THE EXTRACT OF WARU (Hibiscus Tiliaceus L.

) LEAF AS A
ENVIRONMENTAL-FRIEND CORROSION INHIBITION OF
MILD STEEL IN 1 N HYDROCHLORIC ACID MEDIUM

MASNA AINUL, EMRIADI*, HERMANSYAH AZIZ,

ABSTRACT
The effect of inhibition and adsorption of waru leaf extract on corrosion of mild
steel in hydrochloric acid solution was investigated. Weight loss, potentiodynamic
polarization, Fourier transform infrared spectroscopy (FT-IR), and scanning
electron microscopy (SEM) scans were used to assess the inhibiting properties of
waru leaf extract in a solution of hydrochloric acid (HCl). The results showed that
the rate of corrosion of mild steel in HCl solution sensitive the concentration of the
extract as mass loss and the corrosion rates which decreases with increasing extract
concentration and the corrosion rate increases with increasing temperature. The
inhibition efficiency is above 80 % at room temperature with an increase in extract
concentration and temperature. FTIR indicates that the inhibition is basically by
application through the functional groups the present in the extract while the energy
of Langmuir adsorption activation and isotherm shows inhibition process. SEM
images of the cores which were corroded showed holes as a corrosion mechanism
reduced with the addition of extract. Overall, extract shows efficient used for
inhibition of mild steel in HCl solution.

KEY WORDS: Waru leaf; adsorption; mild steel; inhibition; Langmuir’s

isotherm

INTRODUCTION
Metals and alloys are widely used in various industrial fields, although the
material is very easily corroded in corrosive media. In other words, industry is
very dependent on the use of metals and alloys. One of the most difficult
treatments for the industry is protection of metal from corrosion. The Metal
corrosion in steel is an electrochemical reaction that can cause degradation and
damage to the physical and chemical properties of metals were affected. In
addition to natural factors such as air humidity, it turns out that acid use is the
main factor that causes corrosion. For example, the use of strong acids such as
hydrochloric acid in an industry for various purposes, especially for preservation,
cleaning, etc (Hu et al., 2016).
 The Scientists especially in the field of corrosion have conducted studies
to overcome the effects of corrosion attacks. The effective method for preventing
corrosion is to use an inhibitor. The Corrosion inhibitors are chemicals that are
either synthetic or natural, when added to small amounts in the environment, can
reduce the corrosion rate of the metal. Some inorganic and organic compounds
have been used commercially for corrosion inhibition. However, the
disadvantages of some of these compounds are their toxic properties which cause
health and environmental disorders (Helen et al., 2014).
The growing awareness of health and the environment has encouraged
scientists to find solutions to environmentally friendly corrosion inhibition
selection. Recently, Eco-friendly Inhibitors have been widely studied, because it
shows good inhibition efficiency. The natural inhibitors are also non-toxic,
biodegradable, environmentally friendly and the costs incurred are also not too
expensive compared to synthetic compounds. Several studies on the use of plant
extracts as inhibitors have been carried out, among others: theobroma (Yetri et al.,
2014), Aloe vera (Abiola et al., 2010), Pennisetum purpureum (Alaneme et al.,
2016), Salvia officinallis (Soltani et al., 2012), litchi peels (Singh et al., 2015).
The results showed that the average use of extracts from these plants had a high
inhibitory efficiency.
Waru (Hibiscus tiliaceus L.) is a tree that is widely found in Indonesia,
usually grows on beaches that are not swampy, flat land, and in the mountains to
an altitude of 1700 meters above sea level. The waru leaf are identified to contain
saponin compounds, flavonoids and phenols (Suwandi et al., 2014). Based on this,
waru leaf extract was chosen as a corrosion inhibitor against mild steel in
hydrochloric acid (HCl) solution.
 EXPERIMENTAL

Metal Samples
The composition of mild steel Fe = 99.6 P = 0.0149%, Si = 0.0715%, Ni = 0.01%,
Mn = 0.141, C = 0.189, Se = 0.019%, Cr = 0.0018% used in this study. The metal
is cut into 3x2x1 cm dimensions, and polished using silicon carbide paper. HCl
grade and distilled water are used for electrolyte solutions, then waru leaf are used
for corrosion inhibition.
Preparation of Waru Leaf Extract
The waru leaf extract is made by maceration method. The waru leaf are dried with
wind, after drying and then mashed with a grinding and weighed as much as 500
g. The fine sample was macerated with methanol as much as 1500 mL for 3 days.
The extract obtained was then filtered and evaporated by using a rotary evaporator
to obtain concentrated extract (Patel et al., 2015).
Phytochemical Test of Waru Leaf
The phytochemical test was carried out by examining the content of
flavonoids, triterpenoids, steroids, and phenolic compounds contained in Waru
leaf: a sample of 4 g was put into a test tube. Then macerated with methanol
which has been heated (above the water bath) for 15 minutes. Then, filter it into
another test tube and let the whole methanol evaporate until it dries. Then, add
chloroform and water with a ratio of 1: 1 each of 5 ml, shake well. Then, transfer
it to the test tube, leaving it to form two layers of chloroform-water. The
chloroform layer at the bottom is used to examine triterpenoid and steroid
compounds, while the water layer is used to examine phenolic compounds and
flavonoids (Kumar et al., 2008).
Weight Loss Measurement
The determination of corrosion rate based on the method of heavy loss is done by:
steel soaked in 50 mL of 1 N HCl corrosive medium solution with various
concentrations of waru leaf extract with temperature variations of 30, 40, 50, and
60oC for 7 days using a water bath. Next, the steel is cleaned, washed and dried in
the oven. After drying, the steel is weighed and the weighing results are used as
final weight (m2).
The Corrosion rates are calculated using the following equation:
CR= (1)
Where: CR is the corrosion rate, m1 is the initial weight, m2 is the final weight, t is
time and is the area of the coupon in cm2.
The surface coverage (θ) was calculated by using equation (2)
θ= (2)
Inhibition efficiency (η) was determined using equation (3)
η (%) = (3)
Where CR0 and CRi are the presence and absence of inhibitor, respectively.

FTIR Analysis
FTIR measurements were carried out by: steel soaked in 1 N HCl corrosive
medium without extra waru leaf and with waru leaf extract at a concentration of 1
g/L for 7 days. The steel after immersion is dried and then a layer attached to the
surface of the steel is taken by eroding the layer. After that, FTIR measurements
were carried out using the KBr pellet plate, FTIR measurements were also
performed to extract.
Scanning Electron Microscopy (SEM)
SEM analysis was performed on steel soaked for 7 days in 1 N HCl corrosive
medium without extra waru leaf and and with waru leaf extract 1 g/L. The steel is
soaked with extract, then dried and subjected to surface analysis with SEM.
Analysis was also carried out for steel without immersion.
RESULTS AND DISCUSSION
Phytochemical Test of Waru Leaf Extract
The content of secondary metabolites found in waru leaf extract has the potential
as a corrosion inhibitor. Therefore, phytochemical testing is needed. This test was
conducted to identify the content of secondary metabolites contained in the
extract. Table 1 shows the content of secondary metabolites in this extract
including: phenolic, steroids, flavonoids, alkaloids are signed by (+), while
triterpenoids and saponins are signed by (-).

Table 1. Phytochemical test results of waru leaf extract

Compound Test Result
Flavonoid +
Fenolik +
Steroid +
Triterpenoid -
Alkaloid +
Saponin -

Weight Loss Measurement

Corrosion rate and Corrosion Inhibition Efficiency with the addition of waru leaf
extract in 1 N HCl medium at a temperature variation with soaking for 7 days
CR (30 oC)

4.5 100 CR (40 oC)

CR (50 oC)

4.0 CR (60 oC)

 (30 oC)
80
3.5  (40 oC)
 (50 oC)
3.0  (60 oC)
CR / mg cm-1h-1

60
2.5
%

2.0 40

1.5
20
1.0

0.5 0

0.0
0 2 4 6 8

C / g L-1

Fig. 1. Variation of the corrosion rate (CR) and efficiency corrosion (η%) of the
inhibitor concentration on the corrosion rate of steel in 1 N HCl solution
at a temperature variation with soaking for 7 days

The steel corrosion rate increases with the concentration of waru leaf extract and
the corrosion rate increases with temperature (Figure 1). This causes the more
extracts to be added, the more extracts are adsorbed on the steel surface so that the
corrosion rate accelerates and with high temperatures can accelerate the corrosion
rate in steel. Increasing temperature makes the kinetic energy between particles
larger and the movement of particles more random (Abiola et al., 2010). The
increase in corrosion rate without the addition of extract is much higher than after
adding the extract at high temperatures. This shows that waru leaf extract is still
able to reduce the corrosion rate even at high temperatures.
Figure 1 shows that waru leaf extract is effectively used as a corrosion
inhibitor and can slow the corrosion rate. Functional groups of secondary
metabolites in extracts can bind to metals in steel which form more stable
complex compounds, which can slow down corrosion reactions in steel (Yetri et
al., 2014).
The corrosion inhibition efficiency of steel increased with increasing
concentrations of waru leaf extract (Figure 1), caused by the adsorption of
chemical compounds contained in the extract to form a layer on the surface of the
steel which can protect steel from corrosion reactions (Siregar et al., 2010).
Isotherm Adsorption
The study of the adsorption method can be calculated using the equation
Langmuir, Freundlich and Temkin isotherms. The Adsorption method is one of
the methods used to determine the corrosion inhibition mechanism using natural
material samples (Emriadi et al., 2016).
Blank
-4.0 0.2 g L-1
0.3 g L-1
-4.5 0.4 g L-1
0.5 g L-1
-5.0
1.0 g L-1
ln (CR / g cm-2 s-1)

-5.5 2.0 g L-1

4.0 g L-1
-6.0
6.0 g L-1
-6.5
8.0 g L-1

-7.0

-7.5

-8.0

0.00300 0.00305 0.00310 0.00315 0.00320 0.00325 0.00330

(1/T) / K-1

Fig. 2. Arrhenius 1 / T (K-1) vs ln V flow for corrosion of steel in 1 N HCl

medium with 7 days immersion time

Table 2. Activation energy values (Ea), enthalpy (ΔH0) and entropy (ΔS0)
 Medium Activation ΔH0 ΔS0
1 N HCl + Extract (g / L) Energy (kJ/mol) (kJ/mol) (J/mol)
(Form) 66.204 63.585 216.082
0.2 64.466 61.847 143.101
0.3 60.750 58.139 130.298
0.4 58.946 56.327 123.563
0.5 56.443 53.824 113.670
1 47.165 44.546 82.575
2 43.706 41.087 70.462
4 41.146 38.535 61.350
6 39.857 37.246 56.885
8 38.580 36.961 55.282

The activation energy value with the addition of waru leaf extract is smaller than
the activation energy without the addition of extract (Table 2). This shows that the
more extracts that are added to the energy needed for the occurrence of corrosion
reactions are smaller so that it will reduce the corrosion reaction of steel in acidic
solutions and corrosion reactions will be increasingly difficult to occur (Abiola et
al., 2010).
The values of ΔH0 and ΔS0 in Table 2 are positive from ΔH0, suggesting
that steel immersion and waru leaf extract produce endothermic reactions and the
value of ΔH0 blank greater than ΔH0 with the addition of extracts indicates that
the energy needed is large for the corrosion process (Abiola et al., 2010). As well
as the value of ΔS0 with the addition of an extract smaller than ΔS0 this blank
explains the ability of the extract to slow the corrosion rate (Emriadi et al., 2016).
 12

10

(C / g L-1
6
30 oC
4 40 oC
50 oC
2 60 oC

0 2 4 6 8
-1
C/gL

Fig. 3. Isoterm Langmuir’s adsorption for corrosion of steel in 1 N HCl medium

with 7-days immersion time based on measurement of weight loss method

Adsorption of Langmuir’s isotherm which shows the interaction between

functional groups of secondary metabolites contained in the extract of waru leaf
with steel surfaces (Figure 3). The calculation results obtained by the value of the
correlation coefficient (R2) reached 0.999 (close to 1). The Langmuir’s isotherm
shows the absorption of extract on the steel surface to form a monolayer so that
the bonds between the compounds in the extract and the steel in the steel are
stronger and form more stable complex compounds (Abiola et al., 2010).
Adsorption of the Langmuir’s isotherm can be used to determine the adsorption
constant value (Kads) extract on the steel surface and the Gibb free energy value
(ΔGads) shown in Table 3.
Table 3. Thermodynamic parameters for adsorption Waru leaf extract in steel in 1
N HCl at each temperature based on the results of Langmuir’s isotherm
Temperature (oC) Kads (kJ/mol) ΔGads (kJ/mol)
30 3.2154 -17.8727
40 5.1546 -14.1138
50 4.2017 -24.9849
60 5.2356 -35.6493

The Kads value increases with increasing temperature (Table 3). This shows that
the greater the Kads value the more stable the adsorption of the extract on the steel
surface (Abiola et al., 2010), this is evidenced by the increasing percent efficiency
of corrosion inhibition which increases with increasing temperature. The Gibbs
free energy value (ΔGads) obtained negative indicates that the reaction adsorbs
spontaneously and stably between the extract and the steel surface (Emriadi et al.,
2016).
Electrochemical measurement (Potentiodynamic Polarization)
Measurement of potentiodynamic polarization of a potentiostat by giving a
potential from -1 V to +1 V at a scan rate of 500 V / s (Figure 4). The
measurement uses 3 electrodes, namely steel as working electrde, Pt as counter
electrode and Ag / AgCl as the reference electrode.

-1.5

-2.0

-2.5 Blank
0.2 g L-1
-3.0 0.3 g L-1
ln I (A)

0.4 g L-1
0.5 g L-1
-3.5
1.0 g L-1

-4.0

-4.5

-5.0
-0.55 -0.50 -0.45 -0.40 -0.35
E vs SCE (V)

Fig. 4. Potentiodynamic polarization curves without and with the presence of

waru leaf extract in 1 N HCl

The Potentiodynamic polarization curves showed inhibitory properties of

waru leaf extract on steel surfaces (Figure 4). The potentiodynamic polarization
curve was extrapolated by the Tafel’s method. The waru leaf extract is able to
protect the cathode area showing cathodic inhibitor properties. This is evidenced
by the results of the shifting potentiodynamic polarization curve occurring from
the cathodic direction to anodic direction (Abiola et al., 2010).
 Table 4. Corrosion potential value, corrosion flow and steel corrosion inhibition
efficiency without and with the addition of waru leaf extract
Concentration (g/L) Ecorr Log i/A Icorr ln Icorr Icorr Blank (η%)
0 -0.43 -3.0 0.000042 -10.07 0.000042 0.0
0.2 -0.45 -3.5 0.000013 -11.22 0.000042 68.3
0.3 -0.44 3.5 0.000011 -11.33 0.000042 71.8
0.4 -0.48 -3.6 0.000011 -11.40 0.000042 73.7
0.5 -0.44 -3.6 0.000010 -11.47 0.000042 75.4
1.0 -0.47 -3.6 0.0000090 -11.61 0.000042 78.6

Table 4 shows the value of the corrosion current (Icorr) decreases as the
concentration of waru leaf extract increases and the corrosion efficiency of steel
with heavy loss methods with potentiodynamics is not much different. This
indicates that the inhibition or inhibition of corrosion of steel occurs by extract.
Corrosion currents arise due to the movement of steel electrons oxidized in HCl
medium (Yetri et al., 2014).
The value of corrosion potential (Ecorr) shifts in a more negative direction.
This indicates that waru leaf extract belongs to the type of cathodic inhibitor
(Abiola et al., 2010).

FT-IR Analysis
FT-IR analysis to identify functional groups of organic compounds contained in
waru leaf extract which act as corrosion inhibitors, namely secondary metabolites.
FT-IR is also useful for determining the type of bond that occurs from organic
inhibitors adsorbed on the steel surface (Soltani et al., 2012).
The organic compounds have functional groups that are specific to each
type. Compounds that can be used as corrosion inhibitors are compounds that
have functional groups hydroxyl (OH-), carboxyl (-COOH), carbonyl (═CO), -
CO-, CH, = CH2, -C = C-, -C≡C -, -C-Cl, amines (-C≡N) and others that have
electron pairs that can bind directly to form stable complexes on metal surfaces
(Abiola et al., 2010).
Fig. 5. (a) FT-IR spectrum of waru leaf extract, (b) FT-IR spectrum of steel
corrosion products in 1 N HCl with the addition of 1 g / L of waru leaf
extract with soaking for 7 days.

Figure 6 (a) -OH stretching group (3333 cm-1), -CH stretching group (2929 cm-1),
-C =C stretching (1618 cm-1), methyl CH (1398 cm-1), CO stretching (1239 cm-1)
and Figure 6 (b) there are –OH stretching groups (3374 cm-1), -CH stretching
groups (2927 cm-1), -C =C stretching (1631 cm-1), methyl CH (1444 cm-1), CO
stretching (1051 cm-1) showed no significant difference between the two even
though there was a shift in the number of waves that showed waru leaf extract
adsorbed on the steel surface (Patel et al., 2015).
SEM Analysis

Fig. 6. SEM results of steel surface with 1500x (a) steel magnification before
soaking (without treatment) (b) steel after immersion in HCl 1N (c) steel
after immersion in 1 N HCl + extract 1g / L (d) at 30oC and soaking for 7
days

Figure 6 (a) is a surface treatment of steel without treatment / steel which is not
soaked in steel surface still looks good, flat and not corroded because there is no
interaction of steel with a corrosive medium. Figure 6 (b) steel that has been
soaked for 7 days in 1 N HCl corrosive medium for 7 days has been corroded on
its surface which is a hole and rust. This hole and rust occurs because of the
interaction between steel and 1 N HCl corrosive medium. Figure 6 (c) steel
surface which has been soaked for 7 days in 1 N HCl solution and 1 g / L waru
leaf extract is smoother and flatter from soaking with 1 N HCl. This shows the
presence of a protective layer of extract adsorbed on the steel surface that can
protect steel from 1 N HCl (Amitha et al., 2012).
CONCLUSION
Based on the research that has been done, it can be concluded that, The waru leaf
extract can be used as a corrosion inhibitor. This proves that the addition of waru
leaf extract as a steel corrosion inhibitor which causes the corrosion rate to
decrease and the inhibition efficiency increases with increasing extract
concentration. The Adsorption waru leaf extract fits on the surface of the steel
and matches the Langmuir’s isotherm.

ACKNOWLEDGEMENTS
The authors of the division of research and social services of the Andalas
University for facilitating this grant.

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