20120140505004

International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 – 6480(Print),
ISSN 0976 – 6499(Online) Volume 5, Issue 5, May (2014), pp. 30-39 © IAEME
30
UREA FERTILIZER AS CORROSION INHIBITOR FOR REINFORCED
STEEL IN SIMULATED CHLORIDE CONTAMINATED CONCRETE PORE
SOLUTION
Abdulrasoul Salih Mahdi1*
1
Electrochemical Eng. Department, College of Engineering,
Babylon University, Iraq
ABSTRACT
Urea is worldwide used in agriculture as a fertilizer .This paper presents an experimental
study on the inhibition effect of urea fertilizer on corrosion of reinforced steel in concrete immersed
in simulated concrete Pore (SCP) solution using open circuit potential and potentiodynamic
polarization technique. SCP solution consist of 2% potassium hydroxide and 3% NaCl solution was
used. Various percentage of urea from 0.2%, 0.5%, and 1% in SCP solutions were examined in this
experiment .The open circuit potential tests showed that the potential of reinforced steel samples
immersed in SCP solutions containing urea fertilizer was moved more positive than that in control
sample.
Potentiodynamic polarization measurements showed a shifting in Corrosion potential (Ecor)
toward positive direction and a decreased in corrosion current density (Icor), corrosion rate (CR) of
steel samples immersed 2 hr and 7 days in SCP solutions containing urea inhibitor compared with
control sample which is an indication of formation of protective passive film on steel surface and
also indicate that urea fertilizer maintained stable passivity even in presence of aggressive chloride
ions. Polarization curves showed that urea acts as mixed type inhibitor controlling the anodic
reaction predominantly. The results explained that after 7 days of immersion in SCP solutions the
highest inhibition efficiency was 86.15% at 0.5% urea concentration. Falling the inhibition efficiency
of urea inhibitor to 72.6% at 1% concentration indicate that increasing the concentration is not useful
and appropriate amount of inhibitor must be used. The experimental results of this paper showed that
urea is an effective inhibitor, gave good corrosion inhibition for concrete reinforced steel immersed
in SCP solutions during the period of this study.
Keywords: Urea Fertilizer, Reinforced Steel, Corrosion, Corrosion Inhibitor, Simulated Pore
Solution.
INTERNATIONAL JOURNAL OF ADVANCED RESEARCH
IN ENGINEERING AND TECHNOLOGY (IJARET)
ISSN 0976 - 6480 (Print)
ISSN 0976 - 6499 (Online)
Volume 5, Issue 5, May (2014), pp. 30-39
© IAEME: www.iaeme.com/ijaret.asp
Journal Impact Factor (2014): 7.8273 (Calculated by GISI)
www.jifactor.com
IJARET
© I A E M E

31
INTRODUCTION
Corrosion of reinforced steel in concrete represents the major problem worldwide [1].
Reinforced steel corrosion happen mainly due to the penetration of chloride ions to steel surface
which destroy the passive film that originally formed on the rebar surface due to the alkalinity of
cement paste (PH 12.5–13.5) during concrete casting [2]. Chloride ions act as catalyst to corrosion
when present in sufficient amount at rebar surface, they are not consumed in the process and permit
the corrosion to proceed quickly in addition they are absorb and retain moisture which increase the
water content in concrete pores solution and then increase the electrical conductivity of the concrete
and accelerate the corrosion. [3]
Fe+2
+2Cl-
= Fe Cl2
Fe Cl2+2OH-
= Fe (OH)2 +2 Cl-
The deposition of corrosion products with a volume of two to four times the original steel in a
restricted space around the rebar sets up an expansive stress which may crack and spall the concrete
cover[4,5]. Corrosion prevention of concrete reinforced steel has been widely studied and various
methods were suggested to delay, slow, or stop the corrosion of reinforcement and then enhance the
service life of concrete structure such as cathodic protection, anodic protection, coating and
inhibitors[6,7,8]. Corrosion inhibitors are a chemical substances that when added in small amount to
concrete mix decrease or slow down corrosion rate by changing the surface condition of the
reinforced steel, they are widely used as the most applicable and economical way to prevent
corrosion of concrete reinforcement [9,10]. Most of corrosion inhibitors are classified as organic and
in organic inhibitors according to its chemical nature and to anodic, cathodic or mixed inhibitors
according to the electrochemical reaction on the steel surface and its environment [11].Corrosion
inhibitors, both inorganic and organic, have been developed to prevent or slowing the corrosion rate
of steel rebar . Many authors reported about using inorganic and organic inhibitors in corrosion
prevention of concrete reinforced steel [12, 13, 14].
Inorganic inhibitors interfere with anodic or cathodic reaction of the corrosion process in
order to form passive film on steel surface [15].Inorganic inhibitors were proved as one of the most
effective in preventing corrosion of steel in concrete [16,17, 18] , leaching problem toxicity, as well
as their harmful environmental effect have highly reduced its applications [19, 20].
Organic inhibitors acting over the anodic or cathodic reaction or both to prevent the breakdown of
the passive film by building a mono molecular film act as a barrier between the metal and the
environments (water, oxygen, chloride ions) [21, 22, 23, 24]. Among the organic inhibitors the
compounds that containing nitrogen, oxygen or sulphur atoms have been proven by several
researchers to be effective in decreasing corrosion rate in acidic media, most of these compound
form coordinated bond with the steel surface by electron transferring and then form complexes with
iron which act as a protective film inhibit there bar corrosion[25,26 ]. Research efforts have been
carried out to formulate environmental friendly acceptable, nontoxic organic corrosion inhibitors [27,
28, 29].
To evaluate the efficiency of inhibitors in preventing reinforced concrete steel from corrosion
there are generally two methods, one uses actual concrete specimens and the other uses the simulated
pore solution test [30].Several research papers have been investigated the corrosion behavior of
reinforced concrete steel in simulated alkaline concert pore solutions (pH 12 -13.5), that mainly
consist of saturated calcium hydroxide Ca (OH)2, sodium hydroxide NaOH and potassium hydroxide
KOH [31-33], some researchers used a saturated calcium hydroxide alone to represent concrete pore
solution[21,34-40],others used mixture from saturated calcium hydroxide and sodium hydroxide or
potassium hydroxide and sodium hydroxide to simulate pore solution[19,30,41].In this research 2%
KOH solution contain 3% NaCl (pH 13.46) was used to represent the alkalinity of chloride

32
contaminated concrete pore solution (SCP solution).
Urea fertilizer is organic compound contains two nitrogen atom [CO (NH2)2] and one oxygen
atom enable it to decrease corrosion rate of metals and alloys. Few research works were done on the
corrosion inhibition of urea and its derivatives in sea water and acidic media [27.28, 42]. Urea
fertilizer is cheap environmental friendly, it is used widely and safely in agriculture as a fertilizer, so
in this study urea was examined as a corrosion inhibitor for reinforced concrete steel immersed in
simulated alkaline pore solution containing 3% NaCl salt using open circuit voltage measurements
and potentiodynamic polarization technique.
EXPERIMENTAL WORK
Reinforcement Steel Preparation
The steel rebar was procured from a local supplier which is currently used as concrete
reinforcement. For open circuit voltage four test samples were made by cutting the reinforcing steel
into a pieces each with 5 cm length and 0.95 cm diameter. One end of the test specimen was soldered
to copper wire in order to use as electrical connection. An abrasive grinder was used to remove the
mill scales and rust stains. The specimens were washed thoroughly with deionized water, degreased
with acetone and dried. 25 mm of the bar was defined as the exposed length and the remaining length
painted with PVC resin. For potentiodynamic polarization tests steel discs of 10 mm diameter were
cuts from steel bar and then braded with abrasive grinder machine.
Solutions preparation
Urea fertilizer (locally produced) and potassium hydroxide KOH, Sodium chloride NaCl
(analytical grade) was purchased from local supplier, in order to use in this work. KOH solution was
prepared by stirring appropriate amount of solid KOH substance in de-ionized water to obtain 2%
KOH solution to simulate the alkalinity of concrete pore solution. 3% NaCl was added to this
solution to form SCP solution (control solution PH 13.46). 0.2 %, 0.5% and1% urea fertilizer were
added to the SCP solution to form three urea inhibitor solutions. In this study four different solutions
were prepared, the first one SCP solution (control solution) and the other three solutions were the
urea inhibitor solutions.
Electrochemical Measurements
Open circuit potential and potentiodynamic polarization measurements were used in this
study to evaluate the corrosion behavior of the reinforced steel in SCP solution with and without urea
inhibitors
Open Circuit Voltage Measurement
When corrosion starts excess electrons liberate from the anode (reinforced steel) and tend to
flow toward the cathode (external electrode) which give a negative voltage on voltmeter reading, so
more negative voltage reading indicate higher corrosion process on the rebar surface, open circuit
voltage method only give indication about the corrosion activity at the time of measurement, it does
not give any indication about the corrosion rate [43, 44]
To show the corrosion inhibition of urea fertilizer, open circuit voltage tests were carried out
for reinforced steel specimens in different SCP solutions. The first solution was a control solution,
the other three solutions consist of the control solution with urea inhibitor at concentrations of 0.2 %,
0.5 %and 1%of solution respectively.
Open circuit voltage was measured at interval of 2 days for a period of 28 days using
standard calomel electrode (SCE) as reference electrode and high impedance digital voltmeter to
measure the voltage, the reference electrode was connected to the common terminal of the digital
voltmeter, whereas the reinforced steel (working electrode)was connected to the +ve terminal to get a

33
complete electrical circuit. The more negative reading of the voltmeter means the high corrosion
activity on the reinforced steel at the time of experiments, according to this method if the potential is
more than- 0.276 V (SCE) the probability of active corrosion is very high (95%). Potential less than-
0.126 V(SCE), very high probability of no corrosion. Potential in the range of - 0.126 V to - 0.276 V,
approximately 50% probability of corrosion, and potential more than – 0.426V indicate sever
corrosion condition [45]
Polarization measurements
Polarization measurements were carried out with Wenking M Lab Potentiostat Galvanostat
instrument (GERMAN origin) under potentiodynamic conditions. This instrument itself is having
programs to evaluate corrosion parameters such as corrosion current (Icorr), corrosion potential
(Ecorr), anodic Tafel slope (ba) and cathodic Tafel slope (bc). Three electrode cell consist of a
specimens as a working electrode, Ag/AgCl electrode as a reference electrode, and Platinum wire as
a counter electrode was used in this experiment. The working electrode was rebar steel disk axially
embedded in a Teflon holder to offer a flat disc shaped exposed surface area of 0.785 cm2
. The steel
discs were mechanically polished with different grades of emery papers up to mirror finish,
degreased with acetone then rinsed with distilled water and dried before each electrochemical
experiment. Control specimen was immersed in SCP solution and the other specimens immersed in
SCP solution containing urea fertilizer inhibitor at concentrations of 0.2%, 0.5% and 1%
respectively. The experiments were performed after 2 hour of immersion as initial, and 7 days of
immersion as final to verify the stability of passive film in presence of corrosive chloride ions.
Potentiodynamic polarization curves were conducted by changing the electrode potential
automatically ± 250 mV around the open circuit potential at a scan rate of 1 mV/s. From Tafel plot
corrosion parameters such as Ecorr, Icorr, ba and bc were recorded. Corrosion rate (mmpy),
corrosion inhibition efficiency (IE %) was calculated and reported using the following equations[21].
Corrosion rate (mmpy) = 3.2 x Icor x equivalent weight / density
IE %=(IO- I) /IO× 100
Where:
Equivalent weight of steel=27.93 gm,
Steel density = 7.8 gm/ cm3
,
Icor= current densitymA/ cm2
IE = inhibition efficiency
IOand Iare the corrosion current density without and with the inhibitor respectively.
RESULTS AND DISCUSSION
Open Circuit Potential Measurements
Figure 1 shows the variation of open circuit potential of concrete reinforced steel with
exposure time for the SCP solution (control solution) and SCP solutions containing 0. 2%, 0.5%, and
1% urea respectively. For the first sixteen days of the exposure period, it was observed that the
reinforced steel sample in control solution showed active corrosion condition with a potential reading
increased from-0.38 v to - 0.53 v (SCE), this is an indication of anodic reaction and then corrosion
occurred at the steel surface due to the attack of chloride ions that presents in alkaline medium
around the steel rebar. From about the day 17 to the day 23 the potential shifted toward the less
active region (from - 0.53v to -0.4v), this is may be the corrosion product that accumulated on the
steel surface stifled the corrosion reaction [44].Again the potential shifted toward the active region
after the day 23, potential of - 0.49v at the day 26 indicate that the corrosion started increasing may

34
be due to the dissolution of corrosion products leaving iron surface exposed again to the chloride
ions which succeeded in destroying the passive film.
On the other hand the figure showed that the potential readings of steel rebar immersed in
solutions containing 0.2% , 0.5 %, and 1 %urea fertilizer moved gradually toward the passive region
with fluctuation indicating a passive film building up due to the inhibition effect of urea fertilizer
with these concentration compared with the control sample during the time of the experiment and it
is clear from the figure that the corrosion inhibition of urea fertilizer was more effective starting from
the day 16th
till the end of the experiment. This is may be due to the thickening of the protective film
at that time.
Figure 1: potential variation of reinforced steel samples with the exposure time in chloride
contaminated simulated pore solutions with and without urea inhibitor
Potentiodynamic polarization
Tafel polarization curves of reinforced steel samples in SCP solution without and with
various concentration of urea inhibitor for 2 hr immersion are shown in figures 2. Corrosion current
(Icor), corrosion potential (Ecor), anodic Tafel slope (ba) and cathodic Tafel slope (bc) were
measured from Tafel plots, Corrosion parameters such as corrosion rate (CR), inhibition efficiency
(IE %) were calculated from the measured parameters. All of these parameters were reported in table
1. The table shows that the Icor and CR values of reinforced steel sample in control solution is 20.19
µA/cm2 and 0.236 mmpy respectively, they decreased in the presence of urea inhibitor, the lower
value of 5.26 µA/cm2 for Icor and 0.062 mmpy for CR was achieved at concentration of 0.5% urea.
Corrosion inhibition efficiency is 64.53% for 0.2% urea, 85.53 % for 0.5% urea solution and 70.28%
for 1% urea solution, this observations indicate that maximum inhibition efficiency was achieved at
0.5% urea concentration and the increasing urea concentration to 1% decreased the inhibition
efficiency to 70.28%, this may be at higher concentration of inhibitor the passive film formed (Fe+2
– urea complex) on steel surface goes to the solution which lead to weak protective film [44].
Furthermore it is clear from the table that the reinforced steel corrosion potential immersed in SCP
solution (control solution) was (- 462.4 mV Ag-AgCL) and the presence of urea fertilizer with
various concentration in SCP solution shifted the potential toward the more positive direction (-
414.8 mV Ag-AgCL for 0.2% urea, - 379 mV Ag-AgCL for 0.5% urea, and - 414.9 mV Ag-AgCL
for 1% urea),in addition there was a decreasing in the corrosion current density due to the presence
of inhibitor . This is an indication that urea fertilizer control the anodic reaction predominantly [19,
45]. Also the decreasing of anodic Tafel slopes values (ba) with increasing inhibitor concentration
indicate that urea fertilizer act as mixed type inhibitor inhibited iron dissolution at anodic site by
-0.60
-0.40
-0.20
0.00
0 4 8 12 16 20 24 28
PotentialmVVs.(SCE)
Exposoure time ( day)
control 0.2% urea 0.5% urea 1% urea

35
forming a protective passive film(F+2 – urea complex) on the steel surface and control hydrogen
evolution process at the cathodic site[46, 47].
Figure 2: Tafel polarization curves of the reinforced steel after 2 hr immersion in the SCP solutions
without and with various concentrations of urea fertilizer inhibitor
Table 1: Polarization parameters for reinforced concrete steel after 2 hr immersion in the SCP
solution without and with different concentrations of urea inhibitor
System Ecor
mV
Icor
µA/cm2
ba
mV/dec
bc
mV/dec
CR
mmpy
IE
%
Control -462.4 20.19 456 251 0.236
Control + 0.2% urea - 414.8 7.16 288.6 218.7 0.083 64.53
Control +urea0.5% -378.3 5.26 286.4 250.9 0.062 83.53
Control + 1% urea -414.6 6 241.4 294 0.07 70.28
Corrosion parameters such as Ecor, Icor, ba, bc, corrosion rate (mmpy), IF % for the steel
samples exposed to various inhibitor system for 7 days were measured and calculated from Tafel
plots and reported in table 2 and shown in figure 3. The table shows that Icor and CR values for
samples immersed in SCP solution containing urea fertilizer decreased higher than that after 2hr
immersion, the lower values of Icor (2.77 µA) and CR (0.0324 mmpy) was achieved at 0.5% urea.
Ecor of steel samples in urea inhibitor system also moved toward noble side and ba decreased with
increasing inhibitor concentration. This is an indication that the urea inhibitor maintained stable
passivity even in the presence of aggressive chloride ions. This results indicate that urea has ability to
be a good corrosion inhibitor for reinforced concrete steel, the inhibitive power of urea may be due to
the presence of the nitrogen and the oxygen atoms in its structure which give it the ability to enhance
the inner protective layer of ɤFe3O4 that originally formed on the steel surface due to the high
alkalinity of pore solution by forming protective outer layer of urea – fe+2
complex [21, 42].
Maximum efficiency of 86.25 % was achieved at urea concentration of 0.5% urea. Decreasing
inhibition efficiency to 72.6 % with increasing urea concentration to 1 % indicating that increasing
the concentration is not useful and appropriate amount of inhibitor must be used [25].
-800
-600
-400
-200
0
-5 -4 -3 -2 -1 0
PotentialmVvsAg-AgCL
Log I ( mA)
control 0,2% urea 0.5% urea 1 % urea

International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976
ISSN 0976 – 6499(Online) Volume 5, Issue 5, May (2014), pp.
Figure 3: Tafel polarization plots of reinforced steel after 7 days of immersion in SCP solution with
and without urea fertilizer inhibitor
Table 2: Polarization parameters for reinforced concrete steel after 7 days immersion in in the SCP
solution without and w
CONCLUSION
From this study the following can be concluded:
1- Urea fertilizer can be used as eco
concrete steel.
2- Urea fertilizer that was used in this study at 0.2%, 0.5%
effective for corrosion inhibition of mild steel reinforcement immersed in simulated concrete
pore solution containing 3% sodium chlo
3- The best result and hence the best corrosion inhibition performance of the steel reinforcement
was obtained in this work with 0.5% urea concentration ,
week of immersion in test solution
4- Appropriate amount from the urea inhibitor must be used since increasing the concentration to
1% gave low inhibition efficiency and high corrosion current and corrosion rate.
5- Tafel plots of reinforcement steel in SCP solution witho
as a mixed inhibitor control anodic reaction predominantly by forming F+2
anodic site.
6- Studies with actual concrete specimens are needed to know the effect of urea fertilizer on the
compression strength of the concrete.
7- Long time studies are needed to make final recommendations ab
for the protection of concrete reinforced steel.
-800
-600
-400
-200
0
-5 -4
PotentialmVvs.Ag-AgCl
0,5 % urea
System Ecor
mV
Control - 464.9
Control + 0.2 % urea -416.3
Control+ 0.5 % urea -296.6
Control + 1% urea -345.8
urnal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976
6499(Online) Volume 5, Issue 5, May (2014), pp. 30-39 © IAEME
36
polarization plots of reinforced steel after 7 days of immersion in SCP solution with
and without urea fertilizer inhibitor
Polarization parameters for reinforced concrete steel after 7 days immersion in in the SCP
solution without and with various concentrations of urea inhibitor
From this study the following can be concluded:
rea fertilizer can be used as eco- friendly inhibitor decease efficiently the corrosion rate of
Urea fertilizer that was used in this study at 0.2%, 0.5%, 1% concentrations respectively was
3% sodium chloride at the ambient temperature.
The best result and hence the best corrosion inhibition performance of the steel reinforcement
his work with 0.5% urea concentration , the inhibition efficiency after one
in test solution was 86.15% and corrosion rate was 0.0324 mmpy
Appropriate amount from the urea inhibitor must be used since increasing the concentration to
Tafel plots of reinforcement steel in SCP solution without and with urea showed that urea act
as a mixed inhibitor control anodic reaction predominantly by forming F+2 –
Studies with actual concrete specimens are needed to know the effect of urea fertilizer on the
ength of the concrete.
Long time studies are needed to make final recommendations about the dose of these inhibitor
n of concrete reinforced steel.
-3 -2 -1
Log I mA
0,5 % urea 0.2% urea 1% urea Control
cor
mV
Icor
µA/ cm2
ba
mV/dec
bc
mV/dec
CR
mmpy
464.9 20 456.4 242.7 0.234
416.3 7.24 291.1 218.6 0.085
296.6 2.77 278.6 231.1 0.0324
345.8 5.48 234.7 199.4 0.064
urnal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 – 6480(Print),
polarization plots of reinforced steel after 7 days of immersion in SCP solution with
Polarization parameters for reinforced concrete steel after 7 days immersion in in the SCP
friendly inhibitor decease efficiently the corrosion rate of
1% concentrations respectively was
The best result and hence the best corrosion inhibition performance of the steel reinforcement
the inhibition efficiency after one
te was 0.0324 mmpy.
Appropriate amount from the urea inhibitor must be used since increasing the concentration to
ut and with urea showed that urea act
urea complex on
Studies with actual concrete specimens are needed to know the effect of urea fertilizer on the
out the dose of these inhibitor
0
Control
CR
mpy
IE%
0.234
0.085 63.8
0.0324 86.15
0.064 72.6

37
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