Corrosion Measurement

Techniques
A copy of this presentation is available
in the CAL group in the computers in
the Teaching Lab, or via the WWW at
http://www.cp.umist.ac.uk/CPC/L_Note
s
(c) Bob Cottis 1995

Corrosion Measurement
Techniques
Polarization curves
Linear Polarization Resistance
Open Circuit Potential Decay
AC Impedance Measurement
Electrochemical Noise Measurement
Weight Loss Measurement

(c) Bob Cottis 1995

Polarization Curves
Measurement
Cell

design

Plotting

data

Interpretation

(c) Bob Cottis 1995

methods

Measurement Methods

Objective
determine current density under steadystate conditions as a function of potential
not really practical, as this would strictly
require one sample for each potential
therefore compromise on closeness to true
steady-state

(c) Bob Cottis 1995

Measurement Methods
Connect electrodes to
corresponding terminals
Potential control
on potentiostat
Reference Electrode Luggin
Probe - connection
allows
reference
for
Potentiostat
AE potential
potential
to be detected
measurement
close to metal surface
RE
WE
Counter Electrode (or
Auxilliary Electrode or
Working
Electrode
- Secondary
Electrode)
Potentiostat
controls
metal
being
studied
provides
current
path
potential
into solution
(c) Bob Cottis 1995

Measurement Methods

Current control Current path

Potentiostat

AE
RE
WE

Counter Electrode
R

Reference
Electrode
Current
controlled
by Luggin
Probeacross
still
only
used
monitor
potential,
control
oftovoltage
Working
Electrode
to (I=V/R)
limit
IR error
notneeded
connected
to potentiostat
resistor
(c) Bob Cottis 1995

Measurement Methods

Swept potential or current

Use sweep generator to produce slowly
changing potential
Sweep generator output controls
potentiostat
Record response on chart recorder (or use
computer monitoring)
Swept current not often used, as it moves
through corrosion potential very quickly

(c) Bob Cottis 1995

Measurement Methods

Potential or current step

Step potential or current from one value to
the next, allowing time to stabilise at each
new value
Record current or potential
May be manually controlled, or use
computer to step potential/current and take
readings

(c) Bob Cottis 1995

Measurement Methods

Sweep direction
Aim to perform experiment in such an order
that the initial polarization affects
subsequent results as little as possible
Options

(c) Bob Cottis 1995

new specimen for each potential

one specimen for cathodic polarization, and one
for anodic, both start at corrosion potential
one specimen, sweep from cathodic to anodic

Measurement Methods

Sweep rate (or step rate)

Ideal, all measurements made at steadystate
Time-dependent effects include:

Charging of double layer capacitance (I = C dV/dt)

Mass transport effects (t L2/D)
Adsorbed species and surface films (Faradays
Law)

Typical sweep rates are of the order of 1

mV/s or less
(c) Bob Cottis 1995

Questions

Consider the corrosion of iron in aerated

neutral solution, with the following parameters:

Cdl = 35 F / cm2 DO2 = 1.2 x 10-5 cm2 /s

Boundary layer thickness, = 100 m
Number of iron atoms on surface 21019/cm2
Charge on the electron = 1.6 x 10-19C

Calculate
Capacitive current at 1 mV/s
Characteristic diffusion time
Limiting current density for O2 reduction (8 ppm O2)
Time to oxidise Fe surface to FeOH (Fe+) at ilim

(c) Bob Cottis 1995

Cell Design

Working electrode
Reference electrode
Counter electrode
Solution
Mass transport

(c) Bob Cottis 1995

Working Electrode

Requirements

(c) Bob Cottis 1995

reproducible
representative
free of crevices
free of edge effects
free of galvanic effects
free of water-line effects

Working Electrode

Epoxy embedded electrode:

Apply thin layer of epoxy

Weld or solder connecting
to minimise stress and risk
Apply thick layer of epoxy
wire to specimen
of crevice
Pretreatformation
specimen for
to seal connecting tube and
good
adhesion
Carefully
grind
surface
for strength
to expose metal

Clean surface - dont

use acetone
(c) Bob Cottis 1995

Working Electrode

Stern-Makrides
electrodes:

Metal rod
Retaining nut
Washers
Heavy-walled
glass tube

Lip seal
between
PTFE case
and electrode

PTFE Washer
Electrode

(c) Bob Cottis 1995

Working Electrode

Avesta cell:
Pure
H2O feed

NaCl
Solution

Specimen

(c) Bob Cottis 1995

Filter paper

Reference Electrode

Commonly use Saturated Calomel

Electrode (SCE)
Properties may degrade with time (and
misuse)
check one against another (should not be
more than 1 to 2 mV difference)
do not pass current through the reference
electrode (e.g. do not connect to working or
counter electrode)
do not allow to dry out

(c) Bob Cottis 1995

Reference Electrode

Solution in SCE (or Ag/AgCl electrode) is

saturated KCl
beware of chloride contamination of test
solution by Cl- leaking from reference
electrode
make sure solution remains saturated

(c) Bob Cottis 1995

Luggin Probe
A Luggin probe should be used
whenever there is a significant current
applied to the electrode

Electrode

(c) Bob Cottis 1995

Luggin probe allows point at which potential

is measured to be close to electrode surface
(around 3 times tip diameter is best)

Counter electrode

Counter electrode should allow current to

pass with tolerable polarization
Often claimed that counter electrode should
have much larger area than working
electrode, but this is not often necessary for
corrosion studies
Usually use platinum or graphite, although
stainless steel can be used in some
situations (e.g. where only anodic
polarization of specimen is used)

(c) Bob Cottis 1995

Solution

Requirements:
as high a conductivity as possible (add
supporting electrolyte, such as sodium
perchlorate?)
remain the same (pH, composition) throughout
the experiment - ensure that volume is adequate
oxygen concentration often critical - aerate by
bubbling air or O2 or deaerate with N2 or Ar
most reactions temperature sensitive, so control,
or at least record, temperature

(c) Bob Cottis 1995

Mass transport

Methods of controlling mass transport

(c) Bob Cottis 1995

rotating disk or cylinder

flow channel
jet impingement
gas bubbling

Plotting of Polarization
Curves

Comparison of log-i and linear-i plots

Identification of anodic and cathodic
regions on log-i plots
Orientation of plots

(c) Bob Cottis 1995

E-i Plot
1.000E-01
8.000E-02

Fe anodic

H cathodic

6.000E-02

O2 cathodic

Net

Current Density

4.000E-02
2.000E-02
0.000E+00
-2.000E-02
-4.000E-02
-6.000E-02
-8.000E-02
-1.000E-01
-1.500

-1.300

-1.100

-0.900

-0.700

-0.500
Potential

(c) Bob Cottis 1995

-0.300

-0.100

0.100

0.300

0.500

E log |i| Plot

1.000E-01

Current Density

1.000E-02

Fe anodic

H cathodic

O2 cathodic

Net anodic

Net cathodic

1.000E-03

1.000E-04

1.000E-05

1.000E-06
-1.500

-1.300

-1.100

-0.900

-0.700

-0.500
Potential

(c) Bob Cottis 1995

-0.300

-0.100

0.100

0.300

0.500

E log |I| - old plotting method

log |i|
(c) Bob Cottis 1995

Interpretation of
Polarization Curves

Addition of reactions on log-I graphs

Tafel regions
Mass transport control
Active-passive transition
Transpassive corrosion
Pitting Corrosion

(c) Bob Cottis 1995

Tafel regions

A Tafel region is a straight line in the

E-log|i| plot
For a reliable Tafel slope:
the line should be straight for at least one
decade (in this context a decade implies a
change of current density by a factor of ten,
i.e a difference of 1 in log i )
the region should be next to Ecorr

(c) Bob Cottis 1995

E log |i| Plot

1.000E-01

Current Density

1.000E-02

Fe anodic

H cathodic

O2 cathodic

Net anodic

Net cathodic

1.000E-03

1.000E-04

1.000E-05

1.000E-06
-1.500

-1.300

-1.100

-0.900

-0.700

-0.500
Potential

(c) Bob Cottis 1995

-0.300

-0.100

0.100

0.300

0.500

Tafel Extrapolation

Extrapolate anodic or cathodic Tafel

region, or both, back to Ecorr, when the
current density is icorr
In aerated neutral solutions, where
mass transport limited oxygen reduction
is the main cathodic reaction, the
cathodic reaction does not have a valid
Tafel slope, but the anodic slope can
sometimes be used

(c) Bob Cottis 1995

Question

How can we estimate the rate of

hydrogen evolution during free
corrosion?
Estimate the value for the graph shown.

(c) Bob Cottis 1995

E log |i| Plot

1.000E-01

Current Density

1.000E-02

Fe anodic

H cathodic

O2 cathodic

Net anodic

Net cathodic

1.000E-03

1.000E-04

1.000E-05

1.000E-06
-1.500

-1.300

-1.100

-0.900

-0.700

-0.500
Potential

(c) Bob Cottis 1995

-0.300

-0.100

0.100

0.300

0.500

Mass transport control

When the supply of a reactant becomes

mass transport controlled, we observe a
limiting current density
The most common case occurs for oxygen
as a cathodic reactant in neutral solutions
NOTE - the diffusion of a reaction product
away from the electrode will not affect
the rate of the forward reaction

(c) Bob Cottis 1995

Solution Resistance
Effects

At high currents the potential drop

associated with the solution resistance
can be significant
It is generally referred to as an IR error
Gives a straight line on E-i plots

(c) Bob Cottis 1995

E log |i| Plot

1.000E-01

Current Density

1.000E-02

Fe anodic

H cathodic

Net anodic

Net cathodic

O2 cathodic

1.000E-03

1.000E-04

1.000E-05

1.000E-06
-1.500

-1.300

-1.100

-0.900

-0.700

-0.500
Potential

(c) Bob Cottis 1995

-0.300

-0.100

0.100

0.300

0.500

E-i Plot
2.000E-02

1.500E-02

Fe anodic

H cathodic

O2 cathodic

Net

Current Density

1.000E-02

5.000E-03

0.000E+00

-5.000E-03

-1.000E-02

-1.500E-02

-2.000E-02
-1.500

-1.300

-1.100

-0.900

-0.700

-0.500
Potential

(c) Bob Cottis 1995

-0.300

-0.100

0.100

0.300

0.500

Active-passive transition

As a passive film develops, it covers the

surface and shuts off the dissolution
reaction, leading to an active-passive
transition

log |i|
(c) Bob Cottis 1995

Active-passive transition

For stainless steel we sometimes see

two active-passive transitions, on for
Chromium, and one for Iron

log |i|
(c) Bob Cottis 1995

Transpassive corrosion

A passive metal (notably Cr and Fe) may

start to dissolve at a very positive potential
when a higher oxidation state (e.g. Cr6+ as
chromate) is formed
This is known as transpassive corrosion, and
will give something like a second activationcontrolled reaction
For alloys the behaviour will be complicated
by the differing behaviours of the alloy
components

(c) Bob Cottis 1995

Anodic Polarization Curve

for Stainless Steel

Activation-controlled
Active-passive
Transpassive
Oxygen
Active peak
forcurve
iron
Overall
anodic
corrosion
dissolution
transition
reduction
of Cr

log |i|
(c) Bob Cottis 1995

Pitting Corrosion

Pitting shows up as an increasing anodic

current before (at a less positive
potential than) transpassive corrosion or
oxygen evolution, usually preceded by
noise
E-log|i| plot does not follow same path if
scan direction is reversed, but current is
greater (since pit continues to grow)

(c) Bob Cottis 1995

Pitting Corrosion

Current
continues
Noise
Pit eventually
spikes
due
re-to
to increase
after
meta-stable
passivates
pitting
reversal of scan

log |i|
(c) Bob Cottis 1995

What is going on?

Stainless Steel in Aerated Sulphuric Acid

Anodic
Cathodic

Anodic
Cathodic
log |i|
(c) Bob Cottis 1995

Linear Polarization
Resistance Measurement
Theoretical basis
Measurement
Interpretation

(c) Bob Cottis 1995

methods

LPRM Theory

For an activation controlled reaction

E Eo

i io exp

E Eo
di io

exp
dE

(c) Bob Cottis 1995

Exchange
Equilibrium
current
Tafel slope
based on
potential
density
exponential (i.e. mV
for a change of 1 in
ln(i))

LPRM Theory

Summing for two reactions

ia ic
di

dE a c
a c
1

icorr

Rp
ac

Anodic
Because
partial
partial
is taken
current
Cathodic
Anodic
Tafel
slope
current
Cathodic
slope
cTafel
Tafel
slope
based
on as
a
density
(=i-i
))
(positive)
(=
(negative)
negative
corr
corr
decade
change
in
current
(i.e. a change
Stern-Geary
of 1 in log i )
coefficient

Rearrange and convert to b rather than

ba bc
B
Rp

(c) Bob Cottis 1995

icorr

2.3 ba bc

LPRM Measurement
Methods

Control variable
Waveform
Cell configuration
Sweep rate

(c) Bob Cottis 1995

LPRM Control Variable

Potential control
potential range can be optimised
problems with drift of Ecorr

Current control

(c) Bob Cottis 1995

potential range depends on Rp

measurement inherently centred about i = 0

LPRM Measurement
Waveform

Triangle wave
can measure di/dt at i = 0
requires relatively complex instruments

Square wave (switch between +i and -i)

simple instruments
simple to automate

Sine wave
simplest theory for frequency effects
complex to perform measurement

(c) Bob Cottis 1995

LPRM Cell Configuration

Two electrode
assume Rp is the same for two similar electrodes
and measure cell resistance (= 2Rp + Rsol)
easy, no reference electrode required

Three electrode
use conventional counter, reference and
working electrodes
provides lower solution resistance, therefore
better for low conductivity solutions
more complex instrumentation

(c) Bob Cottis 1995

LPRM Recommendations

Use three electrode measurement with triangle

waveform for laboratory studies
Use two electrode measurement with square
waveform for simple corrosion monitoring (use
three electrodes for high resistance solutions)
Use potential control when icorr variation is large
Use current control when Ecorr varies a lot
When both icorr and Ecorr vary use current
control, but adapt current to keep potential
range reasonable

(c) Bob Cottis 1995

LPRM Interpretation

Determination of B value
calculate from Tafel slopes
ba bc
B
2.3 ba bc
correlation with weight loss
arbitrary value

(c) Bob Cottis 1995

26 mV for activation control

52 mV for one reaction at limiting current

LPRM Sweep Rate

Must be sufficiently slow for current

charging double layer capacitance to be
much less than total current
Characteristic time given by RctCdl - cycle
time should be at least 3 times this
Need not be slow enough to allow
diffusion processes to respond (as the
basic theory is not valid for diffusion
processes)

(c) Bob Cottis 1995

LPRM Problems

Theoretically, either
both reactions must be activation controlled, or
one reaction must be activation controlled and
the other mass-transport limited

In practice it is rare for real systems to

meet these constraints, and application of
LPRM is not theoretically justified
Solution resistance adds to measured Rp,
and produces lower apparent corrosion rate

(c) Bob Cottis 1995

Equivalent Circuits

An electrical circuit with the same

properties as a metal-solution interface
The simplest circuit is a resistor, Rct,
corresponding to the polarization
resistance, in parallel with a capacitor,
Cdl, corresponding to the double layer
capacitance
Solution

(c) Bob Cottis 1995

Equivalent Circuits

An electrical circuit with the same

properties as a metal-solution interface
The Randles equivalent circuit adds a
series resistor, corresponding to the
solution resistance
RRctct
RRsol
sol

(c) Bob Cottis 1995

Analysis of Solution
Resistance

If we analyse the full response to the LPRM

measurement, we can estimate Rsol, Cdl and Rct
The
voltage
Rsol is
Estimate
Cdlacross
from the
given by V
Cdl)
exponential
decay.
Thesoltime
oexp(-t/R
for V to
When
fall to
t=eR-1sol(37%)
Cdl, of
the initial
value
is R C
V=V
i
oexp(-1) sol dl
Vo=iRsol
E

V=iRct
Time

(c) Bob Cottis 1995

Open Circuit Potential

Decay

Similar to analysis of LPRM

measurement
charge double layer capacitance by
applying a current or potential
disconnect charging current
monitor decay of potential

(c) Bob Cottis 1995

Open Circuit Potential

Decay
Charging at current i

Disconnected
Initial voltage drop = iRsol

E
Delayed
voltage drop
= iRct

Time = RctCdl
0.37iRct
Time

(c) Bob Cottis 1995

(c) Bob Cottis 1995