Professional Documents
Culture Documents
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
❖ 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
❖ 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
❖ 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
❖ 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
Solution
Vo=iRsol
E V=iRct
Time
(c) Bob Cottis 1995
Open Circuit Potential Decay
Time
(c) Bob Cottis 1995
(c) Bob Cottis 1995