You are on page 1of 7

African Journal of Pure and Applied Chemistry Vol. 5(8), pp.

265-271, August 2011


Available online at http://www.academicjournals.org/AJPAC
ISSN 1996 - 0840 2011 Academic Journals

Full Length Research Paper

Comparative study of corrosion inhibition of aluminium


alloy of type AA3003 in acidic and alkaline media by
Euphorbia hirta extract
.

L. A. Nnanna1*, I. U. Anozie1, A. G. I. Avoaja2, C. S. Akoma1 and E. P. Eti3


1

Department of Physics/Electronics, Abia State Polytechnic, P. M. B. 7166, Aba, Abia State, Nigeria.
2
Department of Chemistry, Abia State Polytechnic, P. M. B. 7166, Aba, Abia State, Nigeria.
3
Mechanical Engineering Department, Abia State Polytechnic, P. M. B. 7166, Aba, Abia State, Nigeria.
Accepted 5 July, 2011

The inhibitive effect of leaf extract of Euphorbia hirta on aluminium corrosion in HCl and NaOH
solutions were studied using gravimetric technique at 30 and 60C. Results obtained showed that the
leaf extract functioned as effective and excellent inhibitors in the acidic and alkaline media. Also, the
leaf extract suppressed the corrosion reaction in both media. Inhibition efficiency of the extract was
found to vary with concentration, temperature and exposure time. The leaf extracts of E. hirta
demonstrated better inhibition efficiency in the acidic medium than in the alkaline medium. The
adsorption characteristics of the leaf extract were best described by the Langmuir isotherm. Values of
the free energy of adsorption Gads were determined from the isotherm parameters and they showed that
the adsorption was spontaneous. The molecular interaction parameter () between the molecular
species of the inhibitors and the metal surface they cover was also determined. The heat of adsorption
(Qads) and apparent activation energy (Ea) were estimated from the temperature dependence of
inhibition efficiency. Physical adsorption mechanism is proposed from the obtained thermodynamic
parameters.
Key words: Adsorption isotherm, corrosion inhibition, aluminium, leaf extracts, thermodynamics.
INTRODUCTION
The study of the corrosion behaviour of aluminium in
different aggressive environments has continued to
attract considerable attention because of the many
applications of the metal. Aluminium relies on the
formation of a compact, adherent passive oxide film for
its corrosion immunity in various environments. This
surface film is amphoteric and dissolves substantially
when the metal is exposed to high concentrations of
acids or bases (Hurlen et al., 1984; Oguzie, 2007). Bared
metal surface sites become exposed to the corrodent
after the breakdown of the oxide film, leading to a
sequence electrochemical reaction as the metal
dissolves. Corrosion is accompanied by many conjugate
cathodic processes in which hydrogen gas evolution is

*Corresponding author. E-mail: lebennanna@yahoo.com. Tel:


+2348037055932.

often predominant in strong acid and alkaline solutions


(Gomma, 1998; Obot et al., 2009). Hydrochloric acid
solutions are normally used for pickling of aluminium and
for its chemical and electrochemical etching, processes
that normally lead to substantial loss of the metal to
corrosion (Oguzie, 2007; Nnanna et al., 2010). In efforts
to mitigate aluminium corrosion, the main strategy is to
effectively isolate the metal from corrosive agents. This
can be achieved by the use of corrosion inhibitors.
Inorganic substances such as phosphates, chromates,
dichromate and arsenates have been found effective as
inhibitors of metal corrosion, but a major disadvantage is
their toxicity and as such their use has come under
severe criticism (Oguzie, 2007). Among the alternative
corrosion inhibitors, organic substances containing polar
functions with nitrogen, oxygen and/or sulphur atoms in a
conjugated system have been reported to exhibit good
inhibiting properties(Oguzie, 2007; Nnanna et al., 2010;
Abdallah, 2004; Maayta et al., 2004; Oguzie, 2005;

266

Afr. J. Pure Appl. Chem.

Oguzie, 2006; Popova et al., 2004; Rosliza et al., 2008;


Umoren et al., 2008). Corrosion inhibition occurs via
adsorption of their molecules on the corroding metal
surface and efficiency of inhibition depends on the
mechanical, structural and chemical characteristics of the
adsorption layers formed under particular conditions.
Some investigations have in recent time been made
into the corrosion inhibiting properties of natural products
of plant origin, which have been found to generally exhibit
good inhibition efficiencies (Abiola et al., 2007; El-Etre,
2006; Eddy et al., 2008; Ebenso et al., 2009; Oguzie,
2008; El-Etre, 2003; Zucchi et al., 1985; Nnanna et al.,
2010). This area of research is of much importance
because in addition to being inexpensive, readily
available and renewable sources of materials, plant
products are environmentally friendly and ecologically
acceptable. Plant products are organic in nature and
some of the constituents including tannins, alkaloids,
saponins, essential oils, flavones, organic and amino
acids are known to exhibit inhibiting action (Okwu et al.,
2003; Olabiyi et al., 2008; El-Sayed, 1997; Chetouani et
al., 2005; Umoren et al., 2005; Bouklah et al., 2006). As a
contribution to the current interest on environmentally
friendly, green, corrosion inhibitors, the present study
investigates the inhibiting effect of leaf extract of E. hirta
on aluminium corrosion in acidic and alkaline solutions
using the gravimetric technique. The plants, which are
popularly called asthma weed (E. hirta), belongs to the
family of Euphorbiaceae (Spurge family) and are known
to grow in Sub-Sahara Africa and Asia (Okwu et al.,
2003; Olabiyi et al., 2008). The effect of temperature on
the inhibition efficiency has also been studied. Kinetic
and activation parameters that govern metal corrosion
have been evaluated.
MATERIALS AND METHODS
Aluminium sheets of type AA3003 having weight percentage
composition of : Si-0.362%, Fe-0.54%, Cu-0.077%, Mn-1.219%, Ti0.026%, Pb-0.063%, Zn-0.004% and the remainder being Al were
used in this study. The test coupons were prepared having a
dimension of 2 x 2 cm and thickness 1.32 mm, were polished
mechanically with Sic emery papers of grade nos 220, 400 and 600
degreased with ethanol and acetone having been washed with
distilled water. The test coupons were air dried before being
immersed in the acidic and alkaline media. All chemicals and
reagents used were of analytical grade. The blank corrodents were,
respectively, 0.5 M HCl and 0.25 M NaOH solutions.
Stock solution of the leaf extract was prepared by boiling
weighed amount of the dried and ground leaves of E. hirta for 3 h in
the 0.5 M HCl and 0.25 M NaOH, respectively. The solutions were
cooled and then filtered and stored. From the respective stock
solutions, inhibitor test solutions were prepared in the concentration
range 0.1 to 0.3 g/L. The cleaned and dried test coupons were
weighed before in the respective test solution using electronic
balance of series JA 1003A with accuracy of 0.005. Total
immersion time interval was 5 h. Tests were conducted with
different concentration of inhibitors, after which, the specimen were
carefully washed in absolute ethanol having used nitric acid to
quench further corrosion from taking place, and then reweighed.
Triplicate experiments were performed in each case and the

mean values reported.

RESULTS
Gravimetric technique and corrosion rates
The weight loss of the aluminium alloy in 0.5 M HCl and
0.25 M NaOH with and without the various concentrations
of leaf extract was determined after 5 h of immersion at
30C and the corrosion rate values were evaluated using
Equation 1.
(1)
The corrosion rate values were plotted against the
concentration values of the leaf extract (Figure 1). From
the bar chart, the extract showed higher corrosion rate
values in the alkaline medium than in the acidic medium.
This depicts a better corrosion inhibition in the acidic
environment than in the alkaline medium.
Inhibition efficiency
The characterization of the corrosion rate of aluminium
alloy in the inhibitor/corrodent solution was carried out by
an assessment of the inhibition efficiency (I %) using
Equation 2 below.

(2)
The bar chart representing the inhibition efficiency with
respect to the concentration of inhibitor for E. hirta in the
acidic and alkaline environments was plotted (Figure 2).
In all the concentrations, considering the approximate
rise in values, the acidic media exhibited better inhibition
efficiency than the alkaline with as much as about 10%
efficiency.
DISCUSSION
In accounting for the observed protective effect, it should
be noted that the extract comprise mixture of organic and
resinous matter, some of which have good corrosion
inhibiting abilities. The complex chemical compositions
make it rather difficult to assign the inhibiting action to a
particular constituent or group of constituents.
Nevertheless, the net adsorption of the extract organic
matter on the metal surface creates a barrier to charge
and mass transfer, thus protecting the alloy surface from
corrodent attack. The degree of protection varies for
different extracts, with notable sensitivity to the inhibitor
concentration. Tables 1, 2 and 3 are a listing of the
phytochemical components of the extract, which include
tannins, alkaloids, and essential oil. The inhibitive
properties of tannins have been attributed to the reaction

Nnanna et al.

267

Figure 1. Corrosion rates of various concentrations of E. hirta leaf extract in 0.5 m HCI and 0.25 m NaOH
on aluminium alloy AA3003.

Figure 2. Inhibition efficiencies of various concentrations of E. hirta leaf extract in 0.5 m HCI and 0.25 m
NaOH on aluminium alloy AA3003.

of the polyphenolic fraction of the tannins moieties, which


ensures effective protection of the metal surfaces. The
triterpeniod and other constituents also posses functional
groups which are capable of chelating with aluminium
ions and thus facilitate strong coordination on the alloy
surface (Umoren, 2009). Having ascertained the
effectiveness of these leaf materials in the present study,
subsequent studies to enable precise interpretation of the
nature and composition of the absorbed inhibitor layer will

be achieved from in depth studies of the corrosion


morphology and characterization of the active materials
in the absorbed layer is envisaged.
Langmuir adsorption isotherms
Further elucidation of adsorption mechanism from the
experimental data requires estimation of the adsorption

268

Afr. J. Pure Appl. Chem.

Table 1. Constituents of E. Hirta leaf.

S. no.
1
2
3
4
5
6
7
8

Constituents of E. hirta leaf


Triterpenoids
Alkaloids
Tannins
Glycosides
Sterols
Essential oil
Flavones
Phenols

Table 2. Calculated values of inhibition efficiency (I%), apparent activation energy (Ea) and heat of adsorption (Qads) of
Euphorbia hirta extract on AA3003 aluminium alloy in 0.25M NaOH at different temperatures.

Extract concentration
Blank
0.10
0.15
0.20
0.25
0.30

Inhibition efficiency (I %)
at 30C
at 60C
85.22
80.79
81.81
85.35
85.91

Ea (kJmol-1)

Qads (kJmol-1)

4.61
68.77
49.69
61.70
59.76
57.73

-1.36
-1.04
-1.28
-1.18
-1.13

83.03
78.77
79.41
83.48
84.18

Table 3. Calculated values of inhibition efficiency (I%), apparent activation energy (Ea) and heat of adsorption (Qads) of E.
hirta extract on AA3003 aluminium alloy in 0.5 M HCl at different temperatures.

Extract concentration
Blank
0.10
0.15
0.20
0.25
0.30

Inhibition efficiency (I%)


at 30C
at 60C
87.8
88.2
86.4
85.8
85.1

modes of the inhibiting species (whether molecular or


ionic). The predominant adsorption mode will be
dependent on factors such as the extract composition,
chemical changes to the extract and the nature of the
surface charge on metal. A negative surface charge will
favour the adsorption of cations whereas anion
adsorption is favoured by a positive surface charge. The
ability of Cl and OH ions in hydrochloric acid and
sodium hydroxide to be strongly adsorbed on the metal
surface and hence facilitate physical adsorption of
inhibitor cations is an important consideration. The plot of
the ratio of concentration to surface coverage (C/)
against concentration (g/L) displayed a straight line for
the tested inhibitor in the acidic and alkaline media
(Figures 3 and 4). The linear plots, with high correlation

80.1
83.6
82.2
83.0
82.4

Ea(kJmol-1)

Qads(kJmol-1)

0.62
45.30
18.43
9.15
37.83
35.05

-4.83
-3.18
-2.65
-1.77
-1.65

coefficient and slope of about unity in both media, clearly


reveal that the surface adsorption process of E. hirta on
the aluminium alloy surface obey the Langmuir
adsorption isotherm. Therefore, one can infer that
adsorption occurred through physisorption mechanism.
Temkin isotherm
Temkin isotherm assumes a uniform distribution of
adsorption energy which decreases linearly with increase
of the value of the surface coverage () (Figure 5). This
model is often used for the description of chemisorptions
(Praus et al., 2008). In the theory, and C are related
through (Oguzie, 2008).

Nnanna et al.

269

Figure 3. Langmuir isotherm for E. hirta adsorption on AA3003 aluminium alloy in 0.5 m HCI.

Figure 4. Langmuir isotherm for E. hirta adsorption on AA3003 aluminium alloy in 0.25 M NaOH.

(3)

Where C is the concentration, K is the equilibrium


constant and f is a coefficient of inhomogeneity
connected with the range of inhomogeneity C by,

Which implies that?


(5)
(4)

The values obtained by the linear plot of correlation

270

Afr. J. Pure Appl. Chem.

Figure 5. Temkin isotherm for E. hirta adsorption on AA3003 aluminium.

coefficient for the leaf extract in the acidic medium is far


from the assumption for chemisorption, but that of the
alkaline medium showed a good factor of near unity.
This is an assumption that the inhibition is of chemical
adsorption. With the deductions from the Langmuir and
Temkin adsorption isotherms, the acidic medium showed
pure physical adsorption mechanism while the alkaline
medium showed a mixed reaction.
Effect of temperature
Two main types of interaction often describe adsorption
of organic inhibitors on a corroding system viz: chemical
adsorption and physical adsorption. It has been
suggested (Oguzie et al., 2005; Ebenso, 2003; Popova et
al., 2003) that physisorbed molecules are attached to the
metal at the cathodes and essentially retard metal
dissolution by stifling the cathodic reaction whereas
chemisorbed molecules protect anodic areas and reduce
the inherent reactivity of the metal at the sites where they
are attached. The apparent activation energies (Ea) for
the corrosion process in absence and presence of
inhibitor were evaluated from Arrhenius equation.

(6)

(7)
Whereas estimates of the heats of adsorption (Qads) were

obtained from the trend of surface coverage with


temperature as follows (21):

(8)
1 and 2 are the corrosion rates in respective
temperatures T1 and T2, respectively while 1 and 2 are
the degrees of surface coverage at temperature T1 and
T2 and R is the molar gas constant.

(9)
The standard free energy of adsorption, Gads, which
can characterize the interaction of adsorption molecules
and metal surface, was calculated using Equation 9. The
negative values of Gads ensure the spontaneity of
adsorption process and stability of the adsorbed layer on
the aluminium surface. Generally, the values of Gads
around -20 kJ/mol or less negative are consistent with
physisorption, while those around -40 kJ/mol or more
negative involve chemisorptions (Ebenso, 2003; Popova
et al., 2003; Oguzie, 2008). Analysis of the temperature
dependence of inhibition efficiency as well as comparison
of corrosion activation energies in the presence of
inhibitor gives some insight into the possible mechanism
of inhibitor adsorption. A decrease in inhibition efficiency
with rise in temperature, with analogous increase in
corrosion activation energy in the presence of inhibitor
compared to its absence, is frequently interpreted as

Nnanna et al.

being suggestive of formation of an adsorption film of


physical (electrostatic) nature. The effect, corresponding
to an increase in inhibition efficiency with rise in
temperature and lower activation energy in the presence
of inhibitor, suggests a chemisorption mechanism
(Oguzie, 2007; Nnanna et al., 2010; Eddy et al., 2008).
From the foregoing, the trend for the extract of E. hirta
leaf suggests a predominant effect physisorption of
inhibiting species in acidic environment. This is not the
same in the alkaline medium, where a mix reaction was
obtained.
Conclusion
The extract from the studied leaf material was found to be
effective green inhibitor of aluminium alloys corrosion in
both acidic and alkaline environments of 0.5 M HCl and
0.25 M NaOH, respectively. The corrosion process in
acidic medium was inhibited by adsorption of the extract
organic matter on the aluminium alloys surface and the
blocking of active sites. Analysis of all the results yielded
some interesting observations. The extract inhibited the
corrosion of aluminium alloys in acidic media by means of
hindering both cathodic and anodic electrode processes,
because the greater the number of bonds in the extracts,
the higher the inhibition efficiency. It is found that the
inhibitive action was basically controlled by temperature,
exposure time and concentration of the inhibitor. The
inhibitor was found to obey Langmuir adsorption
isotherm, in the acidic and alkaline medium, which is
based on physisorption phenomenon, and also confirmed
Temkin adsorption isotherm in the alkaline medium.
REFERENCES
Abdallah M (2004). Guar Gum as Corrosion Inhibitor for Carbon Steel in
Sulphuric Acid Solution. Port. Electrochim. Acta., 22: 161-175.
Abiola O, Okafor N, Ebenso E, Nwinuka N (2007). Eco-Friendly
Corrosion Inhibitors: Inhibitive Action of Delonis regia Extract for the
Corrosion of Aluminium in Acidic Medium. Anti-Corros. Methods
Mater., 54: 219-224.
Bouklah M, Hammouti B, Lagrenee M, Bentiss F (2006).
Thermodynamic Properties of 2,5-bis(4-methoxyphenyl)-1,3,4oxadiazole as a Corrosion Inhibition for Mild Steel in Normal Sulfuric
Acid Medium. Corros. Sci., 48: 2831.
Chetouani A, Hammouti B, Benhadda T, Daoudi M (2005). Inhibitive
action of bipyrazolic type organic compounds towards corrosion of
pure iron in acidic media. Appl. Surf. Sci., 249: 375.
Ebenso E (2003). Synergistic Effect of Halide Ion on the Corrosion
Inhibition of Aluminium in H2SO4 using 2-acetylphenothiazine. Mater.
Chem. Phys., 79: 58-70.
Ebenso E, Eddy N, Odiongeyi A (2009). Corrosion Inhibition and
Adsorption Properties of Methocarbamol on Mild Steel in Acidic
Medium. Port. Electrochim. Acta., 27(1): 13-22.
Eddy N, Ebenso E (2008). Corrosion Inhibitive Properties and
Adsorption Behaviour of Ethanol Extract of Piper guinensis as a
green Corrosion Inhibitor for mild Steel in H2SO4. Afri. J. Pure Appl.
Chem., 2(6): 046-054.
El-Etre A (2003). Inhibition of Aluminium Corrosion using Opuntia
extract. Corros. Sci., 45: 2485.

271

El-Etre A (2006). Khillah Extracts as Inhibitors for Acid Corrosion of SX


316 steel. Appl. Surface Sci., 252: 8521-8525.
El-Sayed A (1997). Phenothiazine as Inhibitor of the Corrosion of
Cadmium in Acidic Solutions J. Appl. Electrochem., 27: 193-200.
Gomma G (1998). Corrosion of low-carbon steel in sulphuric acid
solution in the presence of pyrazole-halide mixture. Mater. Chem.
Phys., 55 (3): 241-247.
Hurlen T, Lian H, Odegard O, Valand T (1984). Corrosion and passive
behaviour of aluminium in weakly acid solution. Electrochim. Acta.,
29: 579-585.
Maayta A and Al- Rawashdeh N (2004). Inhibition of Acidic Corrosion of
Pure Aluminium by Some Organic Compounds. Corros. Sci., 46: 112119.
Nnanna L, Onwuagba B, Mejeha I, Okeoma K (2010). Inhibition effect of
Some Plant Extracts on the Acid Corrosion of Aluminium Alloy. Afri.
J. Pure Appl. Chem., 4(1): 011-016.
Nnanna L, Onwuagba B, Mejeha I, Okeoma K (2010). The Effect of
Plant Extracts on Corrosion and Adsorption Mechanism process of
Aluminium in alkaline Solution. J. Corr. Sci. Engr., (In press).
Obot I. N Obi-Egbedi (2009). Adsorption Characteristics and Corrosion
Inhibitive Properties of Clotrimazole for Aluminium Corrosion in
Hydrochloric Acid. Int. J. Electrochem. Sci., 4(6): 1277-1288.
Oguzie E (2005). Corrosion inhibition of mild steel in hydrochloric acid
solution by methylene blue dye. Mater. Lett., 59: 1076-1079.
Oguzie E, Onuoha G, Onuchukwu A (2005). Inhibitory Mechanism of
Mild Steel Corrosion in 2 M Sulphuric Acid Solution by Methylene
Blue Dye. Mater. Chem. Phys., 89: 305-311.
Oguzie E (2006). Studies on the inhibition effect of Occinum viridis
extracts on acid corrosion of mild steel. Mater. Chem. Phys., 99: 2-3,
441-446.
Oguzie E (2007). Corrosion inhibition of Aluminium in acidic and
alkaline media Sansevieria trifaciata extract. Corros. Sci., 49: 15271539.
Oguzie E (2008). Corrosion Inhibitive Effect and Adsorption Behaviour
of Hibiscus sabdariffa Extract on Mild Steel in Acidic Media. Port.
Electrochim. Acta., 26: 303-314.
Oguzie E (2008). Evaluation of the inhibitive effect of some plant
extracts on the acid corrosion of mild steel. Corros. Sci., 50: 29932998.
Okwu D, Ekeke O (2003). Inhibition Effect of Some Plant Extracts on
the Acid Corrosion of Aluminium in H2SO4. Global J. Pure Appl. Sci.,
9(2): 236.
Olabiyi T, Oyedunmade E, Ibikunle G, Ojo O, Adesina G, Ogunniran K
(2008). Chemical Composition and Bio-Nematicidal Potential of some
Weed Extracts on Meloidogyne incognita under Laboratory
Conditions. Medwell J. Plant Sci., 1(2): 30-35.
Popova A, Sokolova E, Raicheva S, Christov M (2003). AC and DC
Study of the Temperature Effect on Mild Steel Corrosion in Acid
Media in the Presence of Benzimidazole Derivatives. Corros. Sci., 45:
33.
Popova A, Christov M, Raicheva S, Sokolova E (2004). Adsorption and
Inhibitive Properties of Benzimidazole Derivatives in Acid Mild Steel
Corrosion. Corros. Sci., 46: 1333-1350.
Praus P, Turicova M, Valaskova M (2008). Study of Silver Adsorption
on Montmorillonite. J. Braz. Chem. Soc., 19(3): 549-556.
Rosliza R, Wan Nik WB, Senin HB (2008). The effect of inhibitor on the
corrosion of aluminum alloys in acidic solutions. Mater. Chem. Phys.,
107: 281-288.
Umoren S, Obot I, Ebenso E, Okafor P (2008). Eco-friendly Inhibitors
from Natural Occuring Exudate Gum for Aluminium Inhibition in
Acidic Medium. Port. Electrochim. Acta., 26: 267-282.
Umoren S (2009). Synergistic Influence of Gum Arabic and Iodide Ion
on the Corrosion Inhibition of Aluminium in Alkaline Medium. Port.
Electrochim. Acta., 27: 565-577.
Umoren S, Obot I, Igwe I (2005). Synergistic Inhibition Between
Polyvinylpyrollidone and Iodide Ions on Corrosion of Aluminium in
HCl. The Open Corros., J., 2: 1-7.
ZucchiF OI (1985). Plant Extracts as Corrosion Inhibitors of mild Steel in
HCl Solution. Surf. Tech., 24: 391.