Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Corrosion of Constructional
Steels in Marine and
Industrial Environment
Frontier Work in Atmospheric Corrosion
123
ISSN 1612-1317
ISBN 978-81-322-0719-1
DOI 10.1007/978-81-322-0720-7
Preface
Mild steel is used as prime constructional steel for buildings, bridges, etc. But this
is very much prone to corrosion in industrial and marine environments in presence
of harmful pollutants and other industrial effluents in addition to normal humid
atmosphere. These corrosion problems are much severe in a tropical country like
India with vast coastline. Mild steel corrodes relatively faster and thus leads to
colossal loss in every year and to reduce this loss some kind of protection in the
form of paints and coatings is always used. Weathering steel considerably
improves its corrosion resistance in industrial and rural atmosphere. Engineers and
scientists all over the world are concerned for much indepth research works at
surface science and engineering of atmospheric degradation of construction steels.
Endeavours have been made in the present work for better understanding of the
degradation process and uses of high performance paints formulation and compare
them through various AC/DC electrochemical test methods and surface characterisation through electron microscopy, XRD and Raman spectroscopy.
The protective systems and their corresponding corrosion data are available in
the relevant overseas codes for reference. These data are not applicable in Indian
specific context as atmospheric corrosion is location specific. Atmospheric corrosion is the frontier research area where limited work has been carried out as it
comprises with three phases (solid/atmospheric/liquid environment). Therefore it
is significant to study the rust on MS and WS as well as coated steels in a given
atmospheric environments. This is important for the selection of more suitable
materials as well as for the safety of structures, including the realisation of
essential economic effect.
Weathering steel is used to protect structures from atmospheric corrosion in
specific environments. Rust layers on mild steel are not protective and are permeable to air and moisture. Protective impervious rust coatings are supposed to
form on weathering steel with time and due to high initial cost and sometimes
unfavourable environments this steel cannot be used. Microscopic observation of
rust layers on weathering steel reveals the two phases in layers parallel to the steel
surface. The inner phase extends up to outer surface if exposure periods are longer
than 5 years, and then it becomes the only component of the rust coating. In mild
vii
viii
Preface
steel, corrosion products form as two different phases, and there are two layers
with a common interface allowing moistures to go in and experiences higher
corrosion rate in outdoor exposure.
Present research work has been carried out in two parts: field exposure tests and
accelerated laboratory tests on unexposed panels. Under field exposure test three
representative sites P1: very close to sea shore and free from SO2, P2: away from
sea with presence of SO2 and P3: industrial environment with presence SO2 were
chosen. Analytical techniques (EDX, XRD and Raman spectroscopy) were used
for rust characterisation and SEM was employed for understanding the morphological state. Corrosion rates were estimated after different periods of exposure at
sites. It is found that though accelerated laboratory test can predict the general
trend of corrosion, actual field test data cannot be created in laboratory. So an
attempt was made to simulate protective rust coating in the laboratory that is
typical of field exposure protective rust formation on weathering steel.
It is my proud privilege to record a deep sense of gratitude and indebtedness to
Prof. P. K. Mitra & Prof. S. Paul, Metallurgical & Material Engineering of Jadavpur University, Kolkata, India and Dr. D. D. N. Singh, Sr. Deputy Director of
National Metallurgical Laboratory, Jamshedpur for their encouragement and
endless support throughout the research steps. I also would like to show my
gratitude to my beloved mother, gorgeous wife Mousumi, son Dipanjan and
daughter Debosmita for infinite emotional support, enduring love, encouragement,
patience through my hard times until this work came to completion. Finally I thank
god for granting me the strength to write this book and thank editorial team of
Springer publication for giving the work final shape as book.
Kolkata, India
Contents
Theoretical Evidences . . . . . . . . . . . . . . . . . .
1.1 Rusting of Iron . . . . . . . . . . . . . . . . . . . .
1.2 Corrosion of Steel . . . . . . . . . . . . . . . . . .
1.2.1 Mild Steel . . . . . . . . . . . . . . . . . .
1.2.2 Weathering Steel. . . . . . . . . . . . . .
1.3 Atmospheric Corrosion. . . . . . . . . . . . . . .
1.3.1 Corrosion Products . . . . . . . . . . . .
1.3.2 Atmospheric Corrosion Mechanism .
1.3.3 Effect of Acidity of Solution . . . . .
1.3.4 Effect of Alloying Elements . . . . . .
1.3.5 Environmental Factors . . . . . . . . . .
1.4 Corrosion Protection by Coating . . . . . . . .
1.4.1 Passive Rust Coatings . . . . . . . . . .
1.4.2 Organic Coatings . . . . . . . . . . . . .
1.5 Degradation of Organic Coatings. . . . . . . .
1.5.1 Delamination of Coatings. . . . . . . .
1.6 Corrosion Measurement and Analysis . . . .
1.6.1 Corrosion Rate Measurement . . . . .
1.6.2 Electrochemical Methods . . . . . . . .
1.7 Rust Characterisation . . . . . . . . . . . . . . . .
1.7.1 SEM and EDX . . . . . . . . . . . . . . .
1.7.2 X-ray Diffraction . . . . . . . . . . . . .
1.7.3 Raman Spectroscopy . . . . . . . . . . .
1.8 Rust Simulation. . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Practical Approach . . . . . . .
2.1 Materials Used . . . . . . .
2.1.1 Structural Steels .
2.1.2 Organic Coatings
2.1.3 Test Electrolytes .
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ix
Contents
2.2
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Experimental Evidence. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1 Rust Appearance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2 Corrosion Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3 DC Corrosion Measurement . . . . . . . . . . . . . . . . . . . . . .
3.4 AC Impedance Spectroscopy. . . . . . . . . . . . . . . . . . . . . .
3.4.1 EIS on Uncoated Panels After 42 Months Exposure
3.4.2 EIS of Uncoated Panels After 48 Months. . . . . . . .
3.4.3 EIS of Coated Panels After 18 Months Exposure . .
3.4.4 EIS of Scribed Coated Panels After
18 Months Exposure . . . . . . . . . . . . . . . . . . . . . .
3.4.5 EIS of Coated Panels After 42 Months Exposure . .
3.4.6 EIS of Coated Panels After Humid SO2 Exposure. .
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Contents
3.5
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Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Abbreviations
AR
MS
WS
ZP
ZR
ZP + MS
ZR + MS
ZP + WS
ZR + WS
MIO
PU
CR
T
RH
R
AC
DC
OCP
PD
CP
EIS
RE
WE
CPE
CPE + D
REAP
SCE
PSCT
Ecorr
Icorr
Mod
As received
Mild steel
Weathering steel
Zinc Phosphate system
Zinc Rich system
Zinc phosphate system on MS
Zinc rich system on MS
Zinc phosphate system on WS
Zinc rich system on WS
Micaceous iron oxide
Polyurethane
Corrosion rate
Temperature
Relative humidity
Rainfall
Alternate current
Direct current
Open circuit potential
Polarisation diagram
Cyclic polarisation
Electrochemical impedance spectroscopy
Reference electrode
Working electrode
Constant phase element
CPE with diffusion Fit
Rapid evaluation of paints
Saturated calomel electrode
Potentiostatic current transient
Corrosion potential
Corrosion current
Modulus
xiii
xiv
Zmod
Zimg
Zreal
h
Freq
Z
Ru
Rp
Rpo
C
Cc
Cf /Cdl
Yo
Wd
a
nm
pA
lA
lm
lm/yr
DFT
h
s
m
SEM
EDX
XRD
Raman
a FeOOH
b FeOOH
c FeOOH
a Fe2O3
c Fe2O3
Fe3O4
Fig
Ref
Abbreviations
Modulus of impedence
Imaginary part of impedence
Real part of impedence
Phase angle
Frequency
Impedance
Solution resistance
Polarization resistance
Pore resistance
Capacitance
Coating capacitance
Double layer capacitance
Admittance
Warburg impedance
CPE exponent
Nanometer
Picoampre
Microampre
Micron
Micro meter per year
Dry film thickness
Hours
Seconds
Months
Scanning electron microscope
Energy dispersive X-ray
X-ray diffraction
Raman spectroscopy
Goethite
Akaganeite
Lepidocrocite
Hematite
Maghemite
Magnetite
Figure
Reference
Dr. Jayanta Kumar Saha is serving with Institute for Steel Development & Growth
(INSDAG) as Deputy General Manager spearheading key activities like sourcing,
corrosion, fire protection, tech advisory services of steel structures. He did his
graduation from Bengal Engineering & Science University, Shibpur, Kolkata in
Metallurgical Engineering, Post-graduation from Indian Institute of Technology
Madras in Production Engineering and Ph.D. in Metallurgical & Material
Engineering from Jadavpur University, India. He is an IRCA, UK accredited
lead auditor for ISO 9001. He has authored 11 INSDAG books on steel
applications and has credit of 20 papers published in national and 5 papers in
international journals. He is representing various national bodies/committees. He
had previous experience at Hindustan Aeronautics Ltd, Central Mechanical
Engineering Institute and Philips India Ltd. He has visited several countries like
UK, Netherlands, China, South Korea and Singapore, etc., in connection with the
pioneering work in steel applications.
xv
Introduction
Mild steel (MS) has got versatile application as structural steel for construction of
buildings, bridges, flyovers, pipelines etc. But this is very much prone to corrosion
in industrial and marine environments in presence of harmful pollutants and other
industrial effluents in addition to normal humid atmosphere. These corrosion
problems are much severe in a tropical country like India with vast coastline. MS
corrodes relatively faster and thus leads to colossal loss in every year and to reduce
this loss some kind of protection in the form of paints and coatings is always used.
Painting is an effective means but quite costly amounting 1015 % of the initial
construction cost of superstructures besides cost of repainting at regular interval.
Addition of small percent of minor alloying elements especially Cu, Cr, P etc in
mild steel known as weathering steel (WS) considerably improves its corrosion
resistance in industrial and rural atmosphere. While the organic coatings (paints)
are invariably applied to MS structures, WS is used with or without coatings.
Application of a defect-free paint to the structures improves their life. However,
problems start once coatings develop defects, leading to both uniform and
localized corrosion and ultimately failure of structures. Engineers and scientists all
over the world are concerned for much indepth research works at surface science
and engineering of atmospheric degradation of MS and WS as well as improved
formulation of organic paints. Endeavours have been made in the present
investigation for better understanding of the degradation process and uses of high
performance paints formulation and compare them on MS and WS through various
AC/DC electrochemical test methods and surface characterisation through electron
microscopy, XRD and Raman spectroscopy.
WS is used to protect structures from atmospheric corrosion in specific
environments. Rust layers on MS are not protective and are permeable to air and
moisture. Protective impervious rust coatings are supposed to form on WS with
time and due to high initial cost and sometimes unfavourable environments WS
cannot be used. Studies on atmospheric influences on steels in rural, industrial and
marine environments have indicated that P, Cu, Ni, Cr and Si improve the
resistance to corrosion while Mn does not. In an industrial atmosphere the
weathering process is rapid than rural atmosphere, whereas in coastal environment,
xvii
xviii
Introduction
the protective layer does not form an conventional WS. On MS, major rust phase c
FeOOH transforms to the more stable a FeOOH with time whereas in WS after the
same phase change, a continuous transformation of a FeOOH to either protective c
Fe2O3 or a Fe2O3 along with amorphous d FeOOH with increasing exposure time
takes place. On MS, this does not form in a continuous manner and the amorphous
d FeOOH formed are not protective in nature for this reason. Presence of chlorides
in the atmosphere aggravates corrosion of steels leading to the formation of basic
Fe2+, Fe3+ chlorides and b FeOOH on MS. In case of WS, exposure to coastal
environment causes the formation of a FeOOH, b FeOOH, c FeOOH, Fe3O4 and
amorphous rust. In Industrial environment, formation of a FeOOH is predominant
on steels which remains uniformly distributed throughout the rust layer.
Concentration of a FeOOH is higher and c FeOOH is lower on WS than on
MS. Amorphous rust is found at the bottom of the rust layer on both MS and WS.
On WS, the alloying elements Cu and Cr become enriched in the inner layer of rust
while Si, P and Ni are not found to exhibit any characteristic distribution. The acid
rain triggered atmospheric corrosion of steel and presence of SO2 accelerates
corrosion. Thus in an industrial environment, presence of humid SO2, helps in the
formation of a very thin oxide film composed of an inner layer of Fe3O4 covered
with an outer layer of FeOOH. Investigations on atmospheric corrosion of WS in
the presence of NaCl and SO2 revealed that NaCl can accelerate the corrosion rate
and their combined effect is greater than that caused by each single component. In
the absence of SO2, a FeOOH, b FeOOH, c FeOOH, Fe3O4 and c Fe2O3 are the
dominant corrosion products, while b FeOOH, c FeOOH, Fe3O4 and FeSO4H2O
formed in the presence of SO2. Microscopic observation of rust layers on WS
reveals the two phases in layers parallel to the steel surface. The inner phase
extends up to outer surface if exposure periods are longer than 5 years, and then it
becomes the only component of the rust coating. In MS, corrosion products form
as two different phases, and there are two layers with a common interface allowing
moistures to go in and experiences higher corrosion rate in outdoor exposure.
Organic coatings are used on steels to provide an effective barrier protection.
With time organic coating systems acquire dielectric properties, which cause them
to act as capacitors. Corrosion occurring at the metal surface has a polarisation
resistance related to the corrosion rate, and an electric double layer that also
behaves as a capacitor. Rusting does not occur until the polarisation resistance fall
below 106 ohm cm2.
The performance of protective coatings can be determined through accelerated
laboratory tests but these are not the true representation of actual service
conditions. Hence field tests are carried out to get reliable performance data on
uncoated and coated steels. The protective systems and their corresponding
corrosion data are available in the relevant overseas codes for reference. These
data are not applicable in Indian specific context as atmospheric corrosion is
location specific. Atmospheric corrosion is the frontier research area where limited
work has been carried out as it comprises three phases (solid/atmospheric/liquid
environment). Therefore it is significant to study the rust on MS and WS as well as
coated steels in a given atmospheric environments. This is important for the
Introduction
xix
xx
Introduction
It was envisaged that the slow oxidation of field test can be simulated in
laboratory by selecting a slow scan rate in a potentiodynamic experiment. Na2SO4
solution was taken as test electrolyte because SO2 was created in situ and this is
also available in industrial environment at P3. Slow potentiostatic oxidation is
possible at a low scan rate in Na2SO4. Passivated oxide layers were found only on
WS but not on MS. Results obtained were very encouraging as the corrosion rate
was comparable to field test and rust morphology of WS passivated at -820 mV is
quite identical to rust formed on WS exposed at P3 for 42 months. Raman
characterisation of passivated WS panels showed the presence of c FeOOH along
with stable Fe3O4 and a Fe2O3, which are very similar to the rust of WS exposed at
P3 after 42 months. It was concluded that laboratory simulation by passivating WS
at -820 mV for 80 min, is almost similar with the oxidation state of WS exposed
for 42 months at P3.
Chapter 1
Theoretical Evidences
1 Theoretical Evidences
leading to use without protection and can also extend paint life by decreasing the
amount of corrosion underneath the paint. The rate of rusting is usually higher in
the first year of exposure to atmosphere than in subsequent years, and increase
significantly with the degree of pollution and moisture in the air. Alloying elements contribute to a more compact and less porous corrosion product as surface
film. Adherent, protective films on these steels seal the surface against further
penetration of water, which does not easily wet the oxide surface. Compact surface
oxide films develop more rapidly in industrial atmospheres containing SO2, which
is probably involved in film formation in presence of moisture by forming
sulphurous and sulphuric acids which are very corrosive. This theory was based
largely on the observation that the corrosion products formed on steel when
exposed to industrial atmosphere were usually rich in sulphates. However, the
corrosion rates of weathering steels are not reduced in industrial atmospheres to
levels lower than those in non-corrosive rural or semi rural atmosphere. Periodic
drying is required for the surface film to develop its protective properties [2].
In acidic solution, it involves an oxidation reaction (anodic reaction) where the
metal gets into an ionic state by dissolution and releases electrons. Simultaneously,
a reduction reaction (cathodic reaction) consumes the free electrons released by
the anodic reaction and either a metal gets deposited or more usually the cathodic
reaction. In order to continue the corrosion process in steel, formation of distinct
anodic and cathodic areas is a prerequisite, which are electrically connected. These
anodic and cathodic reactions occur in presence of an electrolyte, which can be a
common aqueous solution, acidic medium or a thin film of moisture present on the
surface, pores and crevices. At higher humidity, corrosion increases due to condensation of moisture film on the metallic surface leading to formation of innumerable galvanic cells. These cells are formed due to generation of electromotive
force between surface film and trapped film in pores and crevices, which act as
cathode and anode. Intrinsically, two important factors influence the corrosion
phenomenon at a fundamental level. These are electromotive forces generated
between the two electrodes and pH of the aqueous media. The electromotive
forcepH relation was first proposed by M. Pourbaix [3] as shown in Fig 1.1 and
these are useful in predicting zones of corrosion, passivity and immunity in metal
aqueous system. Pure iron exhibits formation of protective scale whereas carbon
steel shows formation of incoherent layers of scale which easily flakes off to
expose fresh areas for further attack.
There are different forms of corrosion of which most important one is uniform
corrosion which occurs over the majority of the surface of a metal at a steady and
often predictable rate. Rusting can be slowed or stopped by using paint, controlling
conductivity of solution, by applying current to metals and/or by stopping oxygen
to reach the surface. Other forms of corrosion commonly encountered during
service exposure of iron and steel is localised corrosion which is more severe than
the uniform one as failure occurs without warning in a short period of use or
exposure. Galvanic corrosion can occur when two different metals are placed in
contact with each other and caused by the greater tendency of one of the metal to
give up electrons than the other. Pitting corrosion occurs in materials that have a
1 Theoretical Evidences
tendencies and corrosion products [14, 15]. During atmospheric exposure, steel
gets a reddish brown corrosion product consisting of different constituents. The
electrochemical reactions at wet surface of steel as proposed by Evans [16] in
neutral alkaline condition are:
Anodic half-cell reaction Fe ! Fe2 2e
1:1
1:2
The anodic and cathodic reactions are only the first step in the process of
creating rust. Several more stages must occur for rust to form:
Fe2 + 2OH ! FeOH2
1:3
1:4
In weathering, steel rust formed on atmospheric corrosion in different environments is composed of crystalline compounds like haematite, magnetite and
oxyhydroxides of iron like goethite, akaganeite, lepidocrocite and feroxyhite apart
from amorphous ferric oxyhydroxide rust. These rust constituents transform to one
another during wetdry cycles of atmospheric exposure [17].Various phases of
corrosion products formed in progressive exposure to atmosphere are given in
Table 1.1 [6, 18].
The alloying elements play a major role in modifying the oxyhydroxide rust
layer which inhibits the ingress of oxygen and iron cations. Orange to reddish
brown in colour hydrated ferric oxide formed is called rust and available as non
magnetic a Fe2O3 and magnetic c Fe2O3. Rust layers are not protective because
they are permeable to air and water and steel continues to corrode even after rust
has formed [1].The rusting of steel in the atmosphere is given by:
2 Fe + H2 O + 3/2 O2 ! 2FeOOH
1:5
FeOOH is the main component of the rust formed in presence of water on steel
at room temperature. Misawa [10] has summarised these processes and according
to him metal dissolution is the anodic reaction, while the dominant cathodic
reaction is oxygen reduction. The presence of a thick electrolyte layer on the
surface can limit oxygen reduction rate. In such situations, the following reduction
reaction supports oxidation of steel.
8 FeOOH + Fe2 + 2e- ! 3Fe3 O4 + 4H2 O
1:6
1 Theoretical Evidences
4.60
9.96
c FeOOH
Lepidocrocite
3.06
12.51
d FeOOH
Feroxyhite
a Fe2O3
Haematite
2.94
4.49
c Fe2O3
Maghemite
Fe3O4
Magnetite
b FeOOH
Akaganeite
5.035 13.72
8.33
8.396
10.48
10.48
3.8
Hexagonal/
Plates
5.26 Hexagonal/
Plates
24.99 Cubic/Lath
5.24
4.69
Features
The oxidation of Fe2+ ions to green rust transformed to c FeOOH in wellaerated systems and in turn is transformed to Fe3O4 in oxygen depleted systems.
The phases of change in rust with time in mild steel are c FeOOH transforms to the
more stable a FeOOH. With increasing time, a FeOOH converts to either c Fe2O3
or a Fe2O3, while conversion to a Fe2O3 usually requires higher temperatures.
The rust on weathering steel after 16 years of exposure in a rural environment
was found to be composed of two layers, with the inner dull layer comprising
nano-sized particles of a FeOOH and the outer bright layer, c FeOOH [19]. The
rust on weathering steel after 25 years of exposure in an industrial environment
exhibited similar characteristics [20].
further corrosion. With time, a part of the FeOOH transforms to magnetic oxides
of iron, which are much more protective than these oxyhydroxides. In addition to a
and c FeOOH, there is another oxyhydroxide of amorphous nature called d
FeOOH. In mild steel, this does not form in a continuous manner and amorphous d
FeOOH forms are not protective in nature for this reason. The formation of
amorphous d FeOOH as a continuous layer next to the metal surface is catalysed
by the presence of P, Cu and Cr in the steel. The presence of this amorphous layer
was thought to be the reason for the excellent corrosion resistance of the weathering steels [21]. However, some findings [22, 23] show that the stable rust layer
was not necessarily composed of amorphous rust but densely packed nano-size Cr
substituted goethite. Cr substituted a FeOOH is very fine through which oxygen,
water and corrosive substances are difficult to penetrate. Furthermore, chloride
ions are also difficult to pass through this. However, for the formation of this
protective rust layer, it is necessary that favourable atmospheric conditions exist
for application of steel in bare condition.
After extensive studies it has been found that Cr compounds are effective for
obtaining the protective rust layer in a short period of time [24]. Cr substituted a
FeOOH forms rapidly in presence of Cr2(SO4)3 solution. This accelerates the
dissolution of steel and promotes the formation of goethite. On the other hand,
Cr3+ forms fine particles of Cr substituted goethite and improves the protection
ability of the rust layer.
1 Theoretical Evidences
0.5 % Cu during drying cycle and attributed this to the formation of a dense
corrosion product on Cu containing iron. Kishikawa et al. [30] reported that
weathering steel alloyed with Cr, Cu, P and Ni forms a non-amorphous densely
packed nano-sized Cr substituted a FeOOH, which prevents the permeation of
water, oxygen and corrosive substances. On the other hand, the c FeOOH membrane was found to possess anion selective property. The rust layer formed on the
weathering steel has double-layered structure and protects steel from corrosion
because of the formation of bipolar membrane which suppresses the cathodic
reaction. Thus, the formation of a FeOOH in inner layer and c FeOOH in outer
layer is important for protection ability against rust. The ratio of a FeOOH to c
FeOOH in rust increases gradually as time passes. Corrosion rate decreases to
almost zero when this ratio exceeds 1.4. A value of 2 is considered as rust stability
index for maximum protection [31].
Yamashita et al. [32] observed that atmospheric rusts on weathering steels are
composed of Cr substituted a FeOOH, c FeOOH and a small amount of c Fe2O3
and/or Fe3O4. The dark Cr substituted a FeOOH area was located in the inner layer
while the bright c FeOOH area was in the outer layer. Thus, the innermost Cr
substituted a FeOOH layer may be the final form of the protective rust layer which
suppresses and prevents the transport of corrosive species through the rust layer to
retard further corrosion.
Study conducted in Taiwan by Wei [33] on carbon steels and weathering steel
with high Phosphorous and exposed to rural, urban, coastal and coastal industrial
environments concluded that the characteristics of the protective rust layer and the
corrosion resistance of weathering steels depend on the environment and the test
period. It was observed that c FeOOH formed in the inner rust layer along with
some a FeOOH, a Fe2O3 and Fe3O4 in the initial exposure period and the amount
of a FeOOH gradually increased in weathering steels. The enrichment of crack
free and dense rust layer with Cr, Cu and P is attributed to the corrosion protection
of the substrate steel.
The rust layers on plain carbon and weathering steels exposed to coastal
industrial environment in Japan for 17 years had been characterised by Asami
et al. [34]. They found that the rust was composed of a FeOOH, b FeOOH,
c FeOOH, Fe3O4 and amorphous rust. a FeOOH was predominant on all steels and
appeared uniformly distributed throughout the rust layer. Concentration of a
FeOOH was higher and c FeOOH was lower on weathering steels than on plain
carbon steel. Amorphous rust was located at the bottom of the rust layer irrespective of the steel types. Previous studies by authors on distribution of phases
and alloying elements in the rust layers in weathering and plain carbon steels
reported that the rust oxides consist of three layers: inner, outer and outermost
[35]. The outermost layer was found to be about 3 lm thick and enriched with
atmospheric deposits. The concentration of b FeOOH was reportedly higher on the
skyward surface of both steels. In weathering steel, the alloying elements Cu and
Cr enriched the inner layer of rust, while Si, P and Ni were not found to exhibit any
characteristic distribution.
According to Yamamoto et al. [36], the amorphous and the crystalline constituents were intermingled in the inner rust layer of weathering steels exposed to
rural environment for 35 years. Asami et al. [37] analysed the rust layers formed
after 17 years on weathering steel bridge exposed to coastal industrial environment
reported that c FeOOH and b FeOOH existed in outer layer while the amorphous
rust and a FeOOH with enriched Cr, Ni and Cu were found widespread in the inner
rust. Kihira et al. [38] referring to the work of Sakashita and Sato [39] tried to
explain the difference in protectiveness of weathering steel rust by the phenomenon of ion selectivity of the rust layer. Keiser et al. [40] found d FeOOH in the
weathering steel rust along with about 10 % c FeOOH and a small amount of a
FeOOH. Yamashita et al. [41] investigated the rust layers formed on weathering
steels exposed for 17 years in Japan and reported that the protective properties of
the rust layer on weathering steels containing alloying elements (Cr, Cu etc.)
composed of a FeOOH. The amount of b FeOOH phases increased with the
progressive increasing level of airborne salt. They also suggested that the protective properties of the rust layer were related to the suppression of ion transport
due to its densely packed structure.
Most of the authors have indicated that long-term exposure results are important in terms of protective rust formation on weathering steels and also supported
the view that the early stages of exposure determine the subsequent corrosion rate.
Thus, corrosion rates during the early months of exposure are far more important
than the ultimate rate in the context of a study of the mechanisms of protection
[42].
It is proposed that during rust formation of steel in alkaline solutions the oxidation of Fe2+ proceeds via Fe(OH)2 and yields magnetite as the end product [43].
In another study of transformation of Fe(OH)2 at pH 11 and at temperature 65 C,
it was noticed that initially both Fe3O4 and a FeOOH form but a FeOOH formation
takes place at an early stage of reaction. It was suggested that excess Fe+2 ions
interacted with Fe+3 oxides, resulting in Fe3O4 formation. It is further reported that
Cl- ions retard magnetite formation by binding the neighbouring OH- ions groups
to form FeOFe linkage in alkaline pH 11. Sulphate has a tendency for a FeOOH
formation of 0.1 M concentration of Fe(OH)2 [2]. Moreover, sulphate also plays
role during transformation of green rust to oxides/oxy hydroxides.
Subramanium [44] have shown that the presence of small amount of cations
(Cu, Mn) in rusts may accelerate the oxidation of Fe+2 in solution due to their
compound forming tendency with Fe+3. Thus, magnetite is a major constituent
in the weathering steel grades, which contains 0.30.4 % (wt.) of Cu. This
corroborates the previous studies of Inouye et.al [45]. They indicated the strong
magnetite promoting tendency of Cu during the formation of magnetite from
Fe(OH)2. However, they have specified the maximum limit of Cu (3 % by wt.)
above which it suppresses the magnetite formation. In another study [46], it was
noticed that the presence of traces of Cr decreases the amount of Fe3O4 in oxide
and increase unstable a FeOOH content in the corrosion product. It can be noted
here is that the tendency of Cr ions to form fine particles of a FeOOH which may
increase with passage of time and help in stabilizing the rust layer and protect the
10
1 Theoretical Evidences
surface from corrosion attack. High Si content in weathering steel also gives the
similar protective effect [47].
1:7
The absence of the surface deposit also enhances access of dissolved oxygen,
which, if present, further increases corrosion rate. Dissolved oxygen is cathodically reduced in acid according to
O2 + 4H + 4e ! 2H2 O
1:8
Reactions (1.7) and (1.8) occur simultaneously in acid solutions with dissolved
oxygen. Diffusion of dissolved oxygen controls the corrosion rate at a constant
level in the pH range 410. Thus, metallurgical variables affecting the anodic
reaction [1] have no effect on the corrosion rate. Such is not the case for acid,
where the cathodic reaction is under activation control. The carbide phase shows
low overvoltage (higher rate) for reduction of H+ ions. Thus, high carbon steels
have a higher corrosion rate in acid solution than that of the low carbon steels
[48, 49].
11
Cu, Cr, Ni, Si, P, etc. are added in carbon steel to achieve compact, adherent and
pore free rust layer which in turn provide good corrosion protection to the steel
surface depending on the environment [2730, 51, 52]. Weathering process of steel
with Cu and P promote the formation of a tightly adherent, protective and stable
rust layer to act as a barrier to electrochemical attack under wetdry cycle. Corrosion of weathering steels containing Cu, P and Cr virtually ceases after 3 years
of exposure. It is noteworthy that the formation of protective rust layer does not
depend only on the alloying elements but also on the environment. It is observed
that the formation of protective rust on the steel surfaces containing Cu is easier in
industrial and rural atmospheres and difficult in marine atmospheres containing
chloride ions. In their research work, Larrabee and Coburn [53] have revealed the
effect of alloying elements on the corrosion resistance of steel where Cu and P
additions are most beneficial in improving the resistance of steels. They have
showed that the corrosion rate of plain carbon steels increases progressively with
exposure time whereas same decreases in Cu containing steels in industrial
atmosphere.
Atmospheric attacks on steels have been studied on field exposed steel in
industrial, rural and marine environments and found that P, Cu, Ni, Cr and Si
improve the resistance to corrosion while Mn does not seem to affect it and S
increases nucleation rate. The relative importance reported for marine atmosphere
is P, Si, Cu (up to 0.3 %) and Cr, Ni, Cu (above 0.3 %) [5254].
Horton et al. [55] observed that when steels containing Cu and Ni are exposed
in industrial and marine atmospheres, the Cu and Ni appear in the rust layers both
in the loose outer and adherent inner rust on skyward and ground ward surfaces.
Also it was shown by chemical analysis that Ni, Cu, Cr and Mn from weathering
steel appear in the rust layer and provides protection. Presence of chlorides in the
atmosphere accelerates corrosion of steels leading to the formation of basic Fe2+,
Fe3+ chlorides and b FeOOH. Townsend et al. [56] conducted 8-year atmospheric
corrosion tests on weathering steel in rural, industrial and marine environments
with different heated conditions and indicated that heat treatments have no effect
on the corrosion resistance/performance of weathering steels.
12
1 Theoretical Evidences
atmospheric pollutants like SO2 and showed that corrosion starts in non-contaminated atmospheres only at a relative humidity near to 100 %. Thus, they suggested
that weather resistant steel is not to be used in uncoated condition in severe marine
and severe industrial environments. Weathering steel is 58 times more corrosion
resistant than plain carbon steel in industrial atmosphere and in marine atmosphere, superiority of the weather resistant steel depends on the salt content of the
atmosphere [58, 59].
Effect of Temperature. Temperature plays an important role in atmospheric
corrosion. There is normal increase in corrosion activity which can theoretically
double for each 10 increase in temperature. As the ambient temperature drops
during the evening, metallic surfaces tend to remain warmer than the humid air
surrounding them and do not allow condensation until some time after the dew
point has been reached. As the temperature begins to rise in the surrounding air,
the lagging temperature of the metal structures will tend to make them act as
condensers, maintaining a film of moisture on their surfaces [6063].
Effect of Relative Humidity. Relative humidity is defined as the ratio of the
quantity of water vapour present in the atmosphere to the saturation quantity at a
given temperature. Atmospheric corrosion takes place in presence of a thin film
electrolyte that can form on metallic surfaces when exposed to a critical level of
humidity. While this film is almost invisible, the corrosive contaminants are
known to reach relatively high concentrations, under conditions of alternate
wetting and drying. The critical humidity level is a variable and depends on the
nature of the corroding material, the tendency of corrosion products and surface
deposits to absorb moisture, and the presence of atmospheric pollutants. It has
been shown that, this critical humidity level is 60 % for iron if the environment is
free of pollutants [60]. In the presence of thin film electrolytes, atmospheric
corrosion proceeds by balanced anodic and cathodic reactions. The anodic oxidation reaction involves the corrosion attack of the metal, while the cathodic
reaction is naturally the oxygen reduction reaction. The most important factor in
atmospheric corrosion is moisture, either in the form of rain, dew, condensation or
high relative humidity. In the absence of moisture, most contaminants would have
little or no corrosive effect. Rain also may have a beneficial effect in washing away
atmospheric pollutants that have settled on surfaces. This effect has been particularly noticeable in marine atmospheres. On the other hand, if the rain collects in
pockets or crevices, it may accelerate corrosion by supplying continued wetness in
such areas. Continuous wetting and drying of the surface is required during
atmospheric corrosion which makes distinctly different from the usual corrosion
mechanism under immersed conditions [61].The atmospheric corrosion cannot be
described as a simple oxidation reaction but associated with electrochemical
reaction kinetics [62, 63]. Atmospheric corrosion experiences metal dissolution
and the oxygen reduction during wetdry cycles. In industrial atmosphere having
sulphur bearing compounds, the corrosion product on steel is a basic iron sulphate.
The Cu bearing steels form Cu compound which plugs the pores in the corrosion
product, resulting in better corrosion resistance [6466].
13
1:9
1:10
The acid rain triggered atmospheric corrosion of steel and presence of SO2
accelerate corrosion rate due to formation of sulphuric acid resulting the deposition of iron oxides in zones of decreased pH. Misawa [10] recognised the
importance of amorphous and less crystalline iron oxide phases for the chemistry
involved between iron dissolution and formation of stable FeOOH. Iron ions
initially form green complexes, which are transformed into green rust, magnetite,
FeOOH and finally after long exposure times transformed to a FeOOH. Hence, a
large number of thermodynamically metastable phases exist which are transformed
to stable oxides with the environmental conditions [68]. Stratmann [69] developed
a number of experimental techniques to investigate the electrochemical reaction
mechanism during the atmospheric corrosion even under wet/dry conditions.
Studies indicate the adsorption of gaseous species into the corroding surface and
subsequent chemical reactions occurring in the thin electrolyte layer [66].
Thus, in an industrial environment SO2 in presence of moisture, leads to the
formation of a very thin oxide film composed of an inner layer of Fe3O4 covered
by an outer layer FeOOH. The weak outer layer of FeOOH is penetrated by
fissures and moisture enters into the pores in Fe3O4 layer in form of condensed
water and dissolved O2, SO2 forms H2SO4 in the oxide pores.
2SO2 + 2H2 O + O2 ! 2H2 SO4
1:11
The oxide pores is to permit easier access for the electrolyte solution to the
underlying surface. This H2SO4 partially dissolves the oxide, producing FeSO4 and
thereby opens the oxide pores to permit easier access for the electrolyte to
underlying surface.
Fe3 O4 + 4H2 SO4 ! FeSO4 + Fe2 SO4 3 + 4H2 O
1:12
1:13
14
1 Theoretical Evidences
15
16
1 Theoretical Evidences
The level of dissolved salts of the exposure environment had an effect on the
properties of coatings [85].
Mayne [86] showed that, upon immersion in an aqueous solution, most organic
coatings acquire a negative charge and the acquisition of this charge has the effect
of creating a selectively permeable membrane, which is preferentially permeable
to cations; that is, a film that has gained a negative charge due to immersion.
17
interface can form a concentrated salt solution and that acts to draw water through
the coating, which behaves as a semipermeable membrane from the exposure
environment. Anodic blistering mode of failure was addressed by Koehler [90]
who considered liquid filled blisters to be anodic in nature. Cathodic blistering is
the result of an alkaline environment under the coating caused by the cathodic
reaction, associated with corrosion that occurs at a damaged site of the film
[91]. The fault may take the form of mechanical damage to the coating or may be
inherent coating faults like pores/holidays.
Anodic half-cell reaction:
Fe ! Fe2 + 2e
1:14
Fe2 + O2 + H2 O ! Fe2 O3 + H2 O
1:15
1:16
1:17
Some pathways must exist through the film to allow the sodium ions to the
interface in order to produce the alkaline environment. These pathways could be
due to pores. However, an alternative theory is proposed by Leidheiser [92]
suggests that beyond a given concentration, alkali cations may have a deleterious
effect on the coating, which leads to morphological changes and introducing
conductive pathways to the interface.
2Na + 2OH ! 2NaOH in presence of alkaline solution
1:18
18
1 Theoretical Evidences
required for the process to proceed are water, oxygen and free electrons. The
electrons may be generated by either an anodic reaction or through the application
of cathodic protection [95].
Cathodic delamination is a result of a damaged coating; there are two possible
routes that the reactants for the cathodic reaction may take. The two alternatives
are either through the coating or along the polymermetal interface. An extensive
review of the delamination process was carried out by Leidheiser et al. [96] and the
results indicated that water was transported to the reaction zone through the
coating. It was suggested that a certain fraction of this could be in the form of a
cation as the cathodic nature and may favour the transmission of water associated
with an ion possessing a positive charge. The supply of oxygen to the cathodic site
was found to be largely through the coating, with a small contribution from
interfacial transport, in the case of the epoxy coating studied.
Adhesion plays an important role in the protective mechanism of coatings.
When one considers the process of cathodic delamination it is clear that, once the
paint has become detached from the substrate, the underlying metal is exposed to
the environment and is no longer accorded any protection from the coating system. Whilst the loss of adhesion, resulting from the delamination process, effectively reduces the protection afforded by the coating, it is important to consider
whether the original adhesion is the deciding factor in the delamination process.
Gowers and Scantlebury [97] suggested that the beneficial role of the adhesion of a
paint/coating is due to the impairment of the formation of a layer of electrolyte at
the coatingsubstrate interface, preventing ionic current flow and the spread of
corrosion over the surface. Gosselin [98] showed that good surface preparation is
the key to good adhesion but the type, as well as the condition, of the substrate has
been found to have a strong influence upon the initial dry, and the subsequent wet,
adhesion of a metal/coating .
19
electrochemical impedance spectroscopy (EIS) can provide reliable data on performance in a short time. Capacitance and electrical properties of the coating are
measured as a function of time. Since corrosion is an electrochemical process, it
appears logical that the electrical resistance of a coating would be related to its
protective ability. The DC resistance of the coating was essentially considered to
be the internal resistance of the cell metal/coating/aqueous environment. For good
coatings, the resistance changed slowly but for poor coatings the resistance
dropped more rapidly. Rusting generally was not noted on the test panels until the
DC resistance dropped \106 ohm-cm2. Since it is difficult to accelerate evenly all
the various factors involved, an accelerated method of detecting the deterioration,
or the lack of continued protection, of a coating could be more useful and accurate
than method of actually speeding up the deterioration or the corrosion process.
This is one reason why electrical methods for detecting paint breakdown appear to
show a comparatively high degree of correlation with actual breakdown in the
same environment. The extension of electrical methods for measuring the degree
of deterioration to coatings and uncoated steels exposed in atmospheric environments may thus be promising [100, 101].
87600W
AT D
1:19
20
1 Theoretical Evidences
babc
2:303I corr ba bc
1:20
21
Where, ba and bc are anodic and cathodic Tafel slopes (mV/decade), Icorr is
corrosion current density (A/cm2) and Rp is polarisation resistance (ohm-cm2).
This involves a potential scan 250 mV of Ecorr at a scan rate of 0.11.0 mV/s.
The technique is used to determine the equilibrium corrosion current, potential,
Tafel constants and corrosion rates. The corrosion rate (CR) is determined from
the Faradays law:
CR
0:13IcorrEW
q
1:21
22
1 Theoretical Evidences
1:22
1:23
23
24
1 Theoretical Evidences
Itagaki et al. [120] used EIS to investigate the electrochemical properties of the
rust film membrane formed on low alloy steels. The electrochemical impedance of
the actual rust film membrane formed by wetdry cycles showed the capacitive
semicircle on Nyquist plot corresponding to a single time constant. The time
constant of the capacitive semicircle was found composed of the rust film resistance and the film capacitance. The value of rust film resistance was shown to
depend on the alloying elements in weathering steel and it was shown that the
25
26
1 Theoretical Evidences
treatments with rust converters to rusted steel. Mild steel with mill scale were
prerusted for 2 years in a rural atmosphere before applying conversion treatments.
They found that the shape of the low frequency areas of the Nyquist plots are
markedly influenced by diffusion processes in the rust layer and/or by the porous
nature of the rusted steel electrode itself.
With alloying and increasing period of exposure to saline atmospheres, the
magnitudes of rust pore resistances are expected to increase and rust capacitive
reactance will decrease since capacitance is inversely proportional to AC impedance. It is also likely that the charge transfer resistance which is indicative of metal
corrosion, itself will undergo an increase with alloying thereby signifying higher
corrosion resistance for alloyed steels. Corrosion, coating and diffusion processes
are not always associated with same frequency ranges. Corrosion resistances are
observed at low frequencies, but coating pore resistances can also be observed at
low frequencies, particularly, when a coating is saturated with electrolyte and
metallic corrosion does not occur. Capacitance values can be used to guide
interpretation as to what type of process is associated with each time constant.
Corrosion time constants have capacitance values (120 lF/cm2), coating time
constants have capacitance values (nF/cm2) and oxides have capacitance values
(1000 lF/cm2). Capacitance values of the order of C100 lF/cm2 are found when
surface adsorption occurs in conjunction with corrosion [103].
27
EIS data are analysed by fitting them to an equivalent electrical circuit model
consisting of resistors, capacitors, and inductors. The working electrode interface
undergoing an electrochemical reaction is analogous to an electronic circuit and
can be characterised as an electrochemical system in terms of equivalent circuit.
Typical circuits are shown in Figs. 1.10, 1.11, 1.12 and 1.13 where Yo is admittance (ohm-cm2),Cf is double-layer capacitance and a is the exponents [114]. (R.E:
Reference Electrode and W.E: Working Electrode)
28
1 Theoretical Evidences
weathering steel [128]. This is due to the presence of the nanophase oxides whose
diffraction lines are very broad and are frequently overlooked owing to their
overlapping with sharper peaks for larger particles of the same oxide phases in the
rust and are believed to be incorrectly referred to as amorphous. XRD measurements have lead to general conclusion that weathering steel forms a protective
coating with ratio a FeOOH/c FeOOH [ 2 [129, 130].
In another study, corrosion rates of Mnsteel and CuMn weathering steel in a
simulated coastal environment were measured by wetdry cyclic test. The rust
layer was observed and analysed by SEM and XRD. The experimental results
29
showed that the corrosion rate of CuMn weathering steel was lower than that of
Mnsteel, due to the formation of a denser rust layer. The rusts on the two steels
consisted of Fe3O4, a FeOOH, b FeOOH, c FeOOH and amorphous phases. The
amount of a FeOOH and b FeOOH in the rust of Mnsteel was larger than that of
CuMn weathering steel. The addition of Cu increased the amount of Fe3O4, while
the addition of Mn decreased the amount of c FeOOH in the rusts [131].
226,245,292,411,497,612
381,486,670,718
532,667
Characterised by 4 peaks
Characterised by 2 peaks
a Fe2O3
Haematite
c Fe2O3
Maghemite
Fe3O4
Magnetite
297,392,666
219,252,311,349,379,528,648
314,380,549,722
Characterised
by 4 peaks
Charactersed
by 7 peaks
Gives relatively weak peaks
b FeOOH
Akaganeite
c FeOOH
Lepidocrocite
d FeOOH
205,247,300,386,418,481,549
a FeOOH
Goethite
[138]
[137]
[139]
[140]
[141]
[139]
[140]
[142]
[141]
[143]
[143]
[138]
[138]
[141]
[143]
[137]
[R]
30
1 Theoretical Evidences
31
composed of c FeOOH while the inner layer was comprised mainly of densely
packed nanoparticles of a FeOOH. Further, a FeOOH was found enriched with Cr
and reported to be the stable and protective uniform rust layer. It was proposed that
the c FeOOH, as an initial rust layer of weathering steel, formed after a few year of
exposure, is transformed eventually into the final stable rust layer consisting of
nano-size a FeOOH after decades with amorphous ferric oxyhydroxide as an
intermediate transition product which is formed after several years of exposure in
atmosphere. The mean diameter of the rust particles was found to be approximately 0.5 lm in the outer loose layer aggregate whereas the inner layer was
composed of densely packed fine particles within the larger secondary particles. In
contrast, the corrosion product formed on mild steel contained number of voids
and microcracks.
Microscopic observation of weathering steel exposed outdoors during stable
protective rust coating development, reveal two phases in layers parallel to the
steel surface. The layer adjacent to the steel is grey and compact and the external is
reddish and porous. The thickness of the inner phase increases up to outdoor
exposure periods longer than 5 years, when it becomes the only component of the
patina. It is responsible for the electrochemical potential increase and low corrosion rate of steel, restricting oxygen and water access as a barrier to elements
controlling further corrosion. In carbon steels corrosion products form also as two
optically different phases, but they are mixed up. They experience lower increase
of electrochemical potential during natural or simulated outdoor exposure. Their
corrosion rate remains up to an order of magnitude above those determined for
weathering steels in the respective atmospheres [145, 146].
32
1 Theoretical Evidences
References
1. Graham, J.: Passivity of iron. Electrochem. Soc. Proc. 13, 112115 (2002)
2. Evans, U.R.: Mechanism of atmospheric rusting. Corros. Sci. 12, 227246 (1972)
3. Pourbaix, M.: Atlas of Electrochemical Equilibria in Aqueous Solutions. Pergamon, New
York (1966)
4. Devenpori, A.J., Oblonsky, L.J., Ryan, M.P., Toney, M.F.: Electrochem. Soc. 174, 2162
(2000)
5. Chen, C.T., Cahan, B.D.: The nature of passive film on iron. J. Electrochem, Soc. 129,
1726 (1982)
6. Matsubara, E., Suzuki, S., Waseda, Y.: Corrosion Mechanism of Iron from an X Ray
Structural Viewpoint, Book on Characterisation of Corrosion Products on Steel Surfaces
7. Shastry, C.R., Friel, J.J., Townsend, H.E.: 16 yr atmospheric corrosion performance of
weathering steels in marine, rural, and industrial environments: degradation of metals in
atmosphere, STP 965, pp. 515. S.W. Dean & T. S. Lee, ASTM, Philadelphia (1988)
8. Townsend, H.E.: Estimating the atmospheric corrosion resistance of weathering steels in
outdoor atmospheric corrosion, STP 1421, pp. 292300. ASTM, West Conshohocken
(2002)
9. Pourbaix, M.: The linear bilogarithmic law for atmospheric corrosion. Wiley, New York
(1982)
10. Misawa, T., Asami, K., Hashimoto, K., Shimodaira, S.: Corros. Sci. 14, 279289 (1974)
11. Misawa, T., Yamashita, M., Miyuki, H., Nagano, H.: Protective rust layer formed on
weathering steel by atmospheric corrosion for a quarter of a century, J. Iron Steel Inst. Jpn.
79(1):6975 (1993)
12. Feliu, S., Morcillo, M., Feliu, Jr.S.: The prediction of atmospheric corrosion from
meteorological and pollution parameters I: annual corrosion. Corro. Sci. 34:403
13. Felik, S., Morcillo, M., Felik, Jr.S.: The prediction of atmospheric corrosion from
meteorological and pollution parameters ii: long term forecast, Corro. Sci. 34:415 (1993)
14. Natesan, M., Venkatachari, G., Palaniswamy, N.: Corrosivity and durability maps of india.
Corro. Prev. Control 52(2), 43 (2005)
15. Natesan, M., Palaniswamy, N., Rengaswamy, N.S.: Atmospheric corrosivity survey of
India. Mater. Perform. 45:52 (2006)
16. Evans, U.R.: The Corrosion and Oxidation of Metals, vol. 11. VCH Publishers, New York
(1992)
17. Veleva, L.: Phase Transformation of Iron Hydroxide in the Corrosion Products Formed in
Humid Tropical Climate, 58 NACE Conferences, Corrosion (2003)
18. Ohtsuka, Toshiaki: Passivation Oxide Films and Rust Layers on Iron Characterization of
Corrosion Products on Steel Surfaces. Springer, Berlin Heidelberg (2006)
19. Oh, S.J., Cook, D.C., Townsend, H.E.: Atmospheric corrosion of different steels in marine
rural & industrial environments. Corro. Sci. 41, 16871702 (1999)
20. Balasubramaniam, R., Rameshkumar, A.V., Dillmann, P.: Curr. Sci. 85, 15461555 (2003)
21. Kihira, H., Ito, S., Murata, T.: The behavior of phosphorous during passivation of
weathering steel by protective patina formation, Corr. Sci. 31:383388 (1990)
22. Morcillo, M., Chiro, B., Otero, E.: Mater. Perform. 38, 72 (1999)
23. Mattson, E.: The atmospheric corrosion properties of some common structural metals: a
comparative study. Mater. Perform. 21, 919 (1982)
24. Zhang, Q.C., Wu, J.S., Wang, J.J., Zheng, W.L., Chen, J.G., Li, A.B.: Corrosion Behavior of
Weathering Steel in Marine Atmosphere 77, 603608 (2003)
25. Misawa, T., Hashimoto, K., Shimodaira, S.: The mechanism of formation of iron oxide and
oxyhydroxides in aqueous solutions at room temperature. Corros. Sci. 14, 131141 (1974)
26. Yamashita, M., Maeda, A., Uchida, H., Kamimura, T., Miyuki, H.: J. Jpn. Inst. Metal 65,
967971 (2001)
27. Suzuki, I., Hisamatsu, Y., Masuko, N.: J. Electrochem. Society 127, 2210 (1980)
References
33
28. Oh, S.J., Cook, D.C., Townsend, H.E.: Characterisation of iron oxides commonly formed as
corrosion products on steel. Hyperfine Interact 112, 5965 (1998)
29. Stratmann, M., Bohnenkamp, K., Ramchandran, T.: Corros. Sci. 27, 905 (1987)
30. Kishikawa, H., Miyuki, H., Hara, S., Kamiya, M., Yamashita, M.: Sumitomo Search 20
(1998)
31. Oh, S.J., Cook, D.C., KWon, S.J., Townsend, H.E.: Hyperfine Interact 4:4954 (1999)
32. Yamashita, M., Nagano, H., Misawa, T., Townsend, H.E.: Structure of protective rust layers
formed on weathering steels in industrial atmospheres of Japan and North America. ISIJ Int.
38(3), 285290 (1998)
33. Wei,F.I.: Atmospheric corrosion of carbon steels and weathering steels in Taiwan. British
Corros. J. 26(3):209214 (1991)
34. Asami, K., Kikuchi, M.: Corros. Sci. 45, 26712688 (2003)
35. Townsend, H.E.: The Effects of alloying elements on the corrosion resistance of steel in
industrial environments. In: Proceeding of 14th. International Corrosion Congress,
Corrosion Institute of South Africa (1999)
36. Yamamoto, M., Katayama, H., Kodama, T.: Current dev. Mater. Process 12, 422 (1999)
37. Asami, K. Kikuchi, M.: In-depth distribution of rusts on a plain carbon steel and weathering
steels exposed to coastal industrial atmosphere for 17 years. Corros. Sci. 45(11):26712688
(2003)
38. Kihira, H.: Electrochemical Phenomena at Interface, p.429 Marcel Dekker Inc. New York,
(1998)
39. Sakashita, M., Sato, N.: Corros. Eng. 28, 450 (1979)
40. Keiser, J.T., Brown, C.W., Heidersbach, R.H.: Raman bands of different iron oxides
compared to the bands seen in spectra of the inner rust on weathering steel. Corros. Sci.
23(2), 251 (1983)
41. Yamashita, M., Asami, K., Ishikawa, T., Ohisuka, T., Tamura, H., Misawa, T.: Zairyo to
Kankyo 50, 521 (2001)
42. Fyfe, D. Shanahan, C.E., Shreir, L.L.: Proceeding 4th International Congress On Metallic
Corrosion. NACE 399 (1972)
43. Burstein, G.T., Marshall, P.I.: Growth of passivating films on steel in alkaline solution.
Corros. Sci. 23, 125137 (1983)
44. Balasubramaniam, R.: The protective rust on low alloy steel. Corros. Sci. 14: 279 (1971)
45. Inouye, K., Ishii, S., Kaneko, K.: J Inorg. Gen. Chem. 391:86 (1972)
46. Townsend, H.E., Simpson, T.C., Johnson, G.: Structure of rust on weathering steel in rural
and industrial environments. In: Proceding 20th International Corrosion Congress, NACE,
Houston, 2:624641 (1993)
47. Ishikawa, T., Nakazaki, H., Yasukawa, A.: Corros. Sci. 41, p1665p1680 (1999)
48. Uhlig, H.H., Revie, R.W.: Corrosion and Corrosion Control, 3rd edn, p. 96. Wiley,
NewYork (1985)
49. Cleary, H.J., Greene, N.D.: Corros. Sci. 3 (1969)
50. Oh, S.J., Cook, D.C., Townsend, H.E.: Hyperfine Interact 3, 8487 (1998)
51. Yamashita, M., Miyuki, H., Matsuda, Y., Nagano, H., Misawa, T.: Corros. Sci. 36, 283299
(1994)
52. Cook, D.C., Vanorden, A.C., Reyes, J., Oh, S.J., Balasubramanian, R., Carpio, J.J.,
Townsend, H.E.: Marine Corrosion In Tropical Environments, ASTM STP 1399, (2000)
53. Larrabee, C.P., Coburn, S.K.: Proceeding 1st International Congress on Metallic Corrosion,
London 276 (1962)
54. Townsend, H.E., Simpson, T.C., Johnson, G.L.: Corrosion 50, 546554 (1994)
55. Horton, J.B., Goldberg, M.M., Watterson, K.F: Proceeding 4th. Internatioanl Congress on
Metallic Corrosion, NACE 385391 (1972)
56. Fontana, M.G.: Corrosion Engineering, 3rd.Edn, Mcgraw Hill Book, New York (1986)
57. Vernon, W.H.J.: Trans. Farady Soc. 31, 1668 (1935)
58. Stratmann, M., Streckel, H.: Corros. Sci. 30, 697714 (1990)
34
1 Theoretical Evidences
59. Rendn, J.L., Valencia, A.: Kinetics of structural rust transformation in environments
containing chloride and SO2. Rev. Met. 914 (2003)
60. Bolvar, F., Meneses, C.A.B., Minotas, J., Grenche, J.M.: Variable temperature mssbauer
study of some rust converters. Hyperfine Interact 148, 219225 (2003)
61. Townsend, H.E.: Atmospheric corrosion performance of quenched and tempered
weathering steel. Corrosion 56, 883886 (2000)
62. Itagaki, M., Tajima, S., Nozue, R., Watanabe, K., Katayama, H., Noda, K.: 204th Meeting,
The Electrochemical Society (2003)
63. Tait, W.S.: An Introduction to Electrochemical Corrosion Testing for Practicing Engineers
and Scientists, Wisconsin, (1994) 79115
64. Atmospheric Corrosion Resistant Steels: Product Catalogue. Nippon Steel Corporation,
Japan (2005)
65. Veleva, L., Perez, G., Costa, M.A.: Statistical analysis of the temperature humidity complex
and time of wetness of a tropical climate in the Yucatan peninsula in Maxico. Atmosphere
Environ. 31, 773776 (1997)
66. Evans, U.R., Taylor, C.A.J.: Corros. Sci. 12, 227246 (1972)
67. Pourbaix, M.: Corros. Sci. 14, 25 (1974)
68. Singh, D.D.N., Yadav, S., Saha, J.K.: Role of climatic conditions on corrosion
characteristics of structural steels, Corros. Sci. 50(1):93110 (2007)
69. Stratmann, M.: The Atmospheric corrosion of iron & steel: historic review and future
perspectives. Corros. Rev. 2024 (2001)
70. Kimura, M. Kihira, H., Otha, N.: Use advance weathering steel to Avoid Cr as alloying
element ti dosed to get chloride corrosion resistance. Corros. Sci. 47 (2005)
71. Leygraf, C., Graedel, T.: Atmospheric corrosion. J. Electrochem. Soc. 1497, p1010 (2000)
72. Environmental information system in India, http://envis.tropmet.res.in dated Jan 2007
73. Rao, K.N.P., Lahiri, A.K.: Corrosion Map of India Corrosion Advisory Bureau. Metal
Research, India (1970)
74. Sato, N.: An overview on passivity of metals. Corros. Sci. 31, p1 (1990)
75. Nagayama, G.M., Cohen, M.: J. Electrochem. Soc. 110: 164 (1963)
76. Mizoguchi, T., Ishii, Y., Okada, T., Kimura, M., Kihira, H.: Corros. Sci. 47:24772491
(2005)
77. Usami, A., Kihira, H., Kusunoki, T.: Nippon Steel Technical Report 87, 17 (2003)
78. Okada, H., Hosoi, Y., Yukawa, K., Naito, H.: Proceeding 4th International Congress on
Materials, Corrosion, NACE, 392398 (1972)
79. Antunes, R.A., Costa, I., Faria, D.L.A.: Characterization of corrosion products formed on
steels in the first months of atmospheric exposure, Mater. Res. 6(3):287293 (2003)
80. David, L. Peterson, P. Rodgers, B.: Evaluation of organic coating with electrochemical
impedance spectroscopy, part 2. Application of EIS to coatings. J. Coat. Technol. 8893
(2004)
81. Kittelberger, W.W., Elm, A.C.: Water immersion testing of metal protective paints. role of
osmosis in water absorption and blistering. Ind Eng Chem 38, 695699 (1946)
82. Bacon, C.R., Smith, J.J., Rugg, F.M.: Electrolytic resistance in evaluating protective merit
of coatings on metals. Ind Eng Chem 40, 161167 (1948)
83. Thomas, N.L.: The barrier properties of paint coatings. Prog. Org. Coat. 19, 101121 (1991)
84. Ravie, R.W., Baker, B.G., Bockris, O.M.: Modern aspects of electrochemistry.
Electrochem. Soc. 122 1460 (1975)
85. Greenfield, D., Scantlebury, D.: The protective action of organic coatings on steel a review.
Corros. Sci. Eng. 3, 5 (2000)
86. Mayne, J.E.O.: Paints for the protection of steel: a review of research into their modes of
action. Corrosion 5, 160111 (1970)
87. Scantlebury, J.D.: Organic coatings systems and their future in corrosion protection.
Proceedings of EUROCORR, Budapest, (1982)
References
35
88. Rosales, B.M., Sarli, A.R.D., Rincn, O.D., Rincn, A., Elsner, C.I., Marchisio, B.: An
evaluation of coil coating formulations in marine environments. Prog. Org. Coat. 50,
105114 (2003)
89. Leidheiser, Jr.H. Simmons, G.W., Kellerman, E.: Electrochem. Acta, 45:257 (1973)
90. Koehler, E.L.: under film corrosion currents as the cause of failure of protective organic
coatings. Org. Coat. 8796 (1981)
91. Schwenk, W.: Adhesion Loss for organic coatings causes and consequences for corrosion
protection by organic coatings. Corrosion, 103110 (1981)
92. Leidheiser, Jr.H.: Alkali metal ions as aggressive agents to polymeric corrosion protective
coatings. Corrosion, 43:296297 (1987)
93. Smith, G., Dickie, R.A.: Adhesion failure mechanisms of primers. Ind. Eng. Chem. 17,
4244 (1978)
94. Koehler, E.L.: The influence of contaminants on failure of protective organic coatings.
Corrosion NACE 33, 209217 (1977)
95. Leidheiser, Jr.H., Wang, W., Igetoft, L.: the mechanism for cathodic delamination of
organic coatings from a metal surface. Prog. Org. Coat. 11:1941 (1983)
96. Leidheiser, H., Funke, W.: Water disbandment and wet adhesion of organic coatings on
metals a review and interpretation. Surf. Coat. Int. 70, 121132 (1987)
97. Gowers, K.R., Scantlebury, J.D.: An electrochemical investigation of the effect of the
adhesion of a lacquer coating on the under film corrosion. Surf. Coat. Int. 4, 114121 (1988)
98. Gosselin, C.A.: Effect of surface preparation on the durability of structural adhesive bonds,
polymeric materials for corrosion control. In: ACS Symposium 322:180193 (1986)
99. Funke, W.: The role of adhesion in corrosion protection by organic coatings. JOCCA 68,
229232 (1985)
100. Princeton Applied Research Application note AC-1. Basics of electrochemical impedance
spectroscopy, USA, (2009)
101. Chico, B., Galvn, J.C., Fuente, D.D.L., Morcillo, M.: Electrochemical impedance
spectroscopy study of the effect of curing time on the early barrier properties of saline
systems applied on steel substrates. Prog. Org. Coat. 60(1):4553 (2007)
102. ASTM G1 Standard practice for preparing, cleaning & evaluating corrosion test specimens
(1990)
103. Scully, J.R.: Electrochemical impedance of organic coated steel correlation of impedance
parameters with long term coating deterioration. Electrochem. Soc. 13(6), 979 (1989)
104. Jones, D.A.: Principles and Prevention of Corrosion. Prentice Hall, USA (1996)
105. Scully, J.R.: Polarization resistance method for determination of instantaneous corrosion
rates. Corrosion 56, p199 (2000)
106. Stern, M. Geary, A.L.: Electrochemical polarization, J. Electrochem. Soc. 104(1):5663
(1957)
107. Harvey, F., Schweinsberg, J., Paul, D.D.: Evaluation of corrosion rate from polarisation
curves not exhibiting a tafel region. Corros. Sci. 47, 30343052 (2005)
108. Pourbaix, M.: Atlas of electrochemical equilibria in aqueous solutions, NACE, (1974)
109. Tait, W.S.: An Introduction to Electrochemical Corrosion Testing for Practicing Engineers
and Scientists. Pair O Docs Professionals E-Book, Madison (1994)
110. Corrosion Basics: An introduction, national association of corrosion engineers, (1984)
111. Scully, J.R.: Electrochemical impedance spectroscopy for evaluation of Organic coating
deterioration & under film corrosion. A state of the art technical review, D. W. Taylor
Research Center, Report SME-86/006, (1986)
112. Kendig, M. Scully, J.R.: Basic aspects of the application of electrochemical impedance for
the life prediction of organic coatings on metals. Corrosion 31(1):22 (1990)
113. Mansfeld, F.: Evaluation of corrosion behaviour of coated metals with ac impedance
measurements. Corros. Sci. 2(3), 317 (1983)
114. Equivalent Circuit Modeling using the Gamry EIS 300 Electrochemical Impedance
Spectroscopy Software: Gamry Application Note, USA, (2001)
36
1 Theoretical Evidences
115. Ke, W.: Chinese Corrosion Survey Report, 1st Edn. Chemical Industry Press, Beijing, ISBN
7-5025-4792-4/TQx1816, (2003) p 13
116. Macdonald, J.R.: J. Electrochemical Society 223, 25 (1987)
117. Scibner Assciates Inc, Southern Pines, North Carolina (1998)
118. Kihira, H., Ito, S., Murata, T.: Corros. Sci. 31, 383388 (1990)
119. Nishimura, T., Katayama, H., Noda, K., Kodama, T.: Corros. Sci. 56, 935 (2000)
120. Itagaki, M., Nozue, R., Watanabe, K., Katayama, H., Noda, K.: Corros. Sci. 46, 13011310
(2004)
121. Konishi, H., Yamashita, M., Uchida, H., Mizuki, J.: Characterization of Rust Layer formed
on Fe Fe-Ni and Fe-Cr alloys Exposed to Cl- Rich Environment. Mater. Trans. 46(2),
329336 (2005)
122. Feliu, S., Galvan, J.C., Bastidas, J.M., Simancas, J., Morcillo, M., Almeida, E.M.: Corros.
Sci. 35, 13511358 (1993)
123. Qu, A.Q., Li, L., Bai, W., Yan, C.: Initial atmospheric corrosion of weathering steel in the
presence of NaCl and SO2, 16th Int Corrosion Congress, Beijing, (2005)
124. Cox, A., Lyon, S.B.: An Electrochemical study of the atmospheric corrosion of mild steel,
part iii: the effect of sulphur dioxide. Corros. Sci. 36(7):11931199 (1994)
125. Cornell, R.M., Schwertmann, U.: The iron oxides: structure, properties, reactions,
occurrences and uses. Wiley, Weinheim (2003)
126. Cullity, B.D., Stock, S.R.: Elements of X-ray diffraction, 3rd Edition Addison Wesley,
Weinheim (2001)
127. Azaroff, L.V.: Elements of X-ray Crystallography, Mcgraw Hill, New York (1986)
128. Cook, D.C., Oh, S.J., Balasubramanian, R., Yamashita, M.: Hyperfine Interact. 122, 5970
(1999)
129. Legault, R.A. Preban, A.G.: Kinetics of atmospheric corrosion of low alloy steels in an
industrial environment. Corrosion, 31(4) 117122 (1975)
130. Baker, E. A.: Long term corrosion behaviour of materials in the marine atmosphere,
degradation of metals in the atmosphere, STP 965, ASTM, New Jersey 125144 (1998)
131. Liu, A., Dong, G.C., Han, J.H., Hou, E., Wei, K.: Influence of Cu and Mn on corrosion
behaviour of low alloy steel in a simulated coastal environment. Corros. Sci. Protect.
Technol. 20(4):235238 (2008)
132. Anderson, A.: The Raman Effect. Marcel Dekker, (1973)
133. Herzberg, G.: Molecular Structure and Molecular Spectra. Van Nostrand Reinhold, New
York (2008)
134. Gilson, T.R., Hendra, P.J.: Laser Raman Spectroscopy. Wiley Inter Science, New York
(1970)
135. Loader, J.: Basic Laser Raman Spectroscopy. Heyden & Son, London (1970)
136. Gui, J. Devine, T.M.: Proceeding of 12th International Corrosion Congress, NACE, 2052
(1993)
137. Dunnwald, J., Otto, A.: Corros. Sci. 29, 11671176 (1989)
138. Ohtsuka, T., Kubo, K., Sato, N.: Corrosion 42, 476481 (1986)
139. Ohtsuka, T.: Materials transctions, JIM 37:67 (1996)
140. Brown, C.W., Heidersbach, R.H.: Applied spectroscopy. 32(6):532532 (1978)
141. Boucherit, N., Delicher, P., Joiret, S., Hugot, A.: Mater. Sci. Forum 51, 44 (1989)
142. Thierry, D., Persson, D., Lyegraf, C., Delichere, D., Joiret, S., Pallotta, C., Hugot, A.: J.
Electrochem. Soc. 135(2):350310 (1988)
143. Thibeau, R.J., Brown, C.W., Heidersbach, R.H.: Appl. Spectrosc. 32, 532 (1978)
144. Yamashita, M., Uchid, H.: recent research & development in solving atmospheric corrosion
problems of steel industries in Japan, Hyperfine Inter. 139(4):153166 (2002)
145. Graedel, T.E., Frankonthal, R.P.: Corrosion mechanism for iron and low alloy steel exposed
to the atmosphere. J. Electrochem. Soc. 137(8):23852394 (1990)
146. Ramana, K.V.S., Kaliappan, S., Ramanathan, N., Kavitha, V.: Characterization of rust
phases formed on low carbon steel exposed to natural marine environment of Chennai
harbor, India. Mater. Corros. 5(8), 873 (2007)
References
37
147. Jan, J.A., Muz, A., Justavino, J., Hernndez, C.: Characterization of initial atmospheric
corrosion of conventional weathering steels and a mild steel in a tropical atmosphere
192(13):5159 (2009)
148. Hirofumi, K., Hideaki, M., Syidu, H., Mitsuaki, K., Masato, M.: Development of surface
treatment technique promoting protective surface formations. Sumitomo Search 60, 2026
(1998)
149. Mattson, E.: The atmospheric corrosion properties of some common structural metals: a
comparative study. Mater. Perform. 21, 919 (1982)
150. Bolivar, F., Morales, A.L., Aramburo, C.: Simulation of a long term atmospheric corrosion
process on plain and weathering steels. Rev. Metal 265269 (2003)
151. Uhlig, H.H.: Passivity in metals and alloys. Corros. Sci. 19:777 (1979)
152. Komori, T., Kyono, K., Kato, C.: New surface treatment technology for promoting
protective rust formation on weathering steel. In:132nd Symposium Corrosion Prevention.
6572 (2001)
Chapter 2
Practical Approach
39
40
2 Practical Approach
Fig. 2.1
Properties
Mn
Cu
Cr
Ni
Si
YS (mpa)
Elongation ( %)
0.17
0.09
0.76
0.38
0.01
0.35
0.03
0.45
0.01
0.27
0.01
0.41
0.01
0.01
0.01
0.11
295
418
27
34
41
ZR
Primer coat
Intermediate coat
Top coat
Primer coat
Intermediate coat
Top coat
Coats
1
1
1
1
1
1
9
9
9
9
9
9
DFT
(lm)
75 250
125
50
50 250
150
50
Application
Laboratory and
atmospheric
Laboratory
42
Fig. 2.2
2 Practical Approach
showed MS and WS as received panels, whereas Fig. 2.3 showed panel after
blasting.
43
phosphate as primer; high build epoxy MIO as intermediate coat and PU as topcoat
and ZR system was coated with epoxy zinc rich as primer, epoxy MIO as intermediate coat and PU as top coat. Time lag allowed between blasting and primer
coat was four hours. To ensure the proper curing of each coat, time allowed for
epoxy Zn phosphate was 6 and 8 h for epoxy Zn rich. Finally, MEK double rub
test as per standard [8] was followed to ensure no effect on surface and no Zn on
cloth after 50 double rubs.
Wet film comb gauge (TQO, WG II) was used to measure the wet film thickness
(WFT) of paints immediately after each coating application to ensure the theoretical thickness. The dry film thickness (DFT) of coats were checked (Elcometer
415) and in some cases mist coat was applied to achieve the desired thickness. Top
coat PU was applied after 8 h from the intermediate coat. The paint used for
sealing edges of panels was of two components, low volatile contents, high solids,
modified epoxy, designed to give long term protection in single coat application.
44
Fig. 2.4
panel
2 Practical Approach
Painted scribed
45
Reference plate
ZR on MS/WS
Weathering
Pull off adhesion
Cross cut adhesion
1000 h passed
12.5 mpa
0 (no peeling)
1000 h passed
12 mpa
0 (no peeling)
46
2 Practical Approach
47
C4
C3
C3
High
ZP
Medium high ZP
Medium
ZP
Medium ([5)
Medium ([5)
Medium ([5)
48
2 Practical Approach
Jamshedpur (P3)
Longitude (E)
Latitude (N)
Altitude (Ft)
Dist from sea(km)
Av Temp (C) (minmax)
Av RH ( %) (minmax)
Av rainfall(mm)
Salinity (mg) NaCl/100 cm2/day
SO2 (mg)/100 cm2/day
86.18
22.8
1590
200
27 (847)
80 (3398)
905
Trace
22
87.55
21.86
SL
0.1
25 (2128)
63 (4989)
1782
0.83
Trace
80.18
13.06
20
1.5
32 (3035)
66 (30100)
1084
0.42
16.5
49
Rust appearance
Corrosion rate
Potentiodynamic polarisation
Cyclic polarisation
Electrochemical impedance
Scanning electron microscopy/EDX
X-ray diffraction
Raman spectroscopy
P3
P1
P2
P3
MS/
WS
MS/
WS
MS/
WS
ZP+ ZP+
WS MS
ZP+
WS
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
Ha
H
H
50
2 Practical Approach
MS and WS
MS and WS
MS and WS
ZP ? MS/
ZP ? WS
42 m
18 m
P1
P2
P3
P3
Table no.
Fig. no.
3.5 % NaCl
solution
3.3
2.5 % NaHCO3
? 0.5 %
NaCl ? 0.1 %
CaCl2 for 4080 h
3.4
3.5
3.6
3.7
3.8
For cyclic polarisation (CP) with 1.0 mV/s scan rate, potential scan was started
at Ecorr and continued in the anodic direction up to the transpassive region, where a
large increase in current occurred. At the threshold of current density (1 mA/cm2),
the scan was reversed and continued in the cathodic direction back to or beyond
the OCP followed as per standard [18].
51
Table
no.
Fig.
no.
3.9
3.10
3.11
3.12
3.13
3.14
3.15
3.16
42
P1
3.5
42
P2
3.5
42
P3
3.5
48
P3
3.6
? MS
? WS
? MS
? WS
? MS
? WS
? MS
scribed
ZP ? WS
scribed
ZP ? MS
ZP ? WS
ZP ? MS
ZP ? WS
ZP ? MS
ZP ? WS
ZP ? MS
ZP ? WS
18
P1
18
P2
18
P3
18
P3
Table
no.
Fig.
no.
3.7
3.17
3.18
3.19
3.20
3.21
3.22
3.23
3.7
3.7
3.8
3.24
42
P1
3.9
42
P2
3.9
42
P3
3.9
42
P3
3.10
3.25
3.26
3.27
3.28
3.29
3.30
3.31
3.32
For oxide identification, JCPDS database system [19] was used and phases were
identified comparing with 2h and intensities of reflection. Table 2.11 indicates the
test plan of XRD for rust analysis at different stages.
52
2 Practical Approach
Table 2.10 Test plan of rust formed on MS and WS by SEM and EDX
Panels
Sites
Exposure (m)
SEM
EDX
EDX line
Fig. no.
Table no.
Profile
MS/WS
MS/WS
MS/WS
MS/WS
MS/WS
MS/WS
MS line scan
WS line scan
WS line scan
MS line scan
WS line scan
P1
P2
P3
P1
P2
P3
P1
18
P2
P3
42
42
3.33
3.34
3.35
3.36
3.37
3.38
42
42
3.11
3.12
3.39
3.40
3.41
3.42
3.43
Spectra
Plot no.
A 3.1
(WS)
A 3.2
A 3.3
A 3.4
MS/WS
MS/WS
WS
MS/WS
A
A
A
A
P1
P1
P2
P3
18
42
42
42
3.13
3.14
3.15
3.16
3.5
3.6a and A 3.6b
3.7
3.8a and A3.8b
kept at lowest possible level (6 mW) in order to avoid the transformation of rusts
due to heating effect of laser. The instrument was calibrated by using pure silicon
at peak of 522.28 cm-1. Raman peaks were identified according to the spectra for
the various iron oxide and hydroxide compounds from the references summarised
in the literature review section and test plan is given in Table 2.12.
53
18
MS/WS
42
P1
P2
P3
P1
P2
P3
3.17
3.18
A
A
A
A
A
A
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
ZP+
MS
ZR+
MS
ZP+
WS
ZR+
WS
H
H
H
H
H
H
H
H
H
H
54
2 Practical Approach
Cyclic
polarisation
AR MS/
AR
WS
AR MS/
AR
WS
ARMS/
AR
WS
MS/WS
Table
no.
Fig.
no.
3.46
3.22
3.47
3.48
3.23
3.49
3.50
3.51
3.52
condensed on the surface of panels kept at 45. The spraying of brine solution was
continued for 8 h and subsequently discontinued for 16 h.
55
CH instrument
Gamry
Table no.
Fig. no.
3.26
3.53
3.54
3.55
3.56
3.57
3.58
3.26
3.27
Table 2.17 Test plan of rust formed on MS and WS by SEM and EDX
Panel
SEM
EDX
Spectra plot no.
AR MS
AR WS
AR MS line scan
AR WS line scan
Upper layer of MS
Upper layer of WS
Inner layer of MS
Inner layer of WS
3.59
3.28
3.60
3.61
3.62
3.29
3.63
3.29
3.30
3.31
3.32
A
A
A
A
A
A
3.19a
3.20a
3.21a
3.22a
3.23a
3.24a
and
and
and
and
and
and
A
A
A
A
A
A
3.19b
3.20b
3.21b
3.22b
3.23b
3.24b
56
2 Practical Approach
References
1. IS: 2062:2006: Hot Rolled Low, Medium and High Tensile Structural Steel
2. IS: 11587:2001: Structural Weather Resistant Steels
3. ASTM G1: 1990: Standard Practice for Preparing, Cleaning and Evaluating Corrosion Test
Specimens
4. ISO 12944-5:1998: Corrosion Protection of Steel Structures by Protection Paint Systems
5. SAE J 2334: Laboratory Test Procedure to Determine Corrosion Performance of Coating
System
6. ISO 8501-1:1988: Preparation of steel substrates before application of paints and related
productsVisual assessment of surface cleanlinessRust grades and preparation grades of
uncoated steel substrates and of steel substrates after overall removal of previous coatings
7. ISO 8503-2:1988: Preparation of Steel Substrates before Application of Paints and Related
ProductsMethod for Grading of Surface Profile of Abrasive Blast cleaned Steel
8. ASTM D 4752-2003: Measuring MEK Resistance of Ethyl Silicate Zn Rich Primers by
Solvent Rube
9. ASTM D 4587:2005: Standard Practice for Fluorescent UV Condensation Exposures of Paint
and Related Coatings
10. ASTM D 4541:2002: Standard Test Method for Pull-Off Strength of Coating Using Portable
Adhesion Testers
11. ASTM 3359 :2002: Standard Test Methods for Measuring Adhesion by Tape Test
12. ASTM G 50:1997: Standard Practice for Conducting Atmospheric Corrosion Testing Metals
13. IS: 5555:1997: Standard Practice for Conducting Field Studies on Atmospheric Corrosion of
Metals
14. ASTM G 9:1993: Standard Practice for Characterization of Atmospheric Test Sites
15. ISO 9225:1992: Corrosion of Metal and Alloys, Corrosivity of Atmosphere Measurement of
Pollution
16. ISO 9223:1992: Corrosion of Metals and Alloys: Corrosivity of Atmospheres: Classification
17. ASTM 5:2004: Standard Reference Test Method for Making Potentiostatic and Potentiodynamic Anodic Polarization Measurements
18. ASTM G 61:1993: Std. Test Method for Conducting Cyclic Polarization Measurements for Iron
19. Selected Powder Diffraction Data for Metals & Alloys Data Book, 1st. Edn., vol I & II,
JCPDS International Centre for Diffraction Data, USA
20. ASTM G 60:2001: Standard Practice for Humidity Exposures
21. ASTM B117:1997: Standard Practice for Operating Salt Spray (Fog) Apparatus
22. ASTM 87:1984: Standard Practice for Conducting Moist SO2 Tests
Chapter 3
Experimental Evidence
57
58
3 Experimental Evidence
Fig. 3.1 Rust appearance exposed for 42 m at P1 downward side (a) MS and (b) WS
Fig. 3.2 Rust appearance exposed for 42 m at P1 skywards side (a) MS and (b) WS
The polarisation diagrams are shown in Fig. 3.8 and corrosion rate data are given
in Table 3.4.
59
Fig. 3.3 Rust appearance exposed for 42 m at P2 skywards side (a) MS and (b) WS
Fig. 3.4 Rust appearance exposed for 42 m at P3 skywards side (a) MS (b) WS
MS
WS
MS
WS
MS
WS
60
3 Experimental Evidence
Table 3.2 Corrosion rate (lm/y) of MS and WS exposed at P1, P2 and P3 Sites
Exposure months
Digha (P1)
Chennai (P2)
Jamshedpur (P3)
18
30
42
MS
WS
MS
WS
MS
WS
24.1
24.2
26.4
20.2
19.1
18.2
19.5
18.3
17.4
13.4
13.2
12.1
13.6
12.4
12.3
10.3
9.4
9.5
Fig. 3.5 Polarisation diagram in 3.5 % NaCl exposed for 42 m at P1 (a) MS and (b) WS
61
Fig. 3.6 Polarisation diagram in 3.5 % NaCl exposed for 42 m at P2 (a) MS and (b) WS
62
3 Experimental Evidence
Fig. 3.7 Polarisation diagram in 3.5 % NaCl exposed for 42 m at P3 (a) MS and (a) WS
Table 3.3 Corrosion rate in 3.5 % NaCl exposed for 42 m of MS and WS
Sites
Panels
Icorr lA/cm2
P1
P2
P3
MS
WS
MS
WS
MS
WS
63.80
103.3
45.32
45.52
30.77
27.89
Ecorr mV
-701.8
-643.9
-725.9
-656.2
-637.5
-524.9
63
Fig. 3.8 Cyclic polarisation in SAEJ solution of coated MS and WS exposed at P3 for 18 m
Table 3.4 Cyclic polarisation of coated MS and WS after 18 m exposure at P3
Panel
Electrolyte
Icorr lA/cm2
Ecorr mV
ZP ? MS
ZP ? WS
-700.8
-685.5
50.25
10.30
64
3 Experimental Evidence
Fig. 3.9 Impedance plots in 0.1 N NaCl ? 0.1 M Na2SO4 exposed at P1 for 42 m of MS
SEM was used for rust morphology studies on uncoated MS and WS panels
drawn after 42 m of atmospheric exposure from P1, P2 and P3. Figures 3.36a, b,
3.37a, b, and 3.38a, b indicate rust micrographs of MS and WS, respectively.
Elemental analysis of these rusts is given in Table 3.12 and EDX spectra plots are
given in annexure Figs. A 3.2a, b, A 3.3a, b and A 3.4a, b. Corresponding EDX
line scans are given in Figs. 3.39, 3.40, 3.41, 3.42, 3.43.
65
Fig. 3.10 Impedance plots in 0.1 N NaCl ? 0.1 M Na2SO4 exposed at P1 for 42 m of WS
66
3 Experimental Evidence
Fig. 3.11 Impedance plots in 0.1 N NaCl ? 0.1 M Na2SO4 exposed at P2 for 42 m of MS
gives the Raman shift values along with spectra plots in annexure Figs. A 3.12a, b,
A 3.13a, b and A 3.14a, b, for 42 m atmospheric exposure for MS and WS.
67
Fig. 3.12 Impedance plots in 0.1 N NaCl ? 0.1 M Na2SO4 exposed at P2 for 42 m of WS
68
3 Experimental Evidence
Fig. 3.13 Impedance plots in 0.1 N NaCl ? 0.1 M Na2SO4 exposed at P3 for 42 m of MS
of rusting, blistering on exposed coated panels relevant standard [3] was used as
given in Table 3.21.
69
Fig. 3.14 Impedance plots in 0.1 N NaCl ? 0.1 M Na2SO4 exposed at P3 for 42 m of WS
Table 3.5 EIS in 0.1 M Na2SO4 ? 0.1 N NaCl on MS and WS exposed for 42 m
Cf F/cm2
Sites Panel Ru ohm cm2 Rp ohm cm2 Rpo ohm cm2 Cc F/cm2
P1
P2
P3
MS
WS
MS
WS
MS
WS
2.39
4.0
1.11
2.5
6.52
1.44
9
9
9
9
9
9
10-3
10-3
10-3
10-3
10-3
10-3
6.63
2.66
3.95
2.48
6.66
9.56
9
9
9
9
9
9
106
106
105
107
102
105
13.64
19. 21
55.61
1.52
26.75
4.92
9
9
9
9
9
9
2.86 9 10-6
50.76 9 10-11
8.30 9 10-6
20.84 9 10-11
42.12 9 10-12
16.55 9 10-11
Fit
REAP
REAP
REAP
REAP
REAP
REAP
Cyclic polarisation test carried out in 2.5 % NaHCO3 ? 0.5 % NaCl ? 0.1 %
CaCl2 solution on MS and WS after exposed in humid SO2 environment for 9 m.
The polarisation plots are given in Fig. 3.49 along with corrosion rate (Icorr) in
Table 3.23.
70
3 Experimental Evidence
71
58.70
62.54
3.24 9 10
8.50 9 105
-2
3.25 9 10
8.09 9 104
-6
0.98 9 10
4.44 9 10-6
0.001
0.003
Fit
REAP
REAP
and 3.54, respectively. Similarly, EIS was also carried out after 24 and 168 h
exposure on zinc-rich coated (ZR ? MS) and impedance plots are given in
Figs. 3.55 and 3.56, respectively. The EIS parameters are given in Table 3.26.
EIS was carried out in SAEJ solution exposed for 1,500 h on coated ZP ? WS
and ZR ? WS and impedance plots are given in Figs. 3.57 and 3.58, respectively
and the EIS parameters are given in Table 3.27.
72
3 Experimental Evidence
74
3 Experimental Evidence
ZP
ZP
ZP
ZP
ZP
ZP
?
?
?
?
?
?
MS
WS
MS
WS
MS
WS
2.23
8.67
61.32
8.32
53.38
4.85
9
9
9
9
9
9
10-3
10-3
10-3
10-3
10-3
10-3
7.59
6.15
2.22
3.30
6.61
1.85
9
9
9
9
9
9
108
108
108
109
108
108
41.57 9 10-3
69.14 9 10-3
1.46 9 103
4.77 9 102
39.74 9 10-9
5.76 9 10-9
Fig. 3.23 Impedance plots in SAEJ for 1,000 h exposed for 18 m at P3 of Scribed of ZP ? MS
P3
P2
P1
Table 3.7 EIS of ZP ? MS and ZP ? WS in SAEJ solution for 216 h after exposed for 18 m
Rp ohm cm2
Wd S*s^(-1/2)
Site
Panel
Ru ohm cm2
9
9
9
9
9
9
10-9
10-9
10-9
10-9
10-9
10-9
Yo S*s^a
3.89
3.52
7.29
5.07
2.07
2.57
a
0.88
0.83
0.83
0.81
0.87
0.81
Fit
CPE
CPE
CPE
CPE
CPE
CPE
?
?
?
?
?
?
D
D
D
D
D
D
ZP ? MS
ZP ? WS
11.58 9 10-3
12.39 9 10-3
29.87 9 104
27.23 9 106
4.96 9 10-10
2.60 9 10-9
Fig. 3.24 Impedance plots in SAEJ for 1,000 h exposed for 18 m at P3 of Scribed of ZP ? WS
46.34 9 10-6
Wd S*s^(1/2)
0.93
0.78
CPE
CPE ? D
Fit
76
3 Experimental Evidence
Fig. 3.26 Impedance plots in 3.5 % NaCl for 936 h exposed for 42 m at P1 of ZP ? WS
Fig. 3.25 Impedance plots in 3.5 % NaCl for 936 h after exposed for 42 m at P1 of ZP ? MS
Fig. 3.28 Impedance plots of ZP ? WS in 3.5 % NaCl for 936 h after exposed for 42 m at P2
Fig. 3.27 Impedance plots in 3.5 % NaCl exposed for 42 m at P2 for 936 h of ZP ? MS
78
3 Experimental Evidence
Fig. 3.30 Impedance plots of ZP ? WS in 3.5 % NaCl for 936 h after exposed for 42 m at P3
Fig. 3.29 Impedance plots of ZP ? MS in 3.5 % NaCl for 936 h after exposed for 42 m at P3
ZP
ZP
ZP
ZP
ZP
ZP
?
?
?
?
?
?
MS
WS
MS
WS
MS
WS
P3
P2
P1
20.09
10.89
77.35
34.60
96.73
1.02
9
9
9
9
9
9
10
10-3
10-3
10-2
10-3
10-3
-2
46.18
25.76
12.25
80.54
2.59
16.34
9
9
9
9
9
9
10
104
104
106
103
103
9.39 9 10
9.03
23.68 9 104
24.22 9 106
59.42 9 103
31.85 9 107
-8
3.45 9 10
19.17 9 10-8
71.54 9 10-12
22.20 9 10-12
2.11 9 10-9
2.42 9 10-11
Table 3.9 EIS parameters of ZP ? MS and ZP ? WS in 3.5 % NaCl solution after exposed for 42 m
Rp ohm cm2
Rpo ohm
Cc F/cm2
Site
Panel
Ru ohm cm2
10.64 9 10-4
58.33 9 10-3
4.71 9 10-9
16.30 9 10-11
2.58 9 10-6
11.37 9 10-6
Cf F/cm2
REAP
REAP
REAP
REAP
REAP
REAP
Fit
80
3 Experimental Evidence
81
Fig. 3.31 Impedance plot of ZP ? MS in SAEJ after exposed for 42 m at P3 and in humid SO2
0.72
0.78
1.26 9 10
2.54 9 108
ZP ? MS
ZP ? WS
2.81 9 10
6.37 9 10-10
-10
Fig. 3.32 Impedance of ZP ? WS in SAEJ after exposed for 42 m at P3 and in humid SO2
1.03 9 10
1.86 9 10-3
-4
Wd S*s^(1/2)
0.91
0.89
CPE ? D
CPE ? D
Fit
82
3 Experimental Evidence
83
Cl
P1
P2
P3
0.50
WS
WS
WS
0.37
1.24
0.94
0.81
0.69
0.2
0.54
0.67
0.21
0.79
84
3 Experimental Evidence
85
MS
WS
MS
WS
MS
WS
70.40
70.38
68.52
52.39
59.29
59.32
0.20
0.28
0.24
0.48
0.39
0.54
0.21
0.32
0.22
0.19
Cr: 0.5, Cu: 0.6
Cl
0.50
0.60
86
Fig. 3.40 Line scan
elements of WS rust exposed
at P1 for 42 m (a) oxygen and
(b) iron
3 Experimental Evidence
87
88
Fig. 3.42 Line scan
elements of MS rust exposed
at P3 for 42 m (a) Oxygen
and (b) Iron
3 Experimental Evidence
89
90
3 Experimental Evidence
% Relative
intensity I/I0
% Relative
intensity I/I0
6
5
16
10
7
18
12
9
13
19
100
53
43
40
34
26
23
21
21
21
2.458
2.542
1.511
1.932
2.359
1.442
1.638
2.081
1.609
1.394
100
81
63
50
48
35
33
31
48
38
37
25
2.462
6.232
3.29
1.939
1.533
1.561
1.509
2.193
2.567
1.726
2.354
1.64
7
1
3
12
16
15
17
10
6
13
8
14
% Relative
intensity I/I0
% Relative
intensity I/I0
1
4
8
5
3
2
10
6
7
9
100
22
14
19
27
16
12
18
13
37
2.474
1.936
1.729
3.300
2.578
2.247
3.204
2.775
3.181
2.361
19
100
26
12
24
16
29
9
10
13
2.599
2.479
1.945
1.734
3.304
2.255
2.366
2.195
2.710
2.991
5
1
3
8
4
6
2
10
9
7
17
100
25
26
11
14
19
9
91
% Relative
intensity I/I0
% Relative
intensity I/I0
1
3
6
4
7
9
5
8
100
53
38
51
22
16
44
15
2.448
1.936
3.309
2.695
1.864
2.394
2.023
1.798
100
45
71
66
36
67
39
46
2.478
3.296
2.548
1.846
1.940
2.523
1.691
1.820
1
6
2
4
8
3
7
5
Table 3.17 Rust phases by Raman spectroscopy after 18 m at P1, P2 and P3 of MS and WS
Raman shift cm-1
Panels
P1
MS
1,307.28
251.12
221.48
375.33
695.92
265.37
392.92
241.60
1,292.10
491.01
WS
P2
P3
390.62
298.92
686.51
549.08
252.95
654.26
526.92
374.90
267.71
384.40
210.81
1,292.87
589.62
1,323.19
1,425.66
249.21
654.77
374.49
Table 3.18 Rust phases by Raman Spectroscopy after 42 m at P1, P2 and P3 of MS and WS
Raman shift cm-1
Panels
P1
P2
P3
MS
387.60
387.60
261.22
1,327.83
651.69
398.12
528.32
259.88
1,314.28
253.90
383.57
383.57
656.66
1,310.18
1,305.14
290.63
223.93
414.29
608.43
225.87
484.20
290.81
1,302.04
408.20
WS
92
3 Experimental Evidence
Wt loss mg
Area cm2
CR lm/y
Wt loss mg
Area cm2
CR lm/y
459
850
1,250
1,538
84.17
84.17
85.46
84.17
461
425
418
382
359
706
1,050
1,337
82.49
82.49
84.49
83.20
374
355
341
334
Fig. 3.44 Exposure in salt spray for 1,000 h (a) MS and (b) WS
Fig. 3.45 Exposure in Salt Spray for 4,500 h (a) MS and (b) WS
93
Wt loss mg
Area cm2
CR lm/y
Wt loss mg
Area cm2
CR lm/y
1,000
2,000
3,500
4,500
38,770
57,050
88,670
98,480
336.56
327.07
352.17
335.91
992
742
727
617
37,832
43,673
60,425
78,015
312.24
312.05
306.11
312.63
1,042
592
558
546
Coated
Rating
Coated
Rating
No. effect
Few blisters
Many blisters
Blisters increased
10
9.75
9.5
8
No. effect
0.5 mm rust creepage
Few blister
1.5 mm creepage/Blisters increased
9
8
7.5
7
Fig. 3.46 OCP Plots in 3.5 % NaCl solutions of (a) AR MS and (b) AR WS
94
3 Experimental Evidence
Ecorr mV
-272.7
-260.1
-50.10
-231.7
25.6 9 10-6
4.46 9 10-12
278.8 9 10-6
10.65 9 10-12
MS
WS
MS
WS
3.5 % NaCl
Icorr A/cm2
Fig. 3.48 Polarisation diagram in 0.1 M Na2SO4 ? 0.1 N NaCl (a) AR MS and (b) AR WS
96
3 Experimental Evidence
Fig. 3.49 Cyclic polarisation in SAEJ of MS and WS after exposed in humid SO2
Table 3.23 CP of MS and WS in SAEJ solution after exposed in humid SO2 for 9 m
Ecorr mV
Panel
Electrolyte
Icorr mA/cm2
MS
WS
55.21
4.32
-1,175.5
-1,195.5
98
3 Experimental Evidence
62.47
23.44
16.65
3.15 9 105
646.3 9 10-6
70.72 9 10-12
0.61
0.91
Fit
CPE
CPE
Fig. 3.52 Nyquist plots of WS and MS in SAEJ after exposed in humid SO2 for 9 m
Table 3.25 EIS of MS and WS in SAEJ solution for 48 h after exposed in SO2
Panel
Ru ohm cm2
Rp ohm cm2
Cf F/cm2
a
MS
WS
-3
5.87 9 10
4.35 9 10-3
3.37 9 10
6.01 9 104
-8
1.33S 9 10
2.67 9 10-8
0.64
0.63
Fit
Randle
Randle
99
100
3 Experimental Evidence
101
102
3 Experimental Evidence
24
168
24
168
ZR ? MS
ZP ? MS
1.2
2.1
4.1
3.2
9
9
9
9
10
10-2
10-3
10-3
-3
9
9
9
9
10
103
103
103
Rp ohm cm2
53 9 10-12
0.15 9 10-9
98 9 10-12
0.12 9 10-9
Cc F/cm2
104
3 Experimental Evidence
105
23.23 9 10-3
7.97 9 10-3
10.51 9 107
1.57 9 109
5.96 9 10-9
4.48 9 10-9
2.38 9 10-7
0.85
0.82
Fit
CPE
CPE ? D
Mn
MS
WS
0.38
0.31
28.37
14.28
0.84
0.51
106
Fig. 3.60 Line scan of
elements by EDX of AR MS
(a) Oxygen and (b) Iron
3 Experimental Evidence
107
108
3 Experimental Evidence
Fig. 3.62 SEM of rust upper layer exposed in SO2 (a) MS and (b) WS
Fig. 3.63 SEM of rust inner layer exposed in SO2 (a) MS and (b) WS
Table 3.29 Elemental analysis by EDX of rust of MS and WS after exposed in SO2
Layer
Panel
Mn
Cr
Cu
Upper
Inner
MS
WS
MS
WS
0.68
0.33
0.55
0.62
3.48
Ni
2.32
1.52
WS
1,321.37
671.52
613.34
1,314.79
658.79
611.79
109
2,000 h
3,500 h
4,500 h
MS
1,318.63
296.26
230.32
411.02
612.66
503.87
1,322.58
290.84
226.86
407.91
292.39
227.29
612.30
404.00
1,320.71
299.38
411.27
657.44
293.22
226.41
403.60
1,300.35
254.72
1,305.91
657.20
378.76
WS
2,000 h
3,000 h
4,500 h
MS
1,321.17
233.54
415.69
300.15
617.23
507.09
1,350.80
294.54
294.54
227.46
410.23
297.41
413.02
613.33
500.05
1,310.81
384.34
533.67
648.37
258.85
1,292.5
387.31
584.83
211.72
273.34
387.46
1,298
212.50
274.88
WS
are given in annexure Fig. A 3.18a, b for as received MS and WS, for humidity in
annexure Figs. A 3.19a, b to A 3.21a, b and for salt spray in annexure Figs. A
3.22a, b to A 3.24a, b.
References
1. ASTM G101:1997 Standard guide for estimating the atmospheric corrosion resistance of low
alloy steel
2. ASTM G33:2004 Standard practice for recording data from atmospheric corrosion tests of
metallic-coated steel specimens
3. ASTM 610D:2001 Standard test method for evaluating degree of rusting on painted steel
surfaces
Chapter 4
The results obtained from experiments as recorded in Chapter 3 are discussed in three parts viz.
field tests, laboratory tests and simulation tests.
111
112
this indicates the role of minor alloying elements present in WS and shows a
tendency to form stable protective layer on its surface in presence of SO2. The
skyward surface on MS at P3, shows formation of blackish loosely attached oxide
film (Fig. 3.4a), whereas WS showed compact deep brown fine oxide film
(Fig. 3.4b). Again this is due to the presence of SO2 at P3.
Thus, there is a significant difference in the appearance of oxide film/rust
products on the uncoated exposed panels with respect to site and exposure time.
Uncoated panels exposed are having different rust colour and varying degree of
adherence to surface. The corrosion attack was severe at P1 followed by P2
and P3.
113
P1 MS
25
20
P1 WS
P2 MS
15
P2 WS
P3 MS
10
P3 WS
5
15
20
25
30
35
40
45
4.1.3 DC Measurement
Corrosion rate of exposed panels after 42 m exposure, obtained from the polarisation diagrams (Figs. 3.5, 3.6, and 3.7) in 3.5 % NaCl solution, was found to be
of the order of 10-6 A/cm2 for MS and WS at all sites (Table 3.3a). Such low Icorr
may be due to the formation of compact rust layers which are not allowing
electrolytes to go in except the holidays exposed on the surface. Ecorr values for
both the materials were greater at P3.
To study the effectiveness of coatings, the coated panels after 18 m exposure at
P3 were dipped in SAEJ solution for 4,080 h followed by cyclic polarisation in
same medium. Interestingly, both the polarisation diagram (Fig. 3.8) showed a
tendency to passivate at higher potential and during reverse cycle Zcp (zero current
potential) changed to greater value. Icorr was also lower (Table 3.4).
4.1.4 AC Impedance
EIS carried out in 0.1 N NaCl ? 0.1 M Na2SO4 solution on uncoated WS panels
exposed for 42 m at P2 recorded lower coating capacitance (Cc: 28.00 9 10-8)
and double layer capacitance (Cf: 20.8.4 9 10-11) and higher polarisation resistance (Rp: 2.48 9 107) and pore resistance (Rpo: 1.52 9 103) as per Fig. 3.12.
Identical trend is found at P3 with lower Cc (77.73 9 10-12) and Cf
(16.55 9 10-11) and higher Rp (9.56 9 105) and Rpo (4.92 9 104).with respect to
exposure at P1 with higher Cc (1.06 9 10-6) and Cf (50.76 9 10-11) and lower Rp
(2.66 9 106) and Rpo(19.21 9 102) as per Figs. 3.14 and 3.10, respectively.
Similar trend was also noticed for MS (Table 3.5 and Figs. 3.9, 3.11 and 3.13).
Rust coatings formed showed REAP model fit and typical electrical equivalent
representative circuit as shown in Fig. 1.13 in the literature review section.
Warburg diffusion (Wd) is visible on WS for all the sites as per Nyquist plots and
predominant at P3. Phase angles are varying on WS at P1 (-35), P2 (-21) and
114
115
properties of paint film by the formation of double layer capacitance. REAP model
fit is found suitable. All these corroborate the corrosion rate data as obtained in
Table 3.9 and Figs. 3.27 and 3.29 show the impedance plots of ZP ? MS for P2
and P3, respectively. Compared to exposure of 18 m, after 42 m exposure, Rp has
come down to 103 from 108 due to the degradation of surface with prolonged
exposures.
The effect of presence of SO2 on the coated panels was investigated by subjecting panels withdrawn after 42 m from P3 to SO2 atmosphere for two months.
The EIS behaviour in SAEJ solution is given in (Figs. 3.31 and 3.32). It is
interesting to note that, SO2 being a corrosive agent has quite unlikely improved
the corrosion resistance properties of ZP ? WS indicated by comparatively higher
Rp (2.54 9 108) as per Table 3.10 as compared to the values given in Table 3.9.
These values of ZP ? WS are superior to Rp (1.26 9 106) of ZP ? MS. Diffusion
phenomenon is prominent from the Nyquist plot of ZP ? WS (Fig. 3.32).
116
Spacing
d(A)
2.458
2.542
1.511
1.932
1.638
2.474
1.936
3.300
2.361
Intensity
% I/I0(peak)
100(6)
53(5)
43(16)
40(10)
23(12)
100(1)
22(4)
19(5)
37(9)
Experimental data
50
80
40
72
100
76
72
100
20
c FeOOH
c FeOOH
b FeOOH
b FeOOH
Intensity
% I/I0
(peak)
a FeOOH
b FeOOH
b FeOOH
c FeOOH
b FeOOH
Phase
Published data
Intensity
% I/I0 (peak)
18 m Exposure
2.450
100(7)
2.543
81(1)
1.515
63(3)
1.935
50(12)
2.343
48(16)
1.445
25(14)
42 m Exposure
2.473
19(5)
1.935
100(1)
1.735
26(3)
3.311
24(4)
Spacing d(A)
Experimental data
2.599
2.479
1.945
3.304
2.462
6.232
3.29
1.939
1.533
1.64
Spacing
d(A)
a Fe2O3
c eOOH
c eOOH
b FeOOH
c FeOOH
c FeOOH
c FeOOH
c FeOOH
c FeOOH
b FeOOH
Phase
Published data
70
76
53
100
76
61
100
72
33
100
Intensity
% I/I0(peak)
2.591
2.473
1.940
3.311
2.473
6.27
3.294
1.935
1.534
1.635
Spacing
d(A)
118
Spacing
d(A)
100(1)
25(3)
26(2)
14(7)
2.470
1.939
2.583
2.703
Phase
c FeOOH
c FeOOH
a FeOOH
a Fe2O3
Intensity
% I/I0
(peak)
Spacing
d(A)
76
72
12
100
2.473
1.935
2.583
2.700
obtained in Figs. A 3.9a and b for 42 m exposure, the absolute intensities of these
peaks are rather higher around 3,000 counts. For P2 and P3 sites XRD for 18 m
exposure were not done since for P1, it was seen that peaks were of low intensities.
After 42 m exposure, both oxides and hydroxides phase are detected on WS at
P2 and same phases also detected at P3 along with b FeOOH (Tables 4.2 and 4.3)
After 18 m exposure at P1 as per Table 4.4 Raman spectroscopy detected major
peaks c FeOOH (1307, 252, 379) and b FeOOH (675) on MS and c Fe2O3, d
FeOOH (392), c FeOOH (245,1,307) and a Fe2O3 on WS. After 42 m exposure a
FeOOH (386), b FeOOH (386), c FeOOH and c Fe2O3 were formed on MS and c
FeOOH (255, 528), a Fe2O3 and a FeOOH were found on WS (Table 4.4 and
spectra Figs. A 3.12 and A 3.14). Non-appreciable changes in the molecular dipole
moment explain the absence of b FeOOH on WS [15].
After 18 m exposure at P2 as per Table 4.5, Raman spectroscopy could detect a
FeOOH, a Fe2O3 and Fe3O4 on MS and c Fe2O3, a FeOOH and d FeOOH, on WS
and with further exposure to 42 m Phases detected were c FeOOH (255,1307), d
FeOOH (655),a FeOOH (386) and Fe3O4 on WS. The phases detected after 18 m
of exposure on MS by Raman spectroscopy were unstable,a FeOOH and Fe3O4
and the trend continued even with higher exposure. Presence of stable amorphous
d FeOOH and absence of porous b FeOOH on WS shows less corrosion rate than
MS (Table 3.2).
Raman spectroscopy after 18 m exposure at P3 as per Table 4.6 detected only c
FeOOH on MS and a FeOOH,c FeOOH, c Fe2O3 and Fe3O4 on WS. With further
exposure to 42 m phases transformed to c FeOOH, a Fe2O3 (292, 225, 612) and d
FeOOH on MS and a FeOOH, c FeOOH, a Fe2O3 (292, 225, 386) and d FeOOH
(400) detected on WS.
Thus, WS shows better corrosion resistance than MS due to the presence of d
FeOOH phases at P2 and P3. From the foregoing results and discussion on various
types of phases present, it is rather difficult to relate the rate of corrosion on the
panels with the characteristics of the various phases present on panels. But still
there is some evidence on the presence of c FeOOH phases as the major phases
particularly on WS. As the time of exposure is increased as well as the severity of
corrosive environment at P1 to P2 and P3. There is a tendency of b FeOOH get
converted to c FeOOH with time and reduction of severity of corrosive environment. It is to be noted from corrosion rate data (Table 3.2) that, the corrosion rate
a FeOOH
c FeOOH
c FeOOH
a FeOOH
b FeOOH
2.448
1.936
3.309
2.695
2.394
100(1)
53(3)
38(6)
51(4)
16(9)
50
72
100
35
20
2.450
1.935
3.294
2.693
2.343
100(1)
45(6)
71(2)
66(4)
36(8)
Intensity
% I/I0
Phase
Spacing
d(A)
Intensity
% I/I0
Spacing
d(A)
Published data
Experimental data
Published data
Intensity
% I/I0
WS
2.478
3.296
2.548
1.846
1.940
Spacing
d(A)
c FeOOH
c FeOOH
b FeOOH
a Fe2O3
c FeOOH
Phase
76
100
80
40
53
Intensity
% I/I0
Experimental data
2.473
3.294
2.543
1.840
1.944
Spacing
d(A)
120
WS
1307.28
251.12
221.48
375.33
695.92
265.37
392.92
241.60
1292.10
491.01
Phase
c FeOOH
c FeOOH
d FeOOH
c FeOOH
b FeOOH
c Fe2O3
d FeOOH
c FeOOH
c FeOOH
a Fe2O3
Published
Raman shift
(cm-1)
1307
252
220
379
675
265
392
245
1307
497
Ref Raman
shift
(cm-1)
Phase
[11]
[11]
[10]
[11]
[12]
[9]
[12]
[24]
[11]
[24]
c Fe2O3
Fe3O4
a FeOOH
b FeOOH
c FeOOH
c FeOOH
a Fe2O3
a FeOOH
c FeOOH
261.22
1327.83
387.60
387.60
651.69
259.88
1314.28
398.12
528.32
Published
Raman shift
(cm-1)
265
1322
386
386
654
255
1320
397
528
Ref.
[9]
[8]
[9]
[12]
[11]
[11]
[9]
[8]
[11]
of WS is much less than that of MS under similar condition. The corrosion rate is
decreased with time and decreased in severity of environments due to the presence
of high corrosion resistance phases. In this case, it is the c FeOOH which may be
responsible for decrease in corrosion rate. c FeOOH is a top layer of passive film
as claimed by most investigators [16, 17]. Hence, the formation of stable high
corrosion resistant passive layer may be the reason for substantial mitigation of
corrosion rate when WS is exposed for prolonged time period in corrosive environment of P2 and P3.
121
WS
390.62
298.92
686.51
549.08
267.71
384.40
210.81
1292.87
589.62
Phase
a FeOOH
a Fe2O3
a FeOOH
Fe3O4
c Fe2O3
d FeOOH
a FeOOH
c FeOOH
d FeOOH
Published
Raman
shift
(cm-1)
390
298
685
550
265
385
205
1307
580
Ref. Raman
shift
(cm-1)
Phase
[9]
[14]
[9]
[8]
[9]
[10]
[9]
[11]
c FeOOH
c FeOOH
d FeOOH
a FeOOH
Fe3O4
259.00
1313.83
657.21
387.19
534.80
Published
Raman shift
(cm-1)
Ref.
255
1307
655
386
532
[13]
[13]
[14]
[11]
[24]
Published
Raman shift
(cm-1)
Ref.
WS
252.95
654.26
526.92
374.90
1323.19
1425.66
249.21
654.77
374.49
Phase
c
c
c
c
FeOOH
FeOOH
FeOOH
FeOOH
Fe3O4
c Fe2O3
a FeOOH
c FeOOH
c FeOOH
Published
Raman shift
(cm-1)
252
654
528
379
1322
1425
248
654
379
Ref. Raman
shift
(cm-1)
[11]
[11]
[11]
[11]
[8]
[12]
[8]
[11]
[11]
Phase
1305.14 c FeOOH
290.63
a Fe2O3
414.29 d FeOOH
223.93
a Fe2O3
608.43
a Fe2O3
1302.04 c FeOOH
290.81
a Fe2O3
225.87
a Fe2O3
408.20 d FeOOH
484.20 a FeOOH
1307
292
400
225
612
1307
292
225
400
485
[11]
[14]
[14]
[9]
[14]
[11]
[14]
[9]
[12]
[8]
122
Published data
Raman shift
cm-1
Raman shift
cm-1
1321.37
671.52
613.34
Phase
Fe3O4
c Fe2O3
a Fe2O3
1322
670
612
Experimental data
Ref. Raman shift
cm-1
Phase
[8]
[9]
[14]
a Fe2O3
c FeOOH
a Fe2O3
1314.79
658.79
611.79
Published data
Raman shift
cm-1
1320
660
612
Ref.
[9]
[13]
[14]
FeOOH line for WS panels and maximum intensity for a FeOOH for MS, while
XRD of WS at P2 showed only one strong line, XRDs at P3 showed b FeOOH line
as second strongest line for WS and c FeOOH as second strongest line for MS.
From XRD plots of peaks could be seen at P1 after 18 m exposure, but these
were at very low intensity level. XRD of WS and MS after 42 m exposure at P2
and P3 revealed no informations. Raman spectroscopy on rust products at P2 and
P3 after 18 and 42 m exposure showed the increase of higher oxidation state with
increased in exposure time and from MS to WS as was found at P1. Another
interesting observation that could be seen was that after 42 m exposure two lines
for a Fe2O3 and one line of a FeOOH were found which showed oxidation was
highest at P3 on WS in the presence of SO2. In fact, for MS also three a Fe2O3
lines were found. The difference between these two was that of sharp peaks that
are noticed for WS (Figs. A 3.17a, b).
123
Humidity MS
Humidity WS
SaltSpray MS
Salt Spray WS
450
925
400
825
375
725
350
625
325
500
CR Humidity (m/yr)
1025
425
525
1500
2500
3500
4500
In case of MS less rust developed with respect to earlier (Table 3.20). On uncoated
MS and WS, the nature of rust developed after 1,000and 4,500 h exposures is
shown in Figs. 3.44a and b and Figs. 3.45a and b, respectively. From the figures it
can be seen that the severity of pitting of surface is more in WS. Thus, the rust
spreading across the scribe lines started developing faster for coated WS than MS
and after 4,500 h exposure the corrosion rate of WS (546 lm/y) was found marginally less than MS (617 lm/y) as shown in Table 3.20. Here also the alloying
elements in WS helped in forming compact and adhering oxides which eventually
helped to retard the rate of corrosion.
124
corrosion product as shown (Figs. 3.46a, b). This may be due to the fact that WS
starts forming oxides which fall in the passive region above pH 9 [18] and may be
due to the presence of Cr, Mn as is evidenced from polarisation data (Table 3.22).
Polarisation diagram of as received panels in 3.5 % NaCl indicated higher Icorr
and Ecorr for MS compared to WS with no indication of passivation (Figs. 3.47a, b)
and data Table 2.36. Same trend was also found in 0.1 M Na2SO4 ? 0.1 N NaCl,
where Icorr was higher for MS and lower for WS (Figs. 3.48a, b). Here, WS
showed signs of passivation but could not be stabilised due to high scan rate. The
lower corrosion rate of WS is due to formation of protective and stable oxides in
presence of alloying elements.
Cyclic polarisation was carried out in SAEJ solution on MS and WS panels that
were exposed in humid SO2 for 9 m (Fig. 3.49 and data Table 3.23). Rust formed
on MS and WS exhibited almost identical anodic and cathodic plots but their Icorr
values were quite different. The trend of WS and MS in NaCl and Na2SO4 +NaCl
solution was seen in SAEJ solution also. Interestingly, the passivity was seen in
both the panels which were corroborated by the reverse cycle where current
density surges by an order of 10. This proves that humid SO2 exposure for longer
period helped in developing protective oxide.
4.2.5 AC Impedance
EIS was carried out on uncoated as received panels.WS exhibited different
behaviour than MS at lower frequency ranges in 0.1 M Na2SO4 ? 0.1 N NaCl.
WS showed higher Rp ([105) and lower Yo (10-12) resulting much higher
impedance than MS (Figs. 3.50, 3.51). While both MS and WS exhibited wide
variation in phase angles (-1 to -50), CPE model was found suitable for both
the panels. The electrical parameters are given in Table 3.24 and typical equivalent circuit for this model is given in Fig. 1.11 in the literature review section. This
higher impedance on WS is due to the effect of electrolyte and formation of stable
oxides as was already found in polarisation diagram.
EIS was carried out on uncoated panels exposed in SO2 for 9 m and the Nyquist
plot of MS and WS is given in Fig. 3.52 and parameters are given in Table 3.25.
WS showed higher (Cf: 2.67 9 10-8, Rp: 6.01 9 104) than MS (Cf: 1.33 9 10-8,
Rp: 3.37 9 103). This indicates the formation of protective and compact rust on
WS. Randle model was used to get the electrical elements and equivalent. The
depressed semicircle diameter of WS was found higher than MS. This behaviour
indicates the presence of diffusion resistant layer at the electrolyte/steel interface.
In case of MS, the real component of resistance was found to reduce with decrease
in frequency, a phenomenon attributed to inductive behaviour of the electrolyte/
steel interface. The availability of SO2 reduced dissolution in WS. Presence of
alloying elements in WS may be attributed as the reason.
EIS was carried out on different coating systems on MS substrate (ZP ? MS and
ZR ? MS) in 3.5 % NaCl and after 24 h exposure, Rp([103) values were almost
125
identical with same phase angle (90) as seen from Bode Plot. Nyquist plot
indicated two time constant for ZP ? MS (Fig. 3.53) and one time constant for
ZR ? MS (Fig. 3.55) and parameters are given in Table 3.27. After 168 h exposure it showed higher Rp(53 9 103) of ZR ? MS than ZP ? MS(Rp:1.42 9 103)
indicating comparative better resistance against charge transfer through coating
pores (Figs. 3.54 and 3.56). In Bode plot high Rp in the low frequency limit and the
phase angle remained close to 010 representing inductive behaviour.
EIS was carried out on different coating system on WS substrate (ZP ? WS and
ZR ? WS) in SAEJ solution with higher pH. No damage of coating was found
with initial exposure and after 1,500 h of exposure in electrolyte, ZR ? WS
revealed higher Rp(1.57 9 109). CPE with diffusion model fit was found suitable
and admittance (Y0: [109) was almost equal with ZP ? WS as per Figs. 3.57 and
3.58. The corresponding parameters are given in Table 3.28. Probably, the accumulation of corrosion products in the pores of coatings on ZR ? WS favoured the
appearance of straight line diffusion tail at low frequency of about 45 slope. In
this case due to WS substrate, Rp increased in both the cases and passive/protective
oxides formed on WS.
126
Experimental data
Raman
shift
(cm-1)
2000
3500
4500
WS
1318.63
296.26
411.02
612.66
503.87
292.39
227.29
612.30
404.00
293.22
226.41
403.60
1300.35
Phase
a Fe2O3
d FeOOH
a Fe2O3
a Fe2O3
c Fe2O3
a Fe2O3
a Fe2O3
a Fe2O3
d FeOOH
a Fe2O3
a Fe2O3
d FeOOH
c FeOOH
Published data
Raman
shift
(cm-1)
1320
297
411
612
505
292
227
612
400
293
226
400
1307
Experimental data
Published data
Ref. Raman
shift
(cm-1)
Phase
[9]
[12]
[14]
[14]
[12]
[14]
[14]
[14]
[12]
1322.58
290.84
226.86
407.91
1320.71
299.38
411.27
657.44
Fe3O4
a Fe2O3
a Fe2O3
a Fe2O3
a Fe2O3
a Fe2O3
a Fe2O3
d FeOOH
1322
292
226
411
1320
298
411
655
[8]
[14]
[14]
[14]
[9]
[14]
[14]
[12]
254.72
1305.91
657.20
378.76
c
c
d
c
255
1307
655
379
[11]
[11]
[12]
[11]
[14]
[14]
[12]
[11]
FeOOH
FeOOH
FeOOH
FeOOH
Raman
shift
(cm-1)
Ref.
127
2000
3500
4500
Experimental data
Published data
Raman shift
(cm-1)
Raman
shift
(cm-1)
1321.17
233.54
415.69
300.15
617.23
507.09
297.41
413.02
613.33
500.05
1310.81
387.31
584.83
211.72
273.34
Phase
a Fe2O3
a Fe2O3
a Fe2O3
c Fe2O3
Fe3O4
c Fe2O3
d FeOOH
a Fe2O3
a Fe2O3
a Fe2O3
c FeOOH
a FeOOH
a FeOOH
c Fe2O3
1320
227
415
300
616
505
297
414
612
500
1307
386
205
265
Experimental data
Published
data
Ref.
Raman shift
(cm-1)
Raman
shift
(cm-1)
Ref.
[9]
[14]
[11]
[9]
[14]
[12]
[12]
[14]
[612]
[9]
[11]
[9]
[9]
[9]
1350.80
294.54
294.54
227.46
410.23
384.34
533.67
648.37
258.85
1292.5
387.46
1298
212.50
274.88
1322
295
295
227
411
385
532
648
255
1307
386
1307
219
265
[10]
[10]
[9]
14]
[14]
[10]
[14]
[11]
[11]
[11]
[9]
[13]
[11]
[9]
Phase
Fe3O4
d FeOOH
a Fe2O3
a Fe2O3
a Fe2O3
b FeOOH
Fe3O4
c FeOOH
c FeOOH
c FeOOH
a FeOOH
c FeOOH
c FeOOH
c Fe2O3
protective than a FeOOH [20, 21]. On WS presence of stable oxide phases a Fe2O3
along with Fe3O4 were detected after 2,000 h exposure. Additionally unstable and
non-protective, porous b FeOOH was detected which is less dense than a FeOOH
and c FeOOH was found with further exposure. With further increase in exposure
time to 4,500 h metastable c FeOOH, c Fe2O3 and a FeOOH were detected.
Thus, the corrosion product is mostly a Fe2O3 and c Fe2O3 on MS and does not
change with exposure time, whereas a Fe2O3, a FeOOH and c FeOOH formed on
WS. Overall the percentage of oxy hydroxide phases increased with time.
Raman spectroscopy, thus, revealed that stable oxides formed on WS as
compared to MS when testing was done on as received panels and panels exposed
to extended salt spray test. However, in continuous humidity tests oxides
decomposed to form less stable FeOOH.
128
129
cross section of exposed panels was done. There was distinct resemblance of these
SEM with Fig. 3.38 of field test panels exposed at P3.
In summary, it can be said that the data generated with laboratory tests, though
predict the trend of field tests, are grossly insufficient to predict field behaviour of
WS and MS in absolute terms. Since SO2 is a factor which gives some convergence at some points of two types of tests, separate set of experiments was contemplated to simulate similar field conditions at laboratory.
4.4.1 Hypothesis
E-pH diagram [22] of iron in Na2SO4 shows some passive regions. Raman
spectroscopy of 42 m exposed WS panels revealed a few common oxide and
hydroxide phases as reported in E-pH diagram. It was thought that long field
exposures of WS in some sites lead to the formation of these oxides/hydroxides
phases due to slow interaction with environments. It was envisaged to simulate the
slow oxidation process in laboratory by subjecting WS panels to very slow
potentiodynamic scanning rate. Also laboratory test on WS exposed in humid SO2
for long duration indicated passivation behaviour in cyclic polarisation. Some
experiments were designed to investigate the behaviour by slow polarisation and to
see whether such oxides/hydroxides phases at all formed or not.
130
While polarising WS panels in 0.1 M Na2SO4 at pH 8.8 with scan rate 0.5 mV/
s, it was noticed that a passive region forms with current density of about 10 mA/
cm2 as per Fig. 4.4a where Icorr is found 20 lm/cm2. Repeating the experiment
with scan rate 0.01 mV/s as per Fig. 4.4b, revealed passivity at 1 mA/cm2 with a
tendency to passivate even at lower current density. The experiment was repeated
with even slower scan rate of 0.005 mV/s and it was found that the polarisation
curve yielded a well defined passive region like stainless steel as shown in
Fig. 4.4c.
Encouraged with this result, polarisation of WS was done in 0.1 M Na2SO4 at
pH 9.2 with a scan rate of 0.005 mV/sec. Passivity was obtained and with a current
density of about 500 lm/cm2 and the range continued beyond 850 mV as shown
in Fig. 4.5. Since it has been reported in the literature [23] that very small addition
of Cl- ions enhance passive range, the polarisation experiment of WS was repeated in 0.1 M Na2SO4 ? 0.001 M NaCl at pH 8.6 with 0.005 mV/sec scan rate.
Passivity range was indeed found to be enhanced as indicated in Fig. 4.6.
From Fig. 4.4c passive potentials of -530 and -520 mV, respectively, were
selected and at these potentials in 0.1 M Na2SO4 at pH 8.6, WS panels were
passivated by applying these potentials instantaneously. The respective current
transient plots are shown in Figs. 4.7a, b.
It was noticed that, although in the polarisation diagram passivity is maintained
at 530 and 520 mV, respectively, potentiostatic current transient plots show
very high positive current densities of 21 mA/cm2 and 6.5 mA/cm2, respectively.
However, when the panels were passivated in same solutions by applying
instantaneously potentials of 820 and 800 mV, current densities of 1.6 and
6.25 mA/cm2 were, respectively, obtained as shown in Figs. 4.8a, b.
These curves imply that the panels got into the cathodic regions and got stabilised. The experiments of instantaneous passivity of WS were repeated in 0.1 M
Na2SO4 ? 0.001 N NaCl at pH 8.6 solution at 1100 mV. Here also the panels got
into cathodic region and stabilised at 5.6 mA/cm2 as per Fig. 4.9.
WS passivated as shown in Figs. 4.8a, b and Fig. 4.9 were tested for corrosion
resistance in three types of electrolytes viz. neutral, alkaline and acidic medium.
The details of results are given in Table 4.11 and polarisation diagrams are shown
in Figs. 4.10, 4.11, 4.12, 4.13, 4.14, 4.15.
It is found that, the corrosion rate of WS in different electrolytes of varied pH
level is of lA/cm2 order.
SEM of panels, passivated at -820 and -800 mV, are shown in Figs. 4.16 and
4.17 respectively, at two magnifications. Elemental analysis of WS passivated at
820 mV is shown in Table 4.12. Similarly, Raman spectroscopy of these two
panels passivated at -820 and -800 mV was also done. It was found that
820 mV passivated panels compared very well with rust phases found at P3 while
800 mV passivated did not compare well including Raman Characteristics at P3.
Raman spectroscopy at two spots is shown in Fig. A 4.1 and A 4.2 and phases
identified are given in Table 4.13 where peak values of Fe3O4 and a Fe2O3 were
matched with published data. Raman shift obtained at passivated potential
800 mV with published data were also found matching. In case of 820 mV
131
9.5
0.005
H
0.1 M
Na2SO4
0.1 M
Na2SO4 ? 0.001 N
NaCl
9.2
0.005
H
8.6
0.005
H
H
H
H
H
H
H
stable oxide phase a Fe2O3 is very near to the strongest peak 292 and next to
strongest peak 226 [24]. Hence, at -820 mV stable and protective phases are
formed which are absent at -800 mV.
Similar passivation experiments at slow scan rate were carried out on MS
panels in identical solutions also as per test plan given in Table 4.11. Result
compared with corresponding field exposed panels. Polarisation curves are given
in Figs. 4.18, 4.19, 4.20, 4.21, 4.22.
Stable passivation is not found at pH 9.5 while polarisation carried out in 0.1 M
Na2SO4 ? 0.1 N NaCl gave very low Icorr (2.1 lm/cm2) as shown in Fig. 4.18.
However, passivation was found at pH 9.2 at higher potential with high current
density (approx 5 mA/cm2) as shown in both Figs. 4.19 and 4.20. Passivation did
not sustain for longer period at lower scan rate.
Potentiostatic current transient (PSCT) plots as shown in Figs. 4.21 and 4.22
showed higher current densities of 9 mA/cm2 and 40 mA/cm2 when passivated at
1146 and 1610 mV, respectively.
132
Fig. 4.4 Polarisation
diagram of WS in 0.1 M
Na2SO4 solution. (pH 8.8,
scan (a) 0.5,(b) 0.01 and
(c) 0.005 mV/s)
133
The selected potentials for instantaneous passivation were within the passivation range and in the low passive current density region. SEM of MS as per
Figs. 4.23 and 4.24 shows many cracks and voids in the rust layer.
Raman spectroscopy was carried out at two spots and unstable a FeOOH and
porous b. FeOOH phases were detected at instantaneous passivation potential
1146 mV. Strongest peak of 252 was found for metastable c FeOOH at passivation
potential 1609 mV. Raman spectra are given in Figs. A 4.3 and A 4.4 and detail
of phases is given in Table 3.12. Thus, it is seen that results with MS were not at
all encouraging.
134
4.4.3 Discussions
The corrosion rate of instantaneously passivated WS panels is shown in Table 4.12
compares well with corrosion rate of 42 m field exposure on WS panels in 3.5 %
NaCl as given in Table 3.2. Corrosion rate on WS panels was also almost similar
range and order when tested in SAEJ and as well as NACE solution. It was
interesting to note that corrosion rate was low in SAEJ solution when passivated in
0.1 M Na2SO4 +0.001 N NaCl solution. Very low amount of chloride ions in the
solution perhaps consolidate the passive layer resulting in lower corrosion rate. A
fact which agrees well with similar data that reported chloride ions leads to a shift
of the repassivation potential toward negative side and the sulphates in 0.1 M
135
0.1 M Na2SO4
+
0.001 N NaCl
9.5
0.005
H
9.2
0.005
H
8.6
0.005
H
H
H
H
H
H
H
H
H
Na2SO4 with chlorides broaches the passive region and leads to lower Icorr. This is
explained by the fact that sulphate ions are adsorbed preferentially on the surface
of the steels, promoting retention of the passive condition [25]. Again the corrosion rate was in the same range as with three field exposure sites viz. P1, P2 and
P3, SEM of instantaneously passivated WS panels as given in Figs. 4.16 and 4.17
also compared well with the SEM on WS exposed at P3 for 42 m as per Fig. 3.38.
There is no comparison of similar SEM of either P1 or P2 as given in Figs. 3.36
and 3.37, respectively.
136
Fig. 4.11 Polarisation
diagram in 3.5 % NaCl
solution (pH 6.6) of
passivated WS. in 0.1 M
Na2SO4 ? 0.001 N NaCl
at potential -1100 mV
137
Fig. 4.16
The elemental values of rust formed as per Table 4.13 and Fig. A 4.5 on WS
passivated at 820 mV are very much similar to rust formed on WS exposed at P3
for 42 m Table 3.12 where Cr and Cu are also detected in 42 m. The EDX analysis
of exposed WS showed presence of alloying elements in the rust layer.
Since the morphology of the simulated rust compared well with P3, 42 m
exposure panels, corresponding comparison was done with Raman spectroscopy as
well. Raman characterisation on WS panels passivated at 820 mV showed the
presence of c FeOOH along with Fe3O4 and a Fe2O3 as shown in Table 4.14,
whereas for the panels passivated 800 mV only Fe3O4 and a Fe2O3 phases were
138
Fig. 4.17
Table 4.12 Corrosion rate (Icorr) and Ecorr values of passivated WS in different electrolyte
Ecorr
Electrolyte
pH Passivation details
Passivation potential, Icorr
lA/
mV
mV
cm2
3.5 % NaCl
solution
SAEJ solution
NACE solutiona
6.6
9.1
3.5
0.1 M Na2SO4
-820
64.81
-800
53.28
-1100
75.15
-820
65.99
-800
81.91
-1100
11.92
-800
57.75
-1100
207.5
845.2
822.3
537.5
723.7
759.7
572.7
713.0
584.0
52.25
0.86
1.15
Cr
Cu
At %
0.51
1.71
139
Fig. 4.18 Polarisation diagram of MS in 0.1 M Na2SO4 ? 0.1 N NaCl. solution (pH 9.5, scan
0.005 mV/s)
Fig. 4.19 Polarisation
diagram of MS in 0.1 M
Na2SO4 ? 0.1 N NaCl
solution (pH 9.5, scan
0.005 mV/s)
the experimental Raman shifts of 1311.11 for c FeOOH and 292.65, 224,39 for
a Fe2O3 are in agreement with 1302.04 (c FeOOH), 290.81 (a Fe2O3) and 225.87
(a Fe2O3), respectively, Raman shift of WS exposed for 42 m. The oxide phases
are more stable than the oxy hydroxide, which lowers Icorr, at 820 mV than that at
800 mV and panel becomes greater when passivated at 820 mV. It is also due to
the stable oxide phases (a Fe2O3, Fe3O4) than the less stable oxy-hydroxide phases
(c FeOOH), (Table 4.15).
140
Fig. 4.23
Fig. 4.24
141
perhaps be explained by the difference of time of passivation other than the oxidation potential obtainable at 820 mV and 800 mV, respectively. This opens up
further scope of work i.e. by varying the time of passivation at 820 mV, perhaps
it is possible to form more impervious, compact and stable oxides which will even
give much lower corrosion rate. This idea has tremendous industrial potential.
4.5 Conclusion
From the foregoing series of experimental results and analysis the following
statements can be made.
Among the three field exposure sites, the corrosion rate was found to be highest
at P1 for both weathering as well as mild steels due to the proximity of sea
having high chloride ions in the corrosive environment. The corrosion rate of
mild steels is higher than weathering steels for all the sites.
142
Table 4.14 Rust phases by Raman at pH 8.8 on WS passivated at 820 and 800 mV
820 mV
800 mV
Spot Experimental
Raman
shift
(cm-1)
1
2
1323.64
225.51
1311.11
Published
Phase
Raman shift
(cm-1)
Experimental
Published
Phase
Raman
shift
(cm-1)
Ref.
1322
226
1307
[12]
[17]
[15]
1321.75
415.21
1320.36
Fe3O4
a Fe2O3
a Fe2O3
1322
415
1320
[12]
[13]
[12]
293.65
Fe3O4
a Fe2O3
c
FeOOH
a Fe2O3
293
[17]
655.67
654
[15]
224.39
a Fe2O3
225
[13]
c
FeOOH
Table 4.15 Rust phases by Raman in 0.1 N Na2SO4 & Na2SO4 ? 0.001 N NaCl on MS
-1146 mV
-1609 mV
Spot Experimental
Raman shift
(cm-1)
1323.80
306.52
725.68
307.52
Published
Phase
Fe3O4
a
FeOOH
b
FeOOH
b
FeOOH
Experimental
[14]
1320.82
310
[16]
254.22
Published
Phase
Fe3O4
c
FeOOH
a
Fe2O3
c
FeOOH
[13]
255
[15]
For weathering steels corrosion product accumulated with time leading to the
retardation of corrosion rate with time, whereas for mild steel corrosion rate
increased with time.
Corrosion potential of weathering steels is greater than mild steels for all the
sites as found by DC corrosion measurement. EIS on exposed weathering steel
also supported the fact.
Rust coatings formed on weathering steels are compact except at P1, whereas
micro cracks/voids are seen on mild steels at all the sites as per SEM. Rust
coating developed on weathering steel is more protective than mild steel.
With reference to performance of scribed coated panels, rate of deterioration of
weathering steel substrate was lesser than mild steel substrate as per EIS.
Deterioration of coated panels was highest at P1 for both steels, and also higher
for mild steels at P2 and P3 as found by EIS. Presence of SO2 helped to prevent
deterioration of coated weathering steels at these sites.
More stable and protective phase/oxides (d FeOOH, a Fe2O3 & Fe3O4) formed
on weathering steels at Chennai and Jamshedpur with prolonged exposure as
143
References
1. Madlangbayan, M., Otsuki, N., Saito, T., Min, A.K.: Corrosion behaviour of coated steel
plates with defects exposed to marine environment. J. Soc. Mat. Sc. 58(5), 437442 (2009)
2. Knotkova, D.: Atmospheric corrosion of metals, American Society for Testing and Materials
767, Philadelphia, p. 7 (1982)
3. Kihira, H., Ito, S., Murata, T.: Passive rust layer on low alloy steel exposed in atmospheric
environment. Corros. Sci. 31, 383388 (1990)
144
4. Nishimura, T., Katayama, H., Noda, K., Kodama, T.: Electrochemical behaviour of rust
formed on carbon steel in a wet/dry environment containing chloride ions. Corros. Sci. 56,
935 (2000)
5. Macdonald, J.R.: Impedance spectroscopy and its use in analysing the steady state AC
restorage of solid and liquid electrolytes. J. Electrochem. Soc. 223, 25 (1987)
6. Selected Powder Diffraction Data for Metals & Alloys Data Book, 1st. Edn., vol I & II,
JCPDS International Centre for Diffraction Data, USA
7. International Table for X ray Crystallography, Kyonoch Press, Birmingham, vol. 3, p. 161
(1962)
8. Loader, J.: Basic Laser Raman Spectroscopy. Heyden and Son, London (1970)
9. Gui, J., Devine, T.M.: Proceedings of 12th International Corrosion Congress, NACE, p 2052
(1993)
10. Dunnwald, J., Otto, A.: An investigation of phase transition in rust layers using Raman
spectroscopy. Corros. Sci. 29, 11671176 (1989)
11. Ohtsuka, T., Kubo, K., Sato, N.: Raman spectroscopy of thin corrosion films on iron at 100 to
150 C in air. Corrosion 42, 476481 (1986)
12. Ohtsuka, T.: Raman spectra of passive films of iron in neutral borate solution. Mat. Trans.
JIM. 37, 67(1996)
13. Brown, C.W., Heidersbach, R.H.: Raman spectra of possible corrosion products of iron.
Appl. Spectrosc. 32(6), 532535 (1978)
14. Boucherit, N., Delicher, P., Joiret, S., Hugot, A.: Mater. Sci. Forum 51, 44 (1989)
15. Faria, D.L.A., Silva, S.V., Oliveira, M.T.: Raman spectroscopy of some iron oxides and
oxyhydroxides. J. Raman. Spectrosc. 28, 873878 (1997)
16. Sato, N.: An overview on passivity of metals. Corros. Sci. 31, p1 (1990)
17. Jones, D.A.: Principles and Prevention of Corrosion. Prentice Hall, USA (1996)
18. Goidanich, S., Lazzari, L., Ormellese, M., Pedeferri, M.: Influence of AC on corrosion
kinetics for carbon steel, zinc and copper, Corrosion 5 and 2 (2005)
19. Sam, C.S., Balaya, P.: Investigation of structural disorder in electrode materials. http://
www.nus.edu.sg/nurop/2009/FoE/U066456W.PDF (2010) Accessed Jan 2010
20. Matsubara, E., Suzuki. S., Waseda. Y.: Corrosion mechanism of iron from an X ray structural
viewpoint. Book on Characterisation of Corrosion Products on Steel Surfaces
21. Ohtsuka, T.: Passivation oxide films and rust layers on iron. Characterization of Corrosion
Products on Steel Surfaces, Springer, Heidelberg (2006)
22. Pourbaix, M.: Atlas of Electrochemical Equilibria in Aqueous Solutions. Pergamon, New
York (1966)
23. Leygraf, C., Graedel, T.: Atmospheric corrosion. J. Electrochem. Soc. 1497, 1010 (2000)
24. Thibeau, R.J., Brown, C.W., Heidersbach, R.H.: Raman spectra of possible corrosion
products of iron. Appl. Spectrosc. 32, 532 (1978)
25. Dong, J.H., Han, E.H., Ke, W.: Progress in research on rust layer of weathering steel. Corros.
Sci. 18, 414 (2006)
Appendix
P2
P1
P3
Temperature (C)
45
30
15
0
0
10
11
12
P2
Relative Humidity(%)
100
P1
P3
90
80
70
60
50
10
11
12
145
146
Appendix
P2
600
P1
P3
Rainfall (mm)
500
400
300
200
100
0
0
10
11
12
Table A 2.1 Average Temperature, Relative Humidity and Rainfall of Exposure Site 2007
Site
P1
P2
P3
Month
RH
RH
RH
J
F
M
A
M
J
J
A
S
O
N
D
16.96
28.78
29.80
33.12
33.45
33.65
31.22
23.14
31.60
30.31
29.21
26.63
92.38
78.07
79.94
77.07
80.03
81.47
85.96
84.61
83.06
85.74
76.77
73.67
0.00
0.00
1.16
0.43
4.38
5.65
8.03
10.94
23.29
25.01
0.03
0.00
31.70
36.00
37.20
37.00
41.00
41.00
40.00
38.60
36.20
35.40
34.00
30.60
89.00
93.00
83.00
98.00
81.00
81.00
92.00
92.00
93.00
98.00
96.00
98.00
0.30
6.70
1.60
162.50
52.40
14.30
90.90
66.90
140.8
499.7
450.2
462.8
32.90
33.80
37.20
43.00
40.60
34.40
33.80
34.20
34.00
32.00
31.40
26.40
86.00
92.00
89.00
76.00
90.00
92.00
94.00
95.00
89.00
95.00
95.00
86.00
0.00
153.30
22.30
1.90
102.70
133.40
240.20
198.80
92.60
127.70
11.00
0.00
J Jan, F Feb etc, T Temperature (C), RH Relative humidity (%), R Rainfall (mm)
Appendix
147
148
Appendix
Appendix
149
150
Appendix
Appendix
151
152
Appendix
Fig. A 3.6 a XRD spectra of MS rust exposed at P1 for 42 m. b XRD spectra of WS rust
exposed at P1 for 42 m
Appendix
153
154
Appendix
Fig. A 3.8 a XRD spectra of MS rust exposed at P3 for 42 m.b XRD spectra of WS rust exposed
at P3 for 42 m
Appendix
155
156
Appendix
Appendix
157
158
Appendix
Appendix
159
160
Appendix
Appendix
161
162
Fig. A 3.17 EDX plots of inner rust layer of a MS and b) WS in humid SO2
Appendix
Appendix
163
164
Appendix
Fig. A 3.19 Raman spectra of a MS and b WS rust exposed in humidity for 2,000 h
Appendix
Fig. A 3.20 Raman spectra of a MS and b WS rust exposed in humidity for 3,500 h
165
166
Appendix
Fig. A 3.21 Raman spectra of a MS and b WS rust exposed in humidity for 4,500 h
Appendix
Fig. A 3.22 Raman spectra of a MS and b WS rust exposed in salt spray for 2,000 h
167
168
Appendix
Fig. A 3.23 Raman spectra of a MS and b WS rust exposed in salt spray for 3,500 h
Appendix
Fig. A 3.24 Raman spectra of a MS and b WS rust exposed in saly spray for 4,500 h
169
170
Appendix
Fig. A 4.1 Raman spectra of WS after passivated at -820 mV in 0.1 M Na2SO4 (pH 9.5) at 2
spots
Appendix
171
Fig. A 4.2 Raman spectra of WS after pssivated at -800 mV in 0.1 M Na2SO4 (pH 9.5) at 2
spots
172
Appendix
Fig. A 4.3 Raman spectra of MS after passivated at -1,146 mV in 0.1 M Na2SO4 (pH 9.5) at 2
spots
Appendix
173
Fig. A 4.4 Raman spectra of MS after passivated at -1,609 mV in 0.1 M Na2SO4 (pH 9.5) at 2
spots