 9- the degradation of polyphenols, especially during exposure for
octadecenoic acid, and stigmasta-5,22-dien-3-ol. Quantum a long time. Therefore, lower temperatures would be desired.
chemical studies showed that the adsorption of this gum is due However, degradation does not occur immediately, therefore
to the presence of the amide group in stigmasta-5,22-dien-3-ol a shorter exposure time may not be so harmful. The authors
and of the hydroxyl group in 1-piperoylp. Based on the ther- reported that linalool is the main component of the oil, fol-
modynamic calculations, the authors suggested a mixed-type lowed by smaller amounts of eugenol, 1,8-cineole, and geraniol.
(physisorption and chemisorption) mechanism for the adsorp- Halambek and Berković168 investigated the inhibition effec-
tion of Gloriosa superba gum on the aluminium surface. A tiveness of Anethum graveolens L. oil as a corrosion inhibitor for
mixed-type adsorption mechanism was also proposed for Ficus 99.85% aluminium in 1 M HCl solution at 25–75 C (this upper
tricopoda gum152 and for gum arabic on AA1060 aluminium temperature limit might also contribute to the degradation of
alloy in NaOH solutions.155 these compounds, as discussed above). The authors reported
that the main components of the oil are carvone and limonene.
5. Natural oils as corrosion inhibitors Halambek et al.170 studied the inhibition effectiveness of Lav-
andula angustifolia L. oil as a corrosion inhibitor for Al–3Mg
Essential oils, commonly known as volatile or ethereal oils, are (95.5% Al) in 3% NaCl solution at 25–60 C. The authors re-
concentrated hydrophobic liquids containing monoterpene and ported that linalool and linalyl acetate are the main compo-
sesquiterpene hydrocarbons and oxygenated compounds nents of Lavandula angustifolia L. oil. In all three studies the
(alcohols, aldehydes, ketones, acids, phenols, oxides, lactones, authors reported that the inhibition effectiveness of the
ethers, and esters), which are responsible for the characteristic respective oils decreased with increasing temperature, which
odours and avours. Due to the fact that most owers do not might be connected with decomposition. Halambek et al.170
contain enough volatile oil to undergo expression and their attributed this behaviour to the desorption of the inhibitor
chemical components are too delicate and easily denatured by molecules with increasing temperature.
the high heat used in steam distillation, a solvent such as The inuence of the corrosive environment on the inhibition
hexane or SC-CO2 is used to extract the oils from the crude plant effectiveness of two oils was studied by Popoola et al.164 and
Review
Table 7 The inhibition effectiveness of different oils tested as corrosion inhibitors for aluminium and different aluminium alloys in various solutions. The inhibition effectiveness values are
Inhibitor

99.01% Arachis hypogeae natural oil 20–100 vol% 2 M HCl 3.01–45.97 WL aer 12–24 h immersion at 25 C 164
99.01% Arachis hypogeae natural oil 20–100 vol% 2 M HNO3 28.29–92.37 WL aer 12–24 h immersion at 25 C 164
99.01% Arachis hypogeae natural oil 20 vol% 2 M HNO3 78.28 WL aer 36 h immersion at 25 C 164
99.01% Arachis hypogeae natural oil 20–100 vol% 2 M HCl 83.48–95.57a PDP at 25 C 164
99.01% Arachis hypogeae natural oil 20–100 vol% 2 M HNO3 88.55–99.94a PDP at 25 C 164
99.85% Ethanol solution of laurel oil 9–45 mg L1 1% CH3COOH 20.7–76.8 PDP and Rp at 25 C 165
AA5754 Ethanol solution of laurel oil 9–45 mg L1 1% CH3COOH 46.6–84.4 PDP and Rp at 25 C 165
AA6063 Green roasted Elaeis guineensis oil 5% 3.5% NaCl 64–77 WL aer 48–216 h immersion 166
AA6063 Green roasted Elaeis guineensis oil 15% 3.5% NaCl 39–98 WL aer 48–216 h immersion 166
AA6063 Green roasted Elaeis guineensis oil 5% 3.5% NaCl 65 PDP at 30 C 166
AA6063 Green roasted Elaeis guineensis oil 15% 3.5% NaCl 72 PDP at 30 C 166
99.85% Ocimum basilicum L. oil in ethanol 0.2–5.7 g L1 0.5 M HCl 41.9–90.1 WL, PDP, and EIS at 30 C 167
99.01% Ricinus communis oil 20–100 vol% 2 M H3PO4 18.75–82.35 WL aer 12–36 h immersion at 25 C 171
99.01% Ricinus communis oil 20–100 vol% 2 M H3PO4 94.84–99.99a PDP and Rp at 25 C 171
99.01% Ricinus communis oil 20–100 vol% 2 M HCl 95.81–99.59a PDP and Rp at 25 C 171
99.85% Anethum graveolens L. oil in ethanol 20–300 ppm 1 M HCl 76.7–98.0 WL aer 3 h immersion, PDP, and EIS at 25 C 168
Al–3Mg Ethanol solution of 1.0–20 ppm 3% NaCl 73.31–99.84a WL aer 4 h immersion, PDP, and Rp at 25 C 170
(95.5% Al) Lavandula angustifolia L. oil
99.86% Ethanol solution of Laurus nobilis L. oil 10–50 ppm 3% NaCl 49.9–91.3 WL aer 24 h immersion, PDP, and Rp at 25 C 169
AA5754 Ethanol solution of Laurus nobilis L. oil 10–50 ppm 3% NaCl 41.9–84.3 WL aer 24 h immersion, PDP, and Rp at 25 C 169
a
h was calculated on the basis of the values of the corrosion rate, the corrosion current, the corrosion current density, or the resistance of the blank solution and inhibited samples.
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Abdulwahab et al.171 The rst group of authors investigated the layer on the aluminium and alloy surface. In addition to this
inhibition effectiveness of Arachis hypogeae natural oil as protective layer (lm), Halembek et al.169 suggested that the
a corrosion inhibitor for 99.01% aluminium in 2 M HCl and 2 M main component of Laurus nobilis L. oil (1,8-cineole) can adsorb
HNO3 solutions at 25 C.164 A method for SFE and the identi- via the lone pair electrons in the oxygen atoms.
cation of volatile avor components in roasted peanuts (Arachis The inhibition action of Ocimum basilicum L. oil167 was
hypogaea) was described in the review article of Capuzzo et al.62 attributed to its main component, linalool. The latter, apart
It was reported that the obtained extracts contained compounds from protonating in acid solution, contains –OH groups and
such as hexanol, hexanal, methylpyrrole, benzene acetaldehyde, double bonds in its structure, which are probable adsorption
methylpyrazine, 2,6-dimethylpyrazine, ethylpyrazine, 2,3-dime- centres. The authors proposed a two-stage mechanism for the
thylpyrazine, 2,3,5-trimethylpyrazine, 2-furancarboxaldehyde, inhibition action of the oil. In the rst stage, the chloride ions
2-ethyl-5-methyl- and 2-ethyl-6-methylpyrazine, and 3-ethyl-2,5- adsorb electrostatically on the positively charged metal surface,
dimethylpyrazine. Popoola et al.164 reported that Arachis hypo- giving a negative net charge to the surface. In the second stage,
geae natural oil was a better inhibitor in HNO3 than in HCl the protonated linalool electrostatically interacted with the
solution. negatively charged surface, forming a protective layer on the
Abdulwahab et al.171 tested Ricinus communis oil as a corro- aluminium surface. Based on the thermodynamic data, the
sion inhibitor for 99.01% aluminium alloy in 2 M HCl and 2 M authors suggested that the active components of the oil phys-
H3PO4 at 25 C. Danlami et al.172 reported on Soxhlet extraction isorbed on the aluminium surface. A similar mixed-type
of this oil using hexane as a solvent. They reported that the oil mechanism was suggested by Halambek and Berković168 for
contained mainly unsaturated fatty acids (ricinoleic acid) fol- the adsorption of Anethum graveolens L. oil on aluminium
lowed by a moderate content of saturated fatty acids (palmitic, surface. According to the authors, chemisorption can occur
stearic, linoleic, linolineic, and dihydroxylstearic acids). In their either by displacing the water molecules from the aluminium
study, Abdulwahab et al.171 reported that there is no signicant surface and electron sharing between the oxygen atoms and
difference in the performance of the oil (no signicant change aluminium or through donor–acceptor bonds between the p
in the h values) in the two acid solutions. electrons of the aromatic ring and the p-orbitals of Al. Phys-
As seen in Table 7, electrochemical techniques, including isorption can occur between the protonated species and the
PDP, Rp, and EIS, have been used alongside the classic WL negatively charged aluminium surface from the chloride ions.
technique to evaluate not only the performance of the oils as Fayomi and Popoola166 investigated green roasted Elaeis
corrosion inhibitors, but also to determine their inuence on guineensis oil as a corrosion inhibitor for AA6063 aluminium
the corrosion reactions. Based on the PDP measurements, the alloy in 3.5% NaCl solution at 30 C. As shown previously, Elaeis
authors concluded that Arachis hypogeae oil164 and green roasted guineensis oil was extracted by SC-CO2 extraction and it was
Elaeis guineensis oil166 acted as mixed-type corrosion inhibitors shown that the main constituents were carotene, vitamin E,
for the respective aluminium materials. Next, Halambek sterols, and squalene.173 The oil showed good protection (h ¼
et al.,167 Halambek and Berković,168 Halambek et al.,169 and 68–78%) even aer 216 h of immersion. The authors attributed
Halambek et al.170 reported that Ocimum basilicum L. oil, Ane- the inhibition action of this oil to the adsorption of the surface-
thum graveolens L. oil, Laurus nobilis L. oil, and Lavandula active compounds and oxide on the aluminium surface, which
angustifolia L. oil acted as cathodic-type corrosion inhibitors. modify the wettability and the interface.
Finally, Halambek et al.165 tested the ethanol solution of laurel
oil as a corrosion inhibitor for 99.85% aluminium and AA5754
aluminium alloy in 1% acetic acid solution at 25 C. Capuzzo62 6. Other natural products as
reported SC-CO2 extraction as a suitable method for the isola- corrosion inhibitors
tion of volatile and xed oils from dried berries of L. nobilis. The
extracts were rich in volatile fraction, which was mainly Apart from the main groups of green inhibitors described
composed of (E)-b-ocimene, 1,8-cineole, a-pinene, b-pinene, b- above, a few other natural products have been tested as corro-
longipinene, linalyl acetate, d-cadinene, a-terpinyl acetate, and sion inhibitors for aluminium materials in alkaline and
a-bulnesene. The authors reported that the ethanol solution of chloride-containing solutions. The inhibition effectiveness of
the laurel oil protects (higher inhibition effectiveness) AA5754 all the natural products tested was found to increase with
aluminium alloy better than 99.85% aluminium. PDP increasing concentration of the product. The main ndings (as
measurements showed that the ethanol solution of laurel oil described above) are presented in Table 8.
acted as an anodic-type inhibitor in the corrosion of 99.85% Rosliza et al.174 reported on the inhibition effectiveness of
aluminium and as a cathodic-type inhibitor in the corrosion of natural honey as a corrosion inhibitor for Al–Mg–Si alloy
AA5754 aluminium alloy. (97.36% aluminium) in seawater at 25 C. Gudić et al.175 inves-
Several possible mechanisms were suggested by the authors tigated the inhibition effectiveness of ve types of honey dis-
to explain the inhibition action of the oils tested. Based on the solved in NaCl, i.e. oak honey (H1), coniferous honeydew honey
thermodynamic calculations, Halambek et al.165 concluded that (H2), winter savory honey (H3), alder buckthorn honey (H4),
the ethanol solution of laurel oil adsorbed on the surface and carob tree honey (H5), as corrosion inhibitors for AA5052
through a mixed-type mechanism (both physisorption and aluminium alloy in 0.5 M NaCl solution at 20 C. The inhibition
chemisorption), which leads to the formation of a protective effectiveness followed the order H3 < H5 < H4 < H2 < H1.
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Table 8 The inhibition effectiveness of some natural products tested as corrosion inhibitors for aluminium and different aluminium alloys in
various solutions. The inhibition effectiveness values are reported as given in the article. In instances where different techniques were used for the
determination of the inhibition effectiveness, the range from the minimum to the maximum values reported in the article is reported below in this
table

97.36% Natural honey 200–1000 ppm Seawater 63.43–91.85 PDP, Rp, and EIS 174
AA5052 Oak honey dissolved in NaCl 1000 ppm 0.5 M NaCl 81.52–82.67a PDP, Rp, and EIS at 20 C 175
AA5052 Coniferous honeydew honey 1000 ppm 0.5 M NaCl 77.28–80.59a PDP, Rp, and EIS at 20 C 175
dissolved in NaCl
AA5052 Winter savory honey dissolved in NaCl 1000 ppm 0.5 M NaCl 58.88–64.82a PDP, Rp, and EIS at 20 C 175
AA5052 Alder buckthorn honey dissolved in NaCl 1000 ppm 0.5 M NaCl 70.09–72.88a PDP, Rp, and EIS at 20 C 175
AA5052 Carob tree honey dissolved in NaCl 1000 ppm 0.5 M NaCl 65.16–69.93a PDP, Rp, and EIS at 20 C 175
AA5052 Oak honey dissolved in NaCl 400–1200 ppm 0.5 M NaCl 61.87–85.65 PDP and Rp at 20 C 175
AA5052 Coniferous honeydew honey 400–1200 ppm 0.5 M NaCl 56.72–82.65 PDP and Rp at 20 C 175
dissolved in NaCl
Pure Animal glue 2000 ppm 0.1 M NaOH 43.49–59.05 PDP at 30–60 C 176
AA6063 Animal glue 2000 ppm 0.1 M NaOH 41.62–54.80 PDP at 30–60 C 176
20556 alloy Animal glue 2000 ppm 0.1 M NaOH 30.89–40.29 PDP at 30–60 C 176
Pure Animal glue 100–2000 ppm 0.1 M NaOH 10.86–59.05 PDP, EIS, and CV at 30 C 176
AA6063 Animal glue 100–2000 ppm 0.1 M NaOH 8.75–54.80 PDP, EIS, and CV at 30 C 176
20556 alloy Animal glue 100–2000 ppm 0.1 M NaOH 4.12–41.52 PDP, EIS, and CV at 30 C 176
a
h was calculated on the basis of the values of the corrosion rate, the corrosion current, the corrosion current density, or the resistance of the blank
solution and inhibited samples.
PDP measurements performed in both studies showed that biodegradablility, and bioaccumulation tests would need to be
all types of honeys acted as mixed-type inhibitors.174,175 performed.1 In most of the reported articles summarised
However, for all the tested honey types Gudić et al.175 reported herein, these kinds of tests were not performed and this
a predominant action on the anodic reaction. The inhibition remains an open subject for future studies. However, there is
action of the different honey types was attributed to the a high potential that the extracts are non-hazardous as they are
formation of a surface layer (a thin lm) on the surface of the extracted from the natural environment. Some of them were
aluminium materials, which blocked the further attack on also already applied in other different applications, where their
aluminium.174,175 Based on the thermodynamic calculations, non-toxic nature was at least indirectly conrmed. This also
both research groups suggested physisorption as the possible applies to the mentioned drugs, as they have all been proven
adsorption mechanism for the respective honey types safe clinically and are actually even today used in pharmaco-
studied.174,175 therapy in humans. Of course, the actual dose of exposure/
Abdallah et al.176 boiled animal connective tissue for a long intake has to be considered; nevertheless, the latter facts
time and tested the obtained glue as a corrosion inhibitor for cannot be denied. Moreover, as seen herein, the literature
aluminium as well as AA6063 and 20556 (92.47% aluminium) concerning drugs as corrosion inhibitors for aluminium and its
aluminium alloys in 0.1 M NaOH solution at 30 C. The inhi- alloys is scarce yet interesting, and as such could represent an
bition effectiveness decreased with increasing Si content open subject for future studies.
following the order aluminium > AA6063 alloy > 20556 alloy. An One way of quickly assessing environmental acceptability is
increase in temperature resulted in a decrease in inhibition to employ the German WGK classication as the data on this
effectiveness. The PDP measurements showed that the animal classication are readily available by most chemical providers.
glue acted as a mixed-type inhibitor. The authors suggested that WGK (German: Wassergefährdungsklassen) stands for the
the adsorption of the animal glue is carried out through the German Water Hazard Class. In accordance with the national
substitution of the water molecules on the surface of the German VwVwS regulation (German: Verwaltungsvorschri was-
aluminium materials. sergefährdende Stoffe), all substances are classied as either
non-hazardous to water or assigned to one of three classes,
WGK 1, WGK 2, and WGK 3, with increasing water hazard. The
7. Outlook
lowest class, WGK 1, is relatively harmless and close to non-
Green compounds are by far the most attractive area of research hazardous.8
on corrosion inhibitors. However, several aspects need to be Another way to evaluate toxicity is according to the LC50 or
taken into account before these inhibitors can be used in real EC50 categories (lethal or effective concentrations in 50% of the
industrial applications. The “green” aspect of the studied tested subjects, respectively), which rank chemicals from
natural products needs to be evaluated. In order to actually supertoxic to practically non-toxic. Moreover, biodegradability
understand what is green and what is not, toxicity, is usually evaluated by the 60% persistence of the components
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in the environment aer 28 days. Furthermore, bio- the omission of the use of toxic solvents. SC-CO2 is over-
accumulation is evaluated by the partition coefficient Po/w whelmingly the solvent of choice due to its ability to easily
(partition between 1-octanol and water).1 The higher this penetrate inside plant material and high solvent power.
partition coefficient is the higher the possibility for the Nevertheless, SC-CO2 also has important disadvantages, such as
compound to be bioaccumulated. it being limited to the processing of dry raw materials and
Usually, authors do not report the specic components compounds of low polarity and low molecular weight. These
present in the extracts. It would be benecial if, before testing limitations could be overcome through the use of co-solvents
an extract's corrosion inhibition performance, the separation and alternative supercritical uids such as propane, argon,
and analysis of individual components were carried out, e.g. and SF6. Water, as the cheapest solvent, represents another
HPLC-MS or GC-MS analysis, to reveal which compounds are alternative solvent or co-solvent with the aim of modifying the
responsible for the corrosion inhibition effectiveness of the polarity of the solvent. Subcritical water extraction has become
extract used. The choice of the extraction method is of great an increasingly popular alternative technology in the extraction
importance. Taking into account the variety of problems asso- of phenolic compounds. When water is heated well above
ciated with the high processing temperatures and long pro- 100 C its dielectric constant decreases and its ionic product
cessing times in conventional extraction procedures, there is an increases. That means that the same solvent can be used to
essential need to promote the development and application of extract inorganic and organic components. The main limitation
alternative extraction techniques that do not require severe is the extremely high energy required to heat the media.
operating conditions including high processing temperatures Furthermore, water above its critical point (374 C, 221 bar)
and harmful organic solvents. Supercritical uid extraction demonstrates a highly corrosive nature, which might be
represents an alternative to the extraction methods summarised a problem for the high-pressure equipment used to obtain these
in this review, which allows selective isolation of natural products.
compounds from natural materials at moderate temperatures. There is still some room to improve the performance of these
Considering the available studies reporting the use of drugs green corrosion inhibitors. As described above, the authors only
from various pharmacotherapeutic groups as corrosion inhibi- reported the use of corrosion inhibitors, in a few cases with the
tors of aluminium, several aspects need to be claried more addition of intensiers (mainly potassium halides). However,
thoroughly for this eld to be fully acknowledged. From the these corrosion inhibitors would be even more effective if actual
range of drugs tested as potential corrosion inhibitors for corrosion inhibition formulations were employed.8 Moreover,
aluminium, antimicrobial drugs (antibacterial and antifungal a more detailed evaluation of the inhibition mechanisms
drugs) have the highest potential. Since there are still many through the use of electrochemical and surface analysis tech-
open questions related to the corrosion inhibition mechanism niques should be considered.
of these compounds, their interaction with aluminium on the
molecular level should be studied in more detail. There is also 8. Conclusions
the need to systematically evaluate the inuence of other
physico-chemical parameters (e.g. temperature, pH, ionic The research work published over the past two decades on the
strength, etc.) on the corrosion inhibition effectiveness of these corrosion inhibition of aluminium and its alloys in different
drugs before their application becomes more realistic. In solutions, using a variety of natural compounds (including
particular, we need to consider the amount used (usually it is plant extracts, gums, drugs, and natural oils) was presented in
high, considering that large metallic surfaces need to be pro- this review article. Plant extracts were by far the most studied
tected against corrosion) and the potential impact on the natural products. A wide variety of solvents (organic solvents,
environment. Additionally, as already pointed out by Gece,22 not water, acids, and bases) were used to prepare extracts of mainly
all drugs are readily biodegradable and their transformation the leaves, seeds, and stem of the respective plants. Pure
products may be equally or even more hazardous to the envi- aluminium, 1xxx, 3xxx, 6xxx, and 7xxx series aluminium alloys
ronment. Therefore, more studies need to be performed before were among the most tested aluminium materials.
such corrosion inhibitors can be considered green. However, we The inhibition effectiveness of the green corrosion inhibitors
are condent that this type of review can signicantly aid in tested increased with increasing concentration. A synergistic
nding potential candidates for further (very expensive) tests effect upon the addition of halides (especially iodide) was re-
(e.g. biodegradability, toxicity, and bioaccumulation).1 On the ported. The corrosion tests were carried out in a temperature
other hand, considering the possible application of aluminium range of 20 to 75 C. An increase in temperature was usually
and its alloys in medicine (e.g. orthopaedic implants), drugs as reected in the lower inhibition effectiveness of the tested
corrosion inhibitors seem even more attractive. Therefore, the natural products.
additional testing necessary to tackle the remaining open Weight loss and hydrogen evolution were the most
questions will be likely performed rather sooner than later. frequently used techniques to evaluate the corrosion inhibition
In the majority of the studies the authors do not report how effectiveness of the studied green inhibitors. A few studies were
the natural oils were obtained. One of the most convenient and performed using electrochemical techniques. Based on the
efficient methods to extract these oils from plant materials at polarisation measurements, the majority of the studies reported
low temperatures is to apply high-pressure extraction with that these products were found to act as mixed-type inhibitors.
supercritical uids, hence limiting thermal degradation, and Moreover, physisorption was reported as the most probable
View Article Online
Review RSC Advances
mechanism for the adsorption of these products on the surface 12 A. S. Fouda, A. A. Al-Sarawy, F. S. Ahmed and H. M. El-
of the aluminium materials. Alternatively, the inhibition action Abbasy, Corros. Sci., 2009, 51, 485–492.
of these products was attributed to the formation of a protective 13 I. B. Obot and N. O. Obi-Egbedi, E-J. Chem., 2010, 7, 837–
layer (lm) on the surface of the aluminium materials. 843.
According to the authors, adsorption occurred through the 14 S. A. Umoren and E. E. Ebenso, Pigm. Resin Technol., 2008,
adsorption centres present in their active components. 37, 173–182.
However, particular compounds were rarely identied and re- 15 S. A. Umoren, I. B. Obot, E. E. Ebenso, P. C. Okafor,
ported for the natural products tested. O. Ogbobe and E. E. Oguzie, Anti-Corros. Methods Mater.,
Although a considerable number of studies have been per- 2006, 53, 277–282.
formed, this is still a relatively unexplored eld of research with 16 A. M. Al-Turkustani, Mod. Appl. Sci., 2010, 4, 105–124.
great potential for improvement, especially as regards the 17 A. M. Abdel-Gaber, E. Khamis, H. Abo-Eldahab and S. Adeel,
methods used to obtain the green corrosion inhibitors and Mater. Chem. Phys., 2010, 124, 773–779.
corrosion inhibitor formulation designs. 18 S. A. Umoren and M. M. Solomon, J. Ind. Eng. Chem., 2015,
21, 81–100.
Abbreviations 19 L. Pirvu, A. Armatu, C. Bubueanu, G. Pintilie and S. Nita,
Rom. Biotechnol. Lett., 2010, 15, 5683–5689.
20 L. Pirvu, D. Barbulescu, C. Nichita, S. Nita and S. C. Mihul,
EIS Electrochemical impedance spectroscopy Rom. Biotechnol. Lett., 2011, 16, 5937–5943.
GSP Galvanostatic polarisation 21 M. Jayalakshmi and V. S. Muralidharan, Corros. Rev., 1997,
HE Hydrogen evolution 15, 315–340.
PDP Potentiodynamic polarisation 22 G. Gece, Corros. Sci., 2011, 53, 3873–3898.
PSP Potentiostatic polarisation 23 N. Patni, S. Agarwal and P. Shah, Chinese Journal of
Rp Polarisation of resistance
Engineering, 2013, 2013, 784186.
SC-CO2 Supercritical carbon dioxide
24 B. E. A. Rani and B. B. J. Basu, Int. J. Corros., 2012, 2012,
SFE Supercritical uid extraction
380217.
WL Weight loss
25 G. Khan, K. M. S. Newaz, W. J. Basirun, H. B. M. Ali,
h Inhibition effectiveness
F. L. Faraj and G. M. Khan, Int. J. Electrochem. Sci., 2015,
10, 6120–6134.
26 A. Peter, I. B. Obot and S. K. Sharma, Int. J. Ind. Chem., 2015,
6, 153–164.
Acknowledgements 27 K. S. Hari, S. Karthikeyan, P. Jeeva and G. Sundaramali,
The authors would like to acknowledge the nancial support for International Journal of Recent Scientic Research, 2012, 3,
this project received from the Slovenian Research Agency (grant 61–67.
numbers: BI-HR/16-17-045 and P2-0032, and P2-0046). 28 M. Sangeetha, S. Rajendran, J. Sathiyabama and
K. Krishnaveni, Port. Electrochim. Acta, 2013, 31, 41–52.
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Green corrosion inhibitors for aluminium and its

Klodian Xhanari, ab Matjaž Finšgar, *a Maša Knez Hrnčič,a Uroš Maver, c

Željko Kneza and Bujar Seitib

review article have been tested as corrosion inhibitors for

RSC Advances Review

This journal is © The Royal Society of Chemistry 2017

RSC Adv., 2017, 7, 27299–27330 | 27301

RSC Advances Review

using such an approach and the evaluation of the future

WL aer 15–21 days immersion

WL aer 3–24 days immersion

WL aer 3–24 days immersion

Phytocompounds and herbal-based extracts have garnered

screening plant extracts for their inhibitive properties.30

2.1 Extraction methods used to obtain plant extracts

puried compounds have appeared over the past decades. The

decision on selecting the extraction method to prole the target

the extraction technique has an impact on the rate, yield, and

purity and is inuenced by the niche of the compound of

interest and the degree of purity required.

feed ratio, number of repeated extractions of the sample, as

virens bark extract in methanol

virens bark extract in methanol

virens seed extract in methanol

virens leaf extract in methanol

well as the choice of extraction solvents, are the main parame-

ters controlling extraction kinetics. Solubility is highly aﬀected

temperature, the viscosity and surface tension of solvents

Conventional liquid–liquid and solid–liquid extraction

techniques are still commonplace due to their simplicity, eﬃ-

tional solvents such as alcohols (methanol, ethanol, iso-

propanol), acetone, diethyl ether, and ethyl acetate, oen mixed

separation, and detection, and the identication are of both

environmental and economic concern. Additional purication

Review RSC Advances

Inhibitor Test methods and

Material Inhibitor concentration Medium h (%) conditions Reference

27304 | RSC Adv., 2017, 7, 27299–27330

This journal is © The Royal Society of Chemistry 2017

Inhibitor Test methods and

This journal is © The Royal Society of Chemistry 2017

RSC Adv., 2017, 7, 27299–27330 | 27305

RSC Advances Review

Review RSC Advances

RSC Advances Review

Review RSC Advances

RSC Advances Review

This journal is © The Royal Society of Chemistry 2017

RSC Adv., 2017, 7, 27299–27330 | 27311

RSC Advances Review

leaf and seed extracts, prepared by using the reux in NaOH

WL aer 120 min and PSP at 25–50 C leaf extract.

increasing temperature. Nnanna et al.87 investigated the extracts

of Euphorbia hirta and Dialum guineense leaves in NaOH as

Euphorbia hirta were reported to be triterpenoids, alkaloids,