“ CORROSION AND IT’S MONITORING ”

Under the supervision of

Dr. D. D. Sarode

In “ ICT MUMBAI”

SYCE BATCH-B3 SEMESTER-3

17CHE138 MAKRAND JAGTAP

17CHE139 MAYUR PIMPALKAR

17CHE140 MERUL SHAH

17CHE142 NEHA GADEKAR

17CHE143 NIRAJ BHAVAR

Table of Contents

Introduction......................................................................................................................................................6

Corrosion...........................................................................................................................................................7

Uniform Corrosion..........................................................................................................................................8

Localised Corrosion........................................................................................................................................8

Various types of corrosion ......................................................................................................................... 9

Pitting corrosion: .........................................................................................................................................9

Crevice corrosion:..........................................................................................................................................9

Bimetallic corrosion:......................................................................................................................................9

Stress corrosion:.............................................................................................................................................10

Hydrogen embrittlement:...............................................................................................................................11

Corrosion Monitoring:...................................................................................................................................12

What is it? ..................................................................................................................................................12

Inspection Survey:.........................................................................................................................................12

Monitoring:....................................................................................................................................................12

Adding Value:................................................................................................................................................13

Key points : ...................................................................................................................................................13

Instrument for corrosion testing:...................................................................................................................13

Potentiodynamic Polarisation Method:..................................................................................................14

LPR:.......................................................................................................................................................15

IES:.........................................................................................................................................................16

Techniques for corrosion monitoring:..........................................................................................................17

Corrosion Coupons:.......................................................................................................................................17

ER Monitoring:..............................................................................................................................................18

Galvanic Monitoring:....................................................................................................................................20

Biological Method:........................................................................................................................................21

Sand Monitoring:...........................................................................................................................................21

Hydrogen Penetrating Monitoring:................................................................................................................21

 Electrochemical Basis of corrosion:..............................................................................................................22

Quantified Corrosion theory:................................................................................................................23

Polarisation Resistance:.......................................................................................................................26

Calcuations of corrosion rate:...............................................................................................................26

IR compensation:..................................................................................................................................28

Current and Voltage Convention:.........................................................................................................30

Theory for aqueous Corrosion:.............................................................................................................31

Reference Electrode:.................................................................................................................32

Cell potential:............................................................................................................................33

Corrosion Kinetics:...............................................................................................................................34

Experiment:.....................................................................................................................................................47

Abstract:..........................................................................................................................................................47

Introduction:...................................................................................................................................................47

Corrosion in RC structure and monitored by ultasonic guided waves:..........................................................48

Experiment Investigation and testing technology:.........................................................................................50

Result:.............................................................................................................................................................53

Impact:............................................................................................................................................................55

Conclusion:......................................................................................................................................................56
LIST OF TABLES

Table 1: Explaining terms used in equation .................................................................................................... 24

Table 2: Various symbols used in equation ..................................................................................................... 25
Table 3: Faraday's Law .................................................................................................................................... 27
Table 4: Various Terms used in Corrosion Rate equation ............................................................................... 28
Table 5: Corrosion Rate Constants .................................................................................................................. 29
Table 6:Approximate exchange current density (i0) for the hydrogen oxidation reaction on different metals at
25oC ................................................................................................................................................................. 37
LIST OF FIGURES

Figure 1: Corrosion Reaction............................................................................................................................. 7

Figure 2: Mechanism of corrosion in steel ........................................................................................................ 9
Figure 3: Mechanism of crevice corrosion ........................................................................................................ 9
Figure 4: Mechanism of Stress corrosion ........................................................................................................ 10
Figure 5: Mechanism of fretting corrosion ...................................................................................................... 10
Figure 7: Graph showing the result .................................................................................................................. 20
Figure 6: Wire loop .......................................................................................................................................... 20
Figure 8:Corrosion process showing anodic and cathodic components of current. ........................................ 22
Figure 9:Classic Tafel analysis. ....................................................................................................................... 26
Figure 10: Current-interrupt potential versus time. ......................................................................................... 30
Figure 11: Corrosion current experiment ......................................................................................................... 32
Figure 12:Saturated Calomel Electrode ........................................................................................................... 32
Figure 13:Standard Hydrogen Electrode ......................................................................................................... 33
Figure 14:Electrochemical instrumentation ..................................................................................................... 38
Figure 15:Current vs. overpotential polarization plot of the ferric/ferrous ion reaction on palladium ........... 40
Figure 16: Plot of Log(i) vs Overpotential ...................................................................................................... 41
Figure 17:pH diagram for iron superimposed on the chromium diagram (enhanced passivity range due to
stable ................................................................................................................................................................ 43
Figure 18: Potentiostatic Anodic polarization curve ....................................................................................... 43
Figure 19:Decay of passivity showing Flade potential .................................................................................... 44
Figure 20: Corrosion rate measurement with the modulated confinement of the current method. ................. 47
Figure 21: Steel bar embedded in Concrete ..................................................................................................... 52
Figure 22: Cracks ............................................................................................................................................. 52
 1)INTRODUCTION:

Corrosion can be viewed as a universal phenomenon, omnipresent and omnipotent. It is there everywhere,
air, water, soil and in every environment, we encounter.
There is no single figure for loss to the nation due to corrosion. It can be a minimum of 3.5% of the nation‟s
GDP. Losses due to corrosion could be around Rs. 2.0 lakh crores per annum in India. Corrosion costs
manifest in the form of premature deterioration or failure necessitating maintenance, repairs and replacement
of damaged parts.

In the US, total direct cost of corrosion is estimated at about 300 billion dollars per year; which is about
3.2% of domestic product. Corrosion has a huge economic and environmental impact on all facets of
national infrastructure; from highways, bridges, buildings, oil and gas, chemical processing, water and waste
water treatment and virtually on all metallic objects in use. Other than material loss, corrosion interferes
with human safety, disrupts industrial operations and poses danger to environment. Awareness to corrosion
and adaptation of timely and appropriate control measures hold the key in the abatement of corrosion
failures.

The concrete is embedded with steel bar giving rise to reinforce concrete. Reinforce concrete is found to be
strong in tension as well as compression. So, it is used in construction like massive bridges and building.
There is an issue with this concrete regarding its durability. Among all these issues the most prominent one
is the corrosion of the steel used for reinforcement of the concrete. The corrosion of the steel bar drastically
reduces the life of the concrete structure which requires a frequent maintainance and rehabilitation. This is a
very serious issue because the failure in the structures may involve loss of life. The study must be
imdertaken covering the basics in chemistry of corrosion and corrosion models and type of anti-corrosive
surface coatings available to us and how they help us to prevent corrosion. We have further carried the
studies of corrosion in continuation of the past batch. Corrosion being a long process for experimental
purpose we carry out accelerated corrosion using anodic current.
 2) CORROSION: (Corrosion)

Corrosion is the deterioration or destruction of metals and alloys in the presence of an environment by
chemical or electrochemical means. In simple terminology, corrosion processes involve reaction of metals
with environmental species.

As per IUPAC, “Corrosion is an irreversible interfacial reaction of a material (metal, ceramic, polymer) with
its environment which results in its consumption or dissolution into the material of a component of the
environment. Often, but not necessarily, corrosion results in effects detrimental to the usage of the material
considered. Exclusively physical or mechanical processes such as melting and evaporation, abrasion or
mechanical fracture are not included in the term corrosion”

Corrosion is an electro-chemical process involving an anode, a cathode and an electrolyte. In the case of
steel, when favourable condition for corrosion occurs, the ferrous ions go into solution from anodic areas.
Electrons are then released from the anode and move through the cathode where they combine with water
and oxygen to form hydroxyl ions. These react with the ferrous ions from anode to produce hydrated ferrous
oxide, which further gets oxidised into ferric oxide, which is known as the ‘red rust’.
For example, if we can wipe out the ‘drop of water’ shown in Fig 1. the corrosion will not take place! Hence
using the “eliminate the electrolyte” principle, wherever possible we need to device detailing and protection
to surfaces of structural steel work to ensure that the combination of oxygen and water are avoided and
hence the corrosion batteries are avoided. On the other hand, steel is anodic in the presence of stainless steel
or brass and cathodic in the presence of zinc or aluminium and the second property can be used to protect it
from corrosion.
 Fe  Fe+4 +4e- Oxidation of anode
 O2 + 2H2O + 4e-  4OH- Hydrogen atoms on iron surface reduce dissolved oxygen.
 2Fe + O2 + 2H2O  2Fe(OH)2 Overall reaction

Figure 1: Corrosion Reaction

 Fe(OH)2 + O2  2H2O + 2Fe2O3.H2O Further oxidation to give rust.

The 2Fe2O3.H2O is a soft, brown hydrated oxide of iron which is rust.

The process has basic five facts:

1. Ions are involved and need a mdium to move in (usually water)

2. Oxygen is involved and needs to be supplied.
3. The metal has to be willing to give up electrons to start the process.
4. A new material is formed and this may react again or could be protective of the original metal.
5. A series of simple steps are involved and a driving force is needed to achieve them. The most
important fact is that interfering with the steps allows the corrosion reaction to be stopped or slowed
to a manageable rate.

2.1) Uniform Corrosion(30% of failures)

Steady and predictable corrosion over a majority of the metal surface is uniform corrosion. Due to the
predictable rate, it is easily prevented. The simple solution is to make the material thick enough to prevent
premature failure. Uniform corrosion can also be stopped/prevented by Coating surface with non-conducting
medium (paints, lacquers, or oils) or galvanisation.

It can be slowed or stopped by using five basic steps:

 Slow down or stop the movements of electrons.

 Slow down or stop oxygen from reaching the surface. Difficult to do completely but coating helps.
 Prevent metal from giving up electrons by using a more corrosion resistant metal higher in the
electrochemical series.Use a sacrificial coating which gives up its electron more easily than the metal
being protected.
 Select a metal that forms an oxide that is protective and stops the reaction.
Control and consideration of environmental and thermal factors is also essential.

2.2) Localized corrosion(70% of failures)

Localised Corrosion is defined as the selective removal of metal by corrosion at small areas or zones on a
metal surface in contact with a corrosive environment, usually a liquid. It usually takes place when small
local sites are attacked at a much higher rate than the rest of the original surface.
 3) Various Types of Corrosion (A.K.Natrajan)
Even though the fundamental mechanism of corrosion involves creation or existence of corrosion cells, there
are several types or forms of corrosion that can occur. It should however be borne in mind that for corrosion
to occur, there is no need for discrete (physically independent) anodes and cathodes. Innumerable micro
level anodic and cathodic areas can be generated at the same (single) surface on which anodic (corrosion)
and cathodic (reduction) reactions occur.

3.1) Pitting corrosion:

As shown in Fig.1.11, The anodic areas form a corrosion pit. This can occur with mild steel immersed in
water or soil. This common type of corrosion is essentially due to the presence of moisture aided by
improper detailing or constant exposure to alternate wetting and drying. This form of corrosion could easily
be tackled by encouraging rapid drainage by proper detailing and allowing free flow of air, which would dry
out the surface .

Figure 2: Mechanism of corrosion in steel

3.2) Crevice corrosion:

The principle of crevice corrosion is shown in Fig.1.12. The oxygen content of water trapped in a crevice is
less than that of water which is exposed to air. Because of this the crevice becomes anodic with respect to
surrounding metal and hence the corrosion starts inside the crevice.

Figure 3: Mechanism of crevice corrosion

3.3) Bimetallic corrosion:

When two dissimilar metals (for e.g. Iron and Aluminium) are joined together in an electrolyte, an electrical
current passes between them and the corrosion occurs. This is because, metals in general could be arranged,
depending on their electric potential, into a table called the ‘galvanic series’. The farther the metals in the
galvanic series, the greater the potential differences between them causing the anodic metal to corrode. A
common example is the use of steel screws in stainless steel members and also using steel bolts in
aluminium members. Obviously such a contact between dissimilar metals should be avoided in detailing.

3.4) Stress corrosion:

This occurs under the simultaneous influence of a static tensile stress and a specific corrosive environment.
Stress makes some spots in a body more anodic (especially the stress concentration zones) compared with
the rest as shown in Fig.1.13. The crack tip in Fig.1.13 is the anodic part and it corrodes to make the crack
wider. This corrosion is not common with ferrous metals though some stainless steels are susceptible to this.

Figure 4: Mechanism of Stress corrosion

3.5) Fretting corrosion:

If two oxide coated films or rusted surfaces are rubbed together, the oxide film can be mechanically removed
from high spots between the contacting surfaces as shown in Fig. 1.14. These exposed points become active
anodes compared with the rest of the surfaces and initiate corrosion. This type corrosion is common in
mechanical components.

Figure 5: Mechanism of fretting corrosion

3.6) Hydrogen embrittlement:

This occurs mostly in fasteners and bolts. The atomic hydrogen may get absorbed into the surface of the
fasteners. When tension is applied to these fasteners, hydrogen will tend to migrate to points of stress
concentration. The pressure created by the hydrogen creates and/or extends a crack. The crack grows in
subsequent stress cycles. Although hydrogen embrittlement is usually included in the discussion about
corrosion, actually it is not really a corrosion phenomenon.
 4) CORROSION MONITORING (IQnection Digital Marketing)

4.1) Corrosion Monitoring - What is it?

"It would be very costly to learn of a systems corrosive condition only at its demise"

"It is more judicious to detect any signs of corrosion early on"

Some definitions assigned to corrosion monitoring have been wide ranging.Essentially including any type of
corrosion related measurement or observation. For example, a glossary published by the NATURAL
CORROSION SERVICE of theNATIONAL PHYSICAL LABORATORY (NPL,UK) has defined corrosion
as " Any method used to observe or measure the program of corrosion".

Such broad definitions highlight the multidisciplinary nature of corrosion monitoring,covering a wide range
of materials, measurement techniques, instrumentation, rules and regulations and standards, logical support,
data analysis, communication and information management.

4.2) INSPECTION SURVEY:

A "snapshot" of corrosion conditions at a specific point in time.

4.3) MONITORING:

A series of surveys, planned and organized to obtain more comprehensive information on conditions over
time (through time, as a function oftime).

The above role of corrosion monitoring, in defining changes in corrosion conditions over time. represents a
longer-term commitment compared with once-off corrosion inspections, surveys. Furthermore, it represents
a deeper commitment to quantifying the rate of corrosion and determining underlying causes of corrosion
damage. It has been noted that the rate of corrosion ultimater determines how long a process can be operated
usefully and safely.

The measurement of corrosion condition changes over time obviously also falls in the domain of on line
corrosion monitoring, which facilitates "continuous" corrosion monitoring as such on line monitoring can be
viewed as a continuous series of surveys (in relatively rapid succession). In this context, the term "corrosion
surveillance" has been introduced. 1! refers to the possibility of using corrosion monitoring (with sufficiently
sensitive sensors and instrumentation) as a form of process control by linking corrosion "events" to process
parameter changes; with process parameters being measured together with the corrosion sensor signals. The
term "real time monitoring" is also applicable to on line monitoring with sufficiently senstive techniques.

The important concepts of obtaining "early warning" before serious corrosion damage sets in and avoiding
process "upset windows" associated with excessive corrosion rates are all pan of the corrosion monitoring
philosophy of characterizing corrosion conditions over time.

4.4)Adding value:

Most importantly, to generate real value from corrosion monitoring initiatives, the information gathered over
time has to be translated into effective corrosion mitigation/control programs. "Making sense of it all", from
a deeper understanding of information from corrosion monitoring and other sources is required. For effective
corrosion control it is important to understand "where, when and why" corrosion damage takes place
corrosion monitoring can be helpful for these purposes.

4.5) Key points in corrosion monitoring:

 corrosion monitoring as multi disciplinary activities;

 corrosion monitoring as a means of characterizing corrosion conditions over time more than a ins ection
"snapshot" at one oint in time;
 ......and hence (hopefully) gaining an understanding of the rate and causes of corrosion damage;
 continuous corrosion monitoring as a form of process control (see above);
 longer term commitment to deeper understanding with corrosion information from various sources, "making
sense of it all";
 ....."where, when, why" does excessive corrosion damage occur;
 ultimate aim of translating corrosion monitoring information into more effective corrosion mitigation and
control, the real value and justification.

4.6) Instrumentation for corrosion testing:

Most electrochemical work with an electmchemical cell is achieved using what is called a potentiostat. A
potentiostat is an electronic device that cgntrols the voltage difference between a working electrode and a
reference electrode. In almost all applications. the potentiostat measures the current flow between the
working and auxiliary electrodes. The controlled variable in a potentiostat is the cell potential and the
measured variable is the cell current. A potentiostat typically functions with an electrochemical cell
containing three electrodes and that is true for both field probes and lab cells reference):

 Working Electrode: Electrochemical reactions being studied occur at the working electrode. ln corrosion
testing, the working electrode is a sample of the corroding metal. Generally, the working electrode is not the
 actual metal structure being studied. Instead a small sample is used to represent the structure. This is
analogous to testing using weight loss coupons. The working electrode can be bare metal or coated.
 Reference Electrode: A reference electrode is used in measuring the working electrode potential. A
reference electrode should have a constant electrochemical potential as long as no current flows
through it.
 Auxiliam Electrode: The Auxiliary electrode is a conductor that completes the cell circuit. The
auxiliary (counter) electrode in lab cells is generally an inert conductor like platinum or graphite. In
field probes it's generally another piece of the working electrode material.
 Electrometer: The electrometer circuit measures the voltage difference between the reference and
working electrodes. Its output has two major functions: it is the feedback signal in the potentiostat
circuit and it is the signal that is measured whenever the cell voltage is needed. An ideal electrometer
has zero input current and infinite input impedance.
 l/E Converter: The Current to Voltage (I/E) converter in the simplified schematic measures the cell
current. It forces the cell current to flow through a current measurement resistor. The voltage drop
across that resistor is a measure of the cell current.
 Control Amplifier: The control amplifier is a servo amplifier. It compares the measured cell voltage
with the desired voltage and drives current into the cell to force the voltages to be the same. Under
normal conditions, the cell voltage is controlled to be identical to the signal source voltage.
 The Signal: The signal circuit is a computer controlled voltage source. It is generally the output of a
Digital to Analog (D/A) converter that converts computer generated numbers into voltages
 . Galvanostats and Zero Resistance Am -|ifiers ZRAs : Most laboratory grade potentiostats can also
be operated as galvanostats or ZRAs.

4.6.1) Potentiodynamic polarization methods :

Polarization methods such as potentiodynamic polarization, potentiostaircase, and cyclic voltammetry are
ohen used for laboratory corrosion testing. These techniques can provide significant useful information
regarding the corrosion mechanisms, corrosion rate and susceptibility of specific materials to corrosion in
designated environments. Polarization methods involve changing the potential of the working electrode and
monitoring the current which is produced as a function of time or potential.

 Anodic polarization: the potential is changed in the anodic (or more positive direction) causing the
working electrode to become the anode and causing electrons to be withdrawn from it.
 Cathodic mlarization: the working electrode becomes more negative and electrons are added to the
surface, in some cases causing electrodeposition.

 Cyclic polarization: both anodic and cathodic polarization are performed in a cyclic manner.
Several methods may be used in polarization of specimens for corrosion testing. Potentiodynamic
polarization is a technique where the potential of the electrode is varied at a selected rate by application of a
current through the electrolyte. It is probably the most commonly used polarization testing method for
measuring corrosion resistance and is used for a wide variety of functions:

 Cyclic polarization tests: These tests are often used to evaluate pitting susceptibility. The potential
is swept in a single cycle (or slightly less than one cycle), and the size of the hysteresis is examined
along with the differences between the values of the starting open circuit corrosion potential and the
return passivation potential. The existence of the hysteresis is usually indicative of pitting, while the
size of the loop is often related to the amount of pitting.
 Cyclic voltammetry: Cyclic voltammetry involves sweeping the potential in a positive direction
until a predetermined value of current or potential is reached, then the scan is immediately reversed
toward more negative values until the original value of potential is reached. In some cases, this scan
is done repeatedly to determine changes in the current-potential curve produced with scanning.
 Potentiostaircase method: This technique polarizes an electrode in a series of potential steps where
the time spent at each potential is constant, while the current is often allowed to stabilize prior to
changing the potential to the next step. The step increase may be small, in which case, the technique
resembles a potentiodynamic curve, or it may be large.
 Electrochemical potentiodynamic reactivation (EPR): This technique allows to measure the
degree of sensitization of stainless steels such as S30400 and S30403 steels. This method uses a
potentiodynamic sweep over a range of potentials from passive to active (called reactivation).
 Linear polarization resistance (LPR): A widely used technique, the polarization resistance of a
material is defined as the slope of the potential-current density curve at the free corrosion potential,
yielding the polarization resistance, as described in the next section.

4.6.2)Linear Polarization Resistance (LPR)

... and the Stern-Geary Equation:

With this widely used technique in corrosion monitoring, the polarization resistance of a material is defined
as the slope of the potential-current density (DE/Di) curve at the free corrosion potential, yielding the
polarization resistance Rp that can be related (for reactions under
activation control) to the corrosion current by the Stern-Geary equation:

where:

 Rp is the polarization resistance

  icorr the corrosion current
 The proportionality constant , B, for a particular system can he determined empirically (calibrated
from separate weight loss measurements) or, as shown by Stern and Geary, can be calculated from
ba and bc, the slopes of the anodic and cathodic Tafel

The Tafel slopes themselves can be evaluated experimentally using real polarization
plots. The corrosion currents estimated using these techniques can be converted into
penetration rates using Faraday's law or a generic conversion chart.

The study of uniform corrosion or studies assuming corrosion uniformity are probably the most widespread
application of electrochemical measurements both in the laboratory and in the field. The widespread use of
these electrochemical techniques does not mean that they are without complications. Both linear polarization
and Tafel extrapolation need special precautions for their results to be valid. The main complications or
obstacles in performing polarization measurements can be summarized in the following categories:

 Effect of Scan Rate: The rate at which the potential is scanned may have a significant effect on the
amount of current produced at all values of potential. The rate at which the potential is changed, the
scan rate, is an experimental parameter over which the user has control. If not chosen properly, the
scan rate can alter the scan and cause a misinterpretation of the features.
 Effect of Solution Resistance: The distance between the Luggin capillary (of the salt bridge to the
reference electrode) and the working electrode is purposely minimized in most measurements to limit
the effect of the solution resistance. In solutions that have extremely high resistivity, this can be an
extremely significant effect.
 Changing Surface Conditions: Since corrosion reactions take place at the surface of materials,
when the surface is changed, due to processing conditions, active corrosion or other reasons, the
potential is usually also changed. This can have a strong effect on the polarization curves.
 Determination of Pitting Potential: In analyzing polarization curves the appearance of a hysteresis
(or loop) between the forward and reverse scans is often thought to denote the presence of localized
corrosion (pitting or crevice corrosion).
4.6.3) Electrochemical impedance spectroscopy(EIS):

Electrochemical Impedance Spectroscopy (EIS) is a frequency domain measurement made by applying a

sinusoidal perturbation, often a voltage, to a system. The impedance at a given frequency is related to
processes occurring at timescales of the inverse frequency (e.g. f=10 Hz, t=0.1 s). Although many other
electrochemical measurements focus on driving a system far from equilibrium with potential sweeps or
steps, such as cyclic voltammetry or chronoamperometry, EIS uses small perturbations.

These small departures from equilibrium are assumed to have a linear response thus greatly simplifying
the frequency analysis; however, linearization of physical models can lead to indistinguishable cases, as will
be discussed in the Nonlinear EIS (NLEIS) section. Furthermore, operating conditions for relevant devices
(e.g. batteries and fuel cells) are often far from equilibrium and exhibit nonlinear behavior. Practically
speaking, EIS is performed by sweeping through a wide range of frequencies at a single perturbation
amplitude. As instrumentation has improved over the last several decades, frequencies ranging from 10-4 to
108 Hz are attainable, thus allowing for the study of both fast kinetic and slow transport process1.
5)TECHNIQUES FOR CORROSION MONITORING: (M.Saremi and E.Mahallati)
A large number of corrosion monitoring techniques exist. The following list details the most common
techniques which are used in industrial applications:

• Corrosion Coupons (weight loss measurements)

• Electrical Resistance (ER)
• Electrochemical basis of corrosion
• Galvanic (ZRA) / Potential
• Hydrogen Penetration
• Microbial
• Sand/Erosion

Other techniques do exist, but almost all require some expert operation, or otherwise are not sufficiently
rugged or adaptable to plant applications.

Of the techniques listed above, corrosion coupons, ER, and LPR form the core of industrial corrosion
monitoring systems. The four other techniques are normally found in specialized applications which are
discussed later.
These corrosion monitoring techniques have been successfully applied and are used in an increasing range
of applications because:
• The techniques are easy to understand and implement.
• Equipment reliability has been demonstrated in the field environment over many years of operational
application.
• Results are easy to interpret.
• Measuring equipment can be made intrinsically safe for hazardous area operation.
• Users have experienced significant economic benefit through reduced plant down time and plant life
extension.

5.1) Corrosion Coupons (Weight Loss)

The Weight Loss technique is the best known and simplest of all corrosion monitoring techniques. The
method involves exposing a specimen of material (the coupon) to a process environment for a given
duration, then removing the specimen for analysis. The basic measurement which is determined from
corrosion coupons is weight loss; the weight loss taking place over the period of exposure being expressed
as corrosion rate.

The simplicity of the measurement offered by the corrosion coupon is such that the coupon technique forms
the baseline method of measurement in many corrosion monitoring programs.
The technique is extremely versatile, since weight loss coupons can be fabricated from any commercially
available alloy. Also, using appropriate geometric designs, a wide variety of corrosion phenomena may be
studied which includes, but is not limited to:

• Stress-assisted corrosion
• Bimetallic (galvanic) attack
• Differential aeration
• Heat-affected zones

Advantages of weight loss coupons are that:

• The technique is applicable to all environments - gases, liquids, solids/particulate flow.

• Visual inspection can be undertaken.
• Corrosion deposits can be observed and analyzed.
• Weight loss can be readily determined and corrosion rate easily calculated.
• Localized corrosion can be identified and measured.
• Inhibitor performance can be easily assessed.

In a typical monitoring program, coupons are exposed for a 90-day duration before being removed for a
laboratory analysis. This gives basic corrosion rate measurements at a frequency of four times per year. The
weight loss resulting from any single coupon exposure yields the "average" value of corrosion occurring
during that exposure. The disadvantage of the coupon technique is that, if a corrosion upset occurs during
the period of exposure, the coupon alone will not be able to identify the time of occurrence of the upset, and
depending upon the peak value of the upset and its duration, may not even register a statistically significant
increased weight loss.

Therefore, coupon monitoring is most useful in environments where corrosion rates do not significantly
change over long time periods. However, they can provide a useful correlation with other techniques such as
ER and LPR measurements.
5.2) Electrical Reistance (ER) Monitoring :
ER probes can be thought of as "electronic" corrosion coupons. Like coupons, ER probes provide a basic
measurement of metal loss, but unlike coupons, the value of metal loss can be measured at any time, as
frequently as required, while the probe is in-situ and permanently exposed to the process stream.
 The wire loop represented here is new with its total diameter of 40
mils (total useful probe life of 10 mils).

Here the element has experienced about 5 mils penetration or about

half of its useful life. The increased electrical resistance of the
element will register as 5 mils metal penetration into the piping or
process system.

Here the element has measured 10 mils of penetration .

Figure 6: Wire loop The ER technique measures the change in Ohmic resistance of a
corroding metal element exposed to the process stream. The action
of corrosion on the surface of the element produces a decrease in its cross-sectional area with a
corresponding increase in its electrical resistance. The increase in resistance can be related directly to metal
loss and the metal loss as a function of time is by definition the corrosion rate. Although still a time averaged
technique, the response time for ER monitoring is far shorter than that for weight loss coupons. The graph
below shows typical response times.

Figure 7: Graph showing the result

ER probes have all the advantages of coupons, plus:

• They are applicable to all working environments gases, liquids, solids, particulate flows.
• Direct corrosion rates can be obtained.
• Probe remains installed in-line until operational life has been exhausted.
• They respond quickly to corrosion upsets and can be used to trigger an alarm.

ER probes are available in a variety of element geometries, metallurgies and sensitivities and can be
configured for flush mounting such that pigging operations can take place without the necessity to remove
probes. The range of sensitivities allows the operator to select the most dynamic response consistent with
process requirements.

5.3) Galvanic/Potential Monitoring

The galvanic monitoring technique, also known as Zero Resistance Ammetry (ZRA) is another
electrochemical measuring technique. With ZRA probes, two electrodes of dissimilar metals are exposed to
the process fluid. When immersed in solution, a natural voltage (potential) difference exits between the
electrodes. The current generated due to this potential difference relates to the rate of corrosion which is
occurring on the more active of the electrode couple.

Galvanic/Potential monitoring is applicable to the following electrode couples:

• Bimetallic corrosion
• Crevice and pitting attack
• Corrosion assisted cracking
• Corrosion by highly oxidizing species
• Weld decay

Galvanic current measurement has found its widest applications in water injection systems where dissolved
oxygen concentrations are a primary concern. Oxygen leaking into such systems greatly increases galvanic
currents and thus the corrosion rate of steel process components. Galvanic monitoring systems are used to
provide an indication that oxygen may be invading injection waters through leaking gaskets or deaeration
systems.

5.4) Biological Monitoring

Biological monitoring and analysis generally seeks to identify the presence of Sulphate Reducing Bacteria -
SRB's. This is a class of anaerobic bacteria which consume sulphate from the process stream and generate
sulphuric acid, a corrosive which attacks production plant materials.

5.5)Sand / Erosion Monitoring

These are devices which are designed to measure erosion in a flowing system. They find wide application in
oil/gas production systems where particulate matter is present.

5.6)Hydrogen Penetration Monitoring

In acidic process environments, hydrogen is a by-product of the corrosion reaction. Hydrogen generated in
such a reaction can be absorbed by steel particularly when traces of sulphide or cyanide are present. This
may lead to hydrogen induced failure by one or more of several mechanisms. The concept of hydrogen
probes is to detect the amount of hydrogen permeating through the steel by mechanical or electrochemical
measurement and to use this as a qualitative indication of corrosion rate.

5.7)Electrochemical Basis of corrosion: (Albama Speciality Products,Inc.)

Most metallic corrosion occurs via electrochemical reactions at the interface between the metal and an
electrolyte solution. For example, a thin film of moisture on a metal surface forms the electrolyte for
atmospheric corrosion. A second example is when wet concrete is the electrolyte for reinforcing rod
corrosion in bridges. Although most corrosion takes place in water, corrosion in non-aqueous systems is not
unknown.Corrosion normally occurs at a rate determined by an equilibrium between opposing
electrochemical reactions. One reaction is the anodic reaction, in which a metal is oxidized, releasing
electrons into the metal. The other is the cathodic reaction, in which a solution species (often O2 or H+) is
reduced, removing electrons from the metal. When these two reactions are in equilibrium, the flow of
electrons from each reaction is balanced, and no net electron flow (electrical current) occurs. The two
reactions can take place on one metal or on two dissimilar metals (or metal sites) that are electrically
connected.

Figure 1 sketches this process. The vertical axis is electrical potential and the horizontal axis is the logarithm
of absolute current. The theoretical current for the anodic and cathodic reactions is represented as straight
lines. The curved line is the total current: the sum of the anodic and cathodic currents. This is the current that
you measure when you sweep the potential of the metal with your potentiostat. The sharp point in the curve
is actually the point where the current reverses polarity as the reaction changes from anodic to cathodic, or
vice versa. The sharp point is caused by plotting along a logarithmic axis. The use of a logarithmic axis is
necessary because of the wide range of current values that must be recorded during a corrosion experiment.
Because of the phenomenon of passivity, the current often change by six orders of magnitude during a
corrosion experiment.

Figure 8:Corrosion process showing anodic and cathodic components of current.

The potential of the metal is the means by which the anodic and cathodic reactions are kept in balance. Refer
to Figure 1. Notice that the current from each half reaction depends on the electrochemical potential of the
metal. Suppose that the anodic reaction releases too many electrons into the metal. Excess electrons thus
shift the potential of the metal more negative, which slows the anodic reaction and speeds up the cathodic
reaction. This counteracts the initial perturbation of the system.

The equilibrium potential assumed by the metal in the absence of electrical connections to the metal is called
the open-circuit potential, Eoc. In most electrochemical corrosion experiments, the first step is the
measurement of Eoc.

The value of either the anodic or cathodic current at Eoc is called the corrosion current, Icorr. If we could
measure Icorr, we could use it to calculate the corrosion rate of the metal. Unfortunately, Icorr cannot be
measured directly. However, it can be estimated using electrochemical techniques. In any real system,
Icorr and corrosion rate are a function of many system parameters, including type of metal, composition of the
solution, temperature, movement of the solution, metal history, and many others.

The above description of the corrosion process does not say anything about the state of the metal surface. In
practice, many metals form an oxide layer on their surface as they corrode. If the oxide layer inhibits further
corrosion, the metal is said to passivate. In some cases, local areas of the passive film break down, allowing
significant metal corrosion to occur in a small area. This phenomenon is called pitting corrosion or simply
pitting.

Because corrosion occurs via electrochemical reactions, electrochemical techniques are ideal for the study of
the corrosion processes. In electrochemical studies, a metal sample with a surface area of a few square
centimeters is used to model the metal in a corroding system. The metal sample is immersed in a solution
typical of the metal’s environment in the system being studied. Additional electrodes are immersed in the
solution, and all the electrodes are connected to a device called a potentiostat. A potentiostat allows you to
change the potential of the metal sample in a controlled manner and measure the current that flows as a
function of applied potential.

Both controlled-potential (potentiostatic) and controlled-current (galvanostatic) polarization are useful.

When the polarization is done potentiostatically, current is measured, and when it is done galvanostatically,
potential is measured. This discussion will concentrate on controlled-potential methods, which are much
more common than galvanostatic methods. With the exception of open-circuit potential versus time,
electrochemical noise, galvanic corrosion, and a few others, potentiostatic mode is used to perturb the
equilibrium corrosion process. When the potential of a metal sample in solution is forced away from Eoc, it is
referred to as polarizing the sample. The response (that is, resulting current) of the metal sample is measured
as it is polarized. The response is used to develop a model of the sample’s corrosion behavior.
5.7.1) Quantitative Corrosion Theory:
In the previous section we pointed out that Icorr cannot be measured directly. In many cases, you can estimate
it from current-versus-voltage data. You can measure a logarithmic current versus potential curve over a
range of about one half volt. The voltage scan is centered on Eoc. You then fit the measured data to a
theoretical model of the corrosion process.

The model we use for the corrosion process assumes that the rates of both the anodic and cathodic processes
are controlled by the kinetics of the electron-transfer reaction at the metal surface. This is generally the case
for corrosion reactions. An electrochemical reaction under kinetic control obeys Eq. 1, the Tafel equation.

In this equation,

I is the current resulting from the reaction

I0 is a reaction-dependent constant called the exchange current

E is the electrode potential

E0 is the equilibrium potential (constant for a given reaction)

β is the reaction’s Tafel constant (constant for a given reaction, with units of volts/decade.

Table 1: Explaining terms used in equation

The Tafel equation describes the behavior of one isolated reaction. In a corrosion system, we have two
opposing reactions: anodic and cathodic.

The Tafel equations for the anodic and cathodic reactions in a corrosion system can be combined to generate
the Butler-Volmer equation (Eq. 2).

Where
I is the measured current from the cell in ampères

Icorr is the corrosion current in ampères

E is the electrode potential

Ecorr is the corrosion potential in volts

βa is the anodic β Tafel constant in volts/decade

βc is the cathodic β Tafel constant in volts/decade

Table 2: Various symbols used in equation

What does Eq. 2 predict about the current-versus-voltage curve? At Ecorr, each exponential term equals one.
The cell current is therefore zero, as you would expect. Near Ecorr, both exponential terms contribute to the
overall current. Finally, as the potential is driven far from Ecorr by the potentiostat, one exponential term
predominates and the other term can be ignored. When this occurs, a plot of logarithmic current versus
potential becomes a straight line.

A plot of log I versus E is called a Tafel plot. The Tafel plot in Figure 1 was generated directly from the
Butler-Volmer equation. Notice the linear sections of the cell current curve.

In practice, many corrosion systems are kinetically controlled and thus obey Eq. 2. A curve of logarithmic
current versus potential that is linear on both sides of Ecorr is indicative of kinetic control for the system
being studied. However, there can be complications, such as:

 Concentration polarization, where the rate of a reaction is controlled by the rate at which reactants arrive
at the metal surface. Often cathodic reactions show concentration polarization at higher currents, when
diffusion of oxygen or hydrogen ion is not fast enough to sustain the kinetically controlled rate.
 Oxide formation, which may or may not lead to passivation. This process can alter the surface of the
sample being tested. The original surface and the altered surface may have different values for the
constants in Eq. 2.
 Other effects that alter the surface, such as preferential dissolution of one component of an alloy, can also
cause problems.
 A mixed control process where more than one cathodic, or anodic, reaction occurs simultaneously may
complicate the model. An example of mixed control is the simultaneous reduction of oxygen and
hydrogen ion.
 Finally, potential drop as a result of cell current flowing through the resistance of your cell solution
causes errors in the kinetic model. This last effect, if it is not too severe, may be correctable via IR-
compensation in the potentiostat.
In most cases, complications like those listed above cause non-linearities in the Tafel plot. Use with caution
the results derived from a Tafel plot without a well-defined linear region.

Classic Tafel analysis is performed by extrapolating the linear portions of a logarithmic current versus
potential plot back to their intersection. See Figure 2 (which is Figure 1 reprinted with annotations that
demonstrate the analysis). The value of either the anodic or the cathodic current at the intersection is Icorr.
Unfortunately, many real-world corrosion systems do not provide a sufficient linear region to permit
accurate extrapolation. Most modern corrosion test software, such as Gamry Instruments’ Corrosion
Techniques software, performs a more sophisticated numerical fit to the Butler-Volmer equation. The
measured data are fit to Eq. 2 by adjusting the values of Ecorr, Icorr, βa, and βc. The curve-fitting method has
the advantage that it does not require a fully developed linear portion of the curve.

Figure 9:Classic Tafel analysis.

5.7.2) Polarization Resistance:

Eq. 2 can be further simplified by restricting the potential to be very near to Ecorr. Close to Ecorr, the current-
versus-voltage curve approximates a straight line. The slope of this line has the units of resistance (Ω). The
slope is, therefore, called the polarization resistance, Rp. An Rp value can be combined with an estimate of
the β coefficients to yield an estimate of the corrosion current.

If we approximate the exponential terms in Eq. 2 with the first two terms of a power-series expansion ( ) and
simplify, we get one form of the Stern-Geary equation:
In a polarization resistance experiment, you record a curve of current versus voltage as the cell voltage is
swept over a small range of potential that is very near to Eoc (generally ±10 mV). A numerical fit of the
curve yields a value for the polarization resistance, Rp. Polarization resistance data do not provide any
information about the values for the β coefficients. Therefore, to use Eq. 3, you must provide β values. These
can be obtained from a Tafel plot, or estimated from your experience with the system you are testing.

5.7.3) Calculation of Corrosion Rate from Corrosion Current:

The numerical result obtained by fitting corrosion data to a model is generally the corrosion current. We are
interested in corrosion rates in the more useful units of rate of penetration, such as millimeters per year. How
is corrosion current used to generate a corrosion rate? Assume an electrolytic dissolution reaction involving
a chemical species, S:

S ® Sn+ + ne–
You can relate current flow to mass via Faraday’s Law.

Q = nFM Eq. 4

where

Q is the charge in coulombs resulting from the reaction of species S

n is the number of electrons transferred per molecule or atom of S

F is Faraday’s constant = 96 485 coulombs/mole

M is the number of moles of species S reacting

Table 3: Faraday's Law

A more useful form of Eq. 4 requires the concept of equivalent weight. The equivalent weight (EW) is the
mass of species S that will react with one Faraday of charge. For an atomic species, EW = AW/n (where AW
is the atomic weight of the species).

Recalling that M = m/AW and substituting into Eq. 4 we get:

where m is the mass of species S that has reacted.

In cases where the corrosion occurs uniformly across a metal surface, the corrosion rate can be calculated in
units of distance per year. Be careful: this calculation is only valid for uniform corrosion; it dramatically
underestimates the problem when localized corrosion occurs!

For a complex alloy that undergoes uniform dissolution, the equivalent weight is a weighted average of the
equivalent weights of the alloy components. Mole fraction, not mass fraction, is used as the weighting factor.
If the dissolution is not uniform, you may have to measure the corrosion products to calculate EW.

Conversion from a weight loss to a corrosion rate (CR) is straightforward. We need to know the density, d,
and the sample area, A. Charge is given by Q = It, where t is the time in seconds and I is a current. We can
substitute in the value of Faraday’s constant. Modifying Eq. 5,

where

Icorr The corrosion current in ampères

K A constant that defines the units for the corrosion rate

EW The equivalent weight in grams/equivalent

d Density in g/cm3

A Sample area in cm2

Table 4: Various Terms used in Corrosion Rate equation

Units for corrosion rate K Units

mm/year (mmpy) 3272 mm (A-cm-year)

milli-inches/year (mpy) 1.288 × 105 milli-inches (A-cm-year)

Table 5: Corrosion Rate Constants

5.7.4) IR Compensation

When you pass current between two electrodes in a conductive solution, there are always regions of different
potentials in the solution. Much of the overall change in potential occurs very close to the surface of the
electrodes. Here the potential gradients are largely caused by ionic concentration gradients set up near the
metal surfaces. Also, there is always a potential difference (a potential drop) caused by current flow through
the resistance in the bulk of the solution.

In an electrochemical experiment, the potential that you wish to control or measure is the potential of a metal
specimen (called the Working Electrode) versus a Reference Electrode. We are normally not interested in
the potential drops caused by solution resistances because they are negligible in typical electrolyte solutions
such as 1 M H2SO4 or 5% NaCl.

Gamry Instruments potentiostats, like all modern electrochemical instruments, are three-electrode
potentiostats. They measure and control the potential difference between a non-current-carrying Reference
Electrode and one of the two current-carrying electrodes (the Working Electrode). The potential drop near
the other current-carrying electrode (the Counter Electrode) does not matter when a three-electrode
potentiostat is used.

Careful placement of the Reference Electrode can compensate for some of the IR-drop resulting from the
cell current, I, flowing through the solution resistance, R. You can think of the Reference Electrode as
sampling the potential somewhere along the solution resistance. The closer it is to the Working Electrode,
the closer you are to measuring a potential free from IR errors. However, complete IR compensation cannot
be achieved in practice through placement of the reference electrode, because of the finite physical size of
the electrode. The portion of the cell resistance that remains after placing the Reference Electrode is called
the uncompensated resistance, Ru.

Gamry potentiostats can use current-interrupt or positive-feedback IR compensation to dynamically correct

uncompensated resistance errors. In the current-interrupt technique, the cell current is periodically turned off
for a very short time. With no current flowing through the solution resistance, its IR drop disappears
instantly. The potential drop at the electrode surface remains constant on a rapid time scale. The difference
in potential with the current flowing and without is a measure of the uncompensated IR drop.

The potentiostat makes a current-interrupt measurement immediately after it acquires each data point. The
potentiostat actually takes three potential readings: E1 before the current is turned off, and E2 and E3 while it
is off (see Figure 3). Normally, the latter two are used to extrapolate the potential difference, ∆E, back to the
exact moment when the current was interrupted. The timing of the interrupt depends on the cell current. The
interrupt time is 40 µs on the higher current ranges. On lower current ranges, the interrupt lasts longer.

Figure 10: Current-interrupt potential versus time.

In controlled potential modes, the applied potential can be dynamically corrected for the measured IR error
in one of several ways. In the simplest of these, the IR error from the previous point is applied as a
correction to the applied potential. For example, if an IR free potential of 1 V is desired, and the measured
IR error is 0.2 V, the potentiostat applies 1.2 V. The correction is always one point behind, for the IR error
from one point is applied to correct the applied potential for the next point. In addition to this normal mode,
a Gamry Instruments potentiostat offers more-complex feedback modes in which the two points on the decay
curve are averaged.

By default in the controlled potential modes, the potential error measured via current-interrupt is used to
correct the applied potential. In the controlled current modes, no correction is required. If IR compensation is
selected, the measured IR error is subtracted from the measured potential. All reported potentials are
therefore free from IR error.
5.7.5) Current and Voltage Conventions:

Current polarities in electrochemical measurements can be inconsistent. A current value of –1.2 mA can
mean different things to workers in different branches of electrochemistry or in different countries or even to
different potentiostats. To an analytical electrochemist it represents 1.2 mA of anodic current. To a corrosion
scientist it represents 1.2 mA of cathodic current. A Gamry Instruments potentiostat in default mode follows
the corrosion convention for current in which positive currents are anodic and negative currents are cathodic.
For the convenience of our users around the world, Gamry Instruments potentiostats can provide the current
polarity as per your preference with a simple software command.

The polarity of the potential can also be a source of confusion. In electrochemical corrosion measurement,
the equilibrium potential assumed by the metal in the absence of electrical connections to the metal is called
the open-circuit potential, Eoc. We use the term corrosion potential, Ecorr, for the potential in an
electrochemical experiment at which no current flows, as determined by a numerical fit of current-versus-
potential data. In an ideal case, the values for Eoc and Ecorr are identical. One reason the two voltages may
differ is that changes have occurred to the electrode surface during the scan.

With most modern potentiostats, all potentials are specified or reported as the potential of the working
electrode with respect to either the reference electrode or the open-circuit potential. The former is always
labeled as “vs. Eref” and the latter as “vs. Eoc”. The equations to convert from one form of potential to the
other are:

E vs. Eoc = (E vs. Eref) – Eoc

E vs. Eref = (E vs. Eoc) + Eoc

Regardless of whether potentials are versus Eref or versus Eoc, one sign convention is used. The more positive
a potential, the more anodic it is. More anodic potentials accelerate oxidation at the Working Electrode.
Conversely, a negative potential accelerates reduction at the Working Electrode.

5.7.6) Corrosion current:-

For this experiment you ned a power supply .It could be a battery, a single cell (1.5 volt) or one that can
control the voltage or the current it delivers .We have chosen the latest because we had one kicking around
in the Corrosion Doctors laboratory.

The adjustable potential or current direct current (DC) power supply you see here delivers a continuously
negative or positive potential depending if the electrode is conneted respectively to the black or red terminal.
 Figure 11: Corrosion current experiment
5.7.7)Theory for Aqueous Corrosion
 Reference electrode
 Cell potential
 Kinetics of corrosion reactions

5.7.7.1) Reference Electrode

The standard hydrogen electrode is too complex for routine use in laboratory and field applications.

Figure 12:Saturated Calomel Electrode

 Figure 13:Standard Hydrogen Electrode

5.7.7.2)Cell potential

Dry batteries and Daniell cell

Symbolism of a corrosion cell: Zn | Zn2+ || Cu2+ | Cu

Zn electrode on the left, immersed in Zn2+ ions; Cu electrode on the right, immersed in Cu2+ ions. Ionic
species are separated by ||. Zinc is the anode, copper is the cathode.

The two half-cell reactions are:

 Zn = Zn2+ + 2e-
 Cu2+ + 2e- = Cu

The overall reaction Zn + Cu2+ = Zn2+ + Cu

To find the theoretical cell potential, using Nernst equation for each of the half-cell reactions:

E(Zn/Zn2+)=Eo(Zn/Zn2+) – (0.059/2)lg[Zn2+], and

E(Cu2+/Cu)=Eo(Cu2+/Cu) – (0.059/2)lg{1/[Cu2+]}. So the cell potential
E(cell)=Eo(cell) – (0.059/2)lg{[Zn2+]/[Cu2+]}

Convention:

 do not use oxidation potential

 do use reduction potential

Eo(cell) = Eo(cathode) – Eo(anode) or

Eo(cell) = Eo(right) – Eo(left)

Points to note:

Current flow reduces potential

A system will always react to oppose a change imposed upon it. Le Chatelier’s principle

The cell potential can be thought of as an ability to supply current. As soon as current is drawn, the ability is
reduced.

Thermodynamic can only indicate the tendency of a system to corrode, an equilibrium situation is required
and this causes no net flow of current.

Corrosion reaction causes current to flow.

5.7.8) Corrosion kinetics: (Frankel, 2016)

Corrosion, the environmental degradation of materials, is a complex process that depends on details of the
environment and material, and is controlled by underlying thermodynamic and kinetic factors. The ultimate
goal of a corrosion engineer is to predict and control the rate of corrosion. To do so requires a thorough
understanding of the thermodynamic and kinetic fundamentals. This chapter will review the electrochemical
kinetics important to the overall corrosion process, including activation controlled kinetics, mixed potential
theory, and mass transport effects. The chapter will begin with a description of the typical anodic and
cathodic half reactions that comprise the corrosion phenomenon. This is followed by an introduction to the
most fundamental type of electrochemical kinetics, activation controlled kinetics, which are applicable in
situations where the rate is controlled by the charge transfer reaction. The Tafel equation describes many of
the reactions involved in corrosion. With the basis of simple electrochemical kinetics, it is then possible to
present mixed potential theory, which predicts corrosion potential and rate on the basis of the kinetics and
thermodynamics of all of the reactions occurring on an electrode surface. The Evans diagram, a graphical
representation of this situation, is introduced to, clarify the mixed potential condition. The rate of corrosion
is often controlled by mass transport of species to the surface from the bulk solution, and the kinetics of
mass transport are the next topic of discussion. The inhibition of corrosion, in which the kinetics of one or
more of the corrosion reactions are altered by the presence of species added to the environment, will then be
covered. Passivity, or the spontaneous formation of a thin protective surface film, can be viewed as a form of
anodic inhibition and is introduced at the end .

Faraday's Law

If the current generated by one of the anodic reactions expressed earlier was known, it would be possible to
convert this current to an equivalent mass loss or corrosion penetration rate with a very useful relation
discovered by Michael Faraday, a nineteen century pioneer in electrochemistry. Faraday's empirical laws of
electrolysis relate the current of an electrochemical reaction to the number of moles of the element being
reacted. Supposing that the charge required for such reaction was one electron per molecule, as is the case
for the plating or the corrosion attack of silver described respectively in equations:

According to Faraday’s law, the reaction with one mole of silver would require one mole of electrons, or
one Avogadro's number of electrons (6.022 x 1023). The charge carried by one mole of electrons is known as
one Faraday (F). The Faraday is related to other electrical units through the electronic charge, i.e electron
charge is 1.6 x 10-19 coulomb. Multiplying the electronic charge by the Avogadro number means that one
Faraday equals 96,485 C/(mole of electrons). Combining Faraday’s principles with specific electrochemical
reactions of known stoichiometry leads to equation:

where:

where N is the number of moles and DN the change in that amount

n is the number of electrons per molecule of the species being reacted
I is the total current in amperes (A)
t is the duration of the electrochemical process in seconds (s)
Overpotential

When two or more complementary processes such as those illustrated for zinc in air-free hydrochloric acid,
for magnesium in neutral water, or for zinc in aerated hydrochloric acid occur over a single metallic surface,
the corrosion potential that results from this situation is a compromise between the various equilibrium
potentials of all the anodic and cathodic reactions involved. The difference between the resultant potential (E)
and each individual reaction equilibrium potential (Eeq) is called polarization and quantified in terms of an
overpotential as in equation:

The polarization is said to be either anodic, when the anodic processes on the electrode are accelerated by
changing the specimen potential in the positive (noble) direction or cathodic when the cathodic processes are
accelerated by moving the potential in the negative (active) direction. There are three distinct types of
polarization and these are additive, as expressed in equation:

where:

act is the activation overpotential, a complex function describing the charge transfer kinetics of an
electrochemical reaction. act is always present and mostly dominant at small polarization currents or voltages;

conc is the concentration overpotential, a function describing the mass transport limitations associated with
electrochemical processes. conc is predominant at larger polarization currents or voltages;

iR is the ohmic drop. This function takes into account the electrolytic resistivity of an environment when the
anodic and cathodic elements of a corrosion reaction are separated by this environment while still electrically
coupled.

Activation polarization is usually the controlling factor during corrosion in strong acids. Concentration
polarization usually predominates when the concentration of the active species is low; for example, in dilute
acids or in aerated waters where the active component, dissolved oxygen, is only present at very low levels.
The ohmic drop will become an extremely important factor when studying corrosion phenomena for which
there is a clear separation of the anodic and cathodic corrosion sites, e.g. crevice corrosion. The ohmic drop
is also an important variable in the application of protective methods such as anodic and cathodic protection
that force a potential shift of the protected structure by passing a current in the environment.
Knowing the kind of polarization which is occurring can be very helpful, since it allows an assessment of the
determining characteristics of a corroding system. For example, if corrosion is controlled by concentration
polarization, then any change that increases the diffusion rate of the active species (e.g., oxygen) will also
increase the corrosion rate. In such a system, it would therefore be expected that agitating the liquid or
stirring it would tend to increase the corrosion rate of the metal. However, if a corrosion reaction is
activation controlled then stirring or agitation will have no effect on the corrosion rate.

Activation Polarization

The term activation polarization makes reference to retarding factors that are an inherent part of the kinetics
of all electrochemical reactions. For example, consider the evolution of hydrogen gas illustrated
previously for zinc in air-free hydrochloric acid:

While this reaction seems to be relatively simple, the rate at which hydrogen ions are transformed into
hydrogen gas is in reality a function of several factors, including the rate of electron transfer from a metal to
hydrogen ions. In fact, there is a wide variability in this transfer rate of electrons by various metals and, as a
result, the rate of hydrogen evolution from different metal surfaces can vary greatly.

The exchange current density (i0) is surely the single most important variable that explains the large differences
in the rate of hydrogen on metallic surfaces. Table 5.1 contains the approximate exchange current density for
the reduction of hydrogen ions on a range of materials.

Table 6:Approximate exchange current density (i0) for the hydrogen oxidation reaction on different
metals at 25oC
Note that the value for the exchange current density of hydrogen evolution on platinum is approximately 10-
2 A/cm2 whereas on mercury and lead it is 10-13 A/cm2, eleven orders of magnitude for the rate of this
particular reaction, or one hundred billion times easier on platinum than on mercury or lead!

Propose an alloy modification that would possibly disfavor the production of hydrogen at an electrode. ...
and one that would favor it.

This is the reason why mercury is often added to power cells such as the popular alkaline primary cells to
stifle the thermodynamically favored production of gaseous hydrogen and prevent unpleasant incidents. This
is also why lead acid batteries (car batteries) can provide power in a highly acidic environment in a relatively
safe manner.

However, there is no simple method to estimate the exchange current density for a specific system.. In this
experimental arrangement a potenstiostat/galvanostat power controller is used to pass current through the
sample, or working electrode (W), and an auxiliary electrode (AUX) immersed in solution while monitoring
the potential of the working electrode with a reference electrode and a Luggin capillary.

Figure 14:Electrochemical instrumentation

The following theory explains the basic mathematics that may then be used to extract exchange current density
from the results obtained. A general representation of the polarization of an electrode supporting one specific
reaction is given in the Butler-Volmer equation:

where:

ireaction is the anodic or cathodic current;

b is the charge transfer barrier (symmetry coefficient) for the anodic or cathodic reaction, usually close to
0.5
n is the number of participating electrons
R is the gas constant, i.e. 8.314 J mol-1 K-1
T is the absolute temperature (K)
F corresponds to 96,485 C/(mole of electrons)

The exchange current density is a fundamental characteristic that can be defined as the rate of oxidation or
reduction of the electrode at equilibrium expressed in terms of current. The presence of two polarization
branches in a single reaction expressed in equation is illustrated in the following Figure for the polarization
of a palladium electrode immersed in a solution containing similar concentrations of ferric (Fe3+) and ferrous
(Fe2+) ions with a completely reversible reaction :
 Figure 15:Current vs. overpotential polarization plot of the ferric/ferrous ion reaction on palladium

When reaction is cathodic, i.e. negative, the second term in the Butler-Volmer equation becomes negligible
and the cathodic current density (ic) can be expressed by a simpler equation and its logarithm:

where bc is the cathodic Tafel coefficient described in equation that can be obtained from the slope of a plot
of against log |i|, with the intercept yielding a value for i0 as shown in the following Figure.
 Figure 16: Plot of Log(i) vs Overpotential

Similarly, when reaction is anodic, i.e. positive, the first term in the Butler-Volmer equation becomes negligible
and the anodic current density (ia) can be expressed by equation and its logarithm, with baobtained by
plotting reaction vs. log |i|:

Passivity

In the Eh – pH diagrams, resistance to metallic corrosion is indicated at stability regions where either the
metal remains thermodynamically stable (immunity) or the metal surface is covered with an oxide /
hydroxide layer (passivity).
Passivity is due to the formation of thin, impermeable and adherent surface films under oxidizing conditions
often associated with anodic polarization. Only certain metals and alloys exhibit active-passive behavior,
which is essentially an acquired property.

Faraday in the 1840’s showed that iron reacted rapidly in dilute nitric acid, but was visibly unattacked in
concentrated (fuming) HNO3. An invisible surface oxide film formed in concentrated acid was found to be
unstable in dilute acid and through scratching, the surface oxide could be removed.

Definitions of passivity as proposed by Uhlig are given below:

1. A metal active in the EMF series or an alloy composed of such metals is considered passive when
its electrochemical behavior becomes that of an appreciably less active or noble metal.
2. A metal or alloy is passive if it substantially resists corrosion in an environment where
thermodynamically there is a large free energy change associated with its passage from the
metallic state to appropriate corrosion products.

Examples for definition 1 are Cr, Ni, Ti, Zr and stainless steels.
Examples for definition 2 are lead in sulfuric acid, magnesium in water and iron in inhibited pickling acid.

Two types of passivity thus exist.

a) A metal is passive if it resists corrosion under anodic polarization (noble potential, low corrosion
rate).
b) A metal is passive if it resists corrosion in spite of thermodynamic amenability to react (active
potential, low corrosion rate).

The Eh – pH diagram for the Fe – H2O – O2 system can be superimposed on that for chromium to understand
the role of chromium as an alloying addition in steel for enhanced corrosion resistance (Fig. 20.1).
Chromium forms very stable, thin and resistant surface films in less oxidizing conditions. Chromium
addition is the basis for stainless steels and other corrosion resistant alloys.
 Figure 17:pH diagram for iron superimposed on the chromium diagram (enhanced passivity
range due to stable
Since chromium is capable of forming a very stable oxide at much lower potentials, alloying with chromium
(minimum 12%) leads to development of corrosion resistant stainless steels and cast irons. Other metals that
can form passive surface films include aluminium, silicon, titanium, tantalum and niobium.

Figure 18: Potentiostatic Anodic polarization curve

Epp – Primary passive potential, above which passive film becomes stable. icrit= Critical passivating
anodic current density, at which passivity is induced. ipass – Passive current density.

On increasing the potential beyond the passive region, the passive film breaks down and anodic corrosion
current further increases in the transpassive state. Oxygen evolution at the anode occurs at higher potentials.

Based on the above, it is possible to establish

 a) Passive potential region.
b) Passive corrosion rate and
c) Necessary conditions to achieve and maintain passivity.

Decay of passivity on interruption of anodic current is characterized by Flade potential.

If the potential as a function of time is monitored after interrupting the applied current, the potential value
first changes to a value more noble on the hydrogen scale, then slowly changes and finally rapidly decays
towards the normal active value. The noble potential reached just before rapid decay was found by Flade to
be more noble, the more acid the solution in which passivity decayed .

Figure 19:Decay of passivity showing Flade potential

Tafel Plot:

Armed with the new Arrhenius expression and the generalised reaction:

M ⇌ Mz+ + ze,
Where M is a metal that forms Mz+ ions in solution, we can now derive an equation describing corrosion
kinetics.
Consider the rate of the anodic (oxidation, corrosion) reaction, ka
ka=k′aexp(−ΔG0RT)

Since the reaction involves the release of electrons, its progress can be expressed as a current
density, i (current per unit area).
The exchange current density, i0 is defined as the current flowing in both directions per unit area when an
electrode reaction is at equilibrium (and, hence, at its equilibrium potential).
If i0 is small, then little current flows and the reactions at dynamic equilibrium are generally slow. Likewise,
a high i0gives a fast reaction. The metal itself affects the value of i0, even if the reaction does not involve the
metal directly.
I0=zFka=zFk′aexp(−ΔG/RT)

If overpotential is applied, the activation energy is changed, as described on the previous page:

ia=i0exp(αzFηRT)

This is one form of the Tafel equation.

The Tafel equation can also be written in several equivalent ways.
The quantity 2.303RTαzF is given the symbol ba and is known as the anodic Tafel slope. It has units of volts
per decade of current.
Similarly, if the cathodic reaction were to be considered, the quantity would be −2.303RT(1−α)zF since
(1 − α) is applicable instead of α and E - Ee is negative. This quantity is the cathodic Tafel slope, bc. .
The usual form of Tafel’s equation is η = a + ba log ia where a=−2.303RTαzFlogi0
Through consideration of the reaction as both a chemical and electrical process and manipulation of algebra,
we have found that the applied potential is proportional to the log of the resulting corrosion current.

However, it is recognised the importance of an accurate (non-destructive on-site) identification of the zones
suffering corrosion, in order to make calculations of the residual life based in the loss of reinforcement cross
section.The only electrochemical technique with quantitative ability regarding the corrosion rate
measurement in reinforcement is the so called Polarization Resistance, Rp (1). This technique has been
extensively used in the laboratory. It is based on the application of a small electrical perturbation to the metal
by means of a counter and a reference electrode. Providing the electrical signal is uniformly distributed
throughout the reinforcement, the E/I ratio defines Rp. The corrosion current, Icorr, is inversely proportional
to Rp, Icorr= B/Rp where B is a constant. Rp can be measured by means of D.C. or A.C. techniques (2), both
of which have specific features in order to obtain a reliable corrosion current value in agreement with
gravimetric losses.

On site measurements: Modulated confinement of the current (guard ring) method.

Direct estimation of true Rp values from E/I measurements is usually unfeasible in large real concrete
structures. This is because the applied electric signal tends to vanish with distance from the counter
electrode, CE rather than spread uniformly across the working electrode, WE. Therefore, the polarization by
the electric signal is not uniform, and it reaches a certain distance that is named the critical length, Lcrit.

Hence, E/ I measurements on large structures using a small counter electrode provides an Apparent
polarization resistance (Rpapp) that differs from the True Rp value depending on the experimental conditions
(3). Thus, if the metal is actively corroding, the current applied from a small CE located on the concrete
surface is 'drained' very efficiently by the rebars and it tends to confine itself on a small surface. Conversely,
if the metal is passive and Rp is high, the current applied tends to spread far away (e.g., around 50 cm) from
the application point. Therefore, the Apparent Rp approaches the True Rp for actively corroding
reinforcement. But when the steel is passive, the large distance reached by the current necessitates a
quantitative treatment.

There are several ways of accounting for a True Rp value, among which the most extended one is the use of
a guard ring (3), in order to confine the current in a particular rebar area, as Figure 1 depicts. The
measurement is made by applying a galvanostatic step, lasting 30-100 seconds, from the central counter.
Then, another counter current is applied from the external ring, and this external current is modulated by
means of the two reference electrodes called "ring controllers" in order to equilibrate internal and external
currents, which enables a correct confinement, and therefore, calculation of Rp. By means of this electrical
delimitation to a small zone of the polarized area, any localised spot or pit can be first, localised, and second
its measurement can be made by minimising the inherent error of Rp.

However, not all guarded techniques are efficient. Only that using a "Modulated Confinement" controlled by
two small sensors for the guard ring control placed between the central auxiliary electrode and the ring,
shown in Figure 1, is able to efficiently confine the current within a predetermined area. The use of guard
rings without this control leads into too high values of the Icorr for moderate and low values, and the error
introduced in the case of very localized pits, is very high.
 Figure 20: Corrosion rate measurement
with the modulated confinement of the
current method.

There are on the market several devices reporting to measure in large structures the corrosion rate, Icorr (4-5),
however those not using a modulated confinement only can give more or less accurate Icorr values when the
reinforcement is actively corroding (6). Without modulated confinement the Icorr values result too high, >
0.1 A/cm2 in passive state.

Rilem TC-154 has prepared a Recommendation (6) for the measurement of Rp on-site. There it is suggested
to use slabs of a certain size for checking the reliability of available devices. In present paper results are
given on such suggested calibration for the device Gecor 06 using modulated confinement.
6) EXPERIMENT (Abhijit Mukherjee & Sandeep Sharma, 9-12 December 2014)

6.1)ABSTRACT
Reinforced concrete (RC) structures affected by corrosion of steel bars are often repaired and rehabilitated
by wrapping fibre reinforced polymer (FRP) sheets. Most commonly available FRP materials are glass and
carbon fibre composites. This paper uses ultrasonic guided waves as a non-destructive tool to monitor the
initiation and progression of corrosion in reinforcing bars in concrete after repairing with bonded FRP
sheets. Concrete cylinders embedded with reinforcing bars are subjected to accelerated impressed current
corrosion in chloride environment. After specific days of exposure to corrosive environment the
cylinders are repaired by wrapping with GFRP and CFRP sheets. Anodic current was further continued
for specified times. Specific core and surface seeking guided wave modes were used to ultrasonically
measure the resistance offered by FRP wraps to corrosion.

6.2) INTRODUCTION

Inspection, diagnosis and prognosis of damage in infrastructural installations are fundamental for
theirsatisfactory operation. Visual inspection, although important, is often ineffective due to
elusivedeteriorations deep inside the structures. Although many non-destructive evaluation (NDE)
techniquesare available for investigating the insides of a solid, large size of the Infrastructural installations
makesuse of these techniques unrealistic. For discovering deep hidden structural degradations in
engineeringinstallations, ultrasonic waves offer a potentially effective solution. But the use of ultrasonic
bulkwaves is limited due to high attenuation and inability to quickly scan large domains. For
applicationsinvolving large area inspection in a quick way, guided waves have been suggested by
variousresearchers as an effective and viable tool especially in discovering hidden anomalies. and hence may
quickly provide global information. Corrosion has been recognized as the majorinfrastructural problem
affecting the service life of expensive structures. In this work, suitability ofultrasonic guided waves for
corrosion monitoring in reinforcing bars embedded in concrete andsubmerged plates is investigated. Suitable
ultrasonic guided wave modes have been identified forpicking up delamination and pitting effect of chloride
induced corrosion in reinforcing bars in concrete.similar technique is demonstrated for submerged plated
structures. The main contribution of this investigation is identification of specific mode structures for
discerning different types of damages.
6.3) Corrosion in RC structures and monitoring by guided waves
Concrete is alkaline with pH usually in the range of 11–13 and due to this high alkalinity of the concrete
pore water, the steel reinforcement is protected by an iron oxide film (Fe2O3). In the presence of oxygen,
water, and aggressive ions such as chlorides, the protective film is damaged and as a result, corrosion starts.
Chloride induced corrosion in RC structures is very predominant due to the excessive use of deicing
chemicals in countries, sea water in construction, admixtures like accelerators, water reducers and setting
chemicals. Corrosion results in the formation of rust products having corresponding volume 6–10 times the
original volume of steel. An outward pressure is generated on the surrounding concrete and as concrete is
weak in tension, it results in the formation of cracks and spalling of concrete cover. Another effect of
corrosion is the alteration in the steel–concrete interface in the form of debonding and delamination of the
bar from the embedding concrete. A distinguishing feature of chloride induced corrosion is local degradation
of the rebars wherepits or crevices are formed. Thus, in addition to debonding or delamination chloride
corrosion also weakens the bar locally. These two phenomena affect wave propagation through the
reinforcing bar differently. Researchers have reported various studies on different aspects of corrosion
detection through experimental and analytical investigations using ultrasonic guided waves. Wave energy in
steel bars embedded in concrete attenuates due to material absorption, impurities, and leakage into the
surrounding concrete. Modes that have attenuation minima with minimal energy loss have been reported for
bars in cement grout [36,37], grouted tendons [38,39], rock bolts [39] and buried pipelines [40]. Advent of
Disperse software [41,42] has greatly facilitated the identification of the desired modes. For corrosion
monitoring, one encounters the problem of making the reinforcement corrode at a fast rate. Thus, simulation
of corrosion of rebars has been attempted by researchers. It has been simulated in various ways such as by
introducing delamination between steel and concrete by using Poly-Vinyl Chloride (PVC) sleeves or by
wrapping a soft tape on the bars [43,44]. Debonding impedes the leakage of waves into the surrounding
concrete and causes increase in the signal strength at the receiving end. It indicates increasing corrosion by
loss of bond between steel and concrete. Both low and high frequency guided wave modes to monitor
corrosion damage in reinforced mortar specimens have been attempted [44,45]. Corrosion has been
simulated by artificially incorporating debonds and notches and has been compared with actually corroded
specimens successfully [32]. For reinforcing bars embedded in concrete in RC structures, the waves
propagate in longitudinal, flexural and torsional modes due to the complex effect of the boundaries. Either of
these modes can be excited selectively by choosing a particular frequency. The different modes can be
obtained by using software Disperse [42]. The reinforcing bar is modelled as a solid steel cylinder embedded
in infinite expanse of concrete. Longitudinal waveforms have axial and radial displacements, torsional
waveforms have angular displacements and flexural waveforms have all three displacements. They are
represented by L(m,n), T(m,n), and F(m,n), respectively where ‘m’ and ‘n’ represent the circumferential
displacements and sequential order of mode, respectively. Concrete around the bar allows the energy to leak
from the bar to its surrounding. The amount of leakage experienced by the wave depends on the elastic and
damping properties of the concrete layer relative to that of the bar. Hence, steel–concrete interface can be
investigated by ultrasonic wave guides. Longitudinal guided wave modes experience minimum attenuation
and are easiest to excite and hence are preferred modes. They can be easily produced by placing the
compressional transducers along the two ends of the bar by means of a holder assembly and hence are
considered in this investigation. Different longitudinal modes can be produced by varying the excitation
frequencies. The most preferred longitudinal modes in steel embedded concrete are the ones with lowest
attenuation at low frequency. In this experimental study, 25 mm bar in concrete is used and fundamental
L(0, 1) mode at low frequency of 100 kHz is chosen for ultrasonic investigations. Another high frequency
mode L(0,7) at 1 MHz with displacement profile centred in the middle of the bar which is found efficient for
layered systems is chosen [37,45]. This mode experiences low attenuation and energy velocity maxima at
1 MHz. These frequencies were experimentally validated by confirming the signal fidelity. Transducers with
longer waveform duration and a relatively narrow frequency bandwidth with centre frequency of 0.1 MHz
and 1 MHz were hence, used for further experimental investigations. Another important feature for the
selection of modes was the radial distribution of displacement and energy density of the mode
shape. It has been observed in previous studies is a surface sensitive mode which is sensitive to surface
modifications in the reinforcing bars due to corrosion and picks up the initial delamination of the reinforcing
bar from the surrounding concrete. Similarly, L(0, 7) mode is a core sensitive mode which could pick up
another major effect of chloride corrosion, pitting in the bar. This mode progresses mainly through the core
of the bar and has negligible surface component and is sensitive to local degradations such as pitting or
crevice corrosion in the reinforcing bars. The authors demonstrated that these surface and core sensitive
ultrasonic guided wave modes successfully identify and monitors chloride induced corrosion in a bar
embedded in concrete. In general, pitting and non-uniform area loss highlighted by severe signal attenuation
marks chloride corrosion and is unravelled by the core seeking mode whereas the surface sensitive mode
deciphers surface debonding of the reinforcing bar from the surrounding concrete through the rise in signal
voltage. This led to a pilot study to ultrasonically monitor corrosion of reinforcing bars undergoing
accelerated corrosion in the presence and absence of chlorides [32]. It was concluded that manifestation of
corrosion in the two environments is considerably different. While chloride corrosion leads to predominant
pitting, absence of chlorides is manifested by predominant debonding. These two modes were also
successfully used to distinguish between corrosion mechanisms in two environments of oxides and
chlorides.
6.4) Experimental investigations and testing methodology

6.4.1) Specimen details

Standard concrete cylindrical specimens of 300 mm height and150 mm diameter of M20 grade with a
reinforcing bar of 25 mm nominal diameter at the middle of the cross-section were cast. Ordinary Portland
cement with nominal strength of 43 MPa, fine aggregate (river sand) and crushed stone aggregates with
maximum size of 20 mm were used for making concrete. Ratio of cement, sand and coarse aggregate was
kept as 1: 2.1: 2.4 with a water cement ratio of 0.45. The reinforcing bar of 600 mm total length and
embedded length of 300 mm of Fe 250 grade was used. Before casting of specimens, the bar was sand
blasted to remove any irregularities and immediately dipped in oil. Fig. 1a shows the two locations where a
Teflon tape was wound around the bar. These tapes served as bond breakers. The bar was placed in such a
way that the cover from the bottom face was 40 mm. Before the casting of specimens, each reinforcing bar
was weighed to an accuracy of 0.1 g. The protruded part of the steel bar was coated with liquid epoxy resin
for corrosion protection. The samples were cured for 28 days and the average compressive strength of the
concrete was 38 MPa.

6.4.2) Inducing corrosion in reinforcing bars in concrete

In natural environments, corrosion process takes several years to occur. With the objective of simulating the
corrosion damaged concrete, it was accelerated in the RC cylindrical specimens. There are many available
techniques in literature for inducing accelerated corrosion, most common being salt mist, chloride diffusion,
alternate drying and wetting in salt water and impressing anodic current. However, the quickest method of
inducing corrosion is impressed anodic current technique. This method was adopted in this study. RC
specimens are immersed in 3.5% NaCl solution for 24 h to ensure full saturation maintaining the level of the
solution 3 cm below the top surface to alleviate corrosion of the exposed steel bar beyond the concrete
cylinder. A direct current is passed making the reinforcement bar as an anode and stainless steel wire mesh
wrapped around the cylinders as cathode. A DC regulated constant current source with rating of 64 V and
500 mA was used as the power supply. The positive and negative terminals of the power supply were
connected to the projected bar in the cylinder and the wire mesh to serve as anode and cathode respectively.
Before impressing current the specimens along with the cathode were kept immersed in the 3.5% sodium
chloride (NaCl) solution for 24 h to ensure full saturation. A total of 12 cylindrical specimens were cast and
a constant current was impressed for 3, 6 and 9 days in four different groups each containing three samples .
Every day the anode to cathode voltage corresponding to constant current of 200 mA was monitored. Using
this method the concrete cylinders developed cracks within 2 days of accelerated corrosion. There were red
and brown stains of rust on concrete cylinders. The crack widths were measured after 3, 6 and 9 days. The
cracks initiated at the surface of the reinforcement and ran along the direction of the reinforcement on the
sides of the cylinder (Fig. 1b). Voltage between the reinforcing steel anode and SS mesh cathode decreased
with time indicating that the resistancehas gone down with the progression of the crack.

Figure 21: Steel bar embedded in Concrete

Figure 22: Cracks

6.4.3) Corrosion monitoring using ultrasonic guided waves

The ultrasonic system for the pulse transmission testing mode has been explained in [31–35]. A brief
discussion of the pulse echomode is included here. A standard ultrasonic pulser/receiver system (Karl
Deutsch Make DPR 300) consisting of a contact transducer of selected frequencies and display devices was
used. Driven by the pulser, the compression transducer generates an ultrasonic pulse that travels through the
embedded bar in the form of longitudinal guided waves. The pulse reflected from the interface of bar and
beam is referred as the Interface Echo (IE) and that reflected from the end of the bar is referred as Bar End
Echo (BE). The echoes are received at the same end of the bar where the initial pulse was generated. This is
called the pulse echo (PE) method of testing (Fig. 2). In this study, contact transducers of Karl Deutsch
Make having a longer wave form duration and a relatively narrow frequency bandwidth with central
frequency of 0.1 and 1 MHz were used.

6.5) Results and Discussion

6.5.1) Ultrasonic investigation of control samples

Ultrasonic guided waves have been used to monitor progression of corrosion in control RC cylinders by
using surface seeking mode of L(0, 1) at 0.1 MHz and core seeking mode of L(0,7) at 1.0 MHz in PE mode
till the BE signals vanished in 30 days. The embedded reinforcements in concrete were excited at one end.
The bar acts as a waveguide that assists its propagation. A part of the waves is first reflected back from the
point where the bar enters concrete (bar–concrete interface) and appears as Interface Echo (IE). The rest
travels through the bar and leak into the surrounding concrete and thus attenuate before reflecting from the
back end of the bar (BE). The region between IE and BE is of our interest. For IE the travel distance is 600
mm and for BE it is 1200 mm. The time interval between IE and BE for different modes can be determined
from the corresponding group velocities. However, the time of arrival of the pulses alters due to mode
conversion. Moreover, the signal obtained is the result of interaction of several modes. Thus, in this
investigation, the largest peak obtained within ±30 ls of the computed time of arrival has been considered as
the corresponding peak.

Surface sensitive mode L(0, 1) at 0.1 MHz

The PE voltage signals obtained using 0.1 MHz frequency and L(0,1) mode is shown in Fig. 4. It can be
noted that the signals have similar characteristics for all the control samples. The largest reflection is
obtained right at the transducer face (referred to as initial pulse). This is from the near end of the bar from
where the bar is excited. A sharp IE signal is obtained from the steel–concrete interface at around 150 ls.
Another significant peak from BE is obtained at around 250 ls which is the reflection from the embedded
end of the bar in concrete. These two IE and BE peaks are studied further with increasing corrosion
exposure. It is observed that the variations in voltage amplitude signals increase substantially with corrosion
exposure. The normalisation is done as explained in [31–35]. It can be seen that the voltage amplitude of the
reflected signals from the interface and BE increase with the progression of corrosion. But the rate of
increase in the BE signal is rapid and drastic in comparison to IE. It is due to the fact that IE travels through
the bar in air, not in concrete, which is not subjected to corrosion. On the other hand, BE is received after the
pulse has travelled the length of the bar twice. Hence, the BE only has been used for further ultrasonic
investigations. Using L(0,1) mode it is observed that there is rise in BE initially up to 21 days. It is due to the
fact that the reinforcing bar has initially a good bond with the surrounding concrete. As the corrosion
progresses, it results in the formation of corrosion products which get deposited on the bar. This delaminates
the rebar from the surrounding concrete. Therefore, as the corrosion progresses, the delamination keeps on
increasing which creates a barrier around the rebar and the leakage of the signal into the surrounding
concrete reduces causing rise of the received BE signals. This is depicted by the rise in the peak until 21
days. It is due to surface seeking nature of the L(0, 1) mode which is sensitive to the surface modifications of
the rebar. Beyond 21 days the peaks begin to attenuate. With advancing corrosion the pitting of the bar starts
causing deep voids in the bar.

Core sensitive mode L(0, 7) at 1 MHz

In this case the BE is far more prominent than IE. As this mode travels through the core of the bar it is
insensitive to the interface. Thus, relatively more energy gets reflected from the end of the bar causing
increase in BE. In this case too, IE is weaker in comparison to BE. Hence BE is selected for further
ultrasonic investigations. But as corrosion progressesthe signal starts attenuating until it no longer
appreciable in 30 days. This depicts that initially corrosion starts at the surface of the bar. Thus, the core
seeking mode remains largely unaffected while the surface seeking mode responds to this change .From 13
to 20 days, surface seeking mode signal strength continues to rise and core seeking mode signal drops and
this is referred to as Transition zone when the corrosion has started making inroads into the rebar with
continued delamination. Further, as the chloride induced corrosion progresses, it starts penetrating into the
bar and is marked by the local loss of area in the form of pitting. The growth of the pits inside the bar
attenuates BE of the core seeking mode as well. This phenomenon has been confirmed by digging the bars
out after different days of exposure. Clear formation of pits was noticed after about 20 days. Thus, days 20–
30 is referred to as Pitting Zone.
This experiment demonstrates that effective combination of two guided wave modes in PE using BE can
pick up the mechanism and progression of corrosion due to chlorides. Further, the study illustrates the
effectiveness of the specific guided wave modes for monitoring corrosion. It is also observed that the trend
in the signals remains unaffected by either GFRP or CFRP. Thus, it can be concluded that the corrosion
mechanisms in the control and the wrapped specimens is the same. The effect of wrapping on the rate of
corrosion is reported next.

6.6) IMPACT

This presents a non-destructive monitoring tool to investigatethe rate of reinforcement corrosion in glass
and carbon fibre wrapped concrete cylinders that have embedded corroding reinforcements utilising
ultrasonic guided waves. The specimens were subjected to accelerated anodic current corrosion at constant
current. Before wrapping the specimens, all the samples exhibited similar rate of corrosion and first crack
appeared in two days in all samples. The cell voltages required for maintaining a constant anodic current was
also monitored as a metric for corrosion rate. It is observed that wrapping the concrete cylinders with FRP
dramatically increases the cell voltages by about 300% indicating increased resistance to corrosion.
7) CONCLUSION

Almost 2.5% of GDP is lost due to corrosion of steel and deterioration of steel structures in India. Due to
lack of knowledge amongst proffesionals on corrosion and its protection, India as a country is lagging
behind compared to other developed countries. In addition to economic losses, it can also be life threatening
if not monitored and checked properly.So we as engineers need to use the various monitoring techniques
available to audit the exisisting structures and accordingly renew the damaged structures. However this
becomes sometimes costly so there are various prevention techniques available which if explored can keep a
check on corrosion. Hence at that point of time corrosion monitoring becomes an essential requirement.
Though some of the techniques are expensive if used properly can have a certain impact on a country’s
better GDP. By this report we want more people to be aware of this techniques and use them wisely to have
a better corrosion free world.
Bibliography
A.Bentur,S.Diamond and N.S.Berke. (1997). Steel corrosion in concrete:fundamnetals and civil engineering
practices. London: E& FN Spon.

A.K.Natrajan, P. (n.d.). NPTEL Web course. IISC Banglore .

Abhijit Mukherjee & Sandeep Sharma. (9-12 December 2014). Corrosion Monitoring in Infrastructure using
Ultrasonic Wave Propogation. Mechanics of Structure and Materials(ACMSM23) (p. 7). Byron
Bay,Australia: S.T.Smith.

Albama Speciality Products,Inc. (n.d.). Introduction to Corrosion Monitoring. Retrieved from Metal
Samples: http://www.alspi.com/introduction.htm

Corrosion. (n.d.). Retrieved from Wikipedia: http://www.wikipedia.com

Frankel, G. (2016). Fundamentals of Corrosion Kinetics. Fontana Corrosion Centre .

IQnection Digital Marketing. (n.d.). Getting Started with Electrochemical Corrosion Measuements.
Retrieved from Gamry Instruments: http://www.gampry.com/application-notes/corrosion-coatings/basics-of-
electrochemical-corrosion-measurements/

M.Saremi and E.Mahallati. Cem.Concre.Int.J.Electrochem.Sci.,Vol.2.