Professional Documents
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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_Notes
Measurement methods
Cell design
Plotting data
Interpretation
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
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
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
Working electrode
Reference electrode
Counter electrode
Solution
Mass transport
Requirements
– reproducible
– representative
– free of crevices
– free of edge effects
– free of galvanic effects
– free of water-line effects
Heavy-walled
glass tube
Lip seal
between
PTFE case PTFE Washer
and electrode
Electrode
Avesta cell:
Pure NaCl
Filter paper
H2O feed Solution
Specimen
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
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
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
log |i|
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
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
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
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
log |i|
(c) Bob Cottis 1995
Active-passive transition
log |i|
(c) Bob Cottis 1995
Transpassive corrosion
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
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
Control variable
Waveform
Cell configuration
Sweep rate
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
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
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
Determination of B value
– calculate from Tafel slopes
ba bc
B
2.3ba bc
– correlation with weight loss
– arbitrary value
26 mV for activation control
52 mV for one reaction at limiting current
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
Solution
Rct
Rsol
Vo=iRsol
E V=iRct
Time
(c) Bob Cottis 1995
Open Circuit Potential Decay
Time
(c) Bob Cottis 1995
(c) Bob Cottis 1995