See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/271973609

The Use of Mixture of Piper Betle and Green Tea as a Green Corrosion Inhibitor
for API X-52 Steel in Aerated 3.5 % NaCl Solution at Various Rotation Rates

Article · November 2011

DOI: 10.4028/www.scientific.net/AMR.383-390.5418

CITATIONS READS

5 118

3 authors:

Andi Rustandi Johny Wahyuadi

University of Indonesia University of Indonesia
31 PUBLICATIONS   39 CITATIONS    88 PUBLICATIONS   164 CITATIONS   

SEE PROFILE SEE PROFILE

Bambang Suharno
Faculty of Engineering University of Indonesia
73 PUBLICATIONS   108 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Tin Slag Utilization as Concrete Raw Materials: Corrosion and Mechanical Behaviour View project

Thin Wall Ductile Iron Stage 1 View project

All content following this page was uploaded by Johny Wahyuadi on 30 March 2016.

The user has requested enhancement of the downloaded file.

Advanced Materials Research Vols. 383-390 (2012) pp 5418-5425
Online available since 2011/Nov/22 at www.scientific.net
© (2012) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.383-390.5418

The Use of Mixture of Piper Betle and Green Tea as a Green Corrosion
Inhibitor for API X-52 Steel in Aerated 3.5 % NaCl Solution at Various
Rotation Rates
Andi Rustandi1, a, Johny W. Soedarsono2, b, Bambang Suharno3, c
1, 2, 3
Faculty of Engineering, Universitas Indonesia, Depok 16424
a
rustandia@gmail.com, b jwsono@metal.ui.ac.id, c suharno@metal.ui.ac.id

Keywords: corrosion rate of steel, green corrosion inhibitor, turbulent flow induced

Abstract. Flow induced corrosion due to the presence of turbulent flow often occurs which causes
severe internal thinning and promotes premature leakage. In practice, the common method for
controlling such internal high corrosion rate is chemical injection using corrosion inhibitor such as
amine based which utilizing adsorption or film forming mechanism. Unfortunately, the protection
performance of such inhibitor might be less effective due to turbulent flow induced. The aim of this
work is to study the use of mixture of piper betle and green tea as an alternative of green corrosion
inhibitor (eco-friendly) to reduce the corrosion rate of API X-52 steel in aerated 3.5 % NaCl
solution in turbulent flow condition whether high inhibitor efficiency can be achieved. The method
of corrosion rate measurements was conducted using electrochemical polarization equipped with
CMS100-Gamry Instruments and DC105 software as well as Rotating Cylinder Electrode (RCE)
simulation. The mechanism of inhibition was also investigated using Electrochemical Impedance
Spectroscopy (EIS) method with EIS300 software. The results showed that the addition of mixture
of 1000 ppm piper betle and 4000 ppm green tea extracts with Reynold number ranging from 0 up
to 30000 reduced the corrosion rates significantly with its approximately 90 % inhibitor
efficiencies achieved. In addition, EIS spectra showed that in the absence of corrosion inhibitor,
the Warburg impedance (diffusion controlled) was significantly attributed to the overall impedance
but in the presence of corrosion inhibitor, capacitive impedance (charge transfer controlled) was
mainly attributed to the overall impedance.
Introduction
Internal corrosion attack is one of the major problems in industry such as in the oil and gas
production facilities which causes serious detrimental consequences. It is generally believed that
corrosion inhibitors can effectively reduce the corrosion rate of carbon steel materials in aggressive
media. Inhibitors can be organic or inorganic compounds, and they are usually dissolved in aqueous
environments. Some of the most effective inorganic inhibitors are chromates, nitrites, silicates,
carbonates, phosphates, and arsenates. The organic inhibitors which are widely used include
amines, heterocyclic nitrogen compounds, sulfur compounds (such as thioethers, thioalcohols,
thioamides, thiourea, and hydrazine), some natural compounds (such as glue or proteins) and
mixtures of two or more compounds. Organic compounds containing polar groups including
nitrogen, sulphur, and oxygen and heterocyclic compounds with polar functional groups and/or
conjugated double bonds have been reported to inhibit various metals or alloys. Due to the toxicity
and environmental implications as well as high cost of some corrosion inhibitors currently in use, it
is essential to develop alternative corrosion inhibitors which are environmentally acceptable and
inexpensive ones also known as green inhibitor [1,2]. Natural products can be used as corrosion
inhibitors which are readily available and renewable sources [3]. Several studies have developed
corrosion inhibitor materials derived from natural plants such as green tea, rosemary, thyme,
coriander, hibiscus, anis, black cumin and garden cress, tobacco and even honey [4,5,6].
The protection mechanism of the organic inhibitors mostly based on the adsorption of ions or
molecules into the surface of steel, these inhibitors are able to control the electrochemical reaction,
the rate of diffusion, and surface barriers to minimize the corrosion process [7,8]. However, the
types of inhibitor above still do not provide maximum performance in its use if there is a change of

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of TTP,
www.ttp.net. (ID: 152.118.148.218-25/01/12,04:19:22)
 Advanced Materials Research Vols. 383-390 5419

flow pattern or under turbulent flow condition [9,10,11]. There is a form of internal corrosion
usually occurs in carbon steel such as API X52 which affected by flow induced or turbulent
condition especially at bent line pipe such as elbow or U-shape area where the efficiency of the
inhibitor might be less effective. The aim of this work is to investigate a new environmentally-
friendly corrosion inhibitor based on components from naturally occurring tropical plants which is a
mixture of extract piper betle and green tea whether it can protect carbon steel API X52 in aerated
3.5 % NaCl effectively. Both green tea and piper betle have been known as antioxidant substances.
Green tea contains active substance mostly catechins, especially Epigallocatechin Gallate (EGCG)
and its compound formula is: C22H18O11. Piper Betle is a tropical natural product that contains
chemical substance, especially hydroxychavicol and its compound formula is: C9H10O2. The
molecular structures of those substances are shown in Figure 1a and b.

a) b)
Fig. 1 Molecular Structure of, a) Epigallocatechin Gallate (EGCG) [12]; b) Hydroxychavicol
[13,14]
It is shown that an aromatic ring bearing one to several hydroxyl groups is known as phenolic
compound which is most common in plants product. The inhibition potency of Epigallocatechin
Gallate (EGCG) and hydroxychavicol are believed mainly due to the hydroxy groups in the
aromatic ring which may increase its antioxidant (oxygen scavenger) properties as well as forming a
surface layer so that the corrosion product becoming more protective.
Experimental Methods
The specimen used in this study was carbon steel that complying API X52 standard. The shape of
the specimen was cylindrical, 1.5 cm long and 1.2 cm in diameter (known as Rotating Cylinder
Electrode - RCE) with a central cylindrical hole to fit on the stainless steel shaft, also utilized
elsewhere [15,16]. The specimen became a part of the long cylinder exposing the peripheral
surface of the specimen to the test solution. The surface of specimen was polished with 600-grit
silicon carbide paper to obtain uniform results. The chemical composition of this specimen can be
shown in Table 1.
Table 1 Chemical composition of steel (API 5L X52)
Fe C Mn Cr Mo Ni Cu P S
97.98% 0.21% 0.83% 0.08% 0.01% 0.04% 0.02% max.0.06% max.0.02%
Laboratory tests were carried out to investigate the corrosion behavior of API 5L X52 steel that
immersed in aerated 3.5 % NaCl solution. The tests were performed at different RCE rotation rate
ranging from 0 to 5000 rpm, with and without the addition of corrosion inhibitor at room
temperature, 25oC and atmospheric pressure. The rotation rate of RCE was driven by a rotator
which equipped with digital tachometer and its proximity.
The inhibitors used were derived from the extracts of Piper Betle and Green Tea leaves. Figure 2
shows the preliminary result of UV absorbance measurements of both used extracts at various
concentrations. Based on the measurements, the concentration of mixture of inhibitor was
determined from steady conditions of absorbencies, which consists of 1000 ppm Piper Betle and
4000 ppm Green Tea extracts. The polarization measurements have been performed to evaluate the
corrosion potential and corrosion current density while the mechanism of inhibition is investigated
by using the electrochemical impedance spectroscopy (EIS). The schematic of polarization
measurement and test cell apparatus is shown in Figure 3a and b.
5420 Manufacturing Science and Technology

Fig. 2 Absorbance measurements of Piper Betle and Green Tea extracts at various concentrations

a) b)
Fig. 3 a) Polarization Measurement Schematic, b) Test Cell Apparatus
Polarization Measurements. The Polarization measurements were carried out in a conventional
three-electrode cell assembly. The working electrode was RCE which immersing in 3.5% NaCl
solution. Solid tubular graphite was used as the counter electrode and Standard Calomel Electrode
(SCE) as reference electrode. The polarization cell apparatus associated with the hardware Gamry
Instrument PC3 potentiostat equipped with software CMS 100 and DC 105. The polarization was
carried from a cathodic potential of - 250 mV (vs SCE) to an anodic potential of 250 mV (vs SCE)
with respect to corrosion potential at a sweep rate of 0.1 mV per second. The measurements were
taken at rotation rates of: 0, 1500, 3000 and 5000 rpm or at linier velocities of: 0. 94, 188, and
314 cm.s-1 which are operating conditions commonly observed in practice [17,18].
Electrochemical Impedance Spectroscopy Measurements. The mechanism of corrosion was
investigated by using electrochemical impedance spectroscopy (EIS). This method based on the
response of a circuit to an alternating current voltage as a function of frequency. The
electrochemical impedance measurements were performed under potentiostatic conditions at the
corrosion potential by means of Gamry Instrument PC3 potentiostat equipped with software EIS
300. A sine wave (AC) with amplitude of 10 mV was superimposed on the steady open circuit
corrosion potential. The real part (Z’) and the imaginary part (Z’’) were measured at various
frequencies in the range of 1 kHz to 10 MHz. The Nyquist plots of Z’ vs. Z’’ were commonly
described elsewhere [19,20,21].
Calculation Approach. The corrosion rates can be calculated based on approximately values of
the developed limiting current densities related to the rotation rate which can be derived according
to the following formulas. The corrosion rate as a penetration rate is calculated from the corrosion
current by equation 1:
 Advanced Materials Research Vols. 383-390 5421

a.i corr (1)

CR = K
n.D
where CR = corrosion rate (mil per year or mm per year depending on units of K), K = constant for
converting units (0.129 for mpy), icorr = corrosion current density (micro amp/cm2 ), D = alloy
density (gram/cm3), a = atomic weight, n = atomic valence.
The inhibitor efficiency IE (%) is calculated using equation 2:
CR(uninhibit)-CR(inhibit) (2)
IE(%)= x100%
CR(uninhibit)
The linear velocity U (cm s–1), at the outer surface of the cylinder is given by equation 3:
U = π.d . (F /60) (3)
where the rotation rate F can be expressed as revolution per minute (rpm) and d (cm) is the cylinder
diameter. This parameter can be used to determine the Reynolds number indicating flow
characteristics. The Reynolds number for a rotating cylinder electrode with outer diameter, d (cm) is
calculated according to the relation of equation 4:
Re = U . d . (ρ / µ) (4)
–3 –1 –1
where ρ is the solution density (g cm ) and µ is the absolute viscosity of the solution (g cm s ).
For RCE geometry, turbulent flow is typically encountered for Reynolds number: Re > 200.
The turbulent flow at the RCE induces a wall shear stress τ on the surface of the cylinder which
given by the equation 5:
τ = 0.0791 ρRe–0.3U 2 (5)
Results and Discussion
From results polarization measurements, the polarization curves were obtained at different rotation
rates as shown in Figure 4. As already known, the corrosion of carbon steel in aerated NaCl solution
occurred according to the following reactions:
Fe
Fe+2 + 2e (6)
-
H2O + ½ O2 (dissolved) + 2e
2OH (7)
or:
Fe + H2O + ½ O2 (dissolved)
Fe(OH)2 (8)
The further reaction resulted in more stable corrosion product which is:
2Fe(OH)2 + H2O + ½ O2 → 2Fe(OH)3 (9)
The diffusion of dissolved oxygen towards the steel interface was a controlling step, in this case
the limiting current density would be developed which influenced by the rate of flowing or rotation.
The corrosion rate could be determined from the magnitude of related limiting current density as
resulted from the measured polarization curves. Figure 4 also illustrates, at the cathodic polarization
curves showed that at higher rotation rates the higher limiting corrosion current densities occurred
due to higher oxygen diffusion rates towards the interface, while at the anodic polarization curves
showed that the rotation rates slightly affected the magnitude of the current densities. The corrosion
potentials, Ecorr were shifted towards more positive potential as rotation rates increased due to the
corrosion product that gradually formed.
Table 2 Rotation rates correlation with the polarization measurement results in the absence of
corrosion inhibitor
Corrosion Approx. Approx.
Rotation Linier Reynold Potential vs Limiting Current Corrosion
Rate Velocity Number Shear Stress SCE Density Rate

(rpm) (cm s-1) (unitless) (gr cm-1 s-2) (mV) (uA cm-2) (mpy)

0 0 0 0 -630 40 18
1500 94 9043 47.47 -570 180 82
3000 188 18086 154.23 -530 250 116
5000 314 30144 367.54 -510 420 195
5422 Manufacturing Science and Technology

Fig. 4 Tafel’s Polarization Curves at Different Rotation rates in Aerated 3.5 % NaCl without
Inhibitor
The approximate corrosion rates can be obtained from calculation using equation 1 utilizing
parameters in equation 3, 4 and 5. For a RCE with outer diameter 1.2 cm rotating in aerated 3.5%
NaCl at 25ºC (the density is 1.02 g cm–3 and the absolute viscosity is 0.00891 g cm–1s–1) the
following calculations are obtained along with its approximate polarization results in the absence of
corrosion inhibitor as shown in Table 2.
In the presence of mixed corrosion inhibitor, the higher rotation rate the cathodic current
density slightly increased and limiting current density not likely developed which indicated that
diffusion controlled process not encountered and turned to the charge transfer of oxygen reduction
controlled, as shown in Figure 5. The cathodic current density sharply decreased with the addition
of mixed corrosion inhibitor and the limiting current density decreased turned to typical charge
transfer current density, as shown in Figure 6.

Fig. 5 Tafel’s Polarization Curves at Different Fig. 6 Tafel’s Polarization Curves at 5000
Rotation rates in Aerated 3.5 % NaCl at rpm Rotation rate in Aerated 3.5 % NaCl with
constatnt concentration mixed Inhibitor and without Inhibitor

In the presence of mixed corrosion inhibitor, the corrosion current densities were obtained from
curve’s extrapolations which its results can be shown in Table 3, compared to the absence of
corrosion inhibitor. As results, the corrosion rates reduced significantly with the use of mixed
inhibitor. From calculations using equation 2, it was also pointed out that the mixed inhibitor
efficiency was increased with the increase of rotation rate. In this case, the corrosion was inhibited
more effectively in higher flow rate or in turbulence condition.
EIS measurements as shown in Figure 7 revealed that in the absence of corrosion inhibitor the
overall impedance decreased with the increasing the rotation rates and Warburg impedance mainly
attributed due to diffusion controlled mechanism. In the presence of mixed corrosion inhibitor, the
 Advanced Materials Research Vols. 383-390 5423

overall impedance increased without significantly attributed by the Warburg impedance but the
capacitive impedance due to charge transfer controlled mechanism significantly attributed to the
overall impedance as can be shown in Figure 8.
Table 3 Rotation rates correlation with the polarization measurement results in the absence of
corrosion inhibitor compared to the presence of mixed corrosion inhibitor
Without Inhibitor With Mixed Inhibitor Mixed
Rotation
Approx. Approx. Approx. Approx. Inhibitor
Rate
(rpm) Limiting Current Corrosion Corrosion Corrosion Efficiency
Density Rate Current Density Rate (%)
-2) -2)
(uA cm (mpy) (uA cm (mpy)
0 40 18 5.0 2.3 87
1500 180 82 12.6 3.0 93
3000 250 116 12.6 3.7 95
5000 420 195 15.8 4.6 96
The comparison of corrosion rates had shown good result with the use of the mixed inhibitor.
From the inhibitor experiments, the corrosion rates were significantly reduced and high inhibitor
efficiency was achieved in turbulence flow condition. As standpoint, these mixed Piper Betle and
Green Tea leaves extracts was effective to be used as alternative green corrosion inhibitor for API
5L X52 steel in NaCl solution.
4.00E+02

3.50E+02

3.00E+02 a a : 0 rpm

2.50E+02 b : 1500 rpm

-Imag (Ohm)

2.00E+02
c : 3000 rpm
1.50E+02 b
1.00E+02 d : 5000 rpm
c
5.00E+01 d
0.00E+00
0.00E+00 2.00E+02 4.00E+02 6.00E+02 8.00E+02
Real (Ohm)

Fig. 7 Nquist plots for steel in aerated 3.5 % NaCl at different rotation rates without mixed
corrosion inhibitor

Fig. 8 Nquist plots for steel in aerated 3.5 % NaCl comparing with and without mixed corrosion
inhibitor addition.
5424 Manufacturing Science and Technology

Conclusions
1. Corrosion rates of API X52 steel in aerated 3.5 % NaCl increased significantly with
increasing rotation rates in absence of corrosion inhibitor as shown by cathodic polarization
curves.
2. The corrosion inhibitor of mixture of piper betle and green tea extracts worked as a mixed
corrosion inhibitor type which decreased both cathodic and anodic current densities in
turbulent flow condition. It was found that around 90 % of inhibitor efficiency achieved.
3. In the absence of corrosion inhibitor the diffusion control mechanism encountered that
confirmed by EIS measurement indicating that Warburg impedance mainly attributed to the
overall impedance which decreased with increasing rotation rates.
4. In the presence of corrosion inhibitor the charge transfer control encountered that confirmed
by EIS measurement indicating capacitive impedance attributed to the overall impedance
which decreased with increasing rotation rates.
Acknowledgment
The authors wish to thank Ministry of National Education of Indonesia and Faculty of Engineering,
Universitas Indonesia for providing a grant and facilities that supporting the research.
References
[1] A. Craddock, SPE, S. Caird, H. Wilkinson, and M. Guzmann in: A New Class of Green
Corrosion Inhibitors: Development and Application, SPE International Oilfield Corrosion
Symposium, Aberdeen, (2006).
[2] Sanjay K. Sharma, Ackmez Mudhoo, and Khamis Essam Khamis: JCSE. Vol. 11 Paper 14
(2009).
[3] W. Bogaerts, T. Vuthi, L.Q. Hung, N.N. Phong and R. Addul in: Use of Different Natural
Extracts from Tropical Plants as Green Inhibitors for Metals, Clean Technology Conference &
Expo 2009, Houston, TX, (2009).
[4] Ali Mojaradian III, Mahmoud Peykari and Sirus Javadpour in: Green Tea Extract as a Natural
Effective Oxygen Scavenger, DoD Corrosion Conference, (2009).
[5] C. A. Loto: Journal of Corrosion Science and Engineering. Vol. 13 Preprint 47 (2010).
[6] Ayssar Nahlé, Ideisan Abu-Abdoun, Ibrahim Abdel-Rahman and Maysoon Al-Khayat: Int.
Journal of Corrosion. Vol. 10 (2010).
[7] Ahmed Y. Musa, Abdul Amir H. Kadhum and Abu Baker Muhamad: Int. J. Electrochem. Sci.
Vol. 5 (2010).
[8] Adriana Samide, Ion Bibicu, Mircea Rogalski and Mircea Preda: Acta Chim. Slov. Vol. 51
(2004).
[9] Qasim J. M. Slaimana and Basim O. Hasan in: Study on Corrosion Rate of Carbon Steel Pipe
Under Turbulent Flow Conditions, Canadian Journal of Chemical Engineering. Vol. 88 Issue 6
(2010).
[10] Armando Garnica-Rodriguez , J. Genesca, Juan Mendoza-Flores and Ruben Duran-Romero: J.
Appl. Electrochem. Vol. 39 (2009).
[11] Matthew Bilson and Klaus Bremhorst in: Comparison of Turbulent Scalar Transport in Pipe
and a Rotating Cylinder, Third International Conference on CFD in the Minerals and Process
Industries CSIRO, Melbourne, Australia, (2003).
[12] Tadakatsu Shimamura, Wei-Hua Zhao and Zhi-Qing Hu: Anti-Infective Agents in Medicinal
Chemistry. Vol. 6 No. 1 (2007).
[13] K. Ghosh and T. K. Bhattacharya: Molecules. Vol. 10 (2005).
[14] T. Nalina and Z.H.A. Rahim: American Journal of Biotechnology and Biochemistry. Vol. 3 (1)
(2007), p.10-15.
 Advanced Materials Research Vols. 383-390 5425

[15] Pine Instrumentation, “Study of Mass-Transport Limited Corrosion Using Pine Rotating
Cylinder Electrodes”, An Overview of Theory and Practice, Technical Note 2006-01, REV 003
(2007).
[16] ASTM G 185: Standard Practice for Evaluating and Qualifying Oil Field and Refinery
Corrosion Inhibitors Using the Rotating Cylinder Electrode, ASTM, (2006).
[17] F.Nabhani, A. M. Jasim and S.W.Graham: Electrochemical Behaviour of Low Carbon Steel in
Aqueous Solutions, Proceedings of the World Congress on Engineering. Vol. II (2007).
[18] Ayse Tosun and Mübeccel Ergun in: Protection of Corrosion of Carbon Steel by Inhibitors in
Chloride Containing Solutions, Gazi University, G.U. Journal of Science. Vol. 19 (3) (2006).
[19] Abdel Salam Hamdy, E. El-Shenawy and T. El-Bitar: Int. J. Electrochem. Sci. Vol. 1 (2006).
[20] L. Quej-Aké and R. Cabrera-Sierra: Int. J. Electrochem. Sci. Vol. 3 (2008).
[21] Ismaeel Andijani, “AC Impedance Studies on The Corrosion Behavior of Carbon Steel in
De-aerated Chloride Solution”, 6th Saudi Engineering Conference, KFUPM, Dhahran, Saudi
Arabia, (2002).
 Manufacturing Science and Technology
10.4028/www.scientific.net/AMR.383-390

The Use of Mixture of Piper Betle and Green Tea as a Green Corrosion Inhibitor for
API X-52 Steel in Aerated 3.5 % NaCl Solution at Various Rotation Rates
10.4028/www.scientific.net/AMR.383-390.5418

View publication stats