Tutorial Corrosion II

Electrochemical characterization
with EC-Lab® techniques

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 OUTLINE

1. Introduction
2. Types of corrosion
a) Uniform corrosion

b) Localized corrosion

3. Corrosion experiment
4. EC-Lab® corrosion techniques
a) Uniform corrosion

b) Localized corrosion

5. Conclusions

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 INTRODUCTION

Corrosion is an electrochemical interaction between a material and its environment

which result in changes in the properties of the material

Two types of corrosion

Corrosion is commonly classified based on the appearance of the corroded material:

uniform and localized corrosion

1. Uniform Corrosion
Corrosion over the whole surface of the material

2. Localized Corrosion

Corrosion at small areas or local sites of the material surface in contact with the
corrosive solution

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 INTRODUCTION

Corrosion involves two electrochemical processes: Oxidation and reduction

1. Oxidation
The oxidation process takes place at the anodic sites according to the reaction

M  Mn+ + ne- (1)

2. Reduction
Reduction reaction takes place at the cathodic sites
The main reduction reactions encountered during the corrosion of a material is the
oxygen reduction (2,3) or the hydrogen ion reduction (4)

In acidic media O2 + 4H+ + 4 e-  2H2O (2)

In alkaline/Neutral media O2 + 2H2O + 4 e-  4OH- (3)

Hydrogen ion reduction 2H+ + 2 e-  H2 (4)

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 OUTLINE

1. Introduction
2. Types of corrosion
a) Uniform corrosion

b) Localized corrosion

3. Corrosion experiment
4. EC-Lab® corrosion techniques
a) Uniform corrosion

b) Localized corrosion

5. Conclusions

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 UNIFORM CORROSION

Uniform Corrosion

Also known as general corrosion, this kind of

corrosion corresponds to an uniform attack over
the entire surface of the material.

It is the most classical form of corrosion

characterized by a uniform reduction of
thickness of the surface of material.

It is relatively easy to measure, predict and

control this form of corrosion

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 UNIFORM CORROSION

Cathodic domain Anodic domain

Ecorr Corrosion potential

Oxidation/dissolution reaction
Reduction reactions

Hydrogen reduction
2 H+ + 2 e- H2 M  Mn+ + n e-
Oxygen reduction
O2 + 2 H2O + 2 e-  4 OH-

Polarization curve

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 LOCALIZED CORROSION

1. Introduction
2. Types of corrosion
a) Uniform corrosion

b) Localized corrosion

3. Corrosion experiment
4. EC-Lab® corrosion techniques
a) Uniform corrosion

b) Localized corrosion

5. Conclusions

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 LOCALIZED CORROSION

Localized corrosion types

In this section, six types of localized corrosion are described

1. Pitting corrosion
It is the most insidious form of corrosion. It is resulting in small
cavities or holes extending from the surface into the material
usually occurs in halide containing solutions (Cl-, Br-,..)

2. Crevice corrosion
Usually associated with small volumes of stagnant solution
leading to a limitation in the oxygen diffusion to a confined
space (under gasket, insulation material,..)

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 LOCALIZED CORROSION

3. Selective corrosion
Preferential attack of a particular component of an alloy in
presence of electrolyte. The most well-known examples
are:
dezincification of brass (Cu-Zn)
destannification of tin bronze (Sn-Cu)

4. Intergranular corrosion
As the name suggests, this form of corrosion occurs along
the grain boundaries of metal and is usually results from
local differences in composition due to chemical
segregation effects or to specific phases precipitated on
the grain boundaries

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 LOCALIZED CORROSION

5. Galvanic corrosion
Corrosion resulting from contact between two different metals
or alloys in a conducting corrosive environment.
This corrosion occurs when three conditions are present:

a) Metals must be far apart on the galvanic series

b) These metals must be in electrical contact,
c) The metals must be exposed to a conductive electrolyte

6. Stress corrosion cracking (SCC)

the cracking is induced from the combined action of tensile
stress and a corrosive environment.

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 LOCALIZED CORROSION

Activity Passivity Transpassivity

Cathodic domain Anodic domain

Sharp increase of anodic current

Passive film
M  MxOy

Etp Transpassive potential

Dissolution
(without Halide species)
Passivation

Polarization curve of a passivable material

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 LOCALIZED CORROSION

Activity Passivity Pitting

Pitting corrosion

Cathodic domain Anodic domain

Passivity
breakdown

with Halide species Epit Pitting potential

( Cl-, Br-, I-, F- …)

Polarization curve of a passivable material

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 OUTLINE

1. Introduction
2. Types of corrosion
a) Uniform corrosion

b) Localized corrosion

3. Corrosion experiment
4. EC-Lab® corrosion techniques
a) Uniform corrosion

b) Localized corrosion

5. Conclusions

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 CORROSION EXPERIMENT

Experimental Set up

WE= Working electrode

RE= Reference electrode

Potentiostat

CE= Counter electrode

(Pt, Graphite,..)
Corrosion Cell

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 CORROSION EXPERIMENT

Role of the potentiostat

steady-state current-voltage curves

E
A. Controlled voltage techniques (Except ZRA)
I
1- Apply a voltage between RE and WE
2- Record the current flowing between the WE and the CE

B. Controlled current techniques

1- Apply a current between CE and WE
2- Record the voltage between the WE and the RE

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 CORROSION EXPERIMENT

Connection to the cell Each potentiostat cell cable has 6 terminal leads:

Cell connection modes

VMP3 series SP300 series
Standard mode

EWE= Ref1-Ref2 EWE= S1-S2

CE to Ground mode
(used for multielectrode
inverstigation) EWE= S1-S2
EWE= Ref3-Ref2

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 OUTLINE

1. Introduction
2. Types of corrosion
a) Uniform corrosion

b) Localized corrosion

3. Corrosion experiment
4. EC-Lab® corrosion techniques
a) Uniform corrosion

b) Localized corrosion

5. Conclusions

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 EC-LAB CORROSION TECHNIQUES

Corrosion
techniques

Uniform Corrosion Localized corrosion

• Ecorr vs time • Ecorr vs time

• Linear Polarization (LP) • Cyclic Potentiodynamic Polarization (CPP)

• Corrosimetry (CM) • Multielectrode Potentiodynamic pitting (MPP)

• Generalized Corrosion(GC) • Multielectrode Potentiostatic pitting (MPSP)

• VASP • CPT

• CASP • Depassivation Potential: DP

• ZRA • Corrosimetry (CM)

• ZRA

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 OUTLINE

1. Introduction
2. Types of corrosion
a) Uniform corrosion

b) Localized corrosion

3. Corrosion experiment
4. EC-Lab® corrosion techniques
a) Uniform corrosion

b) Localized corrosion

5. Conclusions

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 EC-LAB CORROSION TECHNIQUES

Ecorr vs time
It is a basic technique used to monitor the corrosion potential of the working electrode
versus time

Passivation / Inhibition

Ecorr
Activation/dissolution

Ecorr vs time set up Time

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 EC-LAB CORROSION TECHNIQUES

Linear Polarization
The LP technique consists of a potential scan around the Ecorr. It is used to determine
polarization resistance, corrosion current and Tafel parameters.

Ecorr vs time
EL-Ei

2 kinds of information

Potential scan

LP description

Linear polarization set up

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 EC-LAB CORROSION TECHNIQUES

Linear Polarization

I corr , βa and βc
Ecorr ± 250 mV
LP Tafel Fit
Polarization in
a wide ΔE

Ecorr ± 25 mV Rp

LP
Rp Fit
Polarization in
a narrow ΔE

LP stainless steel in NaCl media (30 gL-1)

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 EC-LAB CORROSION TECHNIQUES

Corrosimetry: CM
The CM technique is used in corrosion for the determination of Rp versus time by a
repetition of the linear polarization around the corrosion potential at fixed time interval.

 Polarization resistance
 Corrosion rate

Corrosimetry description

Corrosimetry set up

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 EC-LAB CORROSION TECHNIQUES

Corrosimetry (CM)
CM technique is advisable for long-time corrosion study

corrosion rate vs time

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 EC-LAB CORROSION TECHNIQUES

Generalized corrosion
Technique dedicated to study the general corrosion. It consists of half a cycle or a cycle of
usual cyclic voltammetry with a digital potential sweep

Ecorr vs time

Ecorr

GC parameter
I corr

Courbe à ajouter

Reverse scan

Generalized corrosion set up

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 EC-LAB CORROSION TECHNIQUES

VASP
VASP (Variable Amplitude Sinusoïdal micro-Polarization) is based on the EIS measurements.
It consists in the determination of the change of the polarization resistance in function of the
potential amplitude variation

V(t) I(t)
Electrochemical system
Ia
Va

V (t )  Ecorr  Va sin(2f t ) with Va min  Va  Va max

VASP set up

For each amplitude Va , Rp is determined and the Rp=f(Va) is plotted

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 EC-LAB CORROSION TECHNIQUES

VASP

The frequency f is determined by an EIS technique

and corresponds to the Rp parameter where Im(Z) =0
and Z(f)= Rp
f= 0,23 Hz

The impedance response of a non-linear

electrochemical system depends on the
potential amplitude va

Impedance evolution of a non linear

system (Test box-3-2)

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 EC-LAB CORROSION TECHNIQUES

VASP

I corr
VASP Fit

Tafel
parameters

VASP on a Ni electrode in HCl media

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 EC-LAB CORROSION TECHNIQUES

CASP
CASP (Constant Amplitude Sinusoidal microPolarization) technique is used to determine
the corrosion current and the Tafel parameters using Discrete Fourier Transform (DFT)

A voltage V(t) with a frequency f is applied around Ecorr

Corrosion rate icorr

CASP set up
Three harmonics: , , Tafel parameter ba and bc

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 EC-LAB CORROSION TECHNIQUES

CASP

harmonics

CASP Fit

I corr

Tafel parameters

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 EC-LAB CORROSION TECHNIQUES

Zero Resistance Ammeter (ZRA)

ZRA is corrosion technique used to measure the galvanic coupling current between two
dissimilar electrodes. It consists of applying zero volts between the WE and the CE and
then measuring the current and the potentials (Ewe, Ece) versus the reference electrode.

OCV

ZRA
 Coupling current
 Noise resistance

OCV

ZRA Set up

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 EC-LAB CORROSION TECHNIQUES

Three methods are available in EC-Lab® to calculate the noise resistance Rn

1. Standard deviation (SD).
2. Power spectral density (PSD ) with DFT.
3. PSD with MEM (Maximum Entropy Method)

ENA Fit

PSD with MEM method

ZRA curves
PSD with DFT method

SD method

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 OUTLINE

1. Introduction
2. Types of corrosion
a) Uniform corrosion

b) Localized corrosion

3. Corrosion experiment
4. EC-Lab® corrosion techniques
a) Uniform corrosion

b) Localized corrosion

5. Conclusions

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 EC-LAB CORROSION TECHNIQUES

Cyclic Potentiodynamic Polarization (CPP)

CPP is a corrosion technique used to evaluate pitting susceptibility and repassivation
potential of a material. It is based on a potentiodynamic scan

 Pitting potential
 Corrosion potential
 Repassivation potential
 Corrosion rate

CPP Set up

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 EC-LAB CORROSION TECHNIQUES

Cyclic Potentiodynamic Polarization (CPP)

The figure below give an example of the curve obtained by CPP technique

Reverse scan

ip

Epit ip

Ecorr Erepa

The pitting potential is easily determined

in I-E presentation
Epit
Pitting potential

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 EC-LAB CORROSION TECHNIQUES

Multiple Potentiodynamic Pitting (MPP)

This technique is designed to study pitting corrosion on one or several electrodes together in
the electrochemical cell. CE to ground connection is required in the case of MPP experiment

 Pitting potential
 Corrosion potential

MPP description
 Corrosion rate
 Corrosion resistance

MPP set up

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 EC-LAB CORROSION TECHNIQUES

Multielectrode Potentiodynamic Pitting (MPP)

MPP technique can be performed on up to 16 working electrodes simultaneously (with
VMP3 in Ce to ground mode)
“MultiPitting Statistics” allows the user to compute data simultaneously from several
data files.

MP statistics

Ecorr

MPP investigations and Statistics

MPP curves of the four steel electrodes

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 EC-LAB CORROSION TECHNIQUES

Multielectrode Potentiostatic Pitting (MPSP)

This technique is similar to the MPP technique with a potentiostatic control instead of a
potentiodynamic scan. It is designed to study pitting corrosion on one or several electrodes
together in the electrochemical cell

 Pitting potential
 Metastable pits
MPSP description

MPSP set up

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 EC-LAB CORROSION TECHNIQUES

Multielectrode Potentiostatic Pitting MPSP

MPSP technique allows the determination of the latency and growth phases for each
applied potential Ei.

ip

Latency phase

Growth phase

MPSP curve for a stainless steel in 30g.L-1 NaCl.

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 CONCLUSIONS

In the first part of this tutorial:

 an overview of different corrosion forms was presented.

 the main characteristics of each form of corrosion was described with photo
illustrations.
 A corrosion experiment with a three electrodes system was presented.
 The connection modes to Bio-logic potentiostats were also detailed.

In the second part of this tutorial:

 the corrosion techniques available in EC-lab® software were detailed.

 Experimental results were given here to illustrate the use of the corrosion
techniques.
 Numerous corrosion analysis tools, available in EC-Lab® softawre were used.

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