CRITICAL ANALYSIS ON

CHARACTERIZATION
TECHNIQUES AND
TESTING OF
CORROSION
PRODUCTS
AFIA MAZHAR (MM-09)
NED university of Engineering and Technology, Main campus,
materials engineering department. 2017
Submitted to: Sir Ali Dad
Email: afia_mazhar2013@yahoo.com
 Outline
Introduction
Classification of corrosion
Types of corrosion
Need for studying corrosion
Theory
Electrochemical corrosion test
Electrochemical performances
Electron microscopy
X-ray diffraction
Fourier transform infrared spectroscopy
Raman Spectroscopy
Mossbauer Spectroscopy
Techniques for corrosion rate Quantification
Recent researches
Conclusions
Abstract

Corrosion is the naturally occurring process that cannot be stopped

ever, several techniques and experimental work has been developed in
order to minimized corrosion and also find ways to prevent it. In this
paper, there is a review of several characterization techniques for the
corrosion product and as well as corrosion rate quantification is also
discussed. Several recent researches and cases are also studied to
determine the appropriate techniques and testing for the
characterization of different forms of corrosion.
 The problems related to corrosion are present in all the
Introduction domains of the national economy: machine building,
naval and port building, chemistry, petrochemistry,
metallurgy, semi finished production, water and gas
alimentary systems, energy production systems,
transport, etc.
The economic consequences of corrosion affect
technology, too. A great deal of the development of
new technology is held back by corrosion problems
because the materials are required to withstand, with
many cases simultaneously, higher temperatures,
higher pressures and more highly corrosion
environments.
Millions of dollars are lost each year because of
corrosion. Much of this loss is due to the corrosion of
iron and steel, although many other metals may
corrode as well.
Theory The applied methods for the corrosion study must
fulfill the conditions of a firm control of different
factors characterizing the corrosion process.
The real work conditions must be fulfilled, too. The
result of the metal corrosion due to a chemical medium
is, usually, represented by a weight loss together with
changes in the mechanical, structural or physical-
chemical properties of the metal/alloy
Selecting of a corrosion products analysis technique is
depending of some parameters as: corrosion process
rate, corrosive attack type and the nature of the
corrosion products.
 In Table are listed some of the methods applied in
the corrosion studies.

Corrosion process rate Corrosion attack type and characterization Nature of corrosion products
of corrosion products

Macroscopic method: Spectroscopic methods

Gravimetrical methods visual examination (IR, FTIR, Raman Mossbauer
spectroscopy)

Microscopic methods Diffraction methods:

Electrochemical methods optics XRD
electronics (SEM, TEM, STEM, ED
AFM, STM)
Electrochemical Electrochemical corrosion tests rely on electrochemical
theory and electrochemical corrosion measurements to

Corrosion Tests characterize corrosion damage and, where possible,

estimate corrosion rates. Fundamentally, two types of
electrochemical measurements can be made:
1. Applying external current to generate
electrochemical data away from the free corrosion
potential. These tests generally explore the
relationship between electrochemical potential and
current.
2. Electrochemical measurements at the free corrosion
potential, without the application of an external
current
Electrochem Electrochemical techniques rely on electrochemical
corrosion theory and the measurement of

ical electrochemical potentials and/or currents to monitor

corrosion damage.

Techniques The electrochemical potential is fundamentally related

to thermodynamics of corrosion reactions, while
currents are related to reaction kinetics (rate of
corrosion).
The relationship between electrochemical potential
and current is important in several electrochemical
corrosion monitoring techniques. These range from
simple to highly complex techniques.
Electrochemical
Techniques
 Electron Electron microscopy studies, e.g.
Scanning electron microscopy (SEM), transmission

microscopy electron microscopy (TEM), atomic force microscopy

(AFM) and scanning tunnelling microscopy (STM) are
used for
Characterization of corrosion products
Identification of the cause of corrosion
Determination of thickness and nature of the surface
layers and coating
identification of the nature of fracture
identification of extraneous elements, etc.
For instance, TEM and ED are use to determine the
components of rust and in-depth distribution of rusts
on steels exposed to atmosphere.
 Cont
TEM analysis requires a special preparation of specimens using ion-milling method. It means that specimens for
TEM are prepare as follows: a cross-section of resin-embedded specimen is slice as thin as possible, and both sides
of cross-sections of rust layer are polish down to 50 m thick with SiC paper, followed by rinsing in distilled water
and methanol. Then the thick specimen is mechanically polished, followed by ion-milling from both sides. During
milling specimens are cool by liquid nitrogen. In Fig the process of TEM specimen preparation is shown.
 X-ray It is the only analysis method that readily provides
information about the phase-composition of solid

diffraction materials.
For instance, a mixture of Fe3O4 (magnetite),

(XRD) FeO(OH) (goethite) and Fe5O7(OH)x4H2O

(ferrihydrite) can be identified and quantified as such,
while other analysis methods will only reveal that the
corrosion product is Fe-based.
Furthermore, XRD can readily distinguish between
different modifications of phases that have the same
chemical formula. Goethite, lepidocrocite, feroxyhyte
and akaganeite can be told apart, even though they all
have the chemical formula FeO(OH).
Cont Information about the chemical phases is not only
helpful to explain the corrosion process, but can help to
locate the origin of corrosion in a facility and, at the
same time, provide solutions to the problem.
Utilizing microprobe techniques (XRD and PIXE
Proton induced X-ray emission) it may be obtain local
composition and structural information from different
iron/steel constructions and its protective scale.
XRD and SEM analysis are used in order to identify the
various elements that make up the layer of rust, which
produced on steel exposed to different atmosphere.
 Fourier
It is a powerful tool for identifying types of chemical
bonds in a molecule by producing an infrared absorption
spectrum that is like a molecular "fingerprint".

Transform FTIR is most useful for identifying chemicals that are

either organic or inorganic.

Infrared It can be utilized to quantify some components of an

unknown mixture.

Spectroscop It can be applied to the analysis of solids, liquids, and

gasses. The term Fourier Transform Infrared Spectroscopy

y (FTIR)
(FTIR) refers to a recent development in the manner in
which the data is collected and converted from an
interference pattern to a spectrum.
FTIR can be used to identify chemicals from spills, paints,
polymers, coatings, drugs, and contaminants. FTIR is
perhaps the most powerful tool for identifying types of
chemical bonds (functional groups). The wavelength of
light absorbed is characteristic of the chemical bond as
can be seen in the annotated spectrum.
 FTIR
spectra
Cont FTIR spectroscopy is also suitable for fundamental
biofilm research, as well as for monitoring biofilm
formation on surfaces, including reflecting surfaces like
metals, which become especially corroded in the
presence of natural waters in industrial service waters
containing microorganisms.
It is a perfect tool to characterize and locate
deterioration products and bacteria associated with
corrosion occuring on metal coupons.
 Mossbauer Mssbauer spectroscopy is a versatile technique that
can be used in many areas of science in order to obtain

spectroscopy information. It can give very precise information about

the chemical, structural, magnetic and time-
dependent properties of corrosion products.
One of the most suitable methods in analyzing and
characterizing the steel corrosion products is the
Mssbauer spectroscopy. Green rust is a corrosion
product that is easily detected with this method. In Fig
Mssbauer spectra of carbonate green rust is shown.
Aspects on the necessary conditions of a corrosion
investigation procedure may be obtained by consulting
the standardized methods and techniques corrosion
specific.
Cont In Fig Mssbauer spectra of carbonate green rust is
shown.
 Techniques Summary
The methods and procedures defined in this paper offers a

for collection of approaches to predict corrosion rate.

Non electrochemical procedures are easy to use and

Corrosion straightforward.
Weight loss quantification provide straight indication of

Rate the corrosion rate.

Electrical resistance probes can be frequently utilizing in

Quantificati any environment (exposure) and are appropriate for eld

screening.

on The electrochemical techniques are relying on a essential

understanding of corrosion kinetics.
Potentiodynamic polarization data through Tafel
extrapolation is a influential tool for evaluating corrosion
rate and significant data beyond the corrosion rate can be
resolute from the polarization curves.
Case studies Year 2017 (Damage of a pipe wall)
A massive corrosion product that was found in the district
of a damage to a pipe wall was inspected in order to
recognize the cause for the observed quick corrosion
progressions. Raman spectroscopy and energy dispersive
X-ray microanalysis were used to inspect this corrosion
across the whole area or cross-section of the pipe. It was
observed that the internal portion of the corrosion
product at the contact with the pipe's inner surface mostly
comprised of magnetite. The outer or external part of the
corrosion product, which was in link with the water in the
pipe, was mainly goethite.
These discoveries confirmed the supposition that the
magnetite sediments on the top of the new pipe caused
oxygen concentration cell formation, which activated
corrosion dissolution of the pipe wall and led to a rapid
perforation.
Year 2017
(research on corrosion inhibitor compounnd)
In this latest research a novel , eco-friendly and
economically feasible scheme for corrosion inhibition is
planned.
Corrosion limiting performance of a recently
manufactured imine compound namely, 4-(4 methoxy-6-
methylpyrimidin-2-yl) imino)methyl)benzaldehyde
(MMYB) on mild steel in 0.5M H2SO4 solution have been
examined through frequent electrochemical and surface
characterization techniques and methods. The outcomes
have been analysed of the inhibitor molecule and by many
thermodynamic adsorption and activation parameters.
This inhibitor is of highly importance because of its high
inhibition efficiency at low concentrations and high
temperatures.
Characterization is done by several electron microscopy
techniques, most commonly examination is done by
scanning electron microscopy (SEM), energy dispersive X-
ray spectroscopy and atomic force microscopy (AFM).
 Year 2017
(Intergranular corrosion studies)
Intergranular corrosion flaws shaped after a 24 hours absorption in a 1 M NaCl solution in a
2024-T351 Al alloy were characterized by using a combination of several electron
microscopy techniques. outcomes presented the suspension of intergranular Cu-rich
precipitates all along the corroded grain boundaries.
Cu was fused inside the amorphous alumina oxide film recognized in the corroded grain
boundaries leading to the establishment of structural imperfections in the oxide film.
Metallic Cu rich thin film about 0-200 nm-thin also detected at the oxide/metal boundary
and at the tip of the intergranular corrosion flaw
Conclusion Gravimetrical and electrochemical methods are used
to determine the metals/alloys corrosion rate and to
characterize the corrosion damage.
Microscopy and spectroscopy studies are used for
characterization and determination of thickness and
nature of the corrosion products.
The choice of the most appropriate method for metal
corrosion studying depends on the corrosion process,
the ultimate goal and the place of the experiment.
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Thank you