University of Chemical Engineering

Technology .Department

Inhibition of Aluminum Corrosion in HCL Acid Using

.(Hexadecyl trimethyl ammonium bromide (CTABr

.Anwar A. H

The corrosion inhibition of aluminum in hydrochloric

acid solution in the presence of Hexadecyltrimethyl
ammonium bromide (CTABr) at temperature range of 30-
50CO has been studied using galvanostatic polarization
techniques. Results showed that the inhibition occurs
through adsorption of the inhibitor molecules on the metal
surface. The inhibition efficiency(%IE) was found to
increase with increasing inhibitor concentration and
decreased with increasing temperature which is due to the
fact, that the rate of corrosion of Al is higher than the rate
of adsorption. The adsorption of the these compounds on
the metal surface is found to obey Temkin adsorption
isotherm. Thermodynamic parameters for adsorption and
activation processes were determined . Galvanostatic
polarization data indicated that these compounds act as
mixed-type inhibitors. Phenomenon of physical adsorption
.is proposed from the values of Ea and ∆Gads obtained

:INTRODUCTION.1

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 University of Chemical Engineering
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Aluminum and its alloys have a remarkable

economic and attractive materials for engineering
applications owing to its low cost, light weight, high
thermal and electrical conductivity(1) . The interest of the
materials arises from their importance in recent
civilization. Inhibition of metal corrosion by organic
compounds is a result of adsorption of organic molecules
or ions at the metal surface forming a protective layer.
This layer reduces or prevents corrosion of the metal. The
extent of adsorption depends on the nature of the metal,
the metal surface condition, the mode of adsorption, the
chemical structure of the inhibitor, and the type of
corrosion media. To prevent the attack of acid, it is very
important to add a corrosion inhibitor to decrease the rate
of Al dissolution in such solutions. Thus, many studies
concerning the inhibition of Al corrosion using organic
substances are conducted in acidic and basic solutions(2).
The present study aimed to investigate the efficiency of
Hexadecyl trimethyl ammonium bromide (CTABr) as
corrosion inhibitor for Al in acidic media. An attempt was
also made to clarify the effects of concentration and
temperature on the inhibition efficiency of the studied
.inhibitor

:EXPERIMENTAL PART.2

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The experiments were performed with aluminum of

99.2% purity were used. sheets having the chemical
.(composition given in Table (1
.(Table 1. Chemical composition (weight %) of aluminum(3

Aluminum Al 1100
Fe Cu Mn Zn al
0.45 0.20 0.05 0.10 99.2

The measurements were performed in 1 M HCl

without and with the presence of the investigated
surfactant (CTABr) in the concentration range ( 2*10-6 ,
.( 4*10-6 , 8*10-6 , 12*10-6 M
Al sheets with surface area of 1.0 cm2 were used for
galvanostatic polarization techniques. For anodic and
cathodic Tafel polarization measurements. Prior to each
experiment the surface of aluminum was mechanically
polished with different grades of emery paper in order to
obtain a smooth surface followed by ultrasonically
degreasing with ethanol, then rinsed with bi distilled water
and finally dried. The temperature was adjusted to
30±0.1CO. Polarization curves were carried out
.galvanostatically using (Parstat 2273) Galvanostate
Three compartment cell with a saturated calomel
reference electrode (SCE) and a copper as coupled
electrode was used, the third is the working electrode. The
measurements were performed in 1M HCl without and
with the investigated inhibitor and the used anions. The

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 University of Chemical Engineering
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name and the molecular structure of the cationic inhibitor

is

(
Hexadecyl trimethyl ammonium bromide (CTABr)(4

To check the inhabitation effect on the metal the

percentage of inhabitation efficiency as calculated from
galvanostatic polarization techniques by the following
:(relation(5,6
IE= Ifree-I inhIfree *100%

(-(1
θ= Ifree-I inhIfree

(-(2
where Ifree and Iinh are the corrosion current densities in
.absence and in the presence of inhibitor, respectively

:RESULTS AND DISCUSSION .3

Figure 1. Corrosion current density- time curves for Al

corrosion in 1M HCl at different concentrations of the
.used inhibitor (CTABr) at 30Co

.Corrosion inhibition behavior .3.1

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Figure (1) represents the data of corrosion current

density- time curves for Al corrosion in 1M HCl in absence
and in the presence of different concentrations of the
used inhibitor (CTABr) at 30Co. As shown from this Figure,
by increasing the concentration of this compound the
corrosion current density of Al samples are decreased.
This means that the presence of this organic compound
retards the corrosion of Al in 1M HCl or in other words, this
compound act as inhibitor. In absence of any surface films,
the inhibitor is first adsorbed, into the metal surface and
thereafter impede corrosion either by merely blocking the
reaction sites (anodic and cathodic) or by altering the
mechanism of the anodic and cathodic partial processes.
The %IE was calculated and represented in Table (2). In-
spection of the data in Table (2) reveals that (CTABr) acts
as inhibitor for corrosion of Al in hydrochloric acid solution.
A parameter (θ), which represents the part of the metal
surface covered by the inhibitor molecules was calculated
for different inhibitor concentrations and listed in Table
(2). From the data of Table (2) reveals that θ increases as
.(the inhibitor concentration (C) is increased(7

Table 2. Effect of (CTABr) concentration on the %IE and

.θ for Alcorrosion in 1M HCl at 30Co
(Inhibitor Conc. (M T=30 CO
%IE θ
-6
10 *0 0 0
10-6*2 54.64 0.546
10-6*4 60.31 0.603
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10-6*8 66.32 0.663

10-6*12 70.03 0.700

.Adsorption consideration .3.2

The adsorption of an organic inhibitor on the surface of a

corroding aluminum specimen may be regarded as a
substitution process between the organic compound in the
aqueous phase and water molecules adsorbed on the
metal surface. Indeed, the adsorption of ETMAB was found
(
to follow the substitutional isotherm of Timken, given by(8
exp( -2aθ) = KC
(-(3

where ‘a’ is molecules interaction parameter, θ, is the

degree of surface coverage, ‘K’ is equilibrium constant of
adsorption process and ‘C’ is the concentration of the
inhibitor. The plot of surface coverage as a function of
.logarithms of inhibitor concentration
The free energy of adsorption is related to the equilibrium
:constant of adsorption, K by the following equation

( 4 )-

The plot of θ versus log C for Timken isotherm

gave a straight line for Al in 1M HCl inthe presence of
.(CTABr as shown in Figure (2
.The calculated value of K at 30Co amounts to 1.811

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 University of Chemical Engineering
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The free energy of adsorption, ΔGads, is associated with

water adsorption equilibrium. ΔGads was calculated from
the above relation. The obtained value of ΔGads at 30Co is
-11.615 KJ.mol-1. The negative value of ΔGads, here indicate
.that the adsorption process on Al surface is spontaneous

Figure 2. The relationship between covered area and

.CTABr inhibitor concentration at different temperatures

.Effect of temperature .3.3

The influence of temperature on the corrosion rate

of aluminum in 1M HCl is absence and in the presence of
different concentration of the used cationic inhibitor was
investigated by weight loss technique in the temperature
range (30 to 50Co). From the calculated values of %IE at
30, 40 and 50Co (Table 3). It is obvious that the inhibition
efficiency increases with increasing the concentration of
the compound and decreases by increasing the
temperature. The decrease in %IE is due to the desorption
of the molecules from the surface of the aluminum by
increasing the temperature. This indicates that the
inhibitor is physically adsorbed on Al surface. This
suggests that the adsorbed molecules mechanically
screen the coated part of the metal surface from the
.(action of the corrodent(8

Table 3. Effect of (CTABr) concentration on the %IE and

.θ for Alcorrosion in 1M HCl at 30,40 and 50 Co

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 University of Chemical Engineering
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Inhibitor T=30 CO T=40 CO T=50 CO

Conc.
%IE θ %IE θ %IE θ
((M
10-6*2 54.64 0.546 42.01 0.420 34.01 0.340
10-6*4 60.31 0.603 55.42 0.554 47.11 0.471
10-6*8 66.32 0.663 57.09 0.570 50.27 0.502
10-6*12 70.03 0.700 59.37 0.593 51.74 0.517

The values of ∆G (KJ/mole) change with the rang

of temperature, these values are consistent with
electrostatic interaction between charged molecules and a
charged metal (which indicates physical adsorption) these
values are negative in all cases and lie in the range
.(of -11.297 to -12.380 (KJ/mole) as shown in (Table 4

.Table 4. Isotherm Parameters

Isotherm Parameters
Temp. Co
ΔG Kads
30 11.615-
((KJ/mole 1.811
40 11.993- 1.807
50 12.380- 1.810

The apparent activation energies (Ea*) for the corrosion

process in absence and presence of CTABr were Evaluated
.(from Arrhenius equation(9,10

(5 )-
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 University of Chemical Engineering
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where Rcorr is the corrosion rate (mg/cm2.min), A is the

constant frequency factor and Ea* is the apparent
activation energy, R is gas constant (8.314 J/mol/Kelvin),
that by Plots of log (corrosion rate) vs.(1/T) as shown in
.figure 3

Figure 3. Arrhenius equation fitting for couple metals

with different concentration of CTABr. The addition of
CTABr modified the values of Ea*.This is attributed to the
.adsorption of inhibitors on Al surface

Table 5. Activation energy for different CTABr

.concentration

.CTABr conc ( Ea* ( KJ

10-6*2 40.1116-
10-6*4 43.8392-
10-6*8 44.5450-
10-6*12 47.7764-
The activation energy values shown in Table 5 for
HCl–inhibitor systems support the fact that the inhibitors
are physically adsorbed on Al surface. This is in agreement
.(with G.Y. Elewady(1) and E.E.Ebenso(11

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 University of Chemical Engineering
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Figure 4. Polarization curve for Al-Cu couple with CTABr

.inhibitor conc. (2 * 10-6) at different temperatures

Polarization measurements .3.4

Figure (4) shows the galvanostatic polarization curves for

aluminum in 1M HCl solution for (2 * 10-6 M) concentration
of inhibitor at different

.Temperature

The numerical values of the variation of corrosion

current density (icorr), corrosion potential (Ecorr.), Tafel
slopes (Ba and Bc), with the concentration of the inhibitor
:(are given in (Table 6). This indicates that(7

The corrosion current density (icorr) decreases with -1

increasing the concentration of the additive, which

indicates that the presence of this inhibitor retards
the dissolution of Al in 1M HCl and the degree of
inhibition depends on the concentration of the
.inhibitor
The data suggest that this compound act as mixed-2
type inhibitor because it enhances both the anodic
and cathodic processes but the anode is more
.polarized
The values of corrosion potential (Ecorr) shifted to-3
less negative values by increasing the concentration
.of the inhibitor

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 University of Chemical Engineering
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Table 6. Effect of CTABr concentration on the corrosion

potential (Ecorr), corrosion current density (icorr),and
Tafel slopes (Ba & Bc) for (2 * 10-6 M) concentration of
.inhibitor at 30 Co

CTABr E corr. Icorr.

Ba Bc
(Conc. (M ((mV ((µA/cm2

10-6*0 945.32- 217.506 208 97

10-6*2 943.93- 98.983 204 111
10-6*4 942.42- 86.682 199 112.4
10-6*8 939.02- 73.629 196 113
10-6*12 937.87- 65.816 194 115

:CONCLUSIONS .4
The corrosion rate of aluminum increase with rise in-1
.temperature

The corrosion rate decrease with increase in CTABr concentration-2

and the inhabitation efficiency increase with increasing the
.inhibitors concentration

CTABr give a good inhabitation for aluminum-3

.corrosion in hydrochloric acid solution
The CTABr inhibitor increase the value of activation energy of-4
corrosion and consequently decrease the rate of dissolution of
.aluminum in HCl solution
The inhibitor molecules are physically adsorbed on Al-5
.surface following temkin adsorption isotherm
Polarization measurements suggest that CTABr act as-6
.mixed type Inhibitor
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Surfactants as Corrosion Inhibitors for
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