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European Federation of Corrosion

Publications
NUMBER

A Working Party Report

Guidelines on Electrochemical
Corrosion Measurements
Published for the European Federation of Corrosion
by The Institute of Metals

THE INSTITUTE OF METALS


1990

Book Number 497


Published in 1990 by The Institute of Metals
1 Carlton House Terrace, London SWlY 5DB
and
The Institute of Metals
North American Publications Center
Old Post Road, Brookfield VT 05036
US A
0 1990 The Institute of Metals

All rights reserved

British Libra y Cataloguing in Publication Data


European Federation of Corrosion. Working Party on PhysicoChemical Methods of Corrosion Testing
Guidelines on electrochemical corrosion measurements.
1. Corrosion. Testing.
I. Title 11. Institute of metals 1985- 111. Series
620.11223

Libra y -of-Congress -Cataloging-in-Publication-Data


available on application
I S B N b901462-87-X

Text processing by P i c A Publishing Services from original


typescripts and illustrations provided by the authors
Printed in Great Britain

Contents

European Federation of Corrosion Series Introduction

Foreword

11

Introduction

12

Chapter 1 Instrumentation, Performance and Calibration


I. C. Rowlands

13

1.1Introduction

13

1.2 Performance Limitations

13

1.2.1Impedance Matching
1.2.2 Ammeter Loading
1.2.3 Amplifier Bias Current
1.2.4Bandwidth Limitations
1.3 Error Sources

16

1.3.1 Resistance Noise


1.3.2 Triboelectric Noise
1.3.3 Piezoelectric Effects
1.3.4 Thermoelectric Effects
1.3.5 Magnetic Field Loops
1.3.6 Earth Loops
1.3.7 Earth Potentials
1.3.8 Capacitive Transformer Coupling
1.3.9 Long Lead Cable Capacitance
1.4 Instrument Calibration

18

1.5 References

18

Chapter 2 Design of Electrochemical Cells


F. P. IJsseling

19

2.1 Introduction

19

2.2 Electrochemical/Electrical Requirements

19

2.3 Solution Requirements

21

2.4 Construction Requirements

22

2.5 References

25

Chapter 3 Electrode Design


E . Heitz

27

3.1 Introduction

27

3.2 Size of Electrodes

27

3.3 Design with Regard to Various Corrosion Parameters

28

3.3.1 Current and Potential Distribution


3.3.2 Mass Transfer
3.3.3 Heat Transfer
3.3.4 Mechano-chemical Testing
3.3.5 High Temperature/High Pressure Testing.
3.4 Problems Concerning Application Techniques

31

3.5 References

32

Chapter 4 Reference Electrodes


E . Eriksrud and E. Heitz

34

4.1 Introduction

34

4.2 Choice, Stability, Incompatibility

34

4.3 Checking of the Reference Electrode, Some Practical Advice

34

4.4 More Specific Requirements

35

4.5 Some Common Electrodes for Aqueous Systems

35

4.5.1 Mercury-mercurous chloride (calomel)


4.5.2 Mercury-mercurous sulphate
4.5.3 Mercury-mercuric oxide
4.5.4 Silver-silver halide
4.5.5 Reference Electrodes in Non Aqueous Systems
4.6 References

36

Chapter 5 Effectof Specimen Preparation and Surface Condition

37

1. Simpson

5.1 Introduction

37

5.2 Choice of Sample

37

5.3 Sampling and Specimen Preparation

37

5.4 Surface Preparation Before Immersion in the Test Solution

38

5.5 Effect of the Conditions Within the Cell Before Commencement of the Measurement

39

5.6 Changes Caused by the Measurement Itself

39

5.7 References

39

Chapter 6 Evaluation and Compensation of Ohmic Drop


L. Clerbois and F. P. IJsseling

40

6.1 Introduction

40

6.2 Examples

42

6.2.1 Polarisation Resistance


6.2.2 Polarisation Curves in Aqueous Solution
6.2.3 Polarisation Curves in Non Aqueous Solution
6.3 Principal Methods

44

6.3.1 Minimising Ohmic Drop by Cell and Electrode Design


6.3.1.1 Cell Design
6.3.1.2 Microelectrodes
6.3.2 Active Methods
6.3.2.1 Positive Feedback
6.3.2.2 Interrupt Methods
6.3.3 Passive Methods
6.3.3.1 Measurement of Ohmic Drop
6.3.3.2Direct Calculation
6.3.3.3Mathematical Methods
6.4 Conclusions

52

6.5 Acknowledgements

52

6.6 References

52

Chapter 7 Automatic Measurement Systems


0. For& and 1.Aromaa

55

7.1 Introduction

55

7.2 Parts of a Measurement System

56

7.2.1 Computers and Peripherals


7.2.2 Measuring Devices
7.2.3 Data Transfer Busses
7.2.4 Software
7.3 Analysis of Measured Data

58

7.4 Examples of Automatic Systems

59

Chapter 8 Field Testing


G. Turluer

61

8.1 Objectives

61

8.2 Test Methods

61

8.2.1 Polarisation Resistance Measurements (R,)


8.2.2Material (or Component) Potential and Process Redox Potential Monitoring
8.2.3 Impedance Measurements
8.2.4 Potentiodynamic Scanning
8.2.5 Galvanic Current Measurements
8.2.6Spatial Potential Scanning

8.3 Specific Requirements and Precautions

62

8.3.1 General
8.3.2 Probe configuration and location
8.3.3 Reference electrodes
8.3.3.1 Arbitary electrodes
8.3.3.2 In situ reference electrodes
8.3.3.3 External reference electrodes
8.4 Interpretation and Possible Limitations

63

Introduction

At the present time electrochemical test methods in corrosion are becoming more diverse and, as
aconsequence, new techniques have been added to those well established. Each technique has limitations and has requirements for conditions to be satisfied for practical application.This subjectwas
the topic of an international workshop held at Ferrara, Italy, 11-13September 1985, organised by
the European Federation of Corrosion Working Party on Physico-Chemical Methods of Corrosion
Testing [l].This Workshop outlined the range of practical application of electrochemical corrosion
testing as well as reaching conclusions concerning the use, significance and limitations of various
methods. However, this meeting, and others, on electrochemical corrosion measurements have
generally not provided specific information on how experiments should be performed[2-41. It was
the Working Partys intention to fulfil this requirement with the compilation of this booklet. In
undertaking this task, members were confronted with a great variety of techniques to be considered, although, inevitably, the same experimental principles are involved with the various techniques. Various practical aspects in conducting experiments,both in the laboratory and in the field,
have been considered in achieving the objective of this work.
There is a notable absence of specifications or codes of practice on the use of electrochemical
corrosion testing and it is hoped that these guidelines will fill this gap in corrosion science.

REFERENCES
1. Electrochemical Corrosion Testing. Monograph 101, published by DECHEMA, Frankfurt,

FRG,(ed. E.Heitz, J. C. Rowlands and F. Mansfeld) 1986.


2. Electrochemical Techniques for Corrosion. Published by NACE, Houston, USA ( ed. R.
Baboian) 1977.
3. Electrochemical Corrosion Testing. Special Technical Publication727. Published by ASTM
Philadelphia, USA (ed. F. Mansfeld and V. Berucci) 1981.
4. ElectrochemicalMethods in Corrosion Research. Published by Trans. Tech. Publications Ltd.,
Switzerland (ed.M. Duprat), 1986,8.

12

European Federation of Corrosion


Publications

Series Introduction

The EFC, incorporated in Belgium, was founded in 1955with the purpose of promoting European
co-operation in the fields of research into corrosion and corrosion prevention.
Membership is based upon participation by corrosion societies and committees in technical
Working Parties. Member societies appoint delegates to Working Parties, whose membership is
also expanded by co-option of other individuals.
The activities of the Working Parties cover corrosion topics associated with inhibition, education, reinforcement in concrete, microbial effects, hot gases and combustion products, environment
sensitive fracture, marineenvironments,surfacescience, physico-chemicalmethods of measurement,
the nuclear industry, and computer based information systems.Working Parties on other topics are
established as required.
The Working Parties function in various ways, e.g. by preparing reports, organising symposia,
conducting intensive courses, and producing instructional material, including films. The activities
of the Working Parties are co-ordinated, through a Scienceand Technology Advisory Committee,
by the Scientific Secretary.
The administration of the EFC is handled by three Secretariats: DECHEMA in the Federal
Republic of Germany, the Soci6t6de Chimie Industrielle in France, and the Institute of Metals in the
United Kingdom. These three Secretariats meet at the Board of Administrators of the EFC. There
is an annual General Assembly at which delegates fromall member societiesmeet to determine and
approve EFC policy. News of EFC activities, forthcoming conferences, courses etc. is published in
a range of accredited corrosion and certain other journals throughout Europe. More detailed
descriptions of activities are given in an occasional Newsletter prepared by the ScientificSecretary.
The output of the EFC takes various forms. Papers on particular topics, for example, reviews or
results of experimental work, may be published in scientific and technical journals in one or more
countries in Europe. Conference proceedings are often published by the organisation responsible
for the conference.
In 1987, the Institute of Metals was appointed as the official EFC publisher. Although the
arrangement is nonexclusive and other routes for publication are still available, it is expected that
the Working Parties of the EFC will use the Institute of Metals for publication of reports,
proceedings etc. wherever possible.

A D Mercer

EFC Scientific Secretary


Institute of Metals London, UK
9

EFC Secretariats are located at:


Mr. R. Wood
European Federation of Corrosion
The Institute of Metals
1Carlton House Terrace
LONDON SWI Y 5DB
UK

DrD. Behrens
Europaische Foderation Korrosion
DECHEMA
Theodor-Heuss-Allee 25
D-6000
FRANKFURT (M)
FRG
M. R. Mas
Federation Europtkne de la Corrosion
Societe de Chimie Industrielle
28 Rue Saint-Dominique
F-75007 PARIS
FRANCE

10

Foreword

Electrochemicalmethods have been used in corrosion testing ever since the electrochemical nature
of corrosion processes was discovered. In the present age electrochemical measurements involve
the use of sophisticated 'black boxes' which are invariably blamed for any 'pitfalls' which occur.
Hence the European Federation of Corrosion Working Party on Physicochemical Methods of
Corrosion Testing felt it desirable to remind research workers, students and instrument designers
of the more fundamental aspects of the measurements.
Chaptersin this book were prepared by the Working Party members named in the Contentslist.
Copyright of any particular chapter may be the property of the authors or their employers, but the
publication rights havebeengranted to theInstitute of Metals. The Working Party wishes toexpress
its appreciation to Mr A D Mercer for the final editing of this booklet on behalf of the European
Federation of Corrosion.
Members of the Working Party are as follows:
Belgium

L Clerbois

Finland

0 Forsen

France

P Lacombe
G Turluer

Germany

W Fischer
E Heitz

Great Britain

J W Oldfield
J C Rowlands

Italy

F Mazza
G Rocchini

Netherlands

F P IJsseling

Norway

E Eriksrud

Spain

J M Costa

Switzerland

J Simpson

L Clerbois
Chairman EFC Working Party
Physicochemical Methods of Corrosion Testing

CHAPTER 1

INSTRUMENTATION,
PERFORMANCE AND
CALIBRATION
J . C. ROWLANDS
ARE Holton Heath, Poole, Dorset, UK

1.I INTRODUCTION
Since most electrochemical measurements relating to corrosion of metals are satisfied with a
sensitivity of 1 pV or 1 pA, modern instrumentation usually employs electronic operational
amplifiers where the noise limits control the range of measurements. The function of the operational amplifier is to amplify the potential (VJ applied at the input so that it can be displayed on
a low impedance analogue or digital meter (V,) as shown in Fig. 1.1. The output potential of the
operational amplifier is proportional to the source potential and is required to have sufficient input
impedance to avoid polarisation of the potential source.
The basic corrosion instrumentation requirement involves the measurement of potential
difference. Currents are measured as the potential across a resistor (R,) as shown in Fig. 1.2, where
the potential difference is again determined with an operational amplifier. More sophisticated
measurements such as polarisation characteristicsand zero resistance ammetry involve the use of
potentiostats which again use operational amplifiers in a differential mode. The potentiostat is an
instrument for maintaining the potential of an electrode under test at a fixed potential compared
witha reference cell, and the basic circuit is similar to that for potential measurement with the earth
return circuit broken to an auxiliary electrode in the electrochemical cell. Such a circuit would
maintain the potential of the test electrode at the reference cell potential. This potential may be
varied by inserting a variable potential source (V,) in the input circuit as shownin Fig. 1.3.The actual
cell potential (VJ and the current required to polarise the test electrode to this potential may be
measured using the basic circuits shown in Figs. 1.1 andl.2 respectively.
A further modification of the basic voltage measurement, given in Fig. 1.1,is the zero resistance
ammeter (ZRA) shown in Fig. 1.4. The measurement of current as the potential drop acrossa resistor
(R,) shown in Fig. 1.2 involves an error due to the value of resistor A. This may be overcome with
the ZRA in which the current is determined as the potential measured across a feedback resistor (R,)
of the high gain operational amplifier. Thus, the current required to maintain electrodes A and B
shown in Fig. 1.4 at the same potential can be determined and displayed on a high impedance
voltmeter for which most commercial digital multimeters are suitable.

1.2 PERFORMANCE LIMITATIONS


The performance characteristicsof commercial instrumentation should be supplied by the manufacturers. There are, however, measurement limitations which are controlled by the electrochemical cell under investigation.The major limitations and requirements are listed under their separate
headings.

13

Fig.1.1:Voltage measurement

Fig.l.2:Current measurement

REF

AUX

TEST

Fig.l.3:Potentiostat

r-------1

I
I
I
I
I
I

I
I
I

Fig.l.5:Impedance matching
14

&

I
I
I

I
I

I
I
I

I
I
I
1

r------1
.
I

I
I

I
-

I
I
I
I

1.2.1 Impedance Matching

The measurement of a potential difference between two metals or a metal with respect to a reference
electrode in an electrolyte requires the determination of a source voltage (V,) which has a source
resistance ($). This source resistance is the sum of the resistivity of the electrolyte and the
polarisation resistance of the electrodes. In order that the measuring instrument does not draw a
significant current from the source, thus avoiding polarisation, it is necessary that the instrument
or meter impedance must be high compared with the source impedance.Such a circuit of the source
instrument impedance is shown in Fig. 1.5. For this circuit the actual potential measured (Vm)is
related to the source potential (V,) by equation 1. The resultant error if the amplifier input
impedance (R,) is not large is given in equation 2.
Rl
vm=vs Rl RS
+

Error = vsvm

100%

VS

Although it is most desirable to have R, very large compared with% a very high value of I$
may
present problems due to pickup of dc or ac error signals from other instruments and the mains
electricity supply. A high source impedance,&, is invariablypresent in conducting electrochemical
measurements in non aqueous media or when investigating organic coatings on metals. Hence it
may be necessary to compromise the accuracy of the measurement for the sake of reducing error
signals from other sources by limiting the impedance of the measuring instrument. For most
corrosion measurements an error of 1%is acceptable.
1.2.2 Ammeter Loading

The internal resistance of an ammeter (R,) in Fig. 1 . 2 presents a potential drop in the circuit. This
may be overcome using the zero resistance ammeter shown in Fig. 1.4.
In many instruments such as potentiostats the value of resistance (R,) is chosen to provide a
limiting current in case the output becomes shorted.
1.2.3 Amplifier Bias Current

Electronic amplifiers have a small bias current across the input. In electrochemical corrosion
measurements it is a requirement that this bias current is very small, such as less than 1FA to avoid
polarising the electrodes of the corrosion cell.
1.2.4 Bandwidth Limitations

When following potential changes, eg electrochemicalcell capacitance charging or discharging, ac


impedance measurements, or electrochemicalnoise measurements, the bandwidth response of the
measuring instrument may limit the application.
The frequency response of an instrument is usually specified as the 3 dB point (f3 dB) and is
determined by the R, and C, values for the input of the circuit shown in Fig. 1.5.

3 dB

2.rr R, C,

(3)

The rise time (t>, i.e. the time to rise from 10% to 90% of the signal amplitude, is given by the
equation:
tr

2.2

qc,

(4)

15

Thus, from equations 3 and 4:


t-r = -

2.2

(5)

2T f3dB

1.3 ERROR SOURCES


1.3.1 Resistance Noise
Resistance or Johnson noise in a resistor is caused by the thermal energy produced due to the
passage of a current. In a metallic conductor the Johnson voltage noise developed in a resistor is
given by the equation:

E = v4kTRAf

(6)

where k = Boltzmanns Constant, T = temperature K, Af = noise bandwidth in Hz.


In high resistance circuits the noise bandwidth is limited by the time constant (t,>of the source
resistance (RJ in parallel with the input resistance and the input capacitance (q)as shown in Fig.
1.5. The noise bandwidth is then given by the equation:
7
R+R
A solution to this problem is keep the connectingleads from the source to the instrument as short
as possible.
1.3.2 Triboelectric Noise
Currents are generated by charges created due to friction between an insulator and a conductor.
Such noise is dependent on the length, degree of movement and the materials of the cable, but may
give rise to large electrostatic charges which can be minimised using low noise cables.

1.3.3 Piezoelectric Effects


Electrostatic charges are generated when a mechanical stress is applied to some materials, and
hence the cables coupling the source to the instrument should not be under tension and not be free
to vibrate.
1.3.4 Thermoelectric Effects

Due to different parts of the circuit being at different temperatures, or at dissimilar metal joints as
in thermocouples, an error potential in the millivolt range could be generated. Hence the test cell
and the instruments should be maintained at a uniform temperature and equilibrium reached
before undertaking measurements.

1.3.5Magnetic Field Loops


A loop of cable in the circuit between the test cell and the measuring instrument may be subject to
a change in magnetic field which develops a potential. This potential (EB)is given by the equation:
E,a

A-

dB
dt

where dB/dt is the rate of change of magnetic field intensity and A is the area enclosed by the
loop of cable.
This is particularly relevant to remote sensing in field tests where potential errors of the order
of millivolts can be generated.

16

1.3.6Earth Loops
A potential error may be developed due to the use of a common earth line between the test cell and
the measuring instrumentation, due to the current carried in the earth line. This error may be
minimised by earthing both the cell and the measuring instrument to the same earthing point using
separate cables. Similarly, the use of any current carrying lead should be avoided when making a
potential measurement due to the voltage drop in the lead.
1.3.7Earth Potentials
When making measurements in process plant it is not uncommon to have various metallic
conductors making the connectionto earth, resultingin the presence of electrical earths at different
potentials, as shown in Fig. 1.6 where the electrolyte containing the electrodes forms an earth
connection with the plant in which the measurement is being undertaken. It is usually not
acceptableon safety grounds to remove the mains earth, even when the instrumentation is earthed
through the test cell and, in such cases, the problem is best avoided using battery operated
instrumentation.
ELECTROLYTE
RESISTANCE
TO EARTH

ELECTRODE

Fig.l.6: Multiple earth

MAINS EARTH

1.3.8Capacitive Transformer Coupling


Although the primary and secondary windings on a mains transformer are considered as an
inductive coupling there is also an intercapacitive effect between the high and low voltage
windings. Thisresults in an ac voltage to earth superimposed on the secondary output asillustrated
in Fig. 1.7. This error source is usually only applicable when measuring very low potentials and
currents and may be reduced by transformer earth screens. The remedy is to use battery powered
instrumentation.

1 Fig.l.7: Mains supply earth current

1.3.9Long Lead Cable Capacitance


The use of long leads between the potential source and the measuring instrument can result in an
effectivechange of the output capacitance of the measuring instrument, thus altering its frequency
response. Typically the capacitance of a twin core cable is of the order of 100 pF/m. The effect on
the frequency response can be calculated using equations 3 or 4. The remedy to this problem is to
keep the cables as short as possible or, where long cable systems are unavoidable, a driver amplifier
at the source may be required.
17

1.4 INSTRUMENT CALIBRATION


The instrumentation described in this chapter is very dependent on the maker supplying a reliable
specification. Thereafter it is usually only necessary to check the instrument periodically using a
commercially available standard potential or current source. Any deviation found should be
corrected by following the instrument manufacturer's setting up procedure or by returning to the
maker for recalibration.

1.5 REFERENCES
1. A. J. BARD and L. R. FAULKNER: in Electrochemical Methods - Fundamentals and Applications. Chapter 13. Published by John Wiley & Sons Inc., 1980.

2. Instrumental Methods in Electrochemistry,Southampton ElectrochemistryGroup. Published


by Ellis Horwood, Chichester, U. K., 1985.
3. J. F. KEITHLEY, J. R. YEAGER and R. J. ERDMAN: in Low Level Measurements. Revised 3rd
Edition. Published by Keithley Instruments, Ohio, U. S. A., 1984.

18

CHAPTER 2

DESIGN OF ELECTROCHEMICAL
CELLS
F.P. IJSSELING
Corrosion Laboratory of Royal Netherlands Naval College, Den Helder, The Netherlands

2.1 INTRODUCTION
The general purpose of an electrochemical cell is to be able to conduct electrochemical measurementsona metal sample - the working or test electrode - which should have a well-defined area and
surface condition. In the cell the working electrode is brought into contact with the corrosive
environment, usually under well defined conditions i.e., with respect to environmental composition, temperature, flow, etc. [l, 21. Apart from the working electrode an auxiliary electrode is
required to allow electric current to flow through the cell during polarization; in addition a
reference electrode is needed to be used as a zero point for measuring the potential difference
between the working electrode and the solution. Most electrochemicalcells are based on the above
mentioned three electrode system. Only in simple cases, for instance when the measurements are
to be made under zero current (e.g. the free corrosion potential) or very low current flow, a two
electrode cell may suffice. Then a reference electrode is used which, under low current flow, can
also act as the auxiliary electrode. The contents of this chapter are aimed at threeelectrode cells to
be used on polarizing the working electrode. In the following a list of requirements is given, which
are further divided into the following sections:
1. electrochemical/electrical
2. solution
3. construction.

2.2 ELECTROCHEMICAUELECTRICAL REQUIREMENTS


The first and foremost requirement is the need to establish a homogeneous electric field at the
working electrode surfaceand consequentlyaneven current distribution. In this respect the relative
positions of the working-, auxiliary- and reference-electrodes are of paramount importance.
(a).The best way to obtain an even current distribution is to position the auxiliary electrode as
symmetrically as possible to the working electrode, the latter preferably having the smaller or at
least the same dimensions (Fig.2.1). A large distance between the electrodes will also promote a
more even current distribution. However, too large a distance may create an unduly high ohmic
resistance in the cell [3,41.
(b).The reference electrode should be positioned in sucha way as not to disturb the even current
distribution by shielding effects, at the same time keeping the uncompensated ohmic resistance in
the solution at a minimum. The classical solution is to place the reference electrode in a separate
compartment and to use a Luggin capillary, the tip of which is to be placed 1-2 outer diameters of
the capillary opening from the working surface (Fig. 2.2a) [ 5 ] . In any case, positioning of the
reference electrode should be possible in an exact and reproducible way. However, other satisfactory solutions have been found, including the side channel probe and the back probe (Fig. 2.2b, c).
The first consists of a small opening at the side of the working electrode as a connection with the
reference electrode, while in the second case the Luggin probe is attached to the back of a narrow
hole drilled through the electrode 16-81.
(c). In all cases the cell should provide a well-defined electrical system; in the first place good
electrical connections with the electrodes should be ensured, which even at longer exposure times

19

rE

Fig. 2.1: Simple three-electrode cell


containing working electrode (WE),
auxiliary electrode (AE)and reference electrode (RE).

I RE
IRE

II.

WE
b.

a.

c.

Fig. 2.2: Different methods of minimizing IRdrop: a. Luggin capillary b. side channel c. back
channel.

a.

Fig. 2.3:Exampleof cell with separate compartment for AE, connected via a membraneor coarse
sintered glass: a. single separation b. double separation by which an extra compartment is
created in which the possibly contaminated solution can be flushed regularly by means of a
stopcock.

20

do not lead to failures. The problem is most urgent in cases where aggressive ions are present and/
or high temperatures that could eventually lead to oxidation of the contacts. The use of a double
wiring system and detection of possible contact resistance is recommended. The inner electrical
path should also be considered and possible errors resulting from clogging of the Luggin capillary
or the formation of poorly conductive areas in the cell should be avoided as these could give rise
to unduly high electrical resistances in the power loop or the control loop.
The pick-up of electrical and electromagnetic noise should be avoided, especially in the case of
the application of electrochemical pulse methods and sensitive dc measurements involving small
potential perturbations and currents.
The factors which should be taken into consideration in such cases, involve:
1.Earthing - in many laboratory applications the working electrode is earthed or kept at virtual
earth; in a number of commercial potentiostat designs it is possible to disconnect the working
electrode from the instrument zero. All measuring instruments and ancillary equipment should be
fed from the same line connection. In addition all instrument houses and bodies of ancillary
equipment should be interconnected and earthed at one point for safety reasons [9,101.
2. Short connections - generally the control instrument e.g. potentiostat should be located near
the cell to ensure short electrical connections. If this is not feasible the use of a buffer amplifier in
the control loop near the test cell is to be considered.

3. Reference electrode - a high resistance which is common in many commercial products may
induce noise and even instability in the control loop.
The connection with the potentiostat should be shielded; shielded reference electrodes are
commercially available. However, in the case of excessive capacitance to ground instability of the
control potentialmay occur,insuchcases the shieldingmaybemaintained at the referencepotential
via an operational amplifier [5].Another possibility is to provide a platinum wire to be used as the
reference in the control loop, next to the reference electrode proper.
4. Screening - if necessary the cell should be placed in a Faraday cage or screened electrically and
electromagneticallyby other means as, for instance, by tin plate, copper foil, etc.

(e) Also, in the case of sensitive high-performance measurements the potentiostat and the cell
design should be matched to each other. Generally the requirements for rapid and accurate
response are: low total cell resistance, low-resistance reference electrode, small-area working
electrode, and low stray capacitances [ll,121. In general it can be said that the faster the response
of the potentiostat, the greater its sensitivityto interference. So it is not advisable to use fast response
potentiostats for applications where this feature is not required.

2.3 SOLUTION REQUIREMENTS


The solution requirements depend to a large extent on the purpose of the measurement. Generally
the solution consists of a solvent, the electrochemically active redox system and possibly
complexing agents, buffers, a supporting electrolyte to enhance the electrical conductivity, etc. In
the case of industrial measurements, e.g. corrosion monitoring, the solution is generally that being
used in the process.
In laboratory experiments special precautions are often required. The main points can be
summarized as follows:
(a). The solution should be free from contaminants as even small concentrations may exert
relatively large effects on the electrochemicalreactions by adsorption effects, etc. So in appropriate
cases freshly double-distilled water and analytically pure salts should be used.
(b). Moreover, the solution should not be contaminated during the measurements, either by
components of the materials to be used for cell construction or by reaction products evolved at the
current carrying electrodes. The first possibility should be avoided by proper materials selection.
To eliminate the second one the electrochemical reactions at the working as well as the auxiliary
electrode should be taken into account. For this reason the auxiliary electrode is often placed in a
separate compartment, the contents of which are electrically connected with the test solution via a
membrane, glass frit, etc. (Fig. 2.3).
21

As it is not feasible to separate the working electrode from the test solution the first thing to be
considered is to keep the cell volume large enough to avoid the accumulation of an excess of
corrosion products [131. Monitoring the corrosion product concentration is advisable and the cell
contents should be refreshed as soon as unduly high concentrations arise. Other possibilities
include the use of special cells which permit continuous or intermittent replacement of the test
solution and, in the limit, the use of once-through conditions. Apart from the auxiliary electrodethe
reference electrode is also sometimes placed in a separate compartment, for instance when the
release of chloride ions in the test solution from a saturated calomel electrode cannot be tolerated.
Even then contamination by release of chloride ions may become a problem, which can be solved
by placing an extra compartment between the cell proper and the reference compartment (Fig. 2.4).
Reference electrodes with intermediate electrolyte chambers are commercially available.
(c).The test solution should maintain its intended corrosive properties during the experiment,
e.g. O,-content, pH etc. If necessary, the concentration of the corrodents should be monitored and
kept at a specified level. Special care must be exercised when biologically active solutions are used,
in which the bacteriological components interfere with the corrosion process, such solutions often
being prone to ageing. Seawater is an example of a solution in which significant changes of the
corrosive properties may occur on storing and during exposure.
(d). In a number of cases it might be desirable to provide a constant gas-atmosphere in the cell
above the solution. Examples are the removal of oxygen by the addition of nitrogen, hydrogen or
mixtures thereof, or the creation of an oxygen-rich environment by the addition of oxygen. For
many purposes a simple provision to introduce gas in the cell under a slight overpressure,
combined with a device to distribute the gas in the solution in the form of small bubbles, suffices
(Fig. 2.5).
However, in separate cases, for instance when poisonous gases are involved, a more elaborate
methodology is required.

2.4 CONSTRUCTION REQUIREMENTS


The constructional design of a cell also depends to a large extent on the type of measurements to
be made. Generally the construction should be rugged and allow for easy assembly and disassembly as required, for instance, for cleaning purposes. Moreover the positioning of the electrodes
should be accomplished easily and in a reproducible way.
The following points should be kept in mind:
(a). materials - in many cases glass is satisfactory, although sometimes PVC, PTFE or other
plastics are to be preferred, keeping the contamination problem in mind. Often it is possible to
construct a cell from standard laboratory glass components, although care should be taken in the
use of glass at temperatures above about 6OoCbecause of the possibility of contamination by silica
resulting from dissolution of the glass [141.
(b). temperature - in many cases it will be desirable to study the corrosion process at a welldefined temperature, necessitating temperature control of the cell. The following methods can be
envisaged:
1.direct introduction of heatingand/or cooling elementsinto the test solution (Fig. 2.6a), taking
precautions to avoid current leakage from the element into the solution;
2. external circulation of the test solution through a heat exchanger (Fig. 2.6b);
3. positioning of the test cell in a thermostatted bath (Fig. 2.6~);
4. the use of a double walled cell, circulating thermostatted water through the double wall to
ensure temperature constancy of the inner test solution (Fig. 2.6d).
It must be remarked that for high-temperature applications the Luggin capillary also should be
similarly equipped with a double wall for circulation of thermostatted water.
(c).working pressure - most tests are performed under atmospheric pressure, obviating special
requirements. However, in some cases it isessential to test under increased pressure, so the cell has
to be adapted to this purpose. Generally autoclaves have been used for this purpose, one of the
problems involved being the gas-tight isolation of the electrode connections 1151.
(d). solution flow - frequently the flow conditions at the working electrode surface are not too
well defined. However, if so required this aspect can also be taken into account, for instance, by
using rotating disc or cylindrical electrodes.
Another possibility is the use of tubes or plate electrodes in ducts, channels or test loops, e.g.
generally in flow through cells (Fig. 2.7 and Chapter 3) [16].
22

Fig. 2.4: Electrochemical cell with


separate compartments for the
reference and the auxiliary electrodes; to prevent contamination
by the solution in the reference
electrode the contents of this
compartment can be flushed out
regularly by means of a stopcock.

Fig. 2.5: Closed cell with


inlet and outlet for gas.

C.

a.

ti

l+d

b.
IT0
Fig. 2.6:Different methods of temperature control:a. direct b. via external heat-exchanger c. via
temperature bath d. via double walled cell

C.

I RE

1
a.

b.

Fig. 2.7: Different methods for creating solution flow (see


also Chapter 3): a. rotating disk electrode b. rotating cylinder electrode c. pipe system with one test pipe as WE and
two as AE d. pipe system with one test pipe as WE and a
central rod or wire as AE. In cases c and d the RE can be
connected via a hole through the wall of the WE.

23

Fig. 2.8: Example of electrochemical cell for SCC testing u n c r potentiostatic contrc

WE: working electrode, consisting of notched rod possibly isolated from the solution except at
the notched position; AE: auxiliary electrode, consisting of circular platinum gauze around the
working electrode; L :Luggin capillary to reference electrode RE; G : inlet for gas; S : seals.
1 2

5 6

a.

b.

Fig. 2.9: Electrochemicalcell with separated creviced anode and cathode for crevice corrosion
testing [201.

a. General set-up
1. graphite electrode connected to earth for safety precautions;
2. heating element;
3. contact thermometer;
4.cathode (in principle the same material as anode material under test);
5. holder for anode, provided with a large number of microcrevices, obtained by pressing a
rubber O-ring on a scratched metal surface;
6. reference electrode.
b. Detail of anode holder:
7. PVC-pressing plug;
8. anode specimen;
9. rubber O-ring;
10. platinum wire making electrical contact with anode.
24

(e).illumination - in some special cases it might be desirable to control the light conditions at the
working electrode, for instance varying between exposure under dark conditions or under
illumination within a given spectral area.
(f). local corrosion- also dependingon the test involved, it maybe necessary to introduce special
conditions, aimed at the creation of local corrosion attack. Well-known examples are stresscorrosion cracking and fatigue corrosion involving test cells in which the working electrode can be
exposed under stressed condition (Fig.2.8), and crevice corrosion, in which case the working
electrode may be provided with artificial crevices 117, 181. For some applications, e.g. crevice
corrosion and bimetalliccorrosion testing the corroding metal surface(anode)and the cathode have
been separated in space, being electrically connected externally via an appropriate measuring
instrument, e.g. a zero resistance ammeter (Fig. 2.9) 119,201.
In a number of cases the requirements as listed above are conflicting and contradictory,
necessitating a compromise. However, generally it is not necessary to meet all requirements. The
ultimate requirements to be incorporated in a certain cell design are of course strongly related to
the purpose of the test and the test method and should be selected accordingly. In the official
standards and guidelines only a few starting points can be found [e.g. 211. A number of textbooks
and papers contain useful basic information 1e.g. 1,2,5,6,10,221. In the literature a large number
of cells have been described. Apart from the references already given - a more of less random
selection including some general information in addition is presented in refs. 123-411.

2.5 REFERENCES
1. D.T. Sawyer and J. L. Roberts: in Experimental electrochemistry for chemists, Chapter 3.
Published by John Wiley & Sons, Inc. 1974.

2. N.D. Greene: in Experimental electrode kinetics. Published by Rensselaer Polytechnic


Institute, Troy, New York, 1965.
3. J.E. Harrar and I. Shain: Anal. Chem., 1966,-83 1148.
4. W.A. Mueller: Corrosion, 1 9 6 9 , s 473.
5. R. Greef et al.: in Advanced instrumental methods in electrodekinetics, Southampton Electrochemistry Group. Published by Ellis Horwood Ltd., Chichester, U. K., 1985.
6. J.A.von Fraunhofer and C.H. Banks:in Potentiostatand itsapplications. Chapter3. Published
by Buttenvorths, London, 1972.
7. I. Gillet: Bull. Soc. Chim. France, 1962,377,
8. U. Landau, N.L. Weinberg and E. Gileadi: J. Electrochem. Soc., 1988,135, ( 2), 396.
9. R. Morrison: in Grounding and ShieldingTechniques in Instrumentation. Published by John
Wiley & Sons, Inc., 1967.
10.Various potentiostat instruction guides and leaflets to be obtained from manufacturers, for
instance EG and G Princeton Applied Research Application note G-2: Grounding and Shielding in
Electrochemical Instrumentation: Some Basic Considerations.
11, D.D. Macdonald: in Transient techniques in electrochemistry. Chapter 2.2. Published by
Plenum Press, New York and London, 1977.

12. B.D. Cahan, Z. Nagy and M.A. Genshaw: J. Electrochem.Soc.,1972,119,64.


13.L. Clerbois, E. Heitz, F. P. IJsseling,J. C. Rowlands and J. P. Simpson: Br. Corros. J., 1985, X!,
(3), 107.
14. A. D. Mercer and G. M. Brook: Trib. Cebedeau, 1975, Aug.-Sept., (417/418), 299.

25

15. J. Postlethwaite and R.A. Brierly: Corros. Sci., 1970,U


,J' 885.

16. Yu.V. Pleskov and V.Yu. Filinovskii, (transl. by H.S. Wrobla):in The rotating disk electrode.
Chapter 9 . Published by Consultants Bureau, New York and London,1976.

17.E.A. Lizlovs: J. Electrochem. Soc., 1970, 117,1335.


18. F.P. IJsseling:Br. Corros J., 1980,

51.

19. I.R. Scholes et al.: in Proc. 6th Eur.Congress on Met.Corrosion. Published by the Society of
Chemical Industry, London, 1977,161.
20. J.M. Krougman and F.P. IJsseling: in Proc. Intern. Workshop Electrochemical Corrosion
Testing, Ferrara; 1985. Monograph vol. 110. Published by DECHEMA, Frankfurt, FRG, 1985,135.
21. A.S.T.M. G5-82: Standard Practice for Standard Reference Method for making Potentiostatic
and Potentiodynamic Polarization Measurements. Published by A. S. T. M., Philadelphia, U. S. A.
22. Techniques in Electrochemistry, Corrosion and Metal Finishing, a Handbook, part A (ed. A.
T. Kuhn). Published by John Wiley & Sons, Inc., 1987.
23. R.E. Geisert, N.D. Greene and V.S. Agarwala: Corrosion, 1 9 7 6 , z 407.
24. B. Gerodetti and K.H. Wiedemann: Werkst. und Korr., 1 9 7 7 , a 173.
25. J.R. Scully, H.P. Hack and D.G. Tipton: NACE Intern. Corrosion Forum, Boston, 1985, paper
no. 214. Published by NACE, Houston, Tx., U. S. A., 1985.
26. T. Hakkarainen: in Proc. 8th European Corrosion Congress, Nice, 1985. Published by Soc.
Chimie Indus., Paris, France 1985,26.
27. P. E. Francis and A.S. Dolphin: Br. Corros. J., 1 9 8 4 , B 181.
28. R. Manner and E. Heitz: Werkst. und Korr., 1978,

a 559.

29. H. Lajain: Werkst. und Korr., 1972,23- 537.


30. T. Suzuki and Y. Kitamura: Corrosion, 1 9 7 2 , a 1.
31. A. Tamba: Br. Corros. J., 1 9 8 2 , E 29.
32. D. D. Macdonald, B. C. Syrett and S. S. Wing: in NACE Intern. Corrosion Forum, Houston
1978, paper no. 25. Published by NACE, Houston, Tx., U. S. A., 1978.
33. F. Hunkeler and H. Bohni: Werkst. u. Korr., 1981,32- 129.

34. J.R. Scully, H.P. Hack and D.G. Tipton: Corrosion, 1986,42- 462.
35. T. Suzuki, M. Yamabe and Y. Kitamura: Corrosion, 1973,

a 70.

36. R. B. Diegle: Materials Performance, 1982,21, (3), 43.


37. E. Bardal, R. Johnsen and P. 0.Gartland: Corrosion, 1984,

628.

38. G. A. Gehring,Jr. and J. R. Maurer: in NACE Intern. Corrosion Conf.,Toronto,Canada, 1981,


paper no. 202; Published by NACE, Houston, Tx., U. S. A.
39. D. A. Jones: Corrosion, 1984,40-

181.

40. 0. Varjonen and T. Hakkarainen: in Proc. 8th Europ. Corrosion Congress, Nice, 1885.
Published by Soc. Chimie Indus., Paris, France, 1985,44.
41. L.L. Shreir: Werkst. und Korr., 1970,2l- 613.
26

CHAPTER 3

ELECTRODE DESIGN
E. HEITZ
Dechema Institute, Frankfurt, FRG

3.1 INTRODUCTlON
An electrode may be defined as a solid electron conductor which is in contact with a liquid (solid,
gaseous) ion conductor (electrolyte).At the interface charge transfer reactions take place. During
corrosion processes this charge transfer involves anodic and cathodic partial reactions of various
kinds which are dependent on many parameters and which have to be taken into account when
designing an electrode.
Theelectrodemaybea metalor any electron-conductingmaterial, for examplea semi-conductor
which acts as a source or sink for electrons.
The electrolyte usually consists of a solution of salts, acids or bases in water or protic solvents,
such as alcohols, carboxylic acids, etc. [ll. Pure solvents, too, can act as electrolytes if enough conductivity by autodissociation is produced (water, methanol, ethanol, etc.).Moreover, molten salts
constitute electrolyteswith sometimesextremely high conductivity.It is important to state that the
electrolyte should be free from any electronic conductivity otherwise no electrochemical reaction
will occur at the electrode/electrolyte interface.
As discussed in a previous chapter electrodesare used as working electrodes,counter electrodes
and reference electrodes. In this chapter emphasis is laid on working and counter electrodes.

Working electrodes are further divided into:


(a) Electrodes for polarisation measurement in electrochemical cells
(b) Electrodes for free corrosion experiments.
Designs for working electrodes are diverse. Therefore, in the following sections only the most
important design principles will be discussed.
Counter electrodes should be made from a corrosion resistant metal, for example a noble metal,
and their design should allow for uniform current (potential) distribution and free convection of
aggressive agents to the working electrode.

3.2 SIZE OF ELECTRODES


Size and geometry are among the most important aspects to be considered in designing or choosing
a particular electrode configuration [21.
In order to study kinetics and mechanisms small plates, foils, spheres, discs, rods or wires are
used. They permit high current densities with minimumohmic heating or cases where high-current
sources are not available. If localised corrosion has to be studied a certain minimum area must be
guaranteed. The size has to be chosen so that the corrosion effect occurs with high probability on
the electrode surface. This is especially valid when measuring the potential dependence of pitting,
stress corrosion cracking, etc.

27

Another reason for designing electrodes of a certain size is the combination of weight loss with
electrochemicalmeasurements. Thus, very small electrodes should not be used when gravimetric
measurements are required.
On the other hand, the use of microelectrodes has attracted interest in the study of corrosion
effects on a microscopic scale. Microelectrodes the size of a few micrometers have been described
[3,41.
Problems associated with size can be assessed by the principles for scaling corrosion tests. A
report has been published by the European Federation of Corrosion Working Party on
Physicochemicalmethods of corrosion testing - fundamentals and application[51which includes
information on specimen size for testing uniform, bimetallic and pitting corrosion and stressassisted environmental cracking.

3.3 DESIGN WITH REGARD TO VARIOUS CORROSION PARAMETERS


3.3.1 Current and potential distribution

In principle, current measurements only give integral values as current per total electrode surface
exposed.On real electrode surfaces the current distribution is more or less non-uniform. This holds
particularly for cases of non-uniform corrosion attack.
Since measurement of the current distribution is only possible with considerable effort (segmented electrodes), some general rules for minimizing non-uniformity will be presented (for
theoretical background, see refs. [5- 71).
If a working electrode (length L) with a parallel counter electrode (distance h), as in Fig. 3.1, is
considered the current distribution is the more uniform the larger the ratio L/h. From this the
following recommendations can be given:
-a design should be chosen with working and counter electrodes as close as possible (taking into
account possible interference of anodic and cathodic reaction products)
-the smallest electrodes possible should be selected (without interfering with statistical effects,
section3.2).
From the concept of the dimensionless Wagner Number [5, 71 the following conclusions are
derived:

- if possible, low conductivity solutions should be avoided


- polarisation resistances should be as high as possible.
This last statement means that electrodes producing higher currents during polarisation show
a more non-uniform current distribution, since high currents are correlated with low polarisation
resistances.
The rulescited give some useful working/counter electrode designs which are shown in Fig. 3.2.
It should also be mentioned that the cylindrical geometry has also been successfully used to
minimize ohmic drop in media of low conductivity.
When using plate electrodes it is necessary to consider whether the reverse side should be
insulated. This is not necessary in systems with high conductivity and with sufficient distance
between the electrode and the cell wall. Insulated plate electrodes produce problems as a result of
crevice formation. The best solution is, however, to provide the plate electrode with two counter
electrodes situated on both sides of the plate.
Reference electrodes are generally used together with Haber-Luggin capillaries (for details, see
Ref. [2]).The design and position of these capillaries pose current and potential distribution
problems. In order to minimize ohmic drop they have to be placed as close as possible to the
electrode surface.But if the distance is too small they act as a current shield and non-uniform current
distribution arises. In practice the tip of the Luggin probe should be at a distance of about 2 d from
the working electrode where d is the external diameter of the capillary.
28

t-

Pr
/..#..

................

Fig. 3.1: Current distribution on parallel plate electrodes of length L and distance h

cylindrical geometry

?Q

rotating disc
parallel plate
(parallel plane arrangement)

Fig. 3.2: Electrode design with various geometries to minimize non-uniformity of current
distribution

3.3.2 Mass transfer


Mass transfer influenced corrosion reactions can only be investigated on electrodes or specimens
which are exposed under well-defined hydrodynamic conditions. A number of electrode designs
used in the past are shown in Fig. 3.3 [8,91.

For basic studies the most suitable type is the rotating disc which is either placed in the end face
of a rotating cylinder, Fig. 3.2, or is used as a free rotating system with an integral shaft, Fig. 3.3 [71.
Further models are the rotatingcylinder, free or co-axial [ll,121, and pipe and channel flow [7,141.
Compared with the situation with the rotating disc channel and pipe flows will generally
become turbulent at relatively low flow rates although the extent to which this happens will depend
on the dimensions of the cross-section (characteristiclength). Their practical advantage is that they
affordbetter access to themeasurement section thando rotatingmodels,but the flow isnot soeasily
achieved. The test pieces are arranged and the dimensions chosen so that the test pieces are
electrically insulated and inserted flush in the flow path. Care must be taken to ensure that the join
between the wall of the pipe and the test piece is hydrodynamically smooth, this being particularly
necessary with the flow channel. Another possibility is to construct the test piece itself as a rotating
entity. This is the case, for instance, with the rotating disc and the rotating cylinder.
A special arrangement is the ring-disc electrode which is currently often used for kinetic and
mechanistic studies [13]. In this case the rotating disc is surrounded by a ring electrode which is
separated by a thin non-conducting gap.
For measurementsin disturbed turbulent flow which is important for many practical applications
the segmented pipe technique has been successfully applied [14,15]. The pipe is divided into rings
which are arranged in electrical insulation from each other, permitting local mass loss measurements and electrochemical measurements along the pipe axis.

29

@Rotating disc

Disc i n casing

Rotating
cylinder

Coaxial cylinder

Flow in
a channel

Flow in
a pipe

Fig. 3.3: Electrode arrangements for investigation of flow dependent corrosion [8,91

.Referenrn
.- . -. -. . - - elnrtrodn- .- - _.- - Cooler

Heater

--..

Counter electrode
I

Holder
Thermosensor
PTFE Cover
PTFE Container
working electrode/
specimen
Thermal insulation
Corrosive medium

Conductivity sensor

Fig. 3.4: Electrodes for CERTexperimentsin a PTFE cell for aggressive corrosionconditions 1211

3.3.3 Heat transfer

The simultaneous measurement of heat transfer and electrochemicalquantities has been described
in the literature [16-181. Tubular and disc-shaped specimens proved to be suitable although difficulties arose in obtaining uniform heat transfer on the surface. For example, it was found that
crevice corrosion can occur in the side insulation of disc electrodes. This effect may be attributed
in some cases to the decreased heat flux and therefore higher surface temperature on the outer
circumference of the specimen.

30

Electrodes of the "cooling finger" type could also be used for controlled heat flux experiments.
Specific experience with a rotating cooling finger has been made available 1191and a combination
of ring-disc with heat transfer measurements has recently been described [201.
3.3.4 Mechano-chemicaltesting

Mechano-chemical testing comprises the suitable application of stress, pressure, bending, thrust
and torsion on specimens in specific media either in a time constant or cyclic mode. There are no
specialproblems in applying potentials or currents to such specimensprovided suitable provisions
for electrical contacts and electrode insulation are made.
As an example, provisions for electrochemical measurements during CERT (Constant Extension Rate Testing) are shown in Fig. 3.4 [21,221.
Special requirements for this set-up are that for standardized specimensfor CERT the insulated
specimen holder should be of the same material as the test material and there should be low friction
sealing of the specimen holder.
Standardized specimens for CERT are conventional cylindrical specimens, notched or smooth,
which are loaded at a slow strain or continuous extension rate 1231.
In order to avoid bimetallic corrosion the specimen holder of the same material has to be
insulated by a polymer coating. More noble material can be used if bimetallic corrosion is absent,
but this has to be proved by separate electrochemical experiments.
During CERT an extremely slowly moving specimen has to be sealed. A design as shown in Fig.
3.4 may be chosen.
3.3.5 High temperature/high pressure testing
Testing under high temperature/high pressure conditions is done in normal autoclaves or in
refreshed autoclaves. There are a number of problems to be overcome, which include sealing and
insulation of the electrodes, the choice of a suitable (pressure and temperature stable) reference
electrode and possibly control of the parameters discussed above.

Relevant reviews [24, 251 and special papers on technical solutions to problems exist, as, for
example, for high temperature reference electrodes [26,27l, apparatus with exchangeable electrodes for measurements up to 330C and 300 bar [281, CERT experiments under high pressure and
temperature [29] and electrochemical measurements for hydrogen permeation up to 600 bar [30,
311.

3.4 PROBLEMS CONCERNING APPLICATION TECHNIQUES


Essential experimental problems to be overcome are [21:
(a) defining the working area
(b) making good electrical contact
(c) holding the electrode rigidly.
If an electrode is exposed in an electrochemical cell it is necessary to know its working area.
Defined working areas may be achieved by theuse of coatingsor compressiongaskets. A systematic
comparative study of a number of systems revealed that hot-cured epoxy resin and compression
type gaskets are relatively the best solutions 1321. One of the problems encountered with passivating systems is crevice corrosion at the threephase boundary electrode-coating- electrolyte.
Due to the low ratio of volume/surface in the crevice small anodic polarisation or even free
corrosion leads to preferential attack in the crevice. Coatings and gaskets free of crevices therefore
have to be applied. A survey of the literature on attempts to overcome this problem has been
published 121.

In making electricalcontact to electrodes the resistance of the contact between the specimen and
the current lead should be as low as possible. Pressure contact is often used, but problems may arise
as a result of passivation or contamination of the contact if an electrolyte should enter the contact

31

area. Spot welding or soldering are attractive solutions,but care must be taken to avoid preferential
attack at the contact. It is useful to protect the contact area by PTFE tape or an electroplater's
lacquer[21.
If the current lead is a noble metal, for example platinum, and if the working electrode is a metal
in the active state, it is possible to expose the noble metal wire to the electrolyte provided its area
is small compared with that of the working electrode and its polarisation resistance larger than that
of the working electrode.
Electrode holders need to be held rigidly in place and should be easily removable. Ground glass
jointsor screw capadapters withcompression ringsareuseful solutions forsimplelaboratorywork.
Descriptions of techniques for cases of extreme conditions of temperature, pressure, flow and
mechanical load are described elsewhere in this volume.

3.5 REFERENCES
1.E. Heitz: in Advances in Corrosion Science and Technology. Published by Plenum Press, (ed.
M. Fontana and R. Staehle),London, 1974, & 149.
2. A. T. Kuhn: Techniques in Electrochemistry, Corrosion and Metal Finishing. Published by
John Wiley & Sons, Inc., 1987.
3. A. M. Bond, M. Fleischmann and M. Robinson: J. Electroanal. Chem. 1984, 168.299.
4. R. T. Atanasoski, H.S. White, W.H. Smyrl: J. Electrochem. Soc. 1986,133,2435.
5. L. Clerbois, E. Heitz, F.P. IJsseling,J.C.Rowlands and J.P. Simpson: Br. Corr. J. 1985,

a 107.

6. N. Ibl: Current Distribution, in Comprehensive Treatise of Electrochemistry (Eds. E. Yeager,


J. 0.M. Bockris, B. Conway, S. Sarangapani) Vol. 6, Plenum Press, 1983,b.
7. E. Heitzand G. Kreysa: Principlesof ElectrochemicalEngineering; Published by VCH-Verlag,
Weinheim, 1986.
8. U. Lotz and E. Heitz: Werkst. u. Korr. 1983,_34,454.

9. DIN Specification50920 Corrosion Testing in Flowing Liquids: Beuth Verlag, Berlin, 1987.

10. N. Ibl and 0.Dossenbach: Convective Mass Transport, see Ref. [61.
11.0. Dossenbach: Ber. Bunsenges. Phys. Chemie 1976,

34.

12. E. Heitz, G. Kreysa and C. Loss: J. Appl. Electrochem.

243 (1979)

13. Instrumental Methods in Electrochemistry; Southampton Electrochemistry Group. Published by Ellis Horwood Limited, Chichester, U. K. ,1985,113.
14. U. Lotz, M. Schollmaier and E. Heitz: Werkst. u. Korr. 1985, -63 163.
15. T. Kohley and E. Heitz: in The Use of Synthetic Environments for Corrosion Testing', STF
970. ASTM, Philadelphia, U. S. A., 1988, 235.
16. Corrosion under Heat-Transfer Conditions: MTI Publ. Nr. 17, Materials Technology Institute, Columbus, Ohio, U. S. A., 1985.
17. Ya.M. Kolotyrkin, V.S. Pakhomov, A.G. Parshin and A.V. Checkhovski: in 'Proceedings of
the 9th International Congress on Metallic Corrosion', NACE, Houston, Tx, U. S. A., 1984,z 1.

18. M. Yasuda, M. Okada and F. Hine: Corrosion - NACE, 1982,38-

256,

19. M. Shirkhanzadeh, V. Ashworth and G.E. Thompson: Electrochim. A. 1988,3332

265.

20. Arbeitsgemeinschaft Korrosion e.V., Arbeitsblatt Wl, Werkst. u. Korr. 1988,B.


21. H.-G. Fellmann, H. Kalfa, U. Schare and E. Heitz: Werkst. u. Korr. 1 9 8 9 , a 34.
22. E. Heitz, R. Henkhaus and A. Rahmel: Korrosionskunde im Experiment, Verlag Chemie,
1983, (English edition in preparation).
23. DIN Specification 50922, Untersuchung der Bestindigkeit von Metallen gegen Spannungsrisskorrosion, Beuth-Verlag, Berlin.
24. G. Jones, J. Slater and R.W. Staehle (Eds.):HighTemperature/ High Pressure Electrochemistry in Aqueous Solutions;NACE, Intern. Corrosion Conference SeriesNo.4. NACE, Houston, Tx,
U.S.A., 1973.
25. J.V. Dobson: EMFMeasurementsat Elevated Temperatures and Pressures; Adv. in Corr. Sci.
and Technol. (Eds. M. Fontana, R. Staehle); Plenum Press, 1980,2,177.
26. P.D. Macdonald: Corrosion, 1978,34- 75.
27. M. Hishida, H. Takabayashi, T. Kawakubo and Y. Yamashina: Corrosion, 1985,4l-

570.

28. M.L. Brown and G.N. Walton: J. Appl. Electrochem.l976,6- 551.


29. H. Hurst, D.A. Appleton, P. Banks and A.S. Raffel: Corros. Sci. 1985,26-

651.

30. D. Festy: Proc. Eurocorr. 87, DECHEMA, Frankfurt, 1987,641.


31. G. Schmitt : in Wasserstoff und Korrosion (Ed. D. Kuron), p. 332, Verlag Irene Kuron,
Bonn/FRG (English translation in preparation).
32. N. D. Greene, W.D. France Jr. and B.E. Wilde: Corrosion, 1965,2l-

275.

33

CHAPTER 4

REFERENCE ELECTRODES
E . ERIKSR
UD
Veritas Research, Hovik, Norway
AND

E. HEITZ
Dechema Institute, Frankfurt, FRG

4.1 INTRODUCTION
Thebookeditedby Ivesand Janz [ll andmorerecently thatbyBard,Parsons,and Jordan[21 contain
both theoretical and practical aspects related to reference electrodes. Preparation, application and
limitations of various types of reference electrodes such as the hydrogen electrode, the calomel and
other mercury-mercurous salt electrodes, the silver-silver halide electrodes,and sulfide and sulfate
electrodes are covered and general reference to these excellent critical reviews is recommended.
The role of the reference electrodein electrochemicalstudies is to provide a fixed potential which
does not vary during the experiment. In most cases, the potential of the reference electrode relative
to an agreed standard, for example to the normal hydrogen electrode, is required. In other cases it
is only necessary for the reference electrode to remain at the same potential during the experiment,
for example during a linear polarization resistance or a potential sweep experiment.

4.2 CHOICE, STABILITY, INCOMPATIBILITY


In corrosion tests all the types of electrodes listed above may be used depending on the corrosive
environment and the aim of the test.
If possible the reference electrode should be designed to be as similar as possible to the system
under investigation.This is both to minimize contamination of the reference electrode (e.g.chloride
ions diffusing into the sulphate solution of a copper/copper sulphate reference electrode will
change the potential of the reference electrode) and to avoid misleading corrosion test results by
ions from the reference electrode entering the test solution (e.g. chloride ions in a pitting corrosion
test in sulphate solution).With large differencesin the ionic concentration of the test and reference
electrode solution,a liquid junction potential may make an essential contribution to the potential
measured between the working and reference electrodes. However, this is usually not a serious
error in corrosion tests.
It should be pointed out, that if a liquid junction potential is minimized by using a common test
solution and solution for the reference electrode, e.g. by dipping a Ag/AgCl wire directly into the
test solution containing chlorides, the potential of the reference electrode may vary with concentration of the test solution. For the Ag/AgCl electrode the change will be roughly60 mV per decade
change in chloride concentration.

4.3 CHECKING OF THE REFERENCE ELECTRODE SOME PRACTICAL


ADVICE
It is good practice to have reference electrodes to be used only for checking the reference electrodes
used in the tests. Preferably, three saturated calomel reference electrodes should be kept for this
34

purpose. These should be within 2 1-2 mV of each other when checked for example in a chloride
solution. These electrodes should be stored in a dry condition for periods of non use, with a rubber
sealing ring over the filling hole and a black rubber cap on the immersion tip during storage.
The working reference electrode should be checked both before and after a test. In long term
tests, it should also be checked during the experiment.
When using saturated KC1 solution bridged electrodes it is essential that the solution contains
undissolved KCl to ensure that it remains saturated. Air bubbles must not be present inside the
electrode. If KC1 crystals seem to trap air bubbles in the electrode and these cannot be removed by
shaking [31, the working tip should be immersed in warm distilled water, until most of the crystals
are dissolved. The air bubbles can now be removed by shaking the electrode. The inside of the
electrode should never be flushed with anything but saturated KCl solution.
Recently, for environmental reasons Ag/AgCl reference electrodes are becoming more widely
used as they contain no mercury or mercury salts.

4.4 MORE SPECIFIC REQUIREMENTS


In practice the main requirement of a reference electrode is that it hasa stable potential and that this
is not substantially changed during the experiment. This is the case with the hypothetical,
completely non-polarizable electrode, the potential of which is unaffected when electric current
flows across the metal-solution interface. For practical conditions this means that the exchange
current must be large compared with any net current that it is required to pass in use. Ideally no
current flows through the reference electrode (in a three electrode system) if a high impedance
(>lOMn) voltmeter is used.
If temperatures and/or pressures other than 25 Cand 1atmosphere are to be used, the stability
of the reference cell with respect to such environments must be ensured.
In line with requirements for the cell in general, the ohmic resistance of the reference electrode
should be reduced to a minimum in order to make the best use of the sensitivity of the recording
instruments. It may be tempting to use thin capillaries to prevent interdiffusion of the electrode
solutions,but thisis often found to result inan intolerablelossof sensitivity.Theconflictof interests
may sometimes be resolved by inserting a wide-bore tap, opened only when measurements are to
be made, between the electrode vessels. Unobserved gas bubbles trapped in solution bridges are
sometimes responsible for high cell resistance.
A lowering of the internal resistance of the electrode by eliminating ceramic frits and porous
plugs, also has the advantage of a faster response time [4] which is particularly important in the
study of fast electrode reactions using transient techniques.

4.5 SOME COMMON ELECTRODES FOR AQUEOUS SYSTEMS [4]


4.5.1 Mercury-mercurouschloride (calomel)

This is probably the most widely used reference electrode. It is usually made with a saturated
aqueous potassium chloride solution bridge, although 1mol/dm3 and 0.1 mol/dm3 solutions also
are commonly used (see Table 4.1). Calomel electrodes can have very low resistance and good
performance. For this reason they are frequently used for checking other types of electrodes.
4.5.2 Mercury-mercuroussulphate
This electrodecorresponds to the calomel, with sulphate instead of chloride.It is useful for sulphate
solutions, but becomes unstable if the sulphate concentration falls below 0.1 mol/dm3.
4.5.3 Mercury-mercuric oxide

This electrode is recommended for use in alkaline solutions.


4.5.4 Silver-silver halide

These electrodes give very stable potentials in halide solutions provided the halide concentration
is not too high, when the increasing solubility of the silver salt causes problems [2].They are easily
prepared in the laboratory, but must be shielded to exclude light and contamination should be
avoided.

35

~~

~~

Table 4.1: Potentials and fields of application of various reference electrodes

Electrode
system

Electrolyte

Potential
v s SHE
at 25OC

'Brnperature
range

mV

O C

Temperature
coefficient
mV/'C

+ 242

0 to 7 0

-0.65

Field of
application

Hg/Hg, C1 2 / C 1-

KC1. s a t .

Hg/Ngz Cl 2/C 1-

ICC1 1 M

+ 280

0 to 7 0

-0.24

general

HglHg2Cl2/C1-

KC1 0.1 M

+ 334

0 to 70

-0.06

general

Hg/Hg2S04/Sd4

K2SO4 s a t .

+ 640

0 to 70

sulfate containing media

Hg / H go / OH-

NaOH 1 M

+ 98

alkaline media

AgIAgClIC 1-

KC1 0 . 1 M

+ 288

0 to 95

-0.5

general

AgIAgC1 I C1-

KC1 3 M

+ 207

80 to 1 3 0

-1.00

hot media

0 to 150

0.1

HgTI/TlCl

KCl 3.5 M

507

general

hot media

In Table 4.1 the temperature range of applicability,the temperature coefficient and the fields of
application of various reference electrodes are given.
4.5.5 Reference electrodes in non-aqueous systems
All reference electrodesare prepared with aqueous solutions. Their use in non-aqueous systems is
possibleaslongasliquid junction potentialsat theaqueous/non-aqueoussolutionphaseboundary
are small. This is the case for primary alcohols such as methanol, ethanol, isopropanol and for
dioxan solutions. The standard electrode potentials of the calomel electrode and the silver/silver
chloride electrode have been determined in such solutions. If potentials in aprotic (non water-like)
solvents have to be measured, difficultiesarise. More detailed discussions are given in refs. [SI and

El.
4.6 REFERENCES
1. Reference Electrodes, Theory and Practice, Edited by D.J.G. Ives and G.J. Jam, Academic
Press, 1961.
2. A. Bard, R. Parsons and J. Jordan, Standard potentials in aqueous solutions. Marcel Dekker,
New York and Basel, 1985.
3. Fixed Offshore Installations, Monitoring of cathodic protection systems, Technical note TNA
705, Det norske Veritas. April 1984.
4. Instrumental Methods in Electrochemistry, Southampton Electrochemistry Group. Published by Ellis Horwood, Chichester, U.K.,1985

5. E. Heitz, Corrosion of metals in organic solvents from "Advances in Corrosion Science and
Technology" (ed. M. Fontana and R. Staehle),Vol. 4, Plenum Press, 1974.
6. C. T. Mussini and F. Mazza in "Electrochemical Corrosion Testing", Monograph 101.
Published by DECHEMA, Frankfurt, FRG (ed. E. Heitz, J. C. Rowlands and F. Mansfeld) 1986, pages
67 and 79.
36

CHAPTER 5

EFFECTS OF SPECIMEN
PREPARATION AND SURFACE
CONDITION
J . SIMPSON
Sulzer Bros, A. G., Winterthur, Switzerland

5.1 INTRODUCTION
The state of the surface at the time of measurement can have a large influence on the values of the
electrochemical parameters being measured. The surface state is dependant upon the whole
preparation history right up to the moment of measurement.
The stages which must be considered are:
(a) Choice of specimen material
(b) Sampling and specimen preparation
(c) Surface preparation before immersion in the test solution
(d) Effect of the conditions within the cell before commencement of the measurement
(e) Changes caused by the measurement itself.
From the nature of the subject, it is not possible to treat this topic exhaustively within these
guidelines; this section is intended to increase the readers awareness of the many factors in the
preparation stage which can influence subsequent electrochemical corrosion measurements.

5.2 CHOICE OF SAMPLE


It is important that the metallurgical condition and chemical composition of the sample are well
defined. These parameters can vary considerably depending on manufacturing process and heat
treatment .
A further problem is that a material is rarely homogeneous.The choice of the source material for
the specimen will largely depend upon the aims of the experimental work. When studying
corrosion behaviour for practical applications, samples taken from components or material with a
similar production history are preferable. On the other hand, if material is simply taken from the
next available source of material of nominally the same specification,it may not be truly representative of the material as used in practical applications.

5.3 SAMPLING AND SPECIMEN PREPARATION


Metallurgical structure can vary considerably with position and orientation of the sample.
Castings and weldments are obvious examples where structure and chemical composition can
vary considerably. Even wrought material, whether drawn, extruded, rolled or forged, is very
rarely homogeneous; these materials will commonly have a texture (i.e. a preferential grain
orientation) and other directional features such as elongated grains and aligned elongated inclusions. Through section variations must also be considered.

37

The surface composition can differ from the bulk after heat treatment: processes such as
decarburization, nitriding, surface oxidation with diffusion of dissolved oxygen into the metal
(often observed in titanium alloys), or depletion of an alloying element at the surface, can give the
surface very different properties to the bulk material. In such cases it must be decided whether the
properties of the modified surface or the bulk material are of interest .
It is important to bear such points in mind before sampling and preparing the specimen for
mounting.Specimen samplingprocedures,orientation, surface preparation and specimenmounting
techniques should be decided before sectioning the material rather than later.

To illustrate the above points, one may consider the pitting potential of stainless steels in
chloride solutions.The value of this potential is strongly dependent upon the degree of cold work
and the orientation of the sample. A decrease in pitting potential was demonstrated for AISI-316L
stainless steel in physiological saline solutions with increasing degree of cold work.The pitting
potential was lower in the transverse than in the longitudinal direction. Such anisotropy may also
be present in hot worked and annealed samples due to texture effects [ll. Differences in electrochemical behaviour with cold work and specimen orientation were also noted for austenitic
stainlesssteels in acid solutions; the critical current density for passivation in 1M I-$SO,at 25C was
10times greater in the transverse than the longitudinal direction at 30%cold work and the passive
current density in 0.1M HC1 at 25C differed by up to 1000 times depending upon specimen
orientation [21.
Methods used to prepare the sample should not produce any changes in its condition. The most
common problems are heat generation on separation (e.g.from high speed abrasive cutting wheels)
and cold work on machining, grinding, shearing or cutting. In general standard metallurgical
specimen preparation techniques are adequate for separation from bulk material. Water cooled
abrasive high speed wheels for cutting down to the final size are suitable in most cases. For fragile
or extremely heat sensitivespecimensa cold slow speed diamond wheel is often thebest alternative.
Specimen size and mounting are discussed in Chapters 2 and 3 as they are highly dependent
upon cell design and the type of measurement envisaged.

5.4 SURFACE PREPARATION BEFORE IMMERSION IN THE TEST


SOLUTION
The specimen surface is often prepared before measurement to ensure a reproducible and known
surfacecondition. Metallurgical surfacepreparation techniques are commonly used, these include:
wet grinding on silicon carbide abrasive papers, polishing with diamond or alumina media,
electropolishing, chemical polishing, pickling or etching.
Electrochemical corrosion measurement results can be strongly dependent upon surface
preparation technique. The causes can range from a simple surface area effect of different surface
treatments, through secondary effects of the surface preparation technique on the substrate, to
chemicalchangeson the surfaceduringsurfacepreparationand during the timebetween preparation
and immersion in the test medium.
Mechanical preparation techniques such as grinding can introduce significant cold work into
the surface layers e.g. the pitting resistance of ground austenitic [31 and ferritic stainless steel
surfaces [4] has been shown to be inferior to that of electropolished surfaces.This was attributed to
the presence of cold worked surface layers from grinding, although chemical or electrochemical
surface treatments can preferentially remove less resistant phases, e.g.inclusions, which would
otherwise be responsible for an inferior corrosion performance .
A point often neglected is the handling procedure between preparation of the surface and
immersing the specimen in the test medium. For instance, oxide film formation on oxide-passive
materials and or tarnishing layers on copper or iron alloys formed at this stage can influence the
electrochemical behaviour considerably; these chemical changes on the surface depend on such
factors as temperature, humidity and time [5].

38

5.5 EFFECT OF THE CONDITIONS WITHIN THE CELL BEFORE


COMMENCEMENT OF THE MEASUREMENT
The time between placing the specimen in the corrosion cell and the commencement of the
measurement itself must also be counted as part of the surface preparation procedure. The value
of the electrochemical parameter sought may vary considerably if insufficient attention is paid to
this point [6-81. It is preferable to consider this period as part of the measurement itself, reducing
the chances of random variations.
For measurements made at or near the free corrosion potential (e.g. polarization resistance or
some impedance measurements), the most important factors to be considered are:
(i) Control of the medium; e.g. temperature, composition and agitation. For instance, the rest
potential of mild steel in aerated salt solutions is dependant upon the degree of agitation [61, in this
system even convectionmaybe significant,as would consumption of dissolved oxygen by the steel.
(ii) Time; prepared surfaces are rarely in their stable surface state with respect to the medium
when immersed, for instance the zero current potential of a mild steel sample in aerated 0.01 M
NaHCO, at 65C changed from-400mV (S.H.E.)to +240 mV after 100minutes and 6days immersion
respectively due to the formation of surface oxides [71.
The situation becomes more complex when any in situ surface pre-conditioning techniques are
employed; often cathodic or anodic pretreatments are used. These should be treated with caution.
Cathodic treatments can reduce oxide films and introduce hydrogen into the metal, both of which
can effect any subsequent electrochemicalmeasurement [7,8].Anodic treatment may passivate the
surface or roughen it by anodic dissolution.

5.6 CHANGES CAUSED BY THE MEASUREMENT ITSELF


It is important to distinguish between changes in the surface condition caused by the corrosion
process and those forced on the specimen by the measurement technique. The aim may be to
monitor the former, the latter may lead to misleading readings or interpretation problems.
Many electrochemical corrosion techniques are perturbation techniques, i.e. either an external
potential or external current is applied. These can modify the surface, be they anodic causing
dissolution or passivation, or cathodic causing surface oxide reduction or hydrogen production.
The effect is normally one of degree. The measurement of a corrosion potential does not
influence the surface condition. Electrochemical noise and impedance measurements carried out
at the corrosion potential also have little effect as does a polarization resistance measurement if the
perturbation is small, although rest potential drift may be a problem if potential control
techniques are used. Techniques involving large potential differences will in general modify a
surface significantly.
It should be borne in mind when repeating an experiment without using a fresh specimen or
fully repreparing the surface, that the surface condition is unlikely to be the same as the initial state,
it will have been modified either by the exposure to the medium or by the measurement technique.

5.7 REFERENCES
1. A. Cigada, B. Mazza, P. Pedeferri and D. Sinigaglia:J. Biomed. Mater. Res.,1977,l 503.

2. B. Mazza, P. Pedeferri, D. Sinigaglia, A. Cigada, G. Fumagalli and G. Re: Corros. Sci.,


1979,19,907.
3. R. W. Revie and N. D. Greene: Corros. Sci., 1969,a 763.
4. R. P. Frankenthal: Corros. Sci., 1968,& 491.

5. D. E. Dobb, J. P. Storvick and G. K. Pagenkopf: Corros. Sci., 1986,26-

525.

6. D. M. Brasher: Br. Corros. J., 1967,295.


7. G. K. Glass: Corros. Sci., 1986, & 441.
8. C. D. Kim and B. E. Wilde: Corros. Sci., 1970,

735.

39

CHAPTER 6

EVALUATION AND
COMPENSATION OF OHMIC DROP
L. CLERBOIS
Solvay et Cie, Brussels, Belgium
AND

F. P. IJSSELING
Corrosion Laboratory of Royal Netherlands Naval College,
Den Helder, The Netherlands

6.1 INTRODUCTION
Electrochemical systems generally contain a working electrode (WE), an auxiliary or counterelectrode (CE) and a reference electrode (RE).
During current flow the voltage difference between WE and CE consists of two parts :electrode
polarization and ohmic drop through the solution (IR).
The potential measured between WE and RE may be substantially influenced by an IR drop, in
particular if high current densities are applied or an electrolyte of low conductivity is used. This is
due to the fact that the reference electrode is connected with a point in the solution some distance
away from the electrochemical double layer. Thus an ohmic resistance - the so-called uncompensated resistance (Run> -is included in the solutionbetween the tip of the reference electrode and the
surface of the working electrode (Fig. 6.1). As a result an error will be introduced in the measurementof the potentialdifference in sucha way that the potential differencebetween the working and
reference electrodes is not as large in an absolute sense as indicated by the potentiostat or an
auxiliary voltmeter.
The importance of knowing the exact value of the ohmic drop or uncompensated resistance in
an electrochemical system has been pointed out by many workers. In studies of the kinetics of
electrodeprocessesby potentiostatic techniques, the ohmic potential drop produces a distortion of
the steady state polarization curve which, if uncorrected, will yield erroneous values of the
characteristic parameters (Tafel slope, reaction orders) of the electrode reactions (Fig. 6.2).

Also, measurements of the polarization resistance, RPI might be subject to considerable errors
due to the ohmic resistance which may lead to an underestimation of the corrosion rates by up to
several hundred percent.
The effect of uncompensated IR drop on corrosion rate determination using polarization
resistance measurements was discussed in depth by Mansfeld [1-31. He showed that in electrochemical measurements of the polarization resistance the experimental value R * is the sum of the
P
true value R and the uncompensated ohmic resistance RU,, which is essentially the electrolyte
Po
resistance but can also contain the resistance of surface films.

40

CE +e

m
I

WORKING
ELECTRODE

electrolyte

RE o

WE

@
Fig. 6.1 : (a) 3-terminal cell schematic; (b) detail showing Runt between surface of WE and isopotential plane of RE; (c) equivalent circuit.
Rmc = uncompensated resistance
Z = impedance of working electrode
Rs = solution resistance

Fig. 6.2 : Effect of ohmic drop on the shape of polarization curves.


The values of parameters are ba = 30 mV, bc = 120 mV, IC = 0.1 mA/cm2 [l,21.
Since
R * = Rpo + Run,
P

(1)

the relative experimental error is

Even if Runcis low, the error can be appreciable if R is also low, e.g., in systems with high
PO
corrosion rates. The same magnitude of error can be found for systems with low conductivity and
low corrosion rates. It is, therefore, not a question whether the absolute value Runcis low, but
whether the value Run, / Rpo is low. Similar equations were derived by other authors, e.g. Rocchini

MI.
41

Also in crevice and pitting corrosion, the ohmic potential drop may be responsible for the
stability of local attack on passive surfaces.
The subject is treated in most textbooks and introductions to electrochemical experimentation
(for instance refs.[5-14])and two literature reviews have been published 115,161.

6.2 EXAMPLES
Three examples showing the importance of ohmic drop correction are given below.
6.2.1 Polarization resistance
Mansfeld showed that even in highly conducting solutions involving high corrosion rates, the IR
drop, although small, cannot be disregarded, since the polarization resistance and RmCare of the
same order of magnitude. This is in particular true for the corrosion rate determination of carbon
steel in acid solutions [l-31. The dangerous consequence of neglecting Runt is that corrosion rates
willbeunderestimated. AnexamplecanbeseeninFig.6.3: without correctionthecorrosioncurrent
density was very low, whereas weight loss showed a high corrosion rate. After applying a
correction for the ohmic drop a significantly increased corrosion current density was found, which
correlated better with the corrosion rate obtained by weight loss.

4
corrected i

ia

2
h

Tu

E
\
O
4

1
O

-1

-2

..................................................

#' experimental

.................................................

-3

-4
-300

-200

-100

100

200

300

Fig. 6.3 :Effect of ohmic drop on the shape of the polarization curve for the system : low alloy
steel + EDTA 100 g/l; pH = 6, T = 100 "C,exposed area = 60.5 cm2, flow rate = 1m/s [171
6.2.2 Polarizationcurves in aqueous solution
Mansfeld [1,2] also pointed out that the lack of curvature in experimental polarisation curvescould

be a result of a high resistance. Some results of theoretical calculationshave been shown in Fig. 6.2.
A practical example is the case of gas bubbles reducing the conductivity of the solution. Gas
evolution from vertical or inclined working electrodes produces a varying electrolyte resistance,
with the effect being greatest at the top of the electrode.Electrolyte resistance measurements made
during gas evolution may therefore have little meaning.

42

A cathodic polarization curve for hydrogen evolution on platinum in 2.8 M sulfuric acid is
shown in Fig. 6.4.
1.2
1.0

.8
E
u

.6

.-- . 4
K

: .2
3

-.150

-300

-,450

0.600

9.750

-.900

-1.050

potential, U, volts
Fig. 6.4 : Polarization curve during cathodic hydrogen evolution (linear plot without elimination of ohmic drop)

Due to a significant IR-drop, this is nearly a straight line. Elimination of IR-drop yields over a
large range of current density a semi-logarithmic straight line, with a Tafel slope of 27 mV. Such a
result which gives also a reasonable Tafel slope at high current densities up to 1 A/cm2 may be
quoted to demonstrate the reliability of the method (Fig. 6.5).

.2
0.0

/.

-. 2 -. 4 9

4
.-0)

-C0

c.

b = 27 mV
l o g i = -3.1

/ .-

-.6

-.e

-1.0
-1.2

-1.4

2 -1.6
-1 . 8
L-

-2.0
- 2. 2
-.225

,240

7255

-270

,285

-300

potential (U-IR), volts (SCE)

Fig. 6.5 : Tafel plot of IR-drop corrected polarization curve of Fig. 6.4

6.2.3Polarization curves in non aqueous solution


Depending on the conductivity of the solutions the ohmic drop may vary considerably in organic
solvents. Whereas in solutions of primary (waterlike)alcohols such as methanol, ethanol (EtOH)
and propanol polarization curves with ohmic drop corrections can be obtained it is impossible to
make similar measurements in non water-like solvents such as long chain alcohols, halogenated
hydrocarbons and other aprotic solvents.
43

Figure 6.6 shows an example for Fe in 0.01N HCl/EtOH with and without IR-drop compensation. Without IR-drop compensation, a straight line is observed over the entire range of polarization. WhentheIR-dropiscompensated,curvatureisseenand the shape of thecurveindicates that
ba< bc.Without compensation of the ohmic drop Rp* was 357 ohms. On applying a compensation
technique Rp was found to be 74 ohms, R, being 212 ohms.
212
The error e = - = 2,86 or almost a factor of three.
74

Runc
R:

=:

2120

= 740

1-150

Fig. 6.6 :Experimental polarization curve for Fe in 0.01 N HCl/EtOH with and without IR-drop
compensation [21

6.3 PRINCIPAL METHODS


Although ohmic drop cannot be eliminated completely it can be minimized, while the remaining
effect can be taken into account, either by active methods, e.g. by some means of instrumental
compensation or passivelv, by calculation and subsequent correction.
In practice a combination of these methods is often used i.e., a good cell design to minimise the
ohmic drop, instrumental compensation of the greater part of the remaining error and, finally,
removal of the last part by evaluation, calculation and correction of the experimental data.
6.3.1 Minimizing of ohmic drop by cell and electrode design
Thus, the first step of any remedial action will usually be to minimize the value of the uncompensated ohmic drop. The design of the cell and the electrodesare the principal means of achieving this
objective.

Both subjects have already been treated in these guidelines and reference should be made to
Chapters 2 and 3.
6.3.2.1 Cell design
Generally cell design is dedicated to obtaining a constant current density over the surface of the
working electrode in combination with the use of a Luggin capillary for measuring the potential
difference between the surface of the working electrode and the solution. As the distance between
the tip of the Luggin capillary and the electrode surface decreases, so will the ohmic drop error.
However, the distance cannot be made very short without introducing screening effects on the
working electrode surface.
In practice a capillary tip of outer diameter d may be placed as close as 2d from the electrode
surface with negligible shielding error [181.

44

Figure 6.7 shows a schematic diagram of the equipotentials in question for the case of capillary
of diameter d placed 2d from a planar electrode; it can be seen that in this particular case the
potential that is sampled corresponds to anequipotential surfacethat is positioned 5d/3 away from
the electrode [191.

Desired Potential
Measured Potential
Capillary

b
E l.ectro de

Fig 6.7 : Schematic diagram of IR-drop in the electrolyte between capillary tip and electrode
The IR-drop not only depends on the diameter of the Luggin capillary and its distance from the
working electrode, but also on the specific conductivity of the solution and the geometry of the
working electrode. In Table 6.1 the IR-drop has been calculated for some simple geometries,
assuming constant specific conductivity [71.
Table 6.1 Theoretical equations for the IR drop for simple geometry types. Values have been
calculated for the probe placed 2d away from the electrode with 6 = 5d/3; K = 0.02lX' cm-';
ro = 4 x 10-3cm,d = 0.02cm and i = 20mA cm-*[71.

Georne t r y

Planar

Equation

VIR

/mv

33

From the equations given in the table it can be seen that the ohmic error is linearly dependent
on the distance between the RE and WE for a planar electrode. For a cylindrical WE, the error is a
logarithmic function of distance, whereas for a sphere of small radius, the error is less dependent
on RE position.
Although the applicability of spherical electrodes in practical situations is often limited, this is
a definite advantage, the distance between the capillary tip and the electrode being not so critical.
Ahlberg and Parker [20] also warned of the dangers of trying to place the Luggin tip very close
to the WE. Small variations in the positioning of the tip will make a large difference to the uncompensated resistance. They advocate the use of small-diameter spherical electrodes and a large WERE separation.
45

In all cases the ohmic drop is proportional to the current density. Special care should be given
to transients at short times when large currents may flow, possible error sources being current
oscillations, double layer charging and stray capacitance to ground.
Apart fromresistance,capacitiveeffects should also be taken into consideration.Thebest design
of a Luggin probe is one with a narrow capillary at its tip with thin walls to prevent shielding,but
with thick walls in the main body which widen rapidly away from the tip to reduce resistance in
the control loop [211.
A possible solution to avoid ac interferences is the use of a special high-frequency by-pass, for
instance a platinum wire coupled to the normal reference electrode by a 0.1 pF capacitor.
Any additional resistance in the working electrode itself, for example due to the formation of
resistive films, will be included in the uncompensated resistance and can only be reduced by
electronic compensation.
In summary :
1. Large capillaries (diameter > 1 mm) are useful only at relatively low current densities in
solutions of high conductivity.
2. Even with the smallest convenient capillary (0,2 mm diameter)placed as close to the electrode
as possible without incurring shielding errors, the IRcorrectionsgreatly limit themaximumcurrent
density for accurate polarization measurements, especially in solutions of relatively low conductivity.
3. Small cylinders (wires) or spheres if practically feasible may be used advantageously as test
electrodesin polarization studies, since the IR correctiondecreasesas the electrode is made smaller.

6.3.I .2 Microelectrodes
The current can be kept small by the use of small electrodes 1221. The advantages of small-diameter
cylindersand spheres have been described previously.Although there are some possibledisadvantages (for instance the small surface available when studying pitting), microelectrodesare becoming popular for use in non-aqueous and aqueous resistive media. For instance, Genders, Hedges
and Pletcher [23] described an application of microelectrodes to the study of the Li/Li+ couple in
ether solvents. They showed that it is possible to obtain high-quality data for the electrodeposition
and anodic dissolution of lithium. The experiments required only a two-electrode cell and simple
instrumentation because the experimental currents (not current densities) were very small. The
electrodes were constructed from Cu wires (40 and 80 p.m diameter). The electrolyte was always
lithium hexafluoroarsonate LiAsF, in tetrahydrofuran (THF). The resistance of the experimental
cell filled with T H F + LiAsF, (0.6 mol dm3) measured using an a.c. bridge was 5000R. Only cell
currents below 3 p.A (current density 60 mA cmS2)were analysed quantitatively so that the
maximum IR drop was 15 mV. A test of the absence of significant IR-drops is to repeat the
experiment with an electrode of different area when only the current should change and there
should be no shift in peak potentials or changes in shape of transients.

6.3.2Active methods
A number of active methods are available in which the compensation of the ohmic drop is
necessarily incorporated in the control system of the potentiostat.
One of the methods which has been used is the ac method, based on the application of a highfrequency signal (e.g. 50 kHz) through the cell, using the ac voltage after amplification and
rectification as the control signal. The active methods mostly used are :
a. positive feedback
b. current interrupt.
46

6.3.2.2 Positive feedback


In the positive feedback methods a voltage signal is produced which is proportional to IRand which
is added to the control input voltage. The aim is to compensate for IR automatically. Depending on
the principleof the potentiostatic circuit severalsolutionshavebeen proposed 1151(forexampleFig.
6.8).

1
n e g a t i v e feedback l o o p

: Counter E l e c t r o d e
: Reference Electrode
WE : W o r k i n g E l e c t r o d e
CE
RE

CE
WE

Ro

<

-L

VF : V o l t a g e F o l l o w e r
CF : C u r r e n t F o l l o w e r
C : Control Amplifier

R, : M e a s u r i n g R e s i s t o r
R x : Feedback R e s i s t o r
S : Control Voltage

Fig. 6.8 :Basiccircuit forpotentiostat with IRdropcompensationbymeansof positive feedback


in the control loop
The requirement is that at all frequencies the applied positive feedback signal is smaller than the
negative feedback of the control loop of the potentiostat itself.
Often instability problems will arisebecause the systembehaves as a purely capacitiveelectrode
if 100% compensation is obtained [151. Neverthelessthe method is used frequently, many commercially available potentiostats being equipped with, or easily adapted to, this form of IR drop
compensation 1241.
The value of the resistance in the potentiostat feedback circuit (Rx in Fig. 6.8) may be set on the
potentiostat in several ways, the most common being by "trial and errox". For example on applying
a square wave signal of small amplitude (e.g. 50 mV, 50 Hz) to the control input the value of the
resistance is increased gradually until "ringing" (= overshoot + relaxation) is observed with an
oscilloscope connected across the WE and RE. The resistance value is then reduced a few percent
until stability is restored and this value is used in the feedback circuit. An alternative method is first
to measure the resistance, and then to set this value in the feedback circuit. The uncompensated
resistance is assumed constant during the subsequent current-voltage measurements, leading to a
constant correction; hence, errors may arise when for some reason the uncompensated resistance
changes, e.g. due to film formation.
It should be realized that overcompensationdoes not always result in "instability" and so great
care is needed to avoid it. Positive feedback in IRcompensated potentiostats has been discussed in
detail by Britz [15] and by Mc Kubre and MacDonald [131.
An analogue technique of ohmic drop compensation has been proposed by Gabrielli et al. 1251,
which avoids some stability problems related with positive feedback.
Many workers subscribe to the view that any compensation isbetter than none and so will use
positive feedback.

47

6.3.2.2 Interrupt methods


Interrupt methods in particular are becoming popular, being used in conjunction with both
potentiostatic and galvanostatic techniques [lo, 16,26-301. The principle is to measure the rapid
change in potential of the working electrode as the current is suddenly switched off (interrupted).
The ohmic drop is given by the immediate change in potential on switching, the potential change
due to polarization decaying relatively slowly and certainly more slowly than the purely resistive
ohmic drop component i.e., because of the very short time constant of the latter (Fig. 6.9 a). Hence
this method is not applicable when the double layer capacity is very small.

For determining the ohmic drop a transient recorder or an oscilloscope is required. One of the
potential problems associated with this method is the possible measurement of artefacts, i.e. the
decay characteristics of the measuring circuit overlapping the desired potential decay of the
working electrode. Other difficulties are associated with the need for reliable triggering and fast
data acquisition. The method is mostly applied by interrupting the current periodically,necessitating fast current switching of possibly large currents.

f- lnterruptlon-

tlme

A unc = A U / A I
I

to pulse

time

Runc = l i m

C
m

ZKJI

m
m

E
n

R unc

Real part 2'

Fig. 6.9 Different techniques for the measurement of the ohmic potential drop (schematic)
(a) interrupt technique (b) pulse technique (c) high frequency ac technique [311
Some of the more expensive commercially available potentiostats are, or can be, equipped with
these forms of ohmic drop compensation technique. In principle, the method can be applied when
the values of Run, and the measuring resistance change during the measurements.
Some special designs have been published, in which the potentiostat, the interrupter and the
data acquisition apparatus have been combined in a sophisticated computer controlled instrument
[28-311. An example of this is the measuring equipment described recently by Heitzet al.(Fig.6.10)
[XI.

48

F'I

-----

COMPUTER

-I

POTENTIO-

1
I
I
I

I
1
1
1

I
TRANSIENT
RECORDER

I
I

I
I
I

'

INTERRUPTER

POTENTIOSTAT

I-

RE

---------CE
I
-

WE

Fig. 6.10 : Flow diagram of the computer-controlled measuring equipment used to eliminate
ohmic potential drop [321
The method is based on a setup which has been succesfully used to eliminate ohmic potential
drop at gas-evolvingelectrodes at high current densities. With modem equipment for elimination
of ohmic drop as previously described it is possible to make rapid corrections in solutions with
conductivities below 1 k s cm-'.

6.3.3Passive methods
This heading covers all methods in which the ohmic drop is measured or calculated, followed
by mathematical correction afterwards when the experimental data have been collected [15,16,25,
331.
6.3.3.1 Measurement of ohmic drop
The measurement of the ohmic drop can be performed by a number of methods, the most wellknown being :

a. Positive feedback method as described above, determining the resistance at which the potentiostat oscillates by manual adjustment of the feedback resistance.
b. Current interrupt method as described above or alternatively,the measurement of the instantaneous potential change when the current is switched on (pulse methods : Fig. 6.9 b).
c. Alternating current methods, including the use of bridges and four-point methods [MI.
d. An extension of method c is the application of impedance techniques, either the full Nyquist
diagram being determined or the impedance at one or more discrete frequencies (Fig. 6.9 c) [331.
e. Extrapolation technique, in which the distance between the tip of the Luggin capillary and the
surface of the working electrode is varied; the potential difference between the working electrode
and the reference is measured as a function of the distance and extrapolated to zero distance [351.
f. An extension of method e is the multiple potential method, in which the potential of the WE
is measured with respect to several RE positioned at fixed, known distances 1331.

An example of the application of impedance techniques (method d) is shown in Fig. 6.11.


49

1.2

-* -

_ _ _ _ _ _ _ -eo--

--

1 -

-8

- - a U l a-- * - -m- -

.6

.4

-2

=_
_
-- - - - -UAA.&
-

- -A-

-A1

Fig. 6.11 : Determination of solution resistance for different systems consisting of low alloyed
ferritic steels in contact with aqueous solutions [36]:
(a) 100 g/1 EDTA, T = 100 "C,pH = 6 ( 0 )
(b) 100g/1 EDTA, T = 100 "C,pH = 7 (B)
(c) 150 g/1 HC1+ 1g/1 inhibitor, T = 76 "C (A)
The evaluation of ohmic drop with alternating current at high frequenciesis based on the electric
equivalent of the metal-solution interface of Fig. 6.12, where Run,represents the electric solution
resistance between working and reference electrodes.

Fig. 6.12: Equivalent circuit of metal-solution interface


The impedance, Z, between the points A and D, at angular frequency o,is given by
Z = Runc+ Rt/Q - j o CR2,/Q,

50

(3)

where Q is equal to

From equations (3) and (4) it follows that

From a physical point of view the previous relation is intuitive because a capacitor is a short
circuit for alternating current at high frequencies.
Elsener and &hni [371 reported results of investigations that combine measurements of the
ohmic resistance by interrupter and ac impedance technique for pitting systems. It was found that
the ohmic resistance measured by the interrupter technique always corresponds to the primary
current distribution in the cell. In contrast, the ac impedance technique also measures the ohmic
resistance in a pit. The results are compared with calculated valuesof R and discussed with respect
to the applications and limitations of an automatic IR drop compensation in the case of localized
corrosion.
In homogeneous corrosion systems (active dissolution, passive state) where the same electrochemical reactions occur over the whole surface, the interrupter and ac technique can be successfully applied and the same value for theohmic resistance is measured by both techniques.Problems
arise in localized corrosion systems, where small active areas coexist with a large passive surface
and the impedance of the active areas (pits) is short circuited by the surrounding passive surface.

6.3.3.2 Direct calculation


Direct calculation of the theoretical value of the ohmic drop is only possible for a number of welldefined and comparatively simple cases [38].
6.3.3.3 Mathematical mefhods
Independent of the method whereby the value of IRis obtained, the experimental polarizationdata
will have to be corrected. Apart from some less accurate graphical procedures, mathematical
methods such as linear regression analysis and successive approximation have been used [391.
Sophisticated mathematical methods have been reviewed by Britz [15]; they start from the uncorrected experimental data and mathematically extract the desired parameters free from ohmic
error.
The advantages of the mathematical methods are their suitability for computerization, while it
is also possible to apply statistical methods to gain insight into the accuracy of the calculations.
Some examples are given below :
a - A method using a programmable calculator or a minicomputer has been described by Hayes
et al. [161; they showed that the Tafel parameters could be calculated from the experimental q-i
data, using regressional analysis for the interpretation of the deviations from the log-rate law.
b - Ahlberg and Parker 1201 eliminated the effect of Runcby performing linear regressional
analysis on equations derived from the relation :

:E = EP + IPRunc
r

where p refers to values at the current peak (in linear sweep voltammetry)
and m and r refer respectively to measured and real values.

51

c - Kajimoto et al. [391 discussed the effect of uncompensated IR drop in their investigation of
the corrosion rate of pure iron and carbon steel in acid solutions. IR drop compensation was
attempted with thepotentiostat itself, which had a built-in positive feedback IRcompensation unit,
but its sensitivity was not sufficient to perform the task.
To take into account the IR drop, it was assumed that the applied AE included, in addition to
activation polarization (AEA), an IR drop term :
AE=-AE,+RAi=

b)ogi*+b)og

)Ai

+RAi

(7)

where R is the ohmic resistance. The unknown parameters b , i* and R were obtained by a least
squares fit for both carbon steel and commercially pure iron. In all cases a good fitting of the
equation to the experimental data was obtained.
Some form of error assessment should be applied to all data, as shown above by Kajimoto et al.

WI.
d - Hayes and coworkers [161, in their regressional analysis fit to the Tafel equation, described
how to calculate the confidence limits of the Tafel parameters. They found it easy to detect when
"non-Tafel" data were being processed because the confidencelimits were much larger than usual.

6.4 CONCLUSIONS
When performing polarization measurements an error due to the ohmic drop over the uncompensated resistance will be included in the potential between the working and the reference electrode.
The significance of this error is decided by the ratio between the value of the uncompensated
resistance and the polarization resistance of the system. The uncompensated resistance can be
minimized by careful design of the cell and the positioning of the electrodes. Several methods of
instrumental compensation of the ohmic drop are available, of which the interrupt methodsare the
most versatile. Such methods are applied during the polarization measurements.
Finally, it is possible in principle to evaluate and/or calculatethe ohmicdrop, and subsequently,
to correct the experimental data for its influence after the polarization measurements have been
performed.

6.5 ACKNOWLEDGEMENTS
The authors gratefully acknowledge the valuable criticism of Dr. J.C. Verhoef (DSM Research,
Geleen) in compiling this chapter.

6.6 REFERENCES
1. F. Mansfeld: Corrosion, 1976,32-

143.

2. F. Mansfeld: in Adv. in Corr. Science and Technology, vol. VI. Published by Plenum Press,
New York, 1976, p. 163.
3. F. Mansfeld: NACE Intern. Corrosion Forum, Boston, U. S. A, 1985, paper No. 70. Published
by NACE, Houston, Tx, U. S. A, 1985.

4. G. Rocchini: Corrosion, 1988,44-

158.

5. D.T. Sawyer and J. L. Roberts: Experimental Electrochemistry for Chemists. Published by J.


Wiley & Sons, Inc., 1974, ch. 3.
6. N.D. Greene: Experimental Electrode Kinetics. Published by Rensselaer Polytechnic Institute,
Troy, New York, 1965.
7. R. Greef et al.: Advanced Instrumental Methods in Electrode Kinetics. Southampton Electro52

chemistry Group. Published by Ellis Horwood Ltd, Chichester, U. K., 1985.


8. J.A. von Fraunhofer and C.H. Banks. Potentiostat and its applications. Published by Butterworths, London, 1972, ch. 3.
9. D.D. MacDonald:TransferTechniques in Electrochemistry.Published by Plenum Press,New
York, 1977, ch. 2.2.
10. M. Hayes: in Techniques in Electrochemistry,Corrosion and Metal Finishing, a Handbook.
Published by John Wiley & Sons Inc., (Ed. A. T. Kuhn), 1987, ch. 4.
11. A.J. Bard and L.R. Faulkner: Electrochemical Methods, Fundamentals and Applications.
Published by JohnWiley & Sons Inc., 1980, ch. 1.3.4.

12. E. Heitz and G. Kreysa: Principles of Electrochemical Engineering. Published by VCH Verlagsgesellschaft mbH, D-6940, Weinheim, 1986, ch. 1.3.
13. M. C. H. McKubre and D. D. MacDonald: in Comprehensive Treatise of Electrochemistry.
Published by Plenum Press (New York), ( ed. R. E. White, J. O M Bockris, B. E. Conway and E.
Yeager) 1984,l.
14. E. Yeager and J. Kuta: Techniques for the study of electrode processes in physical chemistry
: an advanced treatise. Published by Academic Press, New York/London, 1970,

u.

15. D. Britz: J. Electroanal. Chem., 1978,88,309.


16. M. Hayes, A.T. Kuhn and W. Patefield: J. of Power Sources, 1977/78,& 121.
17. G. Rocchini, private communication.
18. S. Barnartt: J. Electrochem. Soc., 1952,99- 549.
19. S. Barnartt: J. Electrochem. Soc., 1961,108.102.
20. E. Ahlberg andV. D. Parker: J. Electroanal. Chem., 1980,107.197 and ibid., 1981,121.57.
21. A. Bewick, M. Fleischmann and M. Liler: Electrochimica Acta, 1959,1,83.
22. K. Wikiel and J. Osteryoung: J. Electrochem.Soc., 1988,135.1915.
, 3399.
23. J. D. Genders, W. M. Hedges and D. Pletcher: J. Chem. Soc., Faraday Trans., 1984, @

24. P. Doigand P. E. J. Flewitt: Br. Corros. J., 1976,-l 78.


25. C. Gabrielli, M. Ksouri and R. Wiart: Electrochimica Acta, 1977,22-

255.

26. J. Gsellmann and K. Kordesch: J. Electrochem. Soc., 1985,132.747.


27. W. J. Wruck, R. M. Machado and T.W. Chapman: J. Electrochem. Soc., 1987,134,539.
28. P. J. Moran: Corrosion, 1986,42-

432.

29. P.Cassoux, R. Dartiguepeyron, P. -L. Fabre and D. de Montauzon: Electrochim. Acta, 1985,

a 1485.

30. M. Berthold and S. Herrmann: Corrosion, 1982,3831. B . Elsener and H . Biihni: Corros. Sci., 1983,23-

241.

341.

32. M. Kuhn, K. -G. Schiitze, G. Kreysa and E. Heitz: Electrochemical Corrosion T e s t i n g u


Published by DECHEMA, Frankfurt, FRG, (ed. E. Heitz, J. C. Rowlands and F. Mansfeld) 1986,265.
33. M. Eisenberg, R. E. Kuppinger and K. M. Wong: J. Electrochem. Soc., 1980,117,577.
53

34. G.W. Walter: Corros. Sci., 1978,

927.

35. J. OM. Bockris and A. M. Azzam: Trans. Faraday Soc.,1952, @, 145.


36. G. Rocchini: NACE Intern. Corrosion Forum, Boston, 1985, paper No. 188. Published by
NACE, Houston, Tx, U. S. A., 1985.
37. B. Elsener and H. Bijhni: Electrochemical Corrosion Testing. Monograph 101.Published by
DECHEMA, Frankfurt, FRG (ed.E. Heitz, J. C. Rowlands and F. Mansfeld), 1986, 279.
38. K. Tokuda, T. Gueshi, K. Aoki and H. Matsuda: J. Electrochem. Soc., 1985,132,2390.
39. Z. P. Kajimoto, S. Wolynecand H. C. Chagas: Corros. Sci., 1985,

35.

Further information can be found in:

L. L. Scribner and S. R. Taylor (eds): The Measurement and Correction of Electrolyte Resistance in
Electrochemical Tests. Proc. Symposium held in Baltimore, MD; ASTM Special Technical Publication STP 1056, Philadelphia, 1990.

54

CHAPTER 7

AUTOMATIC MEASUREMENT
SYSTEMS
0. F O R S ~AND
N J. AROMAA
Helsinki University of Technology
Vuorimiehentie 2,02150 Espoo, Finland

7.1 INTRODUCTION
The rapid development of inexpensive microcomputers has increased their use in laboratory
instrumentation. The function of laboratory instrumentation is usually simultaneous control of
experiment and acquisition of measurement data. Processing of measurement data to values,
graphs or tables can also be included. The personal computer is a powerful tool with capability for
system control, data acquisition and data processing and combined with measuring equipment it
can perform all the functions of larger and more expensive systems.
Development of an automatic measurement system is practical, if the same kind of measurements are made frequently. Also, the type of experiment affects the demand to develop an
automatic system. Very long or very fast experiments are often impossible to control and follow
manually, because a human operator cannot work long periods without pauses and in rapid experiments the sampling rate can exceed that possible by hand. In large experiments the number of
controlled and measured quantities restrict operators ability to follow every detail. These cases
require automation.
Electrochemistry is a field, where control of experiments and data acquisition methods do not
differ greatly, but proper interpretation of measured data gives information on several different
phenomena. In electrochemical experiments one controls the system with electrical quantities and
also measures electrical quantities, i.e. voltage and current. The electrochemicalcorrosion process,
its probability and rate can be described as a function of three variables; potential,current and time.
Other electrical and electrochemical parameters can be derived from these variables. As an electrochemical process, corrosion can also be studied with electrical measurement methods. The measurements are suitable for automation which has the following advantages:

- continuous manual operation is avoided


- more data can be obtained
- measurements are more accurately controlled and reproducibility is improved, hence
comparability of results from one operator to another is improved
- storing and handling of large quantities of data becomes more efficient thus leading to effective
data analysis
- electrochemical impedance spectroscopyand other sophisticated measurement methods are
more convenient with automatic data processing equipment
The main disadvantage of automatic measurement units is, that if one can get the results ready
processed, they can easily be over-processed. Therefore, persons using automatic systems must
have good theoretical background to assess the reliability of test results. Blind trust on ready values
can lead to wrong conclusions. Potential and current, which are measured from an electrochemical
system, describe only the thermodynamical possibility of reactions to proceed and the net rate of
these reactions. During an experiment the potential of the working electrode is produced by the
complicated interaction between electrode and electrolyte and by an external control signal. The
measured current is a sum of all those reactions, which proceed at the working electrode surface.
55

In a normal system there are always parallel reaction mechanisms and succeeding reaction steps,
and so it may be impossible to interpret measured data.

7.2 PARTS OF A MEASUREMENT SYSTEM


An electrochemicalprocess can be considered as a "black box" with electrical response to excitation
signals and therefore it is possible to study electrochemical processes with electrical measurement
instruments. At the moment there are severalcommercial systemsavailable,whichcontainboth the
equipment and necessary software. If a commercial system meets users, technical and economical
needs, it is advisable to choose it. A commercial systemcanbe installed and put to work much faster
than a sel -built system. However, if the system is self-tailored, it will usually be more suitable to
particular requirements. A self-madesystem with personal computer,adequate I/Ocards and own
software provides flexibility.When developinga selfbuilt system one has to choose the equipment
with care and ensure compatibility.When choosing measurement units it is often wise to buy from
big manufacturers in order to ensure reliable maintenance, installation and operational instructions.

Anautomaticmeasurementsystemconsistsoffour differentblocks:computer and itsperipherals,


measurement devices, data transfer busses and software. It is easy to get hardware devices, but
creating software can be difficult and troublesome.Worst problems are usually found when one is
trying to connect devices to other devices and software. The users manuals are usually not
sufficiently helpful for such purposes and the operation of data transfer busses is not guaranteed.
7.2.1 Computers and peripherals
Good and useful computers can be obtained from big manufacturers, whose systems have become
de facto standards. Even MS-DOS operating systems, which are being developed for office operational environment, are capable of handling laboratory size measurement operations. In laboratory
instrumentation the computer requires at least 256 kB memory and two floppy disk units.
Measurement programs do not require very powerful computer and most of the measurement
procedures can be done in measuring instruments. Data processing with commercial software
requires more memory and often a hard disk unit is also useful. A computer which controls instrumentation must have adequate capacity to handle error situations, even though many errors can be
handled in measurement programs.

A dot matrix printer, which is capable of producing graphics, is adequate as a peripheral device.
For producing higher quality hardcopies one should consider buying a good digital plotter, which
can produce A4- or A3-size printouts.
7.2.2 Measuring devices
For simple measurements a potentiostat and possibly separate multimeters for voltage and current
measurements are adequate. For complicated experiments a function generator, an oscilloscope
and a frequency response analyzer should be added to the system. When choosing an instrument
one should check its capacity (operating rate, accuracy etc), maintenance, compatibility with other
devices and price.

The first instrument to buy is usually the potentiostat. One must choose between analog and
digital devices. Analog instruments are older technology when compared to digital instruments.
Analog instruments may be less accurate, but their operation is easier to follow and their output
capacity is usually greater. Digital potentiostats are more suitable for automatic systems, but
manual operation of these may be almost impossible. When using a digital potentiostat data
transfer is usually made via a digital data transfer bus. When using an analog potentiostat one has
to use analog/digital and digital/analog converters or digital multimeters with data transfer bus.
Controlling the potentiostat can be done via data bus (digital potentiostat) or with an external
voltage signal (digital or analogpotentiostat). Production of the external control signal canbe made
with a D/A converter or with a function generator.
When choosinga function generator one should check the maximum output level and especially
the frequency range. In corrosion experiments potential sweep rates are 1 mV/h - 100 mV/s and
output voltages -10 to +10 volts. Most function generators cannot produce potential sweeps slow
enough forcorrosionstudies. Forexampleina polarizationexperiment with sweeprate lOmV/min
and maximum polarization 2000 mV, the frequency is about 10mHz. Most function generators are
designed for the electronics industry, where high frequencies up to GHz range are used.
56

Special equipment for transient and impedance measurements consists of a digital storage
oscilloscope and a frequency response analyzer. A suitable oscilloscope should have at least two
channels with 1kB (1024 measurement points) storage capacity. A frequency response analyzer is
usually a complete unit which can produce the excitation signal, make measurements, process and
analyze the measurement data.
7.2.3 Data transfer busses
Data transfer between measuring instruments and computer is necessary but it is often prblematic.
The simplest solution is use of analogjdigital and digital/analog converters which convert analog
voltage or current signals to bytes or vice versa. Operating rates of converters depend on the
conversion algorithm and on the resolution (usually 8,12 or 16 bytes) of the converter. A 12 bit
converter is satisfactoryand its relative error is 0.025 % of maximum value of the converter range.
The resolution can be increased by using signal amplifying.

Manufacturers of measuring instruments use standardized digital data busses, which transfer
data as bytes. Best known busses are the RS232C and GPIB busses. GPIB (General Purpose
Instrumental Bus) is known also as HPIB or IEEE-488bus. The serial RS232C bus is a recommended
standard for data transfer between a peripheral and a computer. It is built to handle data transfer
between two instruments, so using more devices in the same system may be troublesome. GPIBbus
is a standard bus and the standard determines mechanical and electrical features but not the
commandsused.GPIB busiscapableof controllingasystemwith 10tol5devicesand so far it seems
to be the best bus system for practical purposes. In the bus configuration every instrument has a
numerical address. One of the instruments, usually the computer, acts as a bus controller while
other instruments are both talkers and listeners. Even though the functions of GPIB bus are
standardized it requires some trial and error to get instruments connected to the software.
7.2.4 Software
Software makes the computer based data acquisitionand control system operational. The software
consists of an operating system of the computer, programming language and programs used for
measurements and data processing. Operating systems, such as MS-DOS, consist of programs and
subroutines, which reside in the memory the whole time that the computer is switched on and deal
directly with computer components. Programming languages are used to allow discussion between machine code and human operator. With programming languages the operator writes
application programs, which in turn control the computer so that the expected functions are done
in the expected order.

Assembly language is close to the instruction code of the machine allowing most efficient
memory space utilization and execution speed. A program written in Assembly language is not
easy to modify by another person unless it is very clearly documented. By using a high level
language the programs can be written more clearly and this allows easy modifications, so that the
software can be fitted to individual experiments more easily.There are several high level programming languages e.g. Basic, Fortran, Pascal and C. Structural languages require good programming
discipline, which enforces planned work. This provides efficient and easily understandable codes,
but for short programs it can be too tedious to program with Pascal or C. Basic is still very useful
even though it is described as a 'crude and quick' way to get a job done.
A language such as Basic is easy to learn and use, but modifications can be dangerous due to
accumulation of GOT0 and GOSUB statements. Programming is not an extremely difficult task to
undertake with high level languages but it is still the hardest part when creating an automatic
measurement system.Writing a measurement program requires knowledge both on programming
techniques and on the measured phenomena. Measurement programs must be capable to control,
data acquisition and data processing without wasting memory space on less important functions.
The role of measurement software is simplified in Fig.7.1. Measurement software is usually a
precisely timed execution of read and write operations for data acquisition and equipment control.
Programs should also output adequate log sheets with experimental details, measured values if
required and preferably a graph of measured data points. Experiments are usually made so that
measured quantity is a function of time, applied potential or applied current. Applied potential
signal can also be time dependent, as in voltammetricexperiments.Time dependent current signals
should be avoided because the signal is more difficult to produce and data interpretation is
ambiguous.

57

-LOG SHEETS

-DATA BASE

Measurement programs are not very large. A Basic program for measurement of polarization
curves, including graphics,file maintenanceetc, is about 200-250 lines. Before starting measurement
operations, the operator must provide experimental parameters, which alter depending on the operating program. Programs need at least the values of rest potential, polarization potentials, polarization rate or polarization time and the area of the working electrode. Input of experimental
parameters should be arranged so that inexperienced users know, how to feed the input data
correctly. A simple way to arrange this is to inform the user of required parameter and its
dimension, e.g. Enter corrosion potential in mV, with every input command. Also the validity of
input parameter should be checked immediately. Complex data input should be avoided and
normally not more than two or three numbers should be requested in one line. After feeding all
input data the operator should once more confirm its validity before starting measurements.
In every measurement timing is one of the crucial factors. Electrochemicalexperiments can be
timed either with the internal clock of the computer or with a linearly changing potential signal. In
electrochemical experiments one usually measures potential or current at predetermined time
intervals or current at predetermined potential intervals. Potentiostatic, galvanostatic and
voltammetric programs can be written so that they use two repetitive loops. One loop controls
continuously time or potential interval between successive measured points and the other loop
controlstotal time or potential of the experiment.When the interval between two pointsisachieved
a new measurement operation is made and when the final time or potential value is achieved the
experiment is stopped.

7.3 ANALYSIS OF MEASURED DATA


When one is conducting an experiment more or less data are collected usually in the form of
numbers. These raw data are only a sequenceof numbers without any value, which require a proper
meaning to become information. A series of potential and current density values is raw data, but
can be processed to give polarization resistance values or anodic polarization curves which provide
valuable information. When the same type of analysis is used for samples of similar nature, the
evaluation and interpretation of a measurement can be totally automated. This situation occurs
mostly in corrosion monitoring. In research laboratories a changing variety of samples requires
flexible evaluation procedures and a more active role of the human operator.
Data processing can be done at two separate occasions, i.e. during the experiment or after the
experiment. During the experiment one must continuously follow the controlling quantity and
change its value if necessary. One must also record the values of measured quantities and this is
usually done asa function of electrode potential or time. During the measuring operations the data
processing must be kept to a minimum, and only those steps that are necessary to control the
experiment should be included. Depending on the type of the experiment it is necessary to follow
time and potential and sometimes also current density. During the experiment it is not necessary
to evaluate and interpret data. However, it is helpful to include some simple function, which allows
the operator to check the status of the experiment. A preliminary graph of measured values plotted
continuously on the computer screen is reasonable, but printing every measured point would be
a waste of paper.

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During the measurement data are collected to mass memory and the most flexible way is to save
the data as an ASCII text file. Data processing should be done only after the measurement with
appropriate software independently of the experiment. Many commercial spreadsheet programs
can read ASCII files, edit the data and finally produce desired numerical values and graphs.

7.4 EXAMPLES OF AUTOMATIC SYSTEMS


The first example is a system for voltammetric measurements and it uses an analog potentiostat.
Analog potentiostats are usually controlled manually but an external voltage signal can also be
used. In this kind of system it is possible to use separate converter cardslocated inside the computer
or an expansion chassis architecture. A converter card system is simple and inexpensive. A single
circuit board fits into one of the expansion slots of the computer and the board provides rear
connector for input and output signals. An expansion chassis system provides more flexibility and
greater performance.The expansion chassis holds 1 / 0 channels and it is connected to the computer
with an interface card.
Figure 7.2 shows a block diagram of an automatic system with analog potentiostat. The
potentiostat is controlled with external voltage signal from D/A converter. Potential is measured
from the monitoring output of the potentiostat and it is converted to bytes with an A/D converter.
Electrode potential can also be measured with an optional voltmeter. The electrode potential must
be measured continuously, so the computer can send control commands to measuring instruments
in correct time. The cell current is measured with an autoranging multimeter and the current value
is sent to the computer using a digital bus. During electrochemicalmeasurements the current can
vary several decades and so using a fixed current range of potentiostat leads to less accurate measurements or to overloading. The system in Fig. 7.2 is suitable for voltammetric experiments and it
can be built from existing instruments.

zd=l

PRINTER

interface

COMPUTER

CONVERTER
CARDS

measure
A/D

ext. control
D/A

J--l

1-

/j

GPIB bus

AMPERE-METER

Fig. 7 . 2 Block diagram of an automatic system with analog potentiostat. The figure also shows
some possible data transfer arrangements.

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The second example is a more sophisticated system with only digital units. A block diagram of
the system is shown in Fig. 7.3. The basic idea of the measuring system is that the computer sends
all the controlling commands, status signals and measured data via the GPIB bus. This type of
system does not require any front panel operations to use the instruments. The cell is polarized with
a digital potentiostat, which also measures working electrode potential and current. Changing of
electrode potential can be done by using computer controlled internal setting of the potentiostat or
by using external voltage signals produced by a function generator. Frequency response analyzer
(FRA) and potentiostat are used together in electrochemical impedance spectroscopy. The FR4
produces an alternating excitation signal, which is used as an external control signal of the
potentiostat and convertsmeasured electrodepotential and cell current to electrodeimpedance. In
these measurements real-time computer control is not necessary. The oscilloscopecan be used to
measure transient signalsand is connected directly to the cell.The computeris used to set, arm and
trigger the oscilloscopeand to control the potentiostat.

GPIB bus

FREQUENCY
RESPONSE
ANALYZER

control
POTENTIOSTAT

FUNCTION
GENERATOR

measure
OSCILLOSCOPE

1
C

Fig. 7 . 3 Block diagram of an automatic system with digital equipment. All data transfer is via
GPIB bus.

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CHAPTER 8

FIELD TESTING
G .TURLUER
CEA, Fontenay-aux-Roses,France

By means of specially designed single or multi electrode probes many electrochemical test
methods can, in principle, be implemented in plant, pilot testing facilitiesor natural environments.

8.1 OBJECTIVES
Theobjectivesof field testingmaydiffer fromthoseinlaboratory testingand may beconcerned with
matters such as:
Corrosion monitoring
Detection of process deviations detrimental to the service life of components
Diagnosis of unexpected corrosive conditions
Data collection in complex environments

8.2 TEST METHODS


Usually the most popular methods rely upon conventional techniques involving rugged equip
ment and preferably using straight forward interpretation of data.
For corrosion monitoringpurposes, or for any other objective, it is advisable to conduct a survey
of the corrosion processes over a significant period of time including operation transients, shut
downs and startups which to a greater or lesser extent are already documented.
8.2.1 Polarization resistance measurements (Rp)

RPmeasurements, preferably with free corrosion potential monitoring can yield real time corrosion
data from which interpretation related to the corrosion regime is possible.
8.2.2 Material (or Component) potential and process redox potential monitoring

This monitoring will provide information with respect to the material corrosion regime, i.e., active,
passive, transpassive, pitting behaviour etc., and diagnostic possibilities exist only if the corrosion
system is well understood particularly as a result of laboratory studies - for example, the
significanceof the free corrosion potential or the potentials under impressed anodic or cathodic
currents.
8.2.3 Impedance measurements

Despite some possible implementation problems and the need for sophisticated requirements for
interpretation, these measurements can prove particularly valuable in low conductivity media such as concrete, soils, condensate corrosion, protection by coatings etc. They therefore provide a
more accurate determination of Rp.

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8.2.4 Potentiodynamic scanning


This method can be recommended as a diagnostic tool when information is needed to determine
and interpret conditions responsible for unexpected corrosion behaviour. The technique has to be
considered as a destructive test of the working electrode as it can irreversibly influence the
subsequent corrosion regime.
8.2.5 Galvanic current measurements
These with, or without, potential monitoring and sometimesreferred to as zero resistanceammetry
find their most common application for the assessment of galvanic coupling between dissimilar
materials or possibly between areas of the same material but exposed respectively to the free
medium and to occluded areas, as for example, in crevice corrosion and differential aeration
conditions.
8.2.6 Spatial potential scanning

This techniqueis mostly applied for the detection of spatial defects in anodic or cathodic protection
systems on complex structures or components. Thus, attempts have been made to detect single
locations in components that are usually passive but which may undergo some form of active
corrosion in particular areas such as welds, crevices, pits, cracks, etc.

8.3 SPECIFIC REQUIREMENTS AND PRECAUTIONS


Among the numerous possible recommendations which will depend on the various objectives,
corrosion systems and available techniques the following specific requirements and precautions
will need to be considered.
8.3.1 General

(i) Check that the insulation of probe leads and electrode pins remains satisfactorybetween
components over a period of time.
(ii) Avoid, if possible, the use of electrochemical equipment (millivoltmeters,potentiostats and
ancillary apparatus) that would ground the working electrode thus leading to a possible
short circuit with the grounded structure being surveyed.
(iii) Preferably use 4 lead connections to minimize ohmic drop in the external lines.
(iv) Avoid loops in grounding the screening and electrochemical equipment to minimize pick
up of electromagnetic noise.

8.3.2.Probe configuration and location


The probe configuration,and the quality of the electrode mounting are of primary importance with
regard to the quality and reliability of the readings.
The following important features should be mentioned.
(i) The probe design should comply with the hydrodynamic conditions. Extreme care is
essential in systems where corrosion is controlled by flow dependent mass transfer, e.g.,of
oxygen, ferric ions, protective corrosion products etc.

(ii) IR drop in the electrolyte should be minimized by an appropriate disposition of the


electrodes (preferably in line for low conductivity media) on the probe.
(iii) Electrode mounting. Crevice formation should be minimized using an appropriate
mechanical design and adequate gasket selection. Waterline effects and the cutting and
mounting of electrode materials that would expose them to preferential end grain attack
should be avoided.

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(iv) Monitoring of crevice or occluded cell corrosion. Considerable care should be taken in
geometrical design of the probe, e.g., anode to cathode area relationship and possible
plugging by deposits, if significant conclusions are to be drawn from the measurements.
(v) Retrievable probes are often desirable and can be used in on-line designs or in side lines of
process streams.

8.3.3. Reference electrodes


True reference electrodes to provide thermodynamic information are not always necessary for in
service applications since their stability with time or with respect to pollution, fouling an and ion
concentration are frequently a cause of concern.
(i) Arbitary electrode used as a reference. It is a common practice to use a reference electrode
material either similar to that of the working electrode, or more noble (platinum, gold, passive
titanium, stainless alloys) or a material whose free corrosion potential is more likely to remain
reasonably stable in the process. With the use of a nonreversible reference electrode, thermodynamic or redox references are not obtained but they are not essential for Rp, or galvanic coupling
monitoring. However, potentiodynamic scansconducted with respect to anarbitary reference basis
can later be approximately relocated on a thermodynamic scale using some other polarisation characteristics, e.g., hydrogen or oxygen evolution or O2or Fe3 reduction).
(ii) In situ reference electrodes. It is advisable to use these as retrievable probes since periodic
checking and renewal of the electrolyte in the cell is necessary. Unfortunately many process
parameters such as pressure, high temperature, temperature fluctuations and thermodynamic
incompatibility restrict the use of in situ reference electrodes.
(iii) External reference electrodes. To avoid the problems mentioned above. the reference can
be mounted externally to the process stream, Le., in more controlled conditions which exclude the
effect of high temperature and aggressive environments. Such electrodescan either be pressurized
or at atmospheric pressure. The problems then become associated with the design and implementation of an electrolytic bridge with the following requirements: evaluation of the thermal and
junction potentials and their possible variation with time; bridge sealing and the possible interruption of the bridge by plugging or accumulation of gas bubbles.

8.4 INTERPRETATION AND POSSIBLE LIMITATIONS


In service the conditions of actual plant processes can vary from those that are relatively straightforward to situations that are extremely complex from the electrochemical and corrosion standpoints: therefore, measured data and their interpretation can provide information that will fall into
the following types:
(i) actual material corrosion rates with complete description of the corrosion regime.

(ii) correlation of fluctuations in process variables with control of these to minimize corrosion.
(iii) obtaining an order of magnitude for the general corrosion rate or the general corrosivity of
a process with respect to a given material.

(iv) the means to compare service data with relevant laboratory testing and/or the means to
devise laboratory testing conditions that will provide better simulation of the process.
(v) qualitative indications which can be checked with experience, inspection or other process
parameters.

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(vi) data that are irrelevant to actual corrosion damage: thus, it should be possible, for example,
to recognize when electrochemical testing has become inappropriate - if not totally inaccurate - or
when the location, size or material of the probe are not relevant to the most damaging corrosion
process. Such situations would be more readily recognized by the simultaneous use of other
monitoring or survey methods such as electrical resistance probes, coupons or component inspections.

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