Mechanism of papaya leaf as organic inhibitor in corrosion process

Giri Nugroho, Atria Pradityana, Nur Husodo, Mahirul Mursid, Gathot Dwi Winarto, and Fransiskus Tommi
Putrandi

Citation: AIP Conference Proceedings 1983, 050017 (2018); doi: 10.1063/1.5046290

View online: https://doi.org/10.1063/1.5046290
View Table of Contents: http://aip.scitation.org/toc/apc/1983/1
Published by the American Institute of Physics
 Mechanism of Papaya Leaf as Organic Inhibitor in
Corrosion Process
Giri Nugroho1, Atria Pradityana 1,a), Nur Husodo1, Mahirul Mursid1, Gathot Dwi
Winarto1, Fransiskus Tommi Putrandi1
1
Departement of Mechanical Industry Engineering, Vocational Faculty, Institut Teknologi Sepuluh Nopember
Surabaya, Kampus Sukolilo, Indonesia
a)
Corresponding author: atriapradityana@gmail.com

Abstract. The inhibitor is a substance added in small amounts which aims to inhibit the corrosion rate. Organic
inhibitors are environmentally friendly inhibitors. Currently organic inhibitors are studied by many researchers.
Natural ingredients are the raw material in research on organic inhibitors. In this research, polarization testing and
FTIR have been done. Papaya leaves as a raw material of organic inhibitors are used, while the corrosive medium is a
1 M HCl solution. Based on the polarization test, the corrosion rate absence inhibitor was 21.43 mm/year. This
corrosion rate decreased to 0.4 mm/year. Highest efficiency generated by 97%. This efficiency occurs in the presence
of 2.5 ml concentration of corrosion solution. In the polarization testing showed that the inhibitory mechanism that
occurs cathodic dominant. This is supported by FTIR test results. The results of this test indicate the absence of the
same functional group between the extract and the specimen with the inhibitor. The inhibitory mechanism of cathodic
inhibitors is that the inhibitor reacts with the corrosion solution so as to decrease the rate of corrosion that occurs.

INTRODUCTION
An acidic medium such as HCl (hydrochloric acid) was widely used in applications pickling, chemical
cleaning, oil well acidification and processes in petrochemical. Because the acidic medium was also highly
corrosive if present in a metal environment, to reduce corrosion attack on the metal, inhibitors were generally
added to the processes.
Inhibitors were substances that when a small amount of concentration was added to the corrosive media
would reduce or prevent the metal from reacting with the medium. The inhibitor worked by absorbing ions or
molecules into the metal surface. The inhibitor reduced the corrosion rate by raising or lowering the anodic and /
or cathodic reactions, reducing the rate of diffusion of the reactants into the metal surface and increasing the
metal surface electrical resistance [1]. Generally the inhibitors for acidic media came from organic compounds
containing N (nitrogen), sulfur (S) and O (oxygen) atoms. Although these synthetic chemicals proved to work
well as anti-corrosion, in fact that these synthetic chemicals were chemicals that are harmful to health and are
not environmentally friendly. The presence of these side effects lead researchers to find alternative anti-
corrosion agents derived from harmless and eco-friendly natural products. Currently already rife developed an
environmentally friendly alternative corrosion inhibitor or better known as green inhibitor [2].
Research conducted by M.A. Quraishi et al [3] to the Salam leaf extract (Murraya koenigii), Atria et al to the
Sarang Semut extract (Myrmecodia Pendans) [4, 5, 6] and A.Y. El-Etre [7] to Olive extracts on mild steel
immersed in acidic solutions proves that the inhibitory effect will increase with increasing concentration of the
leaf extract. Complete data on studies based on "green inhibitors" performed both with extracts from leaves,
fruits, flowers, bark and roots have been done by M.A Quraishi et al [3].
Carbon steel is the most heavily used metal material in an industrial construction. The selection of test
materials using carbon steel because in addition to the above considerations, generally chemical cleaning
process is mostly done on carbon steel.
Based on the assumption that papaya leaf has been able to function as corrosion inhibitor because it
contained antioxidant and no previous research has been done. Inhibition on carbon steel in the environment of
acid solution as usual done on chemical cleaning process.

Disruptive Innovation in Mechanical Engineering for Industry Competitiveness

AIP Conf. Proc. 1983, 050017-1–050017-6; https://doi.org/10.1063/1.5046290
Published by AIP Publishing. 978-0-7354-1699-4/$30.00

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 EXPERIMENTAL PROCEDURES
The carbon steel electrode as a working electrode for electrochemical measurements was prepared from
rectangular steel sealed with epoxy resin, so that only one of side (100 mm 2) was exposed to air. Prior to all
experiments the exposed surface was abraded with a series of emery papers of different grades and rinsed with
deionized water then dried in air. [2, 3, 4].
To making of an inhibitor of papaya leaves use the maceration method of extraction. Papaya leaves that have
been obtained are separated from the stalks, washed and cut into small pieces. Then papaya leaves dried for two
to three days so the leaves become dry. Dried papaya puree with a blender until it becomes a powder. Powdered
papaya leaves wrap with paper filter and enter into a container for maceration with methanol during 3x24 hours.
After that filter with filter paper and steam until all the methanol evaporates and extracts is generally shaped the
oil settles.
The solution used is 1 M HCl. It has done dilution by adding aquades. 1M HCl to make as much as 37% HCl
required 1liter as much as 73ml and blended with the aquades until reach the volume of the solution 1liter.

Electrochemical Measurement
The electrochemical measurements were performed in a typical three-compartment glass cell consisted of a
steel electrode as the working electrode (WE), a platina as the counter electrode (PE) and AgCl as the reference
electrode (RE). Potentiodynamic Polarization is a method for determining the behavior of metal corrosion based
on relationship of potential and the current cathodic or anodic if the metal is in contact with a solution that is
both corrosive. In testing polarization analysis can be performed to obtain data about a current corrosion (Icorr)
and the corrosion rate (CR)[4].The three-electrode cell is a standard laboratory device for quantitative research
on the corrosion properties of the material. Generally the three-electrode cell is composed of working electrodes,
reference electrodes, and auxiliary electrodes connected to a potential source, electric current measuring device,
and an electric potential measuring device. A typical instrument to accommodate these three needs is a
potentiostat. Potentiostat will provide predetermined potential to the working electrode so that current
measurements can be made. Current measurement can only occur if the current through the auxiliary electrode
has such a price that the potential difference between the working electrode and the reference electrode remains
unchanged. The electrochemical experiments were performed using a Autolab PGSAT 302N dengan software
Nova 1.8analyzer. For potentiodynamic polarization experiments, the potential was scanned from −300 mV to
+300 mV with scan rate of 1.0 mV s−1. All potentials are presented in mV (SCE). EIS measurements were
carried out in a frequency range of 10 kHz to 10 mHz with the AC voltage amplitude of 10 mV at the open
circuit potential.

FTIR (Fourier Transform Infra Red)

FTIR spectroscopy method (Fourier Transform Infra Red) is used to determine if inhibitors of papaya leaves
can be adsorption on a metal surface to provide protection against corrosion. FTIR testing will yield curve peak
or waves with different intensity and may be determined the cluster function so that unknown content (type
compounds) that are contained in each sample.

RESULTS AND DISCUSSION

Potentiodynamic Polarization
Polarization can be known from testing the corrosion rate and inhibition efficiency of inhibitors are used.
Based on the result that has been done on six sample solution concentrations of the inhibitor with the variation
of 0.5, 1, 2, 1.5 and 2.5 ml using machine AUTOLAB and processed with software data obtained 1.11 Nova can
be seen in Table 1.
Based on result of the polarization that has been made of the corrosion rate obtained without an inhibitor of
21.43 mm/year. The rate of corrosion is down up to 0.4 mm/year and so the efficiency obtained amounted to
97%. The efficiency of this happening on the addition of a concentration of 2.5 ml of the medium corrosion. On
result polarization suggests that the mechanism of inhibition that occurs predominantly cathodic.

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 TABLE 1. Corrosion Rate and Inhibition Efficiency

- Blank
- 0,5 ml
- 1 ml
- 1,5 ml
- 2 ml
- 2,5 ml

FIGURE 1. The Results of Polarization

From Nova software 1.11 the data obtained can be seen on the image. It can be observed from the Tafel
curves that the different concentrations of extract inhibitor shifted the cathodic and anodic curves. An inhibitor
can be called a cathodic or anodic inhibitor (depending on the direction) if the Ecorr shift more than 85 mV [4-
6]. From the Figure 1, it can be seen that inhibitors of papaya leaves are mixed (cathodic and anodic), because of
all the concentration has the difference with Ecorr absence inhibitor less than 85 mV. Sample without inhibitors
on blue graphic located on the highest of the corrosion rate most have demonstrated high. While the sample with
the inhibitor concentration of 2.5% on the graph that gray lies the lowest corrosion rate has showed the lowest.

FTIR (Fourier Transform Infra Red)

FTIR are conducted to obtain functional groups of papaya leaf extract, specimens without an inhibitor, and
specimens with inhibitors. Specimen form steel API 5L grade B soaked in HCl 1 M with and without inhibitors
with 2.5 ml concentration for 4 hours. Following are the results from the FTIR. From Figure 2 and Table 2,
results of FTIR spectrum of papaya leaf extract contains some peak. This peak each have a frequency value will
be associated with the frequency range on the references.

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 FIGURE 2. FTIR Spectra Papaya Leaf Extract

TABLE 2. Results of FTIR in Papaya Leaf Extract

Wavelength(cm-1) Wavelength Area (cm-1) Functional Groups
921,85 675 – 995 C-H
1046,59 1000 – 1300 C-O
1405,80 1340 – 1470 C-H
1609,28 1550 – 1640 N-H
2924,13 2850 – 2970 C-H
3275,75 3200 – 3600 O-H

FIGURE 3. FTIR Spectra Absence Inhibitors

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 From Figure 3 and Table 3, results of FTIR spectrum of steel API 5L grade B specimens without inhibitors
there are some peak. This peak each have a frequency value will be associated with the frequency range on the
references.
TABLE 3. Result of FTIR Absence Inhibitors
Wavelength (cm-1) Wavelength Area (cm-1) Functional Groups
1458,52 1340 - 1470 C-H
1508,24 1500 - 1580 NO2
1610,33 1550 - 1640 N-H
2031,56 2210 - 2280 C≡N
3281,01 3200 - 3600 O-H

FIGURE 4. FTIR Spectra Presence Concentration of Inhibitor 2.5 ml

From Figure 4 and Table 4, results of FTIR spectrum of steel API 5L grade B specimens with concentrations
of Inhibitor 2.5% there are several peak. This peak each have a frequency value will be associated with the
frequency range on the references.

TABLE 4. Result of FTIR Presence Concentration of Inhibitor 2.5 ml

Wavelength(cm-1) Wavelength Area (cm-1) Functional Groups
1458,38 1340 - 1470 C-H
1636,98 1550 - 1640 N-H
2166,15 2100 - 2260 C≡H
3275,75 3200 - 3600 O-H

FTIR test results showed the absence of functional groups that are the same between the extract with
specimens with inhibitors. This is because of the polarization result, it is known that papaya leaf extract is a
mixed inhibitor (cathodic and anodic), but tend to be on the cathodic side. So there is no layer that protects the
objects on it works [8-10]. Inhibitory mechanism of the cathodic inhibitor is a corrosion inhibitor reacts with the
corrosive solution so that it can reduce the rate of corrosion to occur.

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 CONCLUSIONS
Based on the polarization test, the corrosion rate absence inhibitor was 21.43 mm/year. This corrosion rate
decreased to 0.4 mm/year. Highest efficiency generated by 97%. This efficiency occurs in the presence of 2.5%
concentration of corrosion solution. In the polarization testing showed that the inhibitory mechanism that occurs
cathodic dominant. This is supported by FTIR test results. The results of this test indicate the absence of the
same functional group between the extract and the specimen with the inhibitor. The inhibitory mechanism of
cathodic inhibitors is that the inhibitor reacts with the corrosion solution so as to decrease the rate of corrosion
that occurs.

ACKNOWLEDGMENT
The authors would like to acknowledge ITS (Institute of Technology Sepuluh Nopember) Surabaya as an
institution where the author works as a lecturer.

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