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 methods
Cell design
Plotting data
Interpretation

(c) Bob Cottis 1995

 Measurement Methods
 Objective
– determine current density under steady-
state 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
 Potential control corresponding terminals
on potentiostat
Reference Electrode -
Luggin Probe - connection
reference allows for
Potentiostat AE potential
potential to be detected
measurement
close to metal surface
RE
WE
Counter Electrode (or
Auxilliary Electrode or
Working
SecondaryElectrode - -
Electrode)
Potentiostat controls
metal being
provides studied
current
potential path
into solution
(c) Bob Cottis 1995
 Measurement Methods
 Current control Current path

Potentiostat
V
AE
RE
Counter Electrode
WE R

Reference
Current Electrode
controlled by -
only Luggin
used
control Probeacross
oftovoltage
monitor still
potential,
Working Electrode
notneeded
connected
resistorto (I=V/R)
limit IR error
to potentiostat
(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
 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

(c) Bob Cottis 1995

 Measurement Methods
 Sweep rate (or step rate)
– Ideal, all measurements made at steady-
state
– Time-dependent effects include:
 Charging of double layer capacitance (I = C dV/dt)
 Mass transport effects (t  L2/D)
 Adsorbed species and surface films (Faraday’s
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  21019/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
– reproducible
– representative
– free of crevices
– free of edge effects
– free of galvanic effects
– free of water-line effects

(c) Bob Cottis 1995

 Working Electrode
 Epoxy embedded electrode:
Apply thin layer of epoxy
Weld or solder connecting
Apply thick layer of epoxy to minimise stress and risk
wire to specimen
to seal connecting tube and of crevice
Pretreatformation
specimen for
for strength good
Carefully adhesion
grind surface
to expose metal

Clean surface - don’t

use acetone
(c) Bob Cottis 1995
 Working Electrode
Metal rod
 Stern-Makrides Retaining nut
Washers
electrodes:

Heavy-walled
glass tube
Lip seal
between
PTFE case PTFE Washer
and electrode
Electrode

(c) Bob Cottis 1995

 Working Electrode
 Avesta cell:

Pure NaCl
Filter paper
H2O feed Solution

Specimen

(c) Bob Cottis 1995

 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

Luggin probe allows point at which potential

is measured to be close to electrode surface
(c) Bob Cottis 1995 (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
– rotating disk or cylinder
– flow channel
– jet impingement
– gas bubbling

(c) Bob Cottis 1995

 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

4.000E-02
Current Density

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 -0.300 -0.100 0.100 0.300 0.500
Potential

(c) Bob Cottis 1995

 E log |i| Plot
1.000E-01

Fe anodic H cathodic O2 cathodic

1.000E-02 Net anodic Net cathodic

Current Density

1.000E-03

1.000E-04

1.000E-05

1.000E-06
-1.500 -1.300 -1.100 -0.900 -0.700 -0.500 -0.300 -0.100 0.100 0.300 0.500
Potential

(c) Bob Cottis 1995

 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

Fe anodic H cathodic O2 cathodic

1.000E-02 Net anodic Net cathodic

Current Density

1.000E-03

1.000E-04

1.000E-05

1.000E-06
-1.500 -1.300 -1.100 -0.900 -0.700 -0.500 -0.300 -0.100 0.100 0.300 0.500
Potential

(c) Bob Cottis 1995

 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

Fe anodic H cathodic O2 cathodic

1.000E-02 Net anodic Net cathodic

Current Density

1.000E-03

1.000E-04

1.000E-05

1.000E-06
-1.500 -1.300 -1.100 -0.900 -0.700 -0.500 -0.300 -0.100 0.100 0.300 0.500
Potential

(c) Bob Cottis 1995

 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

Fe anodic H cathodic O2 cathodic

1.000E-02 Net anodic Net cathodic

Current Density

1.000E-03

1.000E-04

1.000E-05

1.000E-06
-1.500 -1.300 -1.100 -0.900 -0.700 -0.500 -0.300 -0.100 0.100 0.300 0.500
Potential

(c) Bob Cottis 1995

 E-i Plot
2.000E-02

Fe anodic H cathodic
1.500E-02

O2 cathodic Net
1.000E-02

5.000E-03
Current Density

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 -0.300 -0.100 0.100 0.300 0.500
Potential

(c) Bob Cottis 1995

 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
activation-controlled 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
Overall forcurve
anodic iron
E 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
Noise continues
Pit eventually
spikes duere-to
to increase
meta-stable after
passivates
pitting
E
reversal of scan

log |i|
(c) Bob Cottis 1995
 What is going on?
Stainless Steel in Aerated Sulphuric Acid

Anodic

Cathodic
E
Anodic

Cathodic
log |i|
(c) Bob Cottis 1995
 Linear Polarization
Resistance Measurement
Theoretical basis

Measurement methods
Interpretation

(c) Bob Cottis 1995

 LPRM Theory
 For an activation controlled reaction
 E  Eo  Exchange
Equilibrium
current
i io exp  Tafel slope based on
   potential
density
exponential (i.e. mV
di io  E  Eo  for a change of 1 in
  exp 
dE     ln(i))
i



(c) Bob Cottis 1995

 LPRM Theory
 Summing for two reactions
di ia ic Anodic
Because partial
partial
is taken
current
  Cathodic
Anodic
Cathodic
Tafel slope Tafel
cTafel
based onas
current
slope
slope a
dE  a c density (=i-i
(=
(positive)
negative
(negative)
decade change corr)in)
corr

  a  c  1 current (i.e. a change

Stern-Geary
icorr    of 1 in log i )
coefficient
  ac  R p
 Rearrange and convert to b rather than
 B ba bc
Rp  , B
icorr 2.3ba  bc 

(c) Bob Cottis 1995

 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
– potential range depends on Rp
– measurement inherently centred about i =
0

(c) Bob Cottis 1995

 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
 26 mV for activation control
 52 mV for one reaction at limiting current

(c) Bob Cottis 1995

 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
Estimate Cdlacross
from the Rsol is
given by V
exponential oexp(-t/R
decay. Cdl)
Thesoltime
for V to
When
fall to
t=eR-1sol(37%)
Cdl, of
i the initial
V=V value is R C
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 Time = RctCdl
= iRct
0.37iRct

Time
(c) Bob Cottis 1995
(c) Bob Cottis 1995