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Corrosion Science
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a r t i c l e
i n f o
Article history:
Received 2 January 2007
Accepted 11 February 2008
Available online 7 March 2008
Keywords:
I. Inhibition efciency
P. Plant extracts
P. Phosphoric acid
T. Tannins
a b s t r a c t
The inhibitive action of mangrove tannins, extracted from mangrove barks and phosphoric acid, on prerusted steel in a 3.5% NaCl solution was evaluated and the inhibitive efciency was compared with that of
mimosa tannins. From the electrochemical studies, the inhibition efciency of solutions containing
3.0 g L1 tannins depended upon the concentration of phosphoric acid added and the pH of the solution.
At pH 0.5 and pH 2.0, inhibition was greatest with mangrove and mimosa tannins alone, while at pH 5.5
the addition of phosphoric acid alone gave the highest inhibition.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
The known hazardous effects of most synthetic corrosion inhibitors are reasons to search for safer and environmentally friendly
natural products. Plant extracts, for example, contain diverse compounds that often can be extracted at low cost. Naturally occurring
substances such as vanillin [1], Opuntia extracts [2], lawsonia extract [3], natural honey [4] and extracts of chamomile, halfabar,
black cumin and kidney bean [5] are plant compounds recently
evaluated as corrosion inhibitors for different metals in various
environments while other studies of plant extracts included the
various tannin extracts [613].
Condensed tannins are a group of phenolic polymers which are
widely distributed in the plant kingdom particularly with woody
growth habit. These compounds consist of avan-3-ol units linked
together through C4C6 or C4C8 bonds. These polyavonoids
present phloroglucinol or resorsinol A-rings and catechol or pyrogallol B-rings (Fig. 1). Mangrove (Rhizophora apiculata) tannins
consist primarily of condensed tannins or proanthocyanidins. HPLC
analyses of condensed tannins from the mangrove following depolymerisation in phloroglucinol and ethanol identied four avonoid monomers namely catechin, epicatechin, epigallocatechin
and epicatechin gallate [14]. Mimosa tannins are also condensed
tannins and according to a comparative C13 NMR study of poly-
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5
6'
HO 7 8
1
9 O
5 10 4
OH
OH
4'
OH
mangrove tannins and phosphoric acid are conducted and compared with that of mimosa tannins.
2. Experimental details
2.1. Tannin isolation
Mangrove bark samples from 15 year old trees were obtained
from the Matang Forest, Malaysia. The barks were dried and grinded to 250 mesh followed by further drying until a constant
weight was obtained. Tannins from mangrove barks were extracted using 70% acetone as described elsewhere [14]. Commercial mimosa tannin powder from bark extracts were obtained
from SILVACHIMICA, Italy and was used without further
purication.
B 117 [22], were immersed in solutions containing 15% (w/v) phosphoric acid, 0.5% (w/v) mangrove tannins and 15% (w/v) phosphoric acid and 0.5% (w/v) mimosa tannins and 15% (w/v) phosphoric
acid at pH 4.0 and for 24 h. The surface morphology was evaluated
by SEM analysis with a SEM S-2500 Hitachi Thermo NORAN
equipped with an energy-dispersive X-ray spectrometer. A Goniometre C diffractometer, incorporating a cobalt radiation
Table 1
Percentage inhibition of 3.0 g L1 mangrove tannins and mimosa tannins with the
addition of 15%, 30% and 50% phosphoric acid in 3.5% NaCl solution
Solution composition
Mangrove tannins
Mangrove tannins + 15% H3PO4
Mangrove tannins + 30% H3PO4
Mangrove tannins + 50% H3PO4
Mimosa tannins
Mimosa tannins + 15% H3PO4
Mimosa tannins + 30% H3PO4
Mimosa tannins + 50% H3PO4
15% H3PO4
30% H3PO4
50% H3PO4
*
pH 0.5
pH 2.0
pH 5.5
77.3
79.0
56.4
59.2
77.4
64.3
50.5
58.5
0.0
57.6
30.7
24.5
26.8
24.1
12.7
0.0
0.0
18.2
38.7
33.1
73.1
54.4
0.0
10.4
60.3
20.4
66.9
90.1
52.6
200
Rp /ohms.cm 2
The standard solution consisted of 3.5% (w/v) NaCl and the test
solutions contained 3.0 g L1 mangrove tannins, 3.0 g L1 mimosa
tannins and 15% (w/v), 30% (w/v) and 50% (w/v) phosphoric acid.
In addition, 15% (w/v), 30% (w/v) and 50% (w/v) phosphoric acid
were added to the 3 g L1 tannin solutions. All solutions were prepared in 3.5% (w/v) NaCl solution. The pH of the solution was adjusted to pH 0.5, 2.0 and 5.5 using 2 M H2SO4 and 3 M NaOH
solutions. All chemicals were AR grade.
NaCl
150
100
50
10
15
20
t /hr
Fig. 3. Variation of polarisation resistance, Rp with time of immersion containing
15%, 30% and 50% phosphoric acid in 3.5% NaCl solution at pH 2.0.
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Fig. 5. Potentiodynamic curves of pre-rusted steel containing 15%, 30%, and 50%
phosphoric acid in 3.5% NaCl solution at pH 5.5.
IE%
Rp Rp0
100
Rp
where Rp 0 and Rp are the uninhibited and inhibited polarisation values, respectively, assuming that bA and bc are unmodied by inhibition, performed at pH 0.5, 2.0 and 5.5 on pre-rusted steels in a 3.5%
NaCl solution. The inhibition efciency of mangrove and mimosa
tannins on pre-rusted steels was found to decrease as the pH increased, a result similar to the trend previously observed for the
inhibition performance of tannins on clean steels [23]. Conversely,
the inhibition efciency increased with increasing pH when phosphoric acid was used alone.
At pH 0.5, an inhibition of almost 80% was achieved when mangrove and mimosa tannins were used. The corrosion protection
provided by both tannins however did not increase with the addition of 15% phosphoric acid. Inhibition efciency was further reduced with increasing phosphoric acid concentrations. From the
potentiodynamic curves of the pre-rusted steels, modications in
the anodic and cathodic curves were observed and the Ecorr also
shifted to more positive values with either the addition of mangrove tannins alone or the addition of mangrove tannins and phosphoric acid (Fig. 2).
At pH 2.0, the mangrove tannins provided a better protection
(57% inhibition) than the mimosa tannins (24% inhibition). The
addition of 15%, 30% and 50% phosphoric acid to the mangrove tannins reduced the inhibition efciency by almost 50%. The addition
of 15% phosphoric acid to mimosa tannin also reduced the inhibition efciency further. The increase in phosphoric acid concentrations to 30% and 50% resulted in essentially no inhibition. This
change was not a surprise since the Rp values decreased with increases in the concentration of phosphoric acid and may have
accelerated corrosion after 18 h of immersion when 30% and 50%
phosphoric acid were used (Fig. 3).
When the inhibition studies were conducted at pH 5.5, which is
the natural pH of a 3.5% NaCl solution, Ecorr initially became more
negative in the presence of mangrove tannins. With the addition
of 15%, 30% and 50% phosphoric acid to the mangrove tannins the
Ecorr gradually shifted to more positive values (Fig. 4). The addition
of both mangrove tannins and phosphoric acid had the effect of
lowering both the cathodic and anodic curves. The addition of
30% phosphoric acid had a greater effect on the anodic reaction than
did the addition of 50% phosphoric acid. This observation is consistent with the results obtained from the potentiodynamic curves of
steels containing phosphoric acid alone (Fig. 5). Anodic shifts were
seen evident for all phosphoric acid concentrations, with the addition of 30% phosphoric acid resulting in the greatest anodic shift to
lower density current and consequently the greatest inhibition. The
use of phosphoric acid alone is favoured at pH 5.5, since the use of
30% phosphoric acid resulted in 90% inhibition (Table 1). Similarly,
the addition of 30% phosphoric acid to mimosa tannin increased the
Fig. 6. XRD pattern of bare rust surface immersed in 0.5% (w/v) mangrove tannins and 15% (w/v) phosphoric acid solutions: L lepidocrocite, M magnetite, V vivianite.
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4. Discussion
In NaCl solution, ferrous chloride and sodium hydroxide are initially deposited at the anode and cathode, respectively. The ferrous
chloride formed often is transformed into ferrous hydroxide, which
in turn combines with oxygen to form rust according to the following reactions [25]:
Fig. 7. SEM micrographs of pre-rusted plates containing: (a) 15% H3PO4; (b) 15%
H3PO4 and 0.5% mangrove tannins and (c) 15% H3PO4 and 0.5% mimosa tannins.
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of ferric phosphates was found to be dependent on the aggressiveness of the solution used [26]. It has also been shown that different
phases of phosphates are formed depending on the surface conditions, exposure time and concentrations of phosphoric acid. Solutions containing 15 and 33% phosphoric acid seem to lead to the
formation of vivianite on rust layers rich in lepidocrocite between
1 and 10 months exposure at natural atmosphere and after 24
months when the main components were lepidocrocite and goethite, precipitation of phosphates was not observed [20].
Based on the data of the surface analysis of the deposits via XRD
and SEM, the phosphoric acid initially dissolves the rust and the
following phosphate precipitation reaction is proposed:
H3 PO4 FeOOH ! FePO4 2H2 O
and
2H3 PO4 3Fe3 O4 5H2 O ! Fe3 PO4 2 8H2 O 3Fe2 O3
3Fe2 O3 3H2 O ! 6FeOOH
2H3 PO4 3Fe3 O4 8H2 O ! Fe3 PO4 2 8H2 Ovivianite 6FeOOH
The joint effect of both the tannins and the phosphoric acid was
unfavourable at this pH due to the competing reactions between
mangrove tannins and the phosphoric acid with the pre-rusted
steel. Gust [10] and Nasrazadani [21] reported that the reaction
kinetics of tannins on the various iron phases was slower to that
of phosphoric acid and consequently more phosphates are formed
as compared to ferrictannates. It is proposed that the phosphoric
acid initially dissolves the rust and ferrictannates are formed
according the mechanism proposed in our previous work [23]. In
addition to the phosphates formation as described above, the reducing ability of mangrove tannins to reduce Fe3+ to Fe2+ ions [14] facilitates the precipitation of phosphates. However, the inhibition
could not exceed that of phosphoric acid alone.
5. Conclusion
The inhibition efciency of pre-rusted steel in 3.5% NaCl solution containing 3 g L1 mangrove tannins depended on the concen-