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Modelling of mild steel corrosion using COMSOL Multiphysics

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MODELLING OF MILD STEEL CORROSION USING COMSOL

MULTIPHYSICS

Azeez Abdullah Barzinjy*, Kadhim Qasim Jabbar, Haidar Jalal Ismael ,

Department of Physics, College of Education, University of Salahaddin

*
azizbarzinjy@[Link]

Abstract: Corrosion is destruction of metals by interaction with the

environment. It can cause structural failure, hazards and also threats in
health and safety issues and great economic damage. Corrosion is an
electrochemical procedure that includes an anodic reaction (metal
oxidation) and a cathodic process (reduction of a solute usually O 2 or H+).
Moreover, corrosion is one of the most damaging types of metal loss. The
aim of this study is to develop a finite element package COMSOL Multi-
physics (Version 5). This Model can be utilized with experimental data to
demonstrate the galvanic corrosion prediction of mild-steel immersed in
aqueous NaCl solution as an electrolyte. The effects of disc radii and
electrolyte conductivity have been examined. The anodic reaction is
presumed to follow Tafel’s law and depends not only on H + concentration
but also on the dissolution rates. The origin of this corrosion is due to the
presence of an insulating film on the mild-steel surface or the kinetics of
either the anodic or cathodic processes. The outcomes of this study are in a
good agreement with the experimental results and available models
reported in literature.

Keywords: Corrosion, Current Density, Electrode, Electrolyte, COMSOL

Multi-Physics

1. Introduction
Corrosion is commonly divided into two main areas, high temperature corrosion
with the contact of solid surfaces by hot and destructive gases and aqueous
corrosion with the degradation of materials in contact with aqueous

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electrolyte.(Marcus & Mansfeld, 2005) Even in the circumstance of

atmospheric corrosion the surface of materials is exposed to thin electrolyte
layers sometimes with consecutive wet and dry periods. Metal surfaces are the
most important area although corrosion may possibly occur to nonmetallic
materials for instance semiconductors, insulators, and even polymers. The
approaches to study corrosion depend conclusively on the systems. Aqueous
corrosion was typically a field of electrochemical research and numerous
electrochemical methods have been applied to the investigation of corrosion of
metals in electrolytes. These methods offer a respectable qualitative and
quantitative vision.(Marcus & Mansfeld, 2005)

The corrosion inhibition of mild steel is a focus of fabulous technological

importance due to the increased manufacturing applications of this
material.(Trabanelli, 1991) Although mild steel is inexpensive, it is very
vulnerable to uniform corrosion in unbiased conditions which are environment
at temperature 25oC, absolute pressure 1 atm and gas constant 8.314 J mol-1 K-1.
These circumstances are also specified as standard conditions.(Li, Feng, Bai,
Zhu, & Zheng, 2007)

Galvanic corrosion can take place once two unlike metallic alloys are in
electrical contact with each other for electron transference and are exposed to a
conductive environment such as salt water that offers a medium for ionic flow.
A material with a lower free corrosion potential (Ecorr) in a galvanic couple turn
out to be more active and corrodes favorably. Corrosion harshness of a galvanic
couple relies upon numerous factors for instance Ecorr difference between the
unlike metal alloys, polarization behavior of specific alloys, anode to cathode
area ratio, electrolyte conductivity, distance between the unlike metal alloys,
etc.(Revie, 2008)

In this article, it seemed interesting to precede with a study of the corrosion of

mild steel in1to 10% NaCl solution. We address the challenge of estimating the

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corrosion behavior of a galvanic couple from the corrosion behavior of the mild
steel samples. The galvanic series delivers qualitative data about the corrosion
harshness based on the free corrosion potentials of the mild steel samples. In
this work, a more sophisticated design using the finite element package
COMSOL Multi-physics (Version 5), which is accomplished of clearly tracking
the moving interface, is used. The corrosion rates of the galvanic reaction
computed using the numerical model is compared with experimental techniques
and the immersion technique. In the immersion technique, a surface profile is
obtained after immersing a galvanic couple over a specific period of time, which
is used to authenticate the same obtained using the present moving boundary
formulation. The experimental details and results are separately reported in ref
(Deshpande, 2010). The electrodes can be cut from mild steel specimens having
2 mm thickness and the composition presented in table1.(Jizhou et al., 2002)

Table 1. The chemical component of mild steel

Element C Mn S P Si Cr Mo Al V
Ti Fe
Mild steel 0.2 0.55 0.009 0.015 0.25 <0.10 <0.05 <0.03 <0.03
<0.03 residual

The electrodes can be fixed to pyrex glass tubing with araldite so that the total
uncovered area was 2 cm2. Electrical contact can be achieved through thick
copper wires soldered to the electrodes. The mild steel electrodes must abrade
before using with sand papers. The abraded electrodes must wash by deionized
water then washing with acetone.

The mild steel rods with 2 cm2 area were used as the working electrode. The
electrodes were sealed and their surfaces were polished as described above. A
saturated calomel electrode and a platinum electrode with 2 cm2 were the
reference and the counter electrodes, respectively. Luggin capillary (Figure 1)

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and an agar saturated potassium chloride electrolyte salt bridge were used for
decreasing IR drop. The Luggin Capillary has been used to control the
placement of the reference electrode corresponding to the working electrode.
The Luggin capillary is filled with NaCl based electrolyte and is used to place
the sensing point of a reference electrode to a favorite point in a cell. The
Luggin capillary is made from glass or plastic and it grips the reference
electrode as shown in Figure 1. The tip of the Luggin capillary close to the
working electrode is open to the test solution. The reference electrode, on the
other hand, senses the solution potential at this open tip.

Figure 1: Luggin capillary

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It can be seen that. Luggin tip is considerably smaller than the reference
electrode itself. The Luggin capillary allows detecting of the solution potential
near the working electrode without the opposing effects that happen when the
large reference electrode is positioned close to the working electrode. Therefore,
the resistance of this electrolyte adds to the reference electrode
impedance.(Mansfeld, Lin, Chen, & Shih, 1988)

Corrosion investigators frequently utilize a pseudo-reference electrode in

electrochemical corrosion testing. The pseudo-reference is a second piece of the
working electrode material immersed in the same solution. If both the working
electrode and pseudo-reference corrode equally, they should possess alike
potentials. In general, the impedance of a pseudo-reference electrode is smaller
than that of typical reference electrodes.(Mansfeld et al., 1988)

2. Galvanic Corrosion
In principle, if two materials have not contacted each other, a corrosion cell will
not pledge. On the other hand, in situation of direct contact between carbon
fibers and steel in the existence of an electrolyte, the wet corrosion cell could
speed up the corrosion of steel and produce possible blistering and following
delamination or debonding. In reality, there are numerous kinds of corrosion:
stress corrosion cracking, galvanic corrosion, chink corrosion, etc. It is decided
that the finest way to model can be divided into two parts: Firstly, is on the
electrochemical reactions utilized and next, is for the technique of modeling.

The straightforward calculate of corrosion currents is problematic, since a

rusting metal surface comprises of many short-circuited corrosion cells with
corresponding currents. This is directly logical for uniform mixed electrodes;
meanwhile the corrosion cells are consistently distributed in time and space.
Nevertheless, with some heterogeneous mixed electrodes there are some
experimental provisions where a cell current is quantifiable. Such an
arrangement is possible, for instance, when two dissimilar metals are in contact

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and anode and cathode reactions are spatially separated. By counting in the
circuit a low-resistance ammeter or standard resistance the cell current can be
measured.(Marcus & Mansfeld, 2005)

In the galvanic corrosion investigation, a mild steel sample utilized as the

working electrode, whereas the counter electrode was a platinum plate specimen
and the reference electrode was again the standard calomel electrode.
Throughout this investigation, the potentials of the two electrodes compared
with the reference electrode were observed. Once reaching the steady state
condition, the values of the potentials were alike, showing that the calculated
current between the working and the counter electrode was the corrosion current
density. Originally, the mild samples were immersed in the aqueous sodium
chloride solution, and the corrosion current densities were obtained, for about
20 minutes on average, for every single test.

3. Mild Steels
Mild steels are the most basic known type of steels. It has a normal structural of
steels and is used in large quantities in general engineering practice as plate,
sections, tubes, and bars. Mild steel is, however, a term that must be used with
carefulness because in commercial practice it might be utilised for just about
any soft steel. Nonetheless, steady development has been made in tailoring
enhancements in the simplest grades to meet more acceptably the needs of
particular markets. At the other extreme, results have been developed to meet
very challenging necessities, the most important being those for extremely
stressed welded structure such as pressure vessels and gas pipelines. The
necessities then are complex since resistance to catastrophic fracture, a property
known as fracture durability, as well as suitable weldability have to be
conserved. These contradictory requirements are not straightforwardly met; they
are reviewed widely in different studies.(Chattopadhyay & Sellars, 1977;
Fullman, 1991; Ridley, 1984)

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Mild steel plain at a temperature of 950 oC exists in a face-centered cubic (fcc)

phase. In an fcc the Fe atoms occupy the sites of an fcc lattice, and the C atoms
are enfolded into octahedral interstices. After the steel has been slaked quickly
to room temperature, the material converts into a body-centered tetragonal (bct)
phase. Due to the technological importance of mild steel, the bct transformation
has been well investigated, but that is not to say it is entirely understood. The
bct transformation also happens in Fe-Ni, Au-Cd, Ti-Nb, In-Tl, Cu-Zn, Cu-Al,
and many other alloys; in superconductors, for example, V3Si and Nb3Sn, and in
ceramic systems such as ZrO2 and BaTiO3.(Pfeiler, 2008)

4. Theory
Corrosion is degradation of a metal through an electrochemical reaction via its
environment.(Chamberlain & Trethewey, 1992) It is continuously easier to
clarify the phenomenon in a basic wet corrosion cell such as that shown in
Figure 2, which has four essential components: the anode, cathode, electrolyte,
and electrical connection. In the nonappearance of any one of these components,
the corrosion reaction will stop. Each of the above components has its
importance. Anode is a place where corrosion of metal occurs. The metal loses
electrons and becomes the ion in the solution, or it might form an insoluble
product.

While Cathode is a part that commonly attracts the electrons created in the
anode. The electrons are used by the reactions at the cathode. Such reactions can
be the creation of a metal film, oxygen reduction, or hydrogen evolution.

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Electrolyte, on the other hand, is a solution with sufficient conductivity for

transferring the ions.
Finally, electrical connection is an essential connection between the anodic and
cathodic sites for corrosion to occur. In circumstances in which the anode and
cathode are not part of the same material, a physical connection is needed for
the current to flow and the corrosion to take place.

Figure 2 :Representation of rudimentary wet corrosion cell

The potential difference between anode and cathode can be willingly measured.
To establish an absolute value for the potential of each material, the potential
difference between the material and the standard hydrogen electrode (SHE),
with the potential of zero volts at 25 oC, can be controlled and represented as the
standard reduction potential. Meanwhile usage of the SHE in routine laboratory
tests is problematic; other reference electrodes have been used.

The most regularly used reference electrode is the standard calomel electrode
(SCE), with a potential of +0.242 V against SHE at 298 K. The SCE contains a
platinum wire in contact with mercury (Hg) and mercury chloride (HgCl),
which is held in a glass tube plugged by an absorbent material. The tube is then
located inside a larger tube comprising saturated potassium chloride (KCl) with

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additional absorbent plug at the end. Absorbent plugs allow the passage of ions
without substantial cross pollution.

The flow of current I (in amperes, A) offers a strong indication of an active

corrosion procedure. To reduce the effect of the relative size of the electrodes,
the current density, I (A/m2), is utilized as the accurate sign of the corrosion
rate. Faraday‘s law of electrolysis and the corrosion current density can be used
to assess the mass lost in the corrosion procedure. Polarization is a significant
corrosion evaluation process.

It assesses the electrochemical reaction as the potential of a material is made to

diverge from its steady-state value under spontaneously corroding conditions,
Ecorr, named the free corrosion potential. Polarization might be cathodic or
anodic, and it has been shown that the correct response, when schemed as
potential against log i, can be idealized as two straight lines crossing at a point
that matches to the corrosion current density of the material. The plot that
contains these two lines is mentioned to as the Tafel plot.(Fontana, 2005)
Usually the extrapolation of the linear part of the Tafel plot obtained from tests
will product in the valuation of corrosion current density, icorr, as shown in
Figure 3.

Figure 3: Characteristic polarization result demonstrating Tafel extrapolation

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By computing the Tafel slopes of both branches of the diagram (cathodic and
anodic) and crossing them, the corrosion current density (icorr) and corrosion
potential (Ecorr) of the specific material in a specific solution can be assessed.
The Tafel plots diverged from linearity for small and large polarization, and the
Tafel slopes were measured as the slopes of the linear portions of the two
branches.

5. Results and discussion

The model is designed in COMSOL Multi-physics (Version 5) as a 2D
axisymmetric model with a particular electrolyte domain of radius 10 cm and
height of 7.5 cm. The magnitude of the conductivity is reliant on the nature of
the ions and the nature of the solvent. The electrolytic conductivity is a result of
ionic movement in a specific solvent, which is associated to the ionic
interactions proceeding inside the solution. A wide range of the electrolyte
conductivity as a function of salt concentrations (Table 2) was examined.

Table 2: solution conductivity versus % NaCl concentration at 20 oC(Haynes, 2010)

% NaCl Conductivity S/m

0.5 0.82

1 1.6

2 3.02

5 7.01

10 12.6

15 17.1

20 20.4

25 22.2

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Table 2 provides the electrical conductivity of aqueous solution of NaCl salt as

a function of concentration. All values denote 20 °C. The conductivity has units
of Siemens per meter (S/m). For this electrolyte the concentration corresponding
to the mass percent values of NaCl.

Practically estimating galvanic corrosion can be done using the direct galvanic
coupling test. In this procedure, no external potential or current is applied, and
the current or potential of a system comprising of two different materials inside
a solution is monitored. In other words the two materials replace the working
and counter electrodes and are connected to each other through a galvanometer.
A reference electrode is then linked to each electrode throughout the test in
order to monitor the potential difference between the electrodes. The experiment
will last until constant current or comparable potentials between the cathode and
the anode is reached.

The mild steel which represents the cathode, located in the center of the
geometry, i.e. Z=0, (Figure 4), spreading in the r direction. Three different disc
radii are investigated: 5, 15, 25, 35 and 45 mm. An anodic Tafel extrapolation is
utilized to express the electrode kinetics on the mild steel disc.

Figure 4: Electrolyte domain with axial symmetry

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On the other hand, a secondary current distribution (SCD) interface is utilized to

model the case, based on electrolyte-electrode boundary interface nodes for the
two electrode surfaces.

As a result of the quicker kinetics and bigger area of the anode, the original
value for the electrolyte is fixed to match up a zero anode polarization. A steady
study step is utilized to solve the problem, with a parametric sweep to change
the disc area. Three-sided mesh is used for interlocking, with an extra smaller
size location for increasing the resolve at the connection point between the
anode and cathode. Corrosion current density achieved from each simulation is
a vital parameter directly related to the corrosion rate. Comparison between the
corrosion rates of samples with varied radius in the electrolyte provides a full
understanding of the phenomenon and assists in developing techniques to
eliminate the galvanic corrosion problem.

Figure 5 shows the effect of the disc radii on the total interface current density
for nominate aqueous solution within only %10 NaCl. From the exponential
behavior it can be seen that the interface current density increases with
increasing the disc radius (Figure 5). This is perhaps due to the dimensional
expansion of corrosion throughout the mild steel electrode. On the other hand
this effect will be noticeable from the edges, therefore the interface current
density decreases dramatically from the disc boundaries. The results showed
that defects or edges are potential initiation points for corrosion and that
extended corrosion leads to a mount like structure. Similar findings were
presented by Miyasaka and Ogawa(Miyasaka & Ogawa, 1990), who
investigated stainless steel in 10% and 3% NaCl. Their results showed that the
Tafel method is a promising method for studies of the initial stage of pitting.
Marcus and coworkers used the same method for ex-situ (in air) studies on
single-crystal surfaces obtaining images with atomic resolution.(Maurice, Talah,
& Marcus, 1994) Excellent agreement between the fitted and experimental data

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was obtained for NaCl solutions using mild and CrN which was done by Liu
and Lu .(Liu, Bi, & Matthews, 2001; Lu, Elsenbaumer, & Wessling, 1995)

Figure 5:Log of total interface current density vs. disc radii for %10NaCl
electrolyte

Figure 6 shows a 2D representation of revolved surface plot of the electrolyte

potential for a disc radius=15mm for 0.5%, 5%, 15% and 25% NaCl electrolyte
respectively. On the other hand Figure 7 shows a 3D representation of revolved
surface plot, of the electrolyte potential for the above description. In Figure 6
and 7 can be seen that when amount of wt% NaCl increased (an impersonator of
sea water); significant corrosion is observed of the mild steel immersed in the
liquids. Obviously the aqueous phase partitions to the steel surface where
corrosion is caused by the relatively high chloride concentration. Similar results
obtained by Abbott et al.(Abbott, Ahmed, Harris, & Ryder, 2014) where choline
chloride is added to the aqueous solution in place of NaCl and it can be seen
that corrosion take places but to a less significant degree. This amazingly shows
that there is a cation influence to the corrosion mechanism which is not
completely understood at the present time but may be associated to the relative
solubility of the corrosion products.

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(a) (b)

(c) (d)

Figure 6: 2D representation of electrolyte potential for disc radius=15mm (a)

0.5%NaCl electrolyte, (b)5 % NaCl electrolyte, (c) 15% NaCl electrolyte and
(d)25 % NaCl electrolyte

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(a) (b)

(c) (d)

Figure 7: 3D representation of electrolyte potential for disc radius=15mm (a)

0.5%NaCl electrolyte, (b)5 % NaCl electrolyte, (c) 15% NaCl electrolyte and
(d)25 % NaCl electrolyte

Figure 8 represents the galvanostatic anodic and cathodic polarization curves

for the mild steel electrodes immersed in the above mentioned solutions at a
temperature of 20 oC. Furthermore, Figure 8 indicates that mild steel in NaCl
solution exhibit a minor sign of passivation alongside the anodic sections. The

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amount of corrosion is proportional to the corrosion current density (from

Faraday‘s law) achieved from these diagrams. For mild steel, the anodic
reaction is the oxidation of the metal or corrosion. The anodic reaction is the
oxidation of carbon that causes the humiliation of the composite. Taking into
consideration the cathodic reaction for both materials is the reduction of oxygen
and the creation of hydroxide ion (OH2) on the surfaces.

Similar polarization curves are obtained by Barakat et al.(Barakat, Hassan, &

Baraka, 1999), they showed that the presence of surfactant in the aqueous media
affects both the anodic and cathodic polarization curves and the corrosion rate
greatly decreases with the increasing of surfactant concentrations. On the other
hand Tavakkolizadeh et al. stated that mild steel have a tendency to corrode
more rapidly when coupled with carbon in aqueous solutions.(Tavakkolizadeh
& Saadatmanesh, 2001)

(a) (b)

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(c) (d)

Figure 8: Total interface current density for disc radius=15mm (a) 0.5%NaCl
electrolyte,

(b)5 % NaCl electrolyte, (c) 15% NaCl electrolyte and (d)25 % NaCl
electrolyte

6. Conclusions
This study has shown that the existence of the galvanic corrosion particularly
when there is a direct contact between an aqueous solution and mild steel
substrate. The galvanic corrosion rate is directly linked to the thickness of the
immersed samples.

A simulated model developed in this work, mild steel exposed to NaCl medium,
is accomplished of clearly tracking a moving boundary during galvanic
corrosion and can handle a wide range of boundary conditions. The results
compared with experimental measurements employing the immersion methods.

At an assumed temperature the corrosion rate significantly increased in the

presence of wt %NaCl. The corrosion potential shifted to more positive values
and corrosion current decreased with the increase of wt %NaCl concentration.

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Sizing representatives decreases the galvanic corrosion rate of the mild steel.
Since the galvanic corrosion only starts when there is direct contact between
two unlike metals in the existence of an electrolyte, processes can be taken to
reduce one or both of these parameters and to reduce this problem.

The local current density of the anodic reaction in the surrounding area of the
mild steel disc increases considerably when the disc radius increase. This is as a
result of the slow kinetics on steel disc, dominating the total reaction current.
Namely, if the size of the cathode is increase the vulnerability to its corrosion
more than that of the anodic increases. Hence as the steel disc radii increase the
boundary current density increases as well, leading to increase in corrosion, this
in fact verify galvanic corrosion theory.

References
Abbott, A. P., Ahmed, E. I., Harris, R. C., & Ryder, K. S. (2014). Evaluating
water miscible deep eutectic solvents (DESs) and ionic liquids as
potential lubricants. Green Chemistry, 16(9), 4156-4161.
Barakat, Y., Hassan, A., & Baraka, A. (1999). Corrosion inhibition of mild steel
by amphoteric surfactants. Materialwissenschaft und Werkstofftechnik,
30(7), 418-425.
Chamberlain, J., & Trethewey, K. R. (1992). Corrosion: For Students of
Science and Engineering: Longman Scientific & Technical.
Chattopadhyay, S., & Sellars, C. (1977). Quantitative measurements of pearlite
spheroidization. Metallography, 10(1), 89-105.
Deshpande, K. B. (2010). Experimental investigation of galvanic corrosion:
Comparison between SVET and immersion techniques. Corrosion
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Fontana, M. G. (2005). Corrosion engineering: Tata McGraw-Hill Education.
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Jizhou, D., Baorong, H., Yanliang, H., Huyuan, S., Yan, L., & Shide, M. (2002).
Corrosion of mild steel in different granularity seabed sediment
saturated with seawater. Materials and Corrosion, 53(11), 845-849.
Li, D., Feng, Y., Bai, Z., Zhu, J., & Zheng, M. (2007). Influence of temperature,
chloride ions and chromium element on the electronic property of

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passive film formed on carbon steel in bicarbonate/carbonate buffer

solution. Electrochimica Acta, 52(28), 7877-7884.
Liu, C., Bi, Q., & Matthews, A. (2001). EIS comparison on corrosion
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aqueous solution. Corrosion Science, 43(10), 1953-1961.
Lu, W.-K., Elsenbaumer, R. L., & Wessling, B. (1995). Corrosion protection of
mild steel by coatings containing polyaniline. Synthetic Metals, 71(1),
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Mansfeld, F., Lin, S., Chen, Y., & Shih, H. (1988). Minimization of High‐
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Remedy for a New Challenge. Corrosion, 47(6), 410-419.

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