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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 : milli-inches 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
?
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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.
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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
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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 small-amplitude 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 ?
- In-situ : electrical properties of the interface between electrode and
electrolyte.
- Nondestructive : using very small amplitude signals.
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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
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Schematic instrumentation for conducting EIS
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The Double Layer
The adsorbed fixed layer and the diffuse mobile layer together are the
ELECTROCHEMICAL DOUBLE LAYER acting as a capacitor.
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AC & The Double Layer
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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 "
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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
)
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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
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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
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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

90 Phase difference between. e


c
and i
c
e
c
e
c
e
c
E
c
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Phasor Diagram
e = E sin t
phasor diagram
radius : amplitude E
frequency of rotation :
rotating vector (or phasor)
rotating at same frequency
I : phasor of the current, i
E : phasor of the voltage, e
: phase angle

e = E sin t
i = I sin ( t - )
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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
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AC Voltage & Current Relation of the R-C 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
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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
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Series Connection of the R-C 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 + = + =
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Series Connection of the R-C 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: Calc-Modulus
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
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Parallel Connection of the R-C 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: Calc-Modulus
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
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Parallel Connection of the R-C 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: Calc-Modulus
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
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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: Calc-Modulus
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
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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: Calc-Modulus
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
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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

R : ideal gas constant


T : absolute temperature
n : the number of electron transferred
F : Faradays constant
C
ox
: conc. of oxidation species
C
red
: conc. of reduction species
D
ox
: diffusivity of oxidation species
D
red
: diffusivity of reduction species
: Warburg impedance coefficient
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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
-1 0 1 2 3 4
3
3
4
4
4
4
5
0
10
20
30
40
50
60
log(f)
l
o
g
(
Z
)
(
o
)
p
h
a
s
e

/

d
e
g
(
+
)
Nyquist plot Bode plot
w
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Nyquist & Bode Plot
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Equivalent Circuit of the Porous Coating
Metal
Coating
Solution
R
s
R
po
C
c
C
dl
R
ct
Pore
R
s
C
c
R
po
R
ct
C
dl
: solution resistance
: capacitance of the coating
: resistance of the porous layer
: charge transfer resistance
: double layer capacitance
l
o
g

|
z
|

log freq.
Bode plot
R
ct
R
po