kr
6. 6. Corrosion Rate Measurements Corrosion Rate Measurements
6.1 Weight loss measurement
Specimen preparation Exposure to environment Specimen cleaning Measurement of
change in specimen weight.
Corrosion rate expressions.
 mm/y : mm penetration per year.
 gmd : grams/m2 day
 ipy : inches penetration per year
 mpy : milliinches per year
 mdd : mg per square decimeter per day.
i) corr. rate < 0.15 mm/y : good corrosion resistance for critical parts.
ii) 0.15 < corr. rate < 1.5 mm/y : satisfactory if higher rate of corrosion can be tolerated, for
example; tanks, piping and bolt heads.
iii) corr. rate > 1.5 mm/y : usually not satisfactory.
[ HOME WORK]
1) Prove that : mpy = 534W/DAT
where, W= weight loss, mg. D= density of specimen
A = area of specimen, inch
2
T = exposure time, hr
2) A piece of iron is observed to exhibit a uniform corrosion rate of 10 mdd. What is the
corrosion current density in A/cm
2
?
http://corrosion.kaist.ac.kr
6.2 Electrochemical Method
 Based on the mixed potential theory.
1) Tafel extrapolation
Corrosion rate is determined by
extrapolation of Tafel region to the corrosion
potential. i
o,H2
on metal M is also determined
by the intersection of the Tafel line with the
reversible hydrogen potential.
Disadvantage of Tafel extrapolation method
 only applied to systems containing one
reduction process
 interferences from conc. polarization in
determining Tafel region.
http://corrosion.kaist.ac.kr
2) Linear polarization method
Within 10mV more noble or active than the E
corr
, i
e
is a
linear function of the electrode potential.
i
e
= I i
a
 i
c
I = f(E)
E = E'  E
corr
= B
a
log i
a
/i
o,M
 B
a
log i
corr
/i
o,M
= B
a
log i
a
/i
corr
= B
a
/2.3 ln i
a
/i
corr
i
a
= i
corr
e
2.3E/B
a
Similarly, i
c
= i
corr
e
2.3E/B
c
i
e
= i
a
 i
c
= i
corr
( e
2.3E/B
a
e
2.3E/B
c
)
= i
corr
(2.3E/B
a
+ 2.3E/B
c
)
= 2.3i
corr
E(B
a
+ B
c
)/B
a
B
c
Stern Geary eq.
assuming that B
a
= B
c
= 0.12
R
p
= E/i
e
= 0.026/i
corr
R
p
: polarization resistance.
E
corr
E'
E
i
c
i
a
i
o,a
log i
http://corrosion.kaist.ac.kr
6.3 Application of Impedance Technique on Corrosion Research Application of Impedance Technique on Corrosion Research
Electrochemical impedance spectroscopy (EIS)
The response of corroding electrodes to smallamplitude alternating
potential signals of widely varying frequency has been analyzed by EIS.
v ( t ) = V
m
sin ( wt ) i ( t )= I
m
sin ( wt + )
Why EIS ?
 Insitu : electrical properties of the interface between electrode and
electrolyte.
 Nondestructive : using very small amplitude signals.
http://corrosion.kaist.ac.kr
Application of EIS to Corrosion & Material Science
 electrode design
 relative dielectric constant
 specific ionic conductivity
battery
mechanism of electrodeposition
surface pretreatment
electrodeposition
 effects of inhibitors on corrosion resistance
 corrosion resistance of the coating
 electrical properties of the passive layer
 corrosion rate
corrosion
http://corrosion.kaist.ac.kr
Schematic instrumentation for conducting EIS
http://corrosion.kaist.ac.kr
The Double Layer
The adsorbed fixed layer and the diffuse mobile layer together are the
ELECTROCHEMICAL DOUBLE LAYER acting as a capacitor.
http://corrosion.kaist.ac.kr
AC & The Double Layer
http://corrosion.kaist.ac.kr
DC & The Double Layer
The distance between the mobile layer and the electrode depends on dc voltage. DC
voltage makes a net current flow through the double layer, from plate to plate,
The double layer capacitor 'leaks'.
Surface atoms ionize and the
electron flow towards the dc
power supply.
: " Faradaic Current "
http://corrosion.kaist.ac.kr
Behavior of The Double Layer
With AC, The double layer behaves like a capacitor (C
dl
)
With DC, The double layer behaves like a resistor, The Faradaic resistor, (R
f
)
http://corrosion.kaist.ac.kr
AC & DC Behavior of The Double Layer
With low frequency, C
dl
is high. current through R
e
(electrolyte resistor) and R
f
,
dc behavior rules.
With high frequency, C
dl
is low. current through C
dl
, ac behavior rules
http://corrosion.kaist.ac.kr
Resistive Circuit
No Phase difference between. e
R
and i
R
t E e
R R
sin =
t I t
R
E
R
e
i
R
R R
R
sin sin = = =
: angular frequency
=2
e
R
e
R
E
R
http://corrosion.kaist.ac.kr
Capacitive Circuit
t E e
C C
sin =
t CE e C q
C C C
sin ) ( = =
= = =
R
e
i t CE
dt
dq
i
C
C
C
cos
C
Xc
1
= Define
: capacitive reactance
) 90 sin(
) 90 sin(
+ =
+ =
t I
t
X
E
i
C
C
C
C
e = E sin t
i = I sin ( t  )
http://corrosion.kaist.ac.kr
Resistive Circuit
e = E sin t
i = (E/R) sin t (Ohms law)
phasor notation
I =E/R
E =I R
Capacitive Circuit
e = E sin t
i = CE cos t = (E/Xc) sin( t +/2 )
E =j X
c
I
I
E =j X
c
I
Re
I
m
e
e
http://corrosion.kaist.ac.kr
AC Voltage & Current Relation of the RC circuit
R
C
i
R
=I
i
C
=I
e
E =E
R
+E
C
E =I ( R jX
C
)
E =I Z
Z =R jX
C
Z() =Z
Re
jZ
Im
E
C
=j X
c
I
E
R
=I R
I
E =I Z
R
j X
c
Z
http://corrosion.kaist.ac.kr
Nyquist Plot & Bode Plot
The variation of the impedance with frequency can be displayed in different way.
1) Nyquist plot : displays Z
Im
vs. Z
Re
for different values of
2) Bode plot : log Z and are both plotted against log
http://corrosion.kaist.ac.kr
Series Connection of the RC Circuit
Z
Re
Z
Im
Z(w)
R
X
c
R
C
i
R
=I
i
C
=I
High frequency : Z =R
Low frequency : Z =
wC
Xc
1
= ( Xc: capacitive reactance )
j
wC
R jwC R Z Z Z
C R
1
) (
1
= + = + =
Z
Re
=R , Z
Im
=1/(wC)
2
2 *
 
C
X R Z Z Z + = =
tan = Z
Im
/Z
Re
= X
c
/R = 1/RC
2
2 2
Im
2
Re
 
C
X R Z Z Z + = + =
http://corrosion.kaist.ac.kr
Series Connection of the RC Circuit
R C
Element Freedom Value Error Error %
R Free(+) 100 N/A N/A
C Free(+) 0.0001 N/A N/A
Data File:
Circuit Model File: C:\Program Files\SAI_Demo\ZModels\Tutor3 Dummy
Mode: Run Simulation / Freq. Range (0.01  100000)
Maximum Iterations: 100
Optimization Iterations: 0
Type of Fitting: Complex
Type of Weighting: CalcModulus
100 10
4
F
0 50 100 150 200
10000
8000
6000
4000
2000
0
Z'
Z
'
'
FitResult
w
10
2
10
1
10
0
10
1
10
2
10
3
10
4
10
5
10
2
10
3
10
4
10
5
10
6
Frequency (Hz)

Z

FitResult
10
2
10
1
10
0
10
1
10
2
10
3
10
4
10
5
100
75
50
25
0
Frequency (Hz)
t
h
e
t
a
High freq.
Z = 0
low freq.
Z =
High freq.
= 0
o
low freq.
= 90
o
Z
Re
Z
I
m
http://corrosion.kaist.ac.kr
Parallel Connection of the RC Circuit
R
C
Element Freedom Value Error Error %
R Free(+) 100 N/A N/A
C Free(+) 0.0001 N/A N/A
Data File:
Circuit Model File: C:\Program Files\SAI_Demo\ZModels\Tutor3 Dummy
Mode: Run Simulation / Freq. Range (0.01  100000)
Maximum Iterations: 100
Optimization Iterations: 0
Type of Fitting: Complex
Type of Weighting: CalcModulus
0 25 50 75 100
100
75
50
25
0
Z'
Z
'
'
FitResult
jwC
R jwC R Z Z Z
C R
+ = + = + =
1
) (
1 1 1 1 1
1
j
C R w
C wR
C R w
R
jwC
R
Z
2 2 2
2
2 2 2
1
1 1
1
+
+
=
+ =
2 2 2
Re
1 C R w
R
Z
+
=
2 2 2
2
Im
1 C R w
C wR
Z
+
=
High frequency : Z =0
Low frequency : Z =R
, w
R
Z
Re
Z
I
m
http://corrosion.kaist.ac.kr
Parallel Connection of the RC Circuit
R
C
Element Freedom Value Error Error %
R Free(+) 100 N/A N/A
C Free(+) 0.0001 N/A N/A
Data File:
Circuit Model File: C:\Program Files\SAI_Demo\ZModels\Tutor3 Dummy
Mode: Run Simulation / Freq. Range (0.01  100000)
Maximum Iterations: 100
Optimization Iterations: 0
Type of Fitting: Complex
Type of Weighting: CalcModulus
0 25 50 75 100
100
75
50
25
0
Z'
Z
'
'
FitResult
100
10
4
F
10
2
10
1
10
0
10
1
10
2
10
3
10
4
10
5
10
2
10
1
10
0
10
1
10
2
10
3
Frequency (Hz)

Z

FitResult
10
2
10
1
10
0
10
1
10
2
10
3
10
4
10
5
100
75
50
25
0
Frequency (Hz)
t
h
e
t
a
Z = R
Z = 0
= 90
o
= 0
o
w
R
Z
Re
Z
I
m
http://corrosion.kaist.ac.kr
Randle Circuit
Rs Cdl
Rct
Element Freedom Value Error Error %
Rs Fixed(X) 10 N/A N/A
Cdl Fixed(X) 0.0001 N/A N/A
Rct Fixed(X) 100 N/A N/A
Data File:
Circuit Model File: C:\Program Files\SAI_Demo\ZModels\Tutor3 Dummy
Mode: Run Simulation / Freq. Range (0.01  100000)
Maximum Iterations: 100
Optimization Iterations: 0
Type of Fitting: Complex
Type of Weighting: CalcModulus
dl
ct dl ct
Cdl Rct dl
jwC
R jwC R Z Z Z
+ = + = + =
1
) (
1 1 1 1 1
1
j
C R w
C wR
C R w
R
jwC
R
Z
dl ct
dl ct
dl ct
ct
dl
ct
dl
2 2 2
2
2 2 2
1
1 1
1
+
+
=
+ =
2 2 2
Re
1 dl ct
ct
s
C R w
R
R Z
+
+ =
2 2 2
2
Im
1 dl ct
dl ct
C R w
C wR
Z
+
=
High frequency : Z =R
s
Low frequency : Z =R
s
+R
ct
,
0 25 50 75 100 125
125
100
75
50
25
0
Z'
FitResult
dl s dl s
Z R Z Z Z + = + =
R
s
R
s
+R
ct
w
R
s
: solution resistance
R
ct
: charge transfer resistance
C
dl
: double layer capacitance
Z
Re
Z
I
m
http://corrosion.kaist.ac.kr
Randle Circuit
Rs Cdl
Rct
Element Freedom Value Error Error %
Rs Fixed(X) 10 N/A N/A
Cdl Fixed(X) 0.0001 N/A N/A
Rct Fixed(X) 100 N/A N/A
Data File:
Circuit Model File: C:\Program Files\SAI_Demo\ZModels\Tutor3 Dummy
Mode: Run Simulation / Freq. Range (0.01  100000)
Maximum Iterations: 100
Optimization Iterations: 0
Type of Fitting: Complex
Type of Weighting: CalcModulus
0 25 50 75 100 125
125
100
75
50
25
0
Z'
Z
'
'
FitResult
w
max
=1/(R
ct
C
dl
)
max
10
2
10
1
10
0
10
1
10
2
10
3
10
4
10
5
10
1
10
2
10
3
Frequency (Hz)

Z

FitResult
10
2
10
1
10
0
10
1
10
2
10
3
10
4
10
5
75
50
25
0
Frequency (Hz)
t
h
e
t
a
w
max
=100 =2, =100/(2) 16 Hz
max
high freq.
R
s
R
s
+R
ct
/2 R
s
+R
ct
R
s
+R
ct
R
s
100
10
4
F
10
R
ct
/2
http://corrosion.kaist.ac.kr
Full Randle Circuit
0 3K 5K 8K 10K 13K 15K 18K 20K
0
3K
5K
8K
10K
13K
15K
18K
20K
Z' / ohm
Z
'
'
/
o
h
m
Warburg impedance, W
diffusion control reaction
Usually observed in low frequency region
slope=1
R
s
R
s
+R
ct
High freq. : W =0
Low freq. : W =
w
2 / 1 2 / 1
W
= j
+ =
2 / 1 2 / 1 2 2
) (
1
) (
1
2
red red ox ox
D C D C F n
RT