EVALUATION NEW CATIONIC SURFACTANT AS

CORROSION INHIBITOR FOR CARBON STEEL IN

A METAL WORKING FLUID
N??? S???? Tantawy
Department of Chemistry, University College for Girls,
Ain Shams University, Cairo, Egypt
email?

ABSTRACT
Metal working straight oil contain large quantities of additive such as
corrosion inhibitors, in this paper we study the following additive as corrosion
inhibitor before will be use.
The corrosion inhibition of carbon steel by Di dodecyl benzyl tri ethyl
ammonium chloride (CS) is investigated in 1M H2SO4 using weight loss
measurements and galvanostatic polarization curves. The corrosion rate decreases The abstract will
with the inhibitor concentration from 10 to 130 ppm. It is found that the corrosion have maximum
rate decreases with immersion time from 5 to 20 days and then tends to be constant.
The results have shown that the lowest corrosion rate is for 75 ppm for (CS). The
10 lines, single
spacing, and should
effect of temperature on corrosion inhibition has been studied and the activation
give a brief account
energy for optimum conditions of the inhibitor has been evaluated. The corrosion
of the most relevant
inhibition of carbon steel in 1M H2SO4 containing (CS) has been attributed to
aspects of the paper.
adsorption of inhibitors over the carbon steel surface. Results are correlated will to
the chemical structure of the inhibitor. Some electrochemical parameters such as
Icorr, Ecorr, ba and bc are evaluated from galvanostatic polarization technique. The
results of inhibition efficiency evaluated from galvanostatic polarization technique
are in a good agreement with those obtained from weight loss technique.
Furthermore, Scanning Electron Microscopy (SEM) is used to examine the surface
morphology of the carbon steel samples both in absence and presence of each
inhibitor at optimum conditions.

KEYWORDS: Corrosion inhibition, Carbon steel, Cationic surfactants, Weight loss.

INTRODUCTION: of the well-known acid inhibitors are organic

Acids are widely used in various technological
processes in industry, e.g., in pickling baths, in the
extraction and processing oil and gas and in other
chemical and petrochemical industries. Also, in the
technical cracking of petroleum, acids appear as a
result of hydrolysis of salts and may have destructive
effect on the equipment. Corrosion due to acids are
important and expensive problem in the petroleum
refining units and it represents a significant portion of
loss as a result of lost production, inefficient
operation, high maintenance and the cost of corrosion
control chemicals. Inhibitors are compounds that
control, reduce, or prevent reactions between a metal
and its surroundings when added to the medium in
small quantities. Inhibitors should be effective in low
concentrations for economy. The use of inhibitors is
one of the most practical methods for protection
against corrosion, especially in acidic media [1]. Most
compounds containing nitrogen, sulphur and oxygen
atoms. The influence of organic compounds containing
nitrogen, such as amines and heterocyclic compounds,
on the corrosion of steel in acidic solutions has been
investigated by several workers [2-5].
In previous studies, ethoxylated fatty acid [6],
ethoxylated fatty amines [7], and propen-ethoxylated
diol [8] had been used as corrosion inhibitors for steel
and aluminum in acidic solutions. The existing data
show that the most organic inhibitors act by
adsorption on the metal surface. This phenomenon is
influenced by the nature and the surface charge of
metal, by the type of aggressive electrolyte and by the
chemical structure of inhibitors [9].
The inhibition efficiency (E %) depends on the
parameters of the system (temperature, pH, duration,
and metal composition) and on the structure of the
inhibitor molecule. It is well known that heterocyclic
compounds containing nitrogen atoms are good
corrosion inhibitors for many metals and alloys in
various aggressive media [1,2,5,9,10-16].
In the present investigation the corrosion
inhibition of carbon steel in 1M H2SO4 solutions in
absence and in presence of a new cationic surfactant
compound (Di dodecyl benzyl tri ethyl ammonium
chloride) (CS) has been studied using weight loss and
galvanostatic polarization techniques. The effect of
temperature and time of immersion on corrosion
inhibition have been studied. The inhibitive effect
upon using the best concentration of the inhibitor in
1M H2SO4 is also examined using scanning electron
microscopy.
1. EXPERIMENTAL RESEARCH
1.1. Materials?? and Solutions
1.1.1. Chemical composition of samples
Rectangular samples of size 10x10 mm were cut
from a sheet of carbon steel alloy for Weight Loss
Measurements, circular sheets of 100mm2 area for
Scanning Electron Microscopy, and a rectangular
samples of size 5x20 mm and 100mm2 area exposed
to the tested solutions for Galvanostatic Polarization
Technique. The chemical composition of the carbon
steel alloy is listed in Table 1.
Table 1: Chemical Composition of
Carbon Steel Alloy.
Element C Mn P Si S Fe
Analysis (%) 0.23 0.44 0.022 0.24 0.006 99.06
1.1.2. Inhibitor and solutions
Inhibitor: New cationic inhibitor supplied by
Omar and prepared as described previously [17] and
listed in Table 2. It is added in different
concentrations from 10 ppm to 130 to 1 M H2SO4 acid
solution.
Solutions: All solutions are prepared from 96 %
sulphuric acid solution with distilled water.
Table 2: Structure and name of the inhibitor
Name: Di dodecyl benzyl tri ethyl
ammonium chloride
Type of surfactant: Cationic (CS)
Structure:
C12H25
CH2N+ (CH2CH3)3 Cl-
C12H25
1.2. Surface Tension measurement
The surface tension was measured with Du Noy
tensiometer (KRUSS 8451) for various concentrations
of the surfactant solution (1M H2SO4) and at different
temperatures 30ºC to 50ºC. Accuracy of the surface
tension measured was ± 0.2 mN/m.
1.3. Procedures used for corrosion
measurements
1.3.1. Weight Loss Technique
The specimens are polished with different
grades of emery papers (300 – 800), cleaned with
distilled water, and then dried with absolute ethyl
alcohol. All the specimens are immersed in the same
volume of solution (50 ml).
1.3.2. Galvanostatic Polarization Technique
Polarization experiments are carried out in a
conventional three-electrode glass cell with a capacity
of 500 ml with a platinum counter electrode and a
saturated calomel electrode (SCE) as reference with a
fine Luggin capillary bridge to avoid ohmic
polarization. All tests were performed in deaerated
solutions under continuously stirred conditions. The
procedure adopted for the polarization measurements
was the same as described elsewhere [18]. A platinum
electrode is used as an auxiliary electrode and all
potential values are measured against a saturated
calomel electrode (SCE).
1.3.3. Scanning Electron Microscopy
A JEOL (5400) Scanning Electron Microscope
(Japan) is utilized to document the surface
morphology of various specimens of carbon steel. All
micrographs of corroded specimens are taken at a
magnification of X=3500.
2. RESULTS AND DISCUSSION
The surface tension ( γ ) as a function of logarithm
of the molar concentration of cationic surfactant (CS) in
1 M H2SO4 at different temperatures is shown in figure
1. From the intersection points in the γ - log C curve,
critical micelle concentration was determined.
The obtained critical micelle concentration
(CMC) shows a increasing trend with the increasing
temperature (Table 3), due to decrease in the
hydration of hydrophilic group which favour
micillization.
Table 3 some physical properties
of the synthesized CS
Temperatures
Parameters
o
30 C 40oC 50oC
CMC 73 78 93
Δ Gmic Kj/mol -23.5 25.6 28.5
γ CMC mN /m 33 35 32
 Fig. 1. Relation between surface tension and different concentration of
cationic surfactant (C).

The corresponding surface tension γ CMC and carbon chain length, where each molecule of (CS)
free energy of micellization Δ Gmic show decreasing contains two-dodecyl chain per molecule (C12) which
trend with the increasing temperature. act as octopus at adsorption. As the results the surface
The weight loss of carbon steel in 1M sulphuric coverage (θ) of compound is increasing more clearly.
acid with the addition of various concentrations of This surface coverage (θ) is calculated using the
cationic (CS) surfactant as chemical inhibitor is following equation:
measured and ploted in figure 2. It shows the effect of ' − R'
R0
θ= (1)
adding various concentrations (10 ppm - 130 ppm) of '
R0
(CS) on the corrosion of carbon-steel at 30oC. From
this figure we notice that the corrosion rate decreases where R '0 and R ' are the corrosion rates in the
and the inhibitor efficiency increases with increasing absence and in the presence of a given inhibitor CS
immersion time from 5 to 20 days, then it give a respectively. The percentage inhibition efficiency,
constant value. This means that, the values of surface (P%), of (CS) is calculated by applying the following
coverage (θ) and the percentage inhibition efficiencies equation [19-20]:
% (P) increase markedly with increase of inhibitor R' − R'
concentration. This behavior confirm the dependence P% = 0 ⋅100 (2)
of inhibition efficiency on carbon number of hydro- R'0

Fig. 2. Variation of the inhibition efficiency of (CS) with concentrations

on carbon steel in 1M H2 SO4 at different time intervals
 Table 4: Inhibition efficiencies of carbon steel: a)?? in different concentrations
of (CS) in 1M H2SO4 solution at different times of immersion

Cationic Inhibitor Concentration (ppm)

Number of days 10 25 50 75
θ P% θ P% θ P% θ P%
5 0.50 50 0.72 72 0.58 85 0.95 95
10 0.45 45 0.67 67 0.79 79 0.90 90
15 0.41 41 0.62 62 0.76 76 0.88 88
20 0.34 34 0.58 58 0.73 73 0.84 84
25 0.858 30 0.869 54 0.901 70 0.943 82

Table5:Inhibition efficiencies of carbon steel: a) in different concentrations of (C) and

b) (N) )??? in 1M H2SO4 solution at different times of immersion

Surface coverage (θ) and corrosion inhibition efficiency P (%)

Cationic inhibitor concentration (ppm)
Time of immersion (days)
10 25 50 75
θ P θ P θ P θ P
5 0.184 18.4 0.22 22 0.364 36.4 0.554 55.4
10 0.465 46.5 0.494 49.4 0.603 60.3 0.78 78
15 0.797 79.7 0.812 81.2 0.843 84.3 0.91 91
20 0.858 85.8 0.869 86.9 0.901 90.1 0.943 94.3
25 0.858 85.8 0.869 86.9 0.901 90.1 0.943 94.3

The measured surface coverage (θ) and the
percentage inhibition efficiency (P%) are represented
in Table 4.
It can be suggested that, cationic inhibitor CS
contact between the steel surface and the acid
solution. It exists at the interface and attaches or
adsorb to the metal surface. The adsorption takes
place by head group-N+- and tail group (hydrocarbon
chain) of each molecule forming barrier film. The
hydrophilic group-N+- with its counter chloride ion is
adsorbed onto the steel.
Surface by electrostatic attraction while the
hydrophobic (two dodecyl group C12H25) covered
the steel. The adsorption takes place by dipole –
induced interaction with the steel surface as a result of
π – electron polarization.
Tail Head
C12H25
CH2N + (C2H5)3
C12H25
At same time, immersion of carbon steel in
1M H2SO4 show an adsorption of the sulphate ions on
the steel surface leading to the availability of more
negative sites on the metal surface. As the result,
hydrophilic group prefer adsorptions on the steel surface.
The optimum concentration of CS is 75 ppm,
this value represents the critical micelle concentration
(CMC) of (CS) (fig. 1).
The decreasing in efficiency with time can be
interpreted in terms of inverse direction of hydrophilic
group adsorption of the cationic surfactant CS and
increase repulsion forces between the adsorbed
molecules of the inhibitor.
At 1M of sulfuric acid, the inhibition efficiency
decreases sharply with the increase in temperature
from 30-50oC (Table 5 ).
This can be attributed to destruction of the
inhibitive layer formed on the steel surface at higher
temperature. Also the adsorbed molecules tend to de-
adsorptions due to increase repulsion forces between
chain of CS molecules, as results the inhibitor
molecule tend to form CMC in solution / air interface
and increases values of CMC (Table 2). It can be
concluded that, the increase of temperature distorted
the adsorbed layer and retard micellization process.
The specific adsorption of the anion having a smaller
degree of hydration, such as chloride ions is expected
to be more pronounced. Being specifically adsorbed,
they create an excess negative charge towards the
solution and favour more adsorption of the cations.
Moreover data in figure 2 and Table 5 reveal
that the corrosion rate decreases with time of
immersion up to 20 days then tend to be constant, this
is due to the formation of oxide layer (Fe2O3)
according to the following equation
2FeSO4 (S) + 3 H2O Fe2O3 + 2H+ + 2H2SO4 + 2e-
The activation energies of the metal dissolution
reaction (Ea) for solution of 1M H2SO4 containing
various concentrations of each inhibitor can be
determined from the Arrhenius relation20 ???from
were
 − Ea 
k = A exp   (3)
 RT 
 Fig. 3. Variation of logarithm of corrosion rate with the reciprocal of absolute temperature
for carbon steel in 1 M H2SO4 containing 75 ppm CS for different time of immersion.

Imposible to read axis names and values! Please replot the diagram!
Figure 4 : Galvanostatic polarization curves for carbon steel in 1M H2SO4 in presence 75 ppm CS inhibitor

That is, by determination of the slopes of the
straight lines that depict the linear dependence of the
logarithm of the corrosion rate, ln(k), on the
reciprocal value of the absolute temperature. The
activation energies increases up to 20 days and then
tend to be in a stable value as shown in figure 3.
The dissolution reaction in presence of (CS) is
higher than blanck. The obtained results of activation
energies are all tabulated in Table 6.
2.1. Galvanostatic Polarization Technique
At optimum conditions the polarization curves
slopes (i.e., cathodic [bc] and anodic [ba] Tafel slopes) are
calculated from Tafel plots and are given in Table 7.
The lower Icorr is for 1M H2SO4 containing 75
ppm of (C), Ecorr values not show any significant
variations for 1M H2SO4 containing 75 ppm and
none of the inhibitor showed significant changes in ba
and bc slopes, indicating that (CS) is adsorbed.
??????rosion inhibition efficiency P(%) is
calculated using equation (21 from were??):
 
I 
P = 1−  corr  ⋅100 (4)
I
  corr ,o 

for these inhibitors are shown in Figure 4.
?????missing words? onto the metal surface without
affecting the anodic- and cathodic-reaction
mechanisms.
Electrochemical parameters such as corrosion
potential (Ecorr), corrosion current density (Icorr), and Tafel
where Icorr,o and Icorr are the corrosion current
densities in the absence and presence of inhibitor
respectively. The comparison between the values of
inhibition efficiencies by weight loss and
galvanostatic polarization techniques after 25 days at
30oC are compared in Table 8.
 Table 6:Activation energies of carbon steel Table 7: Polarization parameters for the
atoptimum concentrations of (CS) in 1M H2SO4 corrosion of carbon steel in 1M H2SO4
solution at different times of immersion containing 75 ppm of (CS)

Time Ea (k J mol-1)

bc (mV.dec-1)

ba (mV.dec-1)
(mA/cm2)
Ecorr (mV)
(Days) Cationic Inhibitor Inhibitor

Icorr
5 8.05 concentration
10 15.26 (ppm)
15 30.18
20 37.85 1M H2SO4 -550 0.39 111 75
25 37.85 75 ppm of (C) -536 0.02 107 70

Table 8: Inhibition efficiencies P(%) from weight loss and galvanostatic polarization techniques
for carbon steel in 1M H2SO4 containing optimum concentrations of (C) at 30oC
Inhibition efficiency P (%)
????hibitor
using using Weight
concentration
Polarization loss
(ppm)
Technique Technique
75 ppm of (CS) 94.86 97

It is observed that the results of surface coverage The micrograph reveals that, there is a decrease
in presence of inhibitor (CS) are in a good agreement in the corrosion sites and pits over the surface of the
with those given by weight loss technique. This carbon steel. In figure 6 it appears that the surface of
means that the inhibition efficiency calculated the specimen is covered greatly due to formation of
???by?? galvanostatic polarization technique are surface film of the inhibitor. From these observations
nearly equal to the values obtained by weight loss we can say that the cationic inhibitor give a good
technique. inhibition effect for the carbon steel and this confirms
the results obtained from the other techniques.
2.2. Scanning Electron Microscopy
Figure 5 shows SEM image of the surface of the
carbon steel specimen after immersion in 1M H2SO4
solution for 20 days at 30oC.
The micrograph reveals that, the surface is
strongly damaged in the absence of the inhibitors
(active corrosion). Figure 5 and SEM image of the
surface of another carbon steel specimen after
immersion for the same time interval in 1M H2SO4
solution containing 75 ppm of the inhibitor (CS).

Fig. 6: Scanning electron micrograph of carbon steel

samples after immersion in 1M H2SO4 solution in
presence of 75 ppm of inhibitor (CS).

3. CONCLUSIONS

Di dodecyl benzyl tri ethyl ammonium chloride

Fig. 5. Scanning electron micrograph of carbon steel
sample after immersion in 1M H2SO4 solution.
(CS) behave as inhibitor for carbon – steel corrosion
in 1M H2SO4 from 5 days to 20 days at 30oC, it was
found that, the corrosion rate decreases with time of
immersion up to 20 days then tend to be constant. The
corrosion rate increases with temperature. The results
of SEM indicate that, the inhibitive efficiencies of
each inhibitor are high and the most effective
inhibitor is the cationic one, which is in a good
agreement with the studied techniques.
 ACKNOWLEDGEMENT
The author gratefully acknowledges Assistant
Professor Dr. A.M.A. Omar, Egyptian Petroleum
Research Institute, Nasr City, Cairo, Egypt for his
assistance and support.
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