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 European Federation of Corrosion Publications
NUMBER 56

Corrosion monitoring in
nuclear systems: research
and applications

Edited by
Stefan Ritter & Anders Molander

Published for the European Federation of Corrosion

by Maney Publishing
on behalf of
The Institute of Materials, Minerals & Mining
Published by Maney Publishing on behalf of the European Federation of Corrosion
and The Institute of Materials, Minerals & Mining

Maney Publishing is the trading name of W.S. Maney & Son Ltd.

Maney Publishing, Suite 1C, Joseph’s Well, Hanover Walk, Leeds LS3 1AB, UK

First published 2010 by Maney Publishing

© 2010, European Federation of Corrosion

The author has asserted his moral rights.

This book contains information obtained from authentic and highly regarded
sources. Reprinted material is quoted with permission, and sources are indicated.
Reasonable efforts have been made to publish reliable data and information, but the
editors, authors and the publishers cannot assume responsibility for the validity of all
materials. Neither the editors, authors nor the publishers, nor anyone else associated
with this publication, shall be liable for any loss, damage or liability directly or
indirectly caused or alleged to be caused by this book.

Neither this book nor any part may be reproduced or transmitted in any form or
by any means, electronic or mechanical, including photocopying, microfilming and
recording, or by any information storage or retrieval system, without permission in
writing from Maney Publishing.

The consent of Maney Publishing does not extend to copying for general distribution,
for promotion, for creating new works, or for resale. Specific permission must be
obtained in writing from Maney Publishing for such copying.

Trademark notice: Product or corporate names may be trademarks or registered

trademarks, and are used only for identification and explanation, without intent to
infringe.

Maney Publishing ISBN-13: 978-1-906540-98-2 (book)

Maney Publishing stock code: B812
ISSN 1354-5116

Typeset and printed by the Charlesworth Group, Wakefield, UK.

Cover photo by Yaw-Ming Chen, MCL/ITRI, Taiwan (from Chapter 12: pipe-
thinning monitor; potential drop measurements on a carbon steel elbow pipe).
 Contents

Series introduction vii

Volumes in the EFC series ix
Preface xiv

Section 1: Introduction
1. Corrosion monitoring – what’s the point?
Bob Cottis 1

Section 2: Research on Corrosion Monitoring for Nuclear Systems

2. Introduction to different electrochemical corrosion
monitoring techniques
Rik-Wouter Bosch & Walter F. Bogaerts 5

3. Electrochemical noise generated during stress corrosion

cracking in high-temperature water and its relationship to
repassivation kinetics
Rik-Wouter Bosch, Marc Vankeerberghen, Serguei Gavrilov
& Steven Van Dyck 32

4. Detection of stress corrosion cracking in a simulated BWR

environment by combined electrochemical potential noise and
direct current potential drop measurements
Stefan Ritter & Hans-Peter Seifert 46

5. Electrochemical noise measurements of stainless steel in

high-temperature water
Carlos R. Arganis-Juarez, José M. Malo & J. Uruchurtu 63

6. Stochastic approach to electrochemical noise analysis of SCC

of Alloy 600 SG tube in caustic environments at high temperature
Sung-Woo Kim, Hong-Pyo Kim, Seong-Sik Hwang, Dong-Jin Kim,
Joung-Soo Kim, Yun-Soo Lim, Sung-Soo Kim & Man-Kyo Jung 81

7. In-situ electrochemical impedance and noise measurements of

corroding stainless steel in high-temperature water
Jan Macák, Petr Sajdl, Pavel Kuch era, Radek Novotný & Jan Vošta 96

8. Monitoring of stress corrosion cracking of sensitised 304H

stainless steel by electrochemical methods and acoustic emission
Wenzhong Zhang, Lucia Dunbar & David Tice 120

v
vi Contents

9. Corrosion monitoring of carbon steel in pasty clayey mixture

as a function of temperature
Christian Bataillon, Frantz A. Martin & Marc Roy 143

Section 3: Corrosion Monitoring Applications in Nuclear Power Plants

(Light Water Reactors)
10. Corrosion monitoring applications in nuclear power
plants – a review
Shunsuke Uchida 158

11. In-core corrosion monitoring in the Halden test reactor

Peter Bennett & Torill Karlsen 171

12. Corrosion monitoring applications in Taiwan’s nuclear

power plants
Hsuan-Chin Lai, Wei-Yun Mao & Charles Fang Chu 194

13. A new technique for in-plant high mass transfer rate

ECP monitoring
Anders Molander & Mats Ullberg 211

14. Precipitation and transformation of iron species in the

presence of oxygen and hydrazine in a simulated stainless steel
feed water system
Jerzy A. Sawicki, Anders Molander & Agnès Stutzmann 221

15. An electrochemical sensor array for in-situ measurements of

hydrogen peroxide concentration in high-temperature water
Shunsuke Uchida, Tomonori Satoh, Yoshiyuki Satoh & Yoichi Wada 239

Index 255
 Preface

Even though the plant availability of nuclear power plants has increased and radia-
tion build-up has been effectively mitigated, corrosion continues to influence plant
performance and availability. Recent examples are stress corrosion cracking (SCC)
attacks on type 316L stainless steel in boiling water reactors (BWRs), attacks on
nickel-base alloys in pressurised water reactors (PWRs) and irradiation-assisted SCC
incidents in both types of reactor. Therefore, reliable prediction of the corrosion
behaviour of given materials is considered important for the future operation of exist-
ing plants, which are commonly subject to life-time extension and power uprating. In
addition, managing corrosion problems in future nuclear waste disposal systems is
another task where reliable corrosion monitoring techniques could help to further
increase safety. Tremendous effort has been spent during the years to mitigate corro-
sion and improve the water chemistry of nuclear power reactors. However, actual
in-plant corrosion monitoring has been performed or developed for only a very
limited number of applications. Therefore a workshop was arranged by Working
Party 4 (‘Nuclear Corrosion’) of the European Federation of Corrosion (EFC) and
the European Cooperative Group on Corrosion Monitoring of Nuclear Materials
(ECG-COMON, www.ecg-comon.org) during EUROCORR 2007, which aimed to
highlight such work and identify monitoring techniques with potential for future
application. Contributions were invited covering research on or the application of
corrosion monitoring techniques (e.g., electrochemical noise, direct and alternate
current potential drop, acoustic emission, electrochemical impedance spectroscopy,
monitoring corrosion potentials, activity monitoring, etc.) for all types of fission
reactors (including the secondary side) and nuclear waste disposal systems. Some of
the responses obtained, including additional contributions, are presented here. The
book is divided into two main parts: ‘Research on corrosion monitoring for nuclear
systems’ and ‘Corrosion monitoring applications in nuclear power plants (light water
reactors)’.
The first part deals mainly with detection of SCC initiation in nuclear power plant
environments – essentially high-temperature water at around 300°C. Research work
on SCC for nuclear applications has, in the past decades, focused more on crack
growth. A reliable well-known technique, the potential drop technique, is used for
crack growth measurements and very low growth rates can be accurately monitored.
A large database has been created for various low-alloy reactor pressure vessel steels,
stainless steels and nickel-base alloys in BWR and PWR environments. The effects of
water chemistry have been studied, including the presence of various impurities and
additives, as well as the effects of material properties, such as the presence of cold
work. It was generally found that all materials can suffer from cracking in tests with
pre-cracked specimens and where initiation of SCC was enhanced by dynamic load-
ing conditions. Through such tests, the available knowledge of SCC conditions has
been significantly improved. However, there are also examples of laboratory cracking
xiv
 Preface xv

of materials known to be very resistant in plants and the observed crack growth
rates were occasionally significantly higher than expected from plant experience.
Such contradictions and differences might be one reason for the increased interest in
initiation studies and initiation data. Unfortunately, for initiation tests, there are no
verified methods analogous to the potential drop technique for crack growth investi-
gations. Initiation tests are often performed using passively loaded specimens such
as U-bends or C-rings, which are exposed to simulated plant environments and peri-
odically inspected for cracks, or small specimens are used, where a complete failure
of the specimen indicates SCC initiation. The test time can be significant – periods of
years for highly resistant materials – and some materials do not crack at all in the
common types of initiation tests. Material (including stress) and environmental con-
ditions must be adjusted more aggressively to obtain cracking within a reasonable
time and a proper experimental set-up with an in-situ SCC initiation monitoring
technique is necessary for future initiation investigations. The formation of the ECG-
COMON is an attempt to improve and develop methods for initiation studies by
gathering a critical mass of international experts in this field. Various methods, but
especially the electrochemical noise technique, are being investigated in this group
as promising methods to detect the early stages of SCC initiation (or other types of
localised corrosion). The chapters in this section demonstrate the state-of-the-art in
this area of research. Very promising results are being obtained but some limitations
of the monitoring methods are also becoming obvious. But it is also shown that
further work is needed before, for example, electrochemical noise can be established
as a reliable monitoring technique for SCC initiation in high-temperature water
environments. Electrochemical techniques have also been tested in other nuclear sys-
tems, e.g. nuclear waste storage systems of which one important example is presented
in this book.
In the second part of the book, work with the goal of developing in-situ techniques
and some application examples of monitoring methods are presented. The contribu-
tions in this book emphasise the importance of corrosion monitoring to limit corro-
sion in power plants and other nuclear applications. The improvement of existing
techniques and the progress of new developments are pointed out. Electrochemical
noise measurements have not been applied for real in-plant measurements so far and
it will take time before the technique is sufficiently developed for such applications.
However, there are other techniques which have already been employed in plants for
many years. These techniques are usually less informative than, for example, noise
measurements could be, but are still extremely valuable. The most commonly used
technique is monitoring of corrosion potentials (often called ECP). The measurement
of ECP is one of the very few techniques that can be applied directly within the system
studied. In this way, sampling, which can be very difficult or even impossible at high
temperature and pressure, can be avoided.
To further improve corrosion monitoring techniques and to limit corrosion and
activity build-up is a future challenge for both researchers and plant chemists. Con-
sidering the present nuclear revival and the increased public confidence in nuclear
power in several countries, monitoring techniques, together with optimised materials
behaviour and water chemistry conditions, will be particularly important in main-
taining stable operating conditions in power plants and safe long-term storage
conditions for radioactive waste.
We hope this book will prove useful for scientists and engineers in future corrosion
mitigation work. Finally, we would like to thank all of the contributors to the
xvi Corrosion monitoring in nuclear systems

workshop and to this book as well as the reviewers. We also appreciate the support
from EFC Working Party 4 and ECG-COMON. Without their participation and
enthusiasm, neither the workshop nor this book would have been possible.
Stefan Ritter, Anders Molander and Damien Féron

Special thanks are expressed to the reviewers of the articles:

Christian Bataillon (CEA Saclay, France)
Thomas Dorsch (Areva NP GmbH, Germany)
Lucia C. Dunbar (Serco Assurance, UK)
Damien Féron (CEA Saclay, France)
John Hickling (CMC, Cyprus)
Petri Kinnunen (VTT, Finland)
Bruno Kursten (SCK-CEN, Belgium)
Jan Kysela (NRI, Czech Republic)
Andraz Legat (ZAG, Slovenia)
Anders Molander (Studsvik Nuclear AB, Sweden)
Stefan Ritter (PSI, Switzerland)
Timo Saario (VTT, Finland)
Sannakaisa Virtanen (University of Erlangen-Nuremberg, Germany)
 Preface xvii

Most important abbreviations

AE Acoustic emission
BWR Boiling water reactor
CE Counter electrode
CERT Constant extension rate test
CGR Crack growth rate
CPE Constant phase element
CS Carbon steel
C(T) Compact tension (specimen)
DCPD Direct current potential drop (technique)
DH Dissolved hydrogen
DO Dissolved oxygen
ECN Electrochemical current noise
ECP Electrochemical (corrosion) potential
EFM Electrochemical frequency modulation (= intermodulation distortion)
EIS Electrochemical impedance spectroscopy
EN Electrochemical noise
EPN Electrochemical potential noise
FDCI Frequency dependent complex impedance
HA Harmonic analysis
[H2] Hydrogen concentration
[H2O2] Hydrogen peroxide concentration
HWC Hydrogen water chemistry
IGSCC Intergranular stress corrosion cracking
LPR Linear polarisation resistance
LVDT Linear voltage differential transformer
LWR Light water reactor
NWC Normal water chemistry
[O2] Oxygen concentration
PWR Pressurised water reactor
RE Reference electrode
RPV Reactor pressure vessel
SCC Stress corrosion cracking
SEM Scanning electron microscope
SG Steam generator
SHE Standard hydrogen electrode
SS Stainless steel
SSRT Slow strain rate test
TGSCC Transgranular stress corrosion cracking
WE Working electrode
YS Yield stress
 1
Corrosion monitoring – what’s the point?

Bob Cottis
University of Manchester, School of Materials, P.O. Box 88,
Sackville Street, Manchester M60 1QD, UK
[email protected]

1.1 Introduction
The paper presents a series of largely philosophical musings on the value, practise and
processes of corrosion monitoring.
When I teach corrosion monitoring, I start by asking the students four questions:
• Does corrosion monitoring reduce the rate of corrosion?
• Does corrosion monitoring reduce the cost of corrosion?
• Does corrosion monitoring reduce the hazards of corrosion?
• Does corrosion monitoring reduce the environmental impact of corrosion?
The response of the students varies a little from year to year, but in general, the
majority answer ‘yes’ to these questions. You may wish to consider your own answers
– so that you are not tempted to read the answers before doing this, this section is
continued at the end of this article.

1.2 Selection of monitoring method

The ideal corrosion monitoring method would give an accurate, real-time, online
indication of many properties of the system, and it would thus have all of the
following capabilities:
• Instantaneous, online measure of corrosion rate
• Instantaneous, online measure of localised corrosion type(s), location and pene-
tration rate
• Online measure of integrated uniform metal loss (i.e. measure of the remaining
thickness)
• Online measure of total local corrosion penetration (i.e. pit depth)
• Location of points of large corrosion penetration
• Detection, location and sizing of SCC and similar defects
• Measure behaviour of plant (not a probe).
Of course, there is currently no such method, and corrosion monitoring necessarily
involves a series of compromises. First, we will consider the compromises involved in
the use of probes.

1.3 Probes for corrosion monitoring

Many corrosion monitoring techniques (e.g. all electrochemical and weight loss
methods and most electrical resistance methods) depend on the use of probes (or test
1
2 Corrosion monitoring in nuclear systems

coupons, for which very similar considerations apply), rather than making measure-
ments of the actual material of the plant. This is convenient for several reasons,
including the easy replacement of probes, the ability to test alternative materials and
the fact that many of the simpler monitoring methods require the use of a probe.
However, it also introduces a number of problems:
• The material of the probe is generally different from that of the plant. While it
may be possible to make probes out of the same batch of material as the plant, it
is much more commonly the case that it is from a different batch and probably
supplied in a different form (e.g. rod rather than plate). Thus it is likely to have a
different chemical composition and metallurgical structure. Even if it is possible
to use the same batch of material as that from which the plant is made, it is likely
that the surface presented to the environment will be different from that exposed
in the plant (e.g. the probe will be a machined cylinder, whereas the exposed
surface of the plant will be the as-received surface of the plate).
• The stress state of the probe will be different from that of the plant.
• The probe will be exposed to only one sample of the range of environments to
which the plant is exposed. This is particularly important in multi-phase systems,
where completely different behaviours can be expected for surfaces exposed in the
different phases or mixtures of phases. It is not always clear that two phases are
present. Thus hydrocarbon pipelines may contain traces of water that will drop
out in low regions of the pipe, or possibly separate out onto hydrophilic surfaces
(such as the oxidised region adjacent to welds). The regions in contact with water
will typically be the sites of corrosion problems, and it may be very difficult to
install probes that will reliably detect these problems.
• The probe will typically experience different flow conditions from the plant. Very
often the probe will create a flow disturbance; this may lead to an increased
corrosion rate, but equally it may inhibit pitting corrosion.
• The area of the probe is usually much smaller than that of the plant, and many
monitoring methods require that the probe is electrically isolated (and there are
questions about galvanic effects if the probe is not isolated). This has important
implications for localised corrosion. First, initiation of pits and other localised
corrosion phenomena is typically a relatively rare event, and it will therefore be
less likely in any given period on a small probe than on a large area of the plant,
meaning that the plant will suffer the localised corrosion before it is revealed by
the probe (assuming of course that a monitoring method capable of detecting the
initiation of localised corrosion is used). Additionally, stable pitting or crevice
corrosion depends on a relatively large cathode area to supply the current to the
active pit or crevice. The small probe may not have a sufficient area to do this, so
that stable pitting cannot be achieved, whereas it can for pits that are driven by
the much larger area of the plant.
Based on these limitations, we must think carefully about the value of probes for
corrosion monitoring. Probes should be regarded as a method of determining the
corrosivity of the environment, rather than measuring the actual corrosion of the
plant, thereby providing information for the management of inhibitor additions or a
warning of upset conditions that result in an increased corrosivity. Consequently,
there is an argument that corrosion probes should be designed to be slightly less
corrosion-resistant than the plant material, so that there is a reasonable expectation
that they will provide an early warning of problems, rather than responding only
 Corrosion monitoring – what’s the point? 3

after corrosion problems have started on the plant. However, this leads to a delicate
balancing act; as an example, we might consider using Type 304 stainless steel as a
probe for the monitoring of a plant constructed out of Type 316. This then implies
that we are going to operate the plant in conditions where 304 will not normally
suffer corrosion. This should certainly avoid corrosion problems with the plant, but
it will not make full use of the capabilities of the 316. We therefore need a probe
material that is closer to 316 in composition, something like a ‘lean’ 316, with chro-
mium and/or molybdenum concentrations just below the specification minimum.
However, this then leads to further questions, as the material would have to be a
specialist cast; it would probably be processed rather differently from a commercial
cast, and it would probably have a quite different concentration and size distribution
of MnS inclusions. As the latter are well known to be very important in the initiation
of pitting corrosion, this leads to uncertainty as to whether the probe is more or less
sensitive to corrosion than the plant, and by how much.
It seems unlikely that corrosion monitoring will be able to do without the use
of probes for the foreseeable future, but careful thought needs to be given to the
implications of the factors indicated above for the reliability of the data obtained.

1.4 Accuracy of electrochemical methods

Electrochemical methods, such as the linear polarisation resistance method, are
popular for corrosion monitoring, offering the advantage of an instantaneous, online
measure of corrosion rate. These methods mostly depend on the Stern-Geary
equation, the derivation of which makes a number of assumptions:
• There is one anodic metal dissolution reaction and one cathodic reduction reac-
tion (oxygen reduction or hydrogen evolution)
• Both anodic and cathodic reactions are far from equilibrium, so that the reverse
reaction can be ignored
• Both reactions obey Tafel’s Law (log i ∝ E, hence i ∝ di/dE)
• The solution resistance is negligible (this can be measured and corrected for using
electrochemical impedance spectroscopy if it presents a problem)
• The measurement is made sufficiently slowly that capacitive currents can be
neglected.
For many (probably most) real systems, these assumptions are not valid; metal dis-
solution is usually not under pure activation control and there will be surface films of
oxide, inhibitor or other absorbed species. Indeed, if the anodic reaction is under
pure activation control, then it is almost inevitable that the alloy will be corroding
too fast to be practically useful (except in a few particularly borderline systems such
as steel in de-aerated water at ambient temperature). Similarly, the cathodic reaction
is often under diffusion or mixed control (e.g. oxygen reduction); while complete dif-
fusion control (when the oxygen reduction reaction is at the limiting current density)
can be approximated by an infinite Tafel slope, mixed control (which is probably
more common in reality) does not provide the required behaviour, and will lead
to errors. Additionally, there may be other, competing reactions; thus copper will
usually be corroding in conditions where the reverse copper deposition reaction
occurs at a significant rate. A related effect is found with nickel-base alloys in hydro-
genated high-temperature water (i.e. pressurised water reactor environments) where
the kinetics of the hydrogen/water redox reaction are faster than the kinetics of
4 Corrosion monitoring in nuclear systems

the corrosion reaction, so that electrochemical measurements do not provide any

information about the corrosion rate.
The harmonic analysis and electrochemical frequency modulation methods are
interesting, in that, according to the theory on which they are based, they permit the
independent determination of the B-value for the Stern-Geary equation. However, it
must be appreciated that the theory still depends on the same assumptions; both
methods will produce a B-value for any system, but this does not prove that the
B-value is valid. If one or other of the anodic and cathodic reactions does not obey
Tafel’s Law, the Stern-Geary equation is not applicable, so the calculated B-value is
meaningless. It may be that the resultant estimate of corrosion rate is not too far from
the true value (‘too far’ in corrosion monitoring is an interesting concept – within a
factor of two or three appears to be doing quite well, and may well be acceptable,
especially if the response to change in rate is detected reliably).

1.5 Epilogue and answers to the questions

The answer to all of the questions in the Introduction is, of course, no. Simply by
monitoring corrosion, we do not change the corrosion rate, the cost of corrosion, the
hazards of corrosion or the environmental impact of corrosion. This does not mean
that corrosion monitoring is of no value, but it does mean that it is only of value when
it forms an input to an active corrosion management programme that has outputs that
will lead to some or all of the above benefits. Corrosion monitoring that does nothing
more than fill filing cabinets or database storage space might as well not have been
measured (except that it may help to explain why that ‘unexpected’ corrosion failure
occurred).
 2
Introduction to different electrochemical corrosion
monitoring techniques

Rik-Wouter Bosch and Walter F. Bogaerts

SCK·CEN, Boeretang 200, B-2400 Mol, Belgium
[email protected]

2.1 Introduction
The corrosion of a metal in an aqueous solution is an electrochemical process involv-
ing anodic oxidation of the metal and cathodic reduction of species from the solution.
We distinguish two types of corrosion: uniform corrosion and localised corrosion.
For uniform corrosion, the corrosion rate is usually expressed as the reduction in
thickness of a particular metallic sample in millimetres per year. For localised corro-
sion, the corrosion rate, expressed as the total amount of material loss, is not
very meaningful and therefore not very important. The aim is to detect the localised
corrosion event itself such as pitting corrosion or stress corrosion cracking (SCC).
To monitor such corrosion phenomena, several techniques are available. Among
others these techniques can be divided into the following two categories:
• Electrochemical techniques
• Non-electrochemical techniques.
An overview of available corrosion monitoring techniques is shown in Table 2.1. This
selection is based on some overview papers and based on the authors’ experiences
[1–4]. We will not discuss all monitoring techniques, but will focus on electrochemical
techniques. For each monitoring technique we will give a short description, the
principle, and some applications.

2.1.1 Electrochemical techniques

The most commonly used electrochemical technique is the Linear Polarisation Resis-
tance (LPR) technique. Other electrochemical techniques that are available to deter-
mine a corrosion rate are Electrochemical Impedance Spectroscopy (EIS) and Tafel
extrapolation [5–7]. For instantaneous corrosion rate measurements, the LPR and
EIS techniques can be used if the anodic and cathodic Tafel parameters are known.
The Tafel extrapolation technique permits determination of the corrosion rate and
the Tafel parameters, but in most cases, it is not suitable for instantaneous corrosion
rate measurements because the system is polarised over a wide potential range such
that the measurement is time consuming and the electrode surface is affected during
the measurement. Special categories are the non-linear distortion techniques such as
Harmonic Analysis (HA) [8–11] and the electrochemical frequency modulation
(EFM) (or intermodulation distortion) technique [12,13]. They provide a corrosion
rate without prior knowledge of the Tafel parameters using only a small perturbation
5
6 Corrosion monitoring in nuclear systems

Table 2.1 Overview of corrosion monitoring techniques

Electrochemical Non-electrochemical
Corrosion Potential (ECP) Electric Resistance (ER) Probe
Redox Potential Direct Current Potential Drop (DCPD)/
Alternating Current Potential Drop (ACPD)
Tafel Extrapolation Field Signature Method (FSM)
Linear Polarisation Resistance (LPR) Contact Electric Resistance (CER)
Electrochemical Impedance Acoustic Emission (AE)
Spectroscopy (EIS)
Harmonic Analysis (HA) and Ultrasonic Testing (UT)
Intermodulation Distortion (EFM)
‘Electrochemical Nose’ (multi wire Hydrogen Concentration
probe sensor)
Electrochemical Noise (potential and
current)*

* Will be discussed in other chapters of this book.

signal. Interpretation of the measured data is, however, not always easy. A very novel
technique is the use of a so-called ‘electrochemical nose’ [14,15]. This technique uses
an array of electrochemical sensors from which the output is interpreted by means of
an artificial neural network. The outcome of the neural network is a degree of cor-
rosiveness of the system. One of the most used techniques for monitoring localised
corrosion is electrochemical noise. This is a generic term used to describe spontane-
ous fluctuations of potential or current, which occur at the surface of freely corroding
electrodes that can be picked up by a suitable electrode arrangement [16]. This tech-
nique will not be discussed here as it receives adequate coverage in several other
chapters of the book.
A major advantage of the electrochemical techniques for on-line corrosion moni-
toring is the rapid response time. Limitations are that a conducting electrolyte is
necessary to perform the measurements, and the complications that arise with the
interpretation of the measurements results.

2.1.2 Non-electrochemical techniques

For the non-electrochemical technique, the Electric Resistance (ER) measurements
are most commonly used. With the ER technique, the change in resistance of a thin
metallic wire or strip sensing element is measured as its cross-section decreases from
metal loss due to corrosion. The corrosion rate is calculated by the loss of metal
between two readings [7]. The ER technique uses the ohmic resistance as a physical
parameter that has to be measured. This principle, which is simply based on Ohm’s
law, is used by a number of other non-electrochemical techniques as well. With the
DCPD (Direct Current Potential Drop) and ACPD (Alternating Current Potential
Drop) techniques, the increasing resistance of a test specimen with a growing crack
is measured. The potential drop is measured with respect to a fixed current and so
related to the ohmic resistance of the test specimen. The Field Signature Method
(FSM) works on the same principle. According to the inventors:
 Electrochemical corrosion monitoring techniques 7

The FSM detects metal loss, cracking, pitting and grooving due to corrosion by detecting
small changes in the way electrical current flows through a metallic structure. With FSM,
sensing pins or electrodes are distributed over the area to be monitored, with a typical dis-
tance between the pins of two to three times the wall thickness. An initial voltage measure-
ment is taken, and subsequent changes in electrical field pattern are detected and compared
against the initial measurement to infer structural changes in the monitored area. [17]

The Contact Electric Resistance (CER) technique developed by the Technical

Research Centre of Finland (VTT) measures in-situ the ohmic resistance of a metal/
metal oxide layer and can so be used to investigate the electronic properties of surface
films formed in-situ [18]. Besides these techniques, a number of other physical based
measurement methods are available. The measurement of hydrogen concentration
on the outside of pipelines can be related to corrosion, assuming that the cathodic
reaction is water reduction. This produces hydrogen that penetrates through the
metallic structure which can be related to the corrosion rate. Ultrasonic Testing (UT)
has been widely used as a non-destructive testing (NDT) technique especially to
investigate welded structures. Acoustic Emission (AE) is still in the picture as a tool
for SCC monitoring [19–21].
ER and LPR techniques found their way into practical applications in industrial
environments. The measurement techniques have been standardised in the ASTM
standard G-96-60, On-Line Monitoring of Corrosion in Plant Equipment (Electrical
and Electrochemical Methods) [7].

2.2 Electrochemical monitoring techniques

2.2.1 Corrosion potential
The corrosion potential is a mixed potential and is a result of the balance between the
anodic oxidation reactions and the cathodic reduction reactions at a metallic surface.
It is a useful measure to determine whether corrosion takes place or not. For the
proper interpretation of the measured values some background knowledge of the
corrosion system is required. The corrosion potential is measured with a suitable
reference electrode. The potential readings have to be recalculated to the Standard
Hydrogen Electrode (SHE) scale to make comparison possible between data obtained
with different reference electrodes. Table 2.2 shows some reference electrodes for use
in ambient environments.
For the interpretation of the corrosion potential value, a Pourbaix or E–pH
diagram [23] is one of the most powerful tools. In a Pourbaix diagram, the thermo-
dynamic stability of a metal in water is given as a function of pH and potential. It
allows one to determine the region where the metal is susceptible to corrosion (active

Table 2.2 Ambient temperature reference electrodes [22]

Reference electrode Electrolyte Potential

(mV vs. SHE)
Hydrogen electrode pH 0 and pH2 1 bar 0
Silver/silver chloride electrode 0.1 M KCl 288
Silver/silver chloride electrode 3 M KCl 197
Copper/copper sulphate electrode 1.43 M CuSO4 (saturated) 300
8 Corrosion monitoring in nuclear systems

region), where there is no corrosion at all (immunity region), and where the metal
is covered by a protective oxide layer (passive region). It should be mentioned,
however, that even though Pourbaix diagrams are very helpful, they do not give any
information on the kinetics of reactions. For instance, the corrosion rate in the
passive range not only depends on the thermodynamic stability of metal oxides,
but moreover on the protective nature of the passive film. Also, the effect of more
complex chemistries in the surroundings, e.g. aggressive or inhibitive ions, is not
considered in these diagrams.
A typical application is the monitoring of a cathodic protection system where
the corrosion potential of a metallic structure is forced to be in the immunity region.
According to the NACE Corrosion Reference Handbook, for steel, a potential of –
850 mV versus the saturated copper/copper sulphate reference electrode is required
[24]. Alternatively, for anodic protection, a potential is chosen in the passive region
of the Pourbaix diagram to maintain a protective oxide layer.
For corrosion in high-temperature water, the application is not much different
to that for ambient applications. Pourbaix diagrams are frequently used to explain
the meaning of the measured corrosion potentials. Pourbaix diagrams for metals
in high-temperature water are however more difficult to obtain than those at room
temperature. Experimental verification is also more complicated.
To measure corrosion potential, a reference electrode is needed. For measurements
in high-temperature water, it is in most cases a technological challenge to develop
such a reference electrode. A number of high-temperature reference electrodes
developed in the last decades are summarised in Table 2.3.
Besides the use of Pourbaix diagrams to interpret the corrosion potential, other
relationships with the corrosion potential are also used. An important corrosion
problem in light water reactors (LWRs) is the sensitivity to SCC of Ni-based alloys
and irradiated stainless steels. Both corrosion processes have a relationship with the
corrosion potential. Figure 2.1 shows these relationships schematically.
It is interesting to see that for both systems, the crack growth rate depends on the
corrosion potential but in a different way. The first example is (irradiated) stainless
steel in a boiling water reactor (BWR). The crack growth rate decreases significantly
with decreasing corrosion potential. This behaviour has resulted in the application of
so-called HWC (hydrogen water chemistry). Hydrogen is added to the primary BWR
circuit to lower the corrosion potential [31,32]. The second example is the behaviour
of Ni-based alloys in high-temperature water. There is a particular region where the

Table 2.3 High-temperature reference electrodes and their potentials at 300°C [25–30]

Reference electrode Electrolyte Potential

(mV vs SHE)
Hydrogen electrode pH 0 and pH2 1 bar 0
Internal silver/silver chloride electrode 0.1 M KCl 7
EPBRE (External Pressure Balanced 0.1 M KCl −37
Reference Electrode) silver/silver
chloride electrode
Yttrium stabilised zirconium electrode Ni/NiO −783 (pH 7.3)
Yttrium stabilised zirconium electrode Cu/CuO −1010 (pH 7.3)
Yttrium stabilised zirconium electrode Fe/Fe3O4 −473 (pH 7.3)
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