Professional Documents
Culture Documents
Corrosion Research
Topics
Corrosion Electrochemistry
Solid surface
Properties
Surface composition Air
Surface structure Temperature, pO2
Mechanical stress Humidity
Material
Soil Solution
Temperature, pH, pH, [O2], [Cl-]
pO2, [Cl-], bacteria Conductivity, flow
ASTM standards:
electrochemistry + corrosion
G102-89 for Calculation of Corrosion Rates from
Electrochemical Measurements
G3-89 for Electrochemical Measurements in
Corrosion Testing
G5-94 for making anodic polarization
measurements
G 106-89 for electrochemical impedance
measurements
G 59-97 for conducting polarization resistance
measurements
ASTM standards:
electrochemistry + corrosion
G69-97 for measurement of Corrosion of aluminum
alloys
G71-81 evaluating galvanic corrosion test
G62-86 for cyclic polarization
G100-89 for conducting cyclic galvano-staircase
polarization
G150-99 critical pitting temperature (CPT) testing
of Stainless steels
etc.
Electrochemical Methods for
Corrosion Research
Typical research directions
in corrosion
Based on
type of corrosion
corrosion protection
corrosion environment (specific
circumstances)
Type of corrosion
mechanism
Specific corrosion aspects
for petrochemical & power
plants
Stress corrosion, cracking (high pressure)
High temperature corrosion
Erosion corrosion (radiation, particles)
Flow accelerated corrosion
Tribo-corrosion (moving parts, turbines)
Metal embrittelment (radiation) etc.
Inhibitors
Specific corrosion aspects
for automotive manifacture
M2+ 2H+ H2
Anode reaction Cathode reaction
M 2e -
+ _ _ + + _ _ +
+ _ _ +
+ _ _ + +
+
_ _ +
+
+ _ _ + _ _
+ _ _ +
+ +
Standard potential
Galvanic series
Standard potential
Potential vs SHE
Equilibrium assumed
Activity=1, T=25 C
Reactions written as cathodic
reactions
Standard potential
Thermodynamic
Nernst equation, Pourbaix diagram
Kinetic
Butler-Volmer equation, Faradays
law, Corrosion rate
Thermodynamic aspects
Thermodynamic aspects
red ox +ne-
Thermodynamic aspects
Pourbaix diagrams
predicts the spontaneous direction
of reactions
estimates the composition of
corrosion products
predicts environmental changes that
will prevent/reduce corrosion attack
Thermodynamic aspects
Pourbaix diagrams: (b)
Line (a)
2H+aq + 2e- H2
Er = E0 RT/2F ln(pH2/aH+2)
Er = 0.059 pH
Line (b)
O2 + 4H+aq + 4e- 2H2O
Er = E0 RT/4F ln(1/pO2 aH+4)
Er = 1.23 0.059pH
(a)
Kinetic aspects
Kinetic aspects
polarization (overvoltage)
= E E0
Kinetic aspects
At equilibrium: =0,
ic=ia=i0
Total net current = 0
ia ia
i i
ic ic
PGSTAT204 PGSTAT101
20 V / 400 mA 10 V / 100 mA
Autolab PGSTAT302F
RRp
Rs
Voltage
follower Cdl
Rp
S
1st Example:
LOW resistance solution 100
HIGH polarization resistance 1M
VCe= -1.0001
Which compliance voltage?
2nd Example:
HIGH resistance solution 30K
LOW polarization resistance 100
3rd Example:
HIGH resistance solution 30K
HIGH polarization resistance 10K
VCe= -4V
MODULES
for corrosion applications:
FRA32M
ECN
MUX-MULTI4 or MUX-SCNR16
BOOSTER 10/20A
pX1000 monitoring pH and T
EQCM
ACCESSORIES:
Sample size:
14mm diameter
3mm thickness
Flat cell
Sample size:
55-85 mm diameter
up to 5 mm
thickness
Optional Instrumentations
DC techniques
LSV (LP), ECN, hydrodynamic LSV
AC techniques
EIS
Specific applications
CPT, H permeation experiment
Direct current methods
Linear sweep voltammetry:
Identification of corrosion processes
Polarization resistance determination
Chrono methods:
Identification of pit initiation
Evolution of corrosion potential (OCP)
Critical pitting corrosion
Why DC techniques?
IN SITU
NON DESTRUCTIVE
Application DC techniques
CHARATERIZATION
corrosion, kinetics, double layer
INVESTIGATION
corrosion, reactions mechanism,
electro-dissolution, electro-deposition,
passivation, reactions kinetics,
Limits of DC techniques
20u
10u
Polarisation curve
i/A
0
-20u
-30u
-0.60 -0.55 -0.50 -0.45 -0.40 -0.35 -0.30 -0.25 -0.20 -0.15
E/ V
-1
10
-2
10
-3
2
10
|i|, A/cm
-4
10
-5
10
with oxygen, pH 7.5, 25 C
-6 0.12M Na 2 SO4
10
0.12M Na 2 SO4 + 0.003M inhibitor
0.003M inhibitor
-7
10
-2 -1 0 1 2
E (vs Hg/Hg 2 SO4 ), V
Passivation
|O2 |O2
|log|I|
|log|I|
E E
Passivation
-3
10
-4
10
|||, A
-5
10
-6
10
de-aerated, pH 7.5
-7 corrected for ohmic drop
10 0.12M NaCl
0.12M NaCl + 0.003M inhibitor
0.003M NaCl + 0.003M inhibitor
-8
0.003M inhibitor
10
Non-invasive method
Statistical approach to corrosion
No external perturbation applied
Current is monitored through a Zero
Resistance Ammeter (ZRA)
ECN - data evaluation
Al rods in
NaOH 0.5mol
Example: value of slope of
the current noise vs time
IN SITU
NON DESTRUCTIVE
RECOGNIZE AS FUNDAMENTAL
TECHNIQUE ON COATING
APPLICATION
CHARACTERIZATION
coatings, corrosion, Galvanic deposition
process, surface treatment process,
insulation control
INVESTIGATION
corrosion, passivation, electro-dissolution,
electro-deposition
LIMITATIONS
- Iron in concrete
- Special alloys
- Galvanic deposition
- Insulation control
EIS Basics
e sin t sin t
Z Z0
i sin t sin t
EIS Basics
it i sin t
et e sin t
Z() Z0e j( )
Z0 cos jsin
Z ZRe j ZIm
EIS Basics: data presentation
Nyquist plot
Plot of Z vs Z, using iso-metric axes
Nyquist
Bode presentation
Plot of |Z| vs log F and vs log F
Phase angle
j( )
Z() Z e
Bode presentation
EIS in Corrosion
Coating
Steel
WE
EIS Coating on steel
Ru
Cdl
EIS Coating on steel
EIS - Carbon steel
RE
CE
RS
Cdl
RP
Steel
WE
EIS - Carbon steel
EIS Failing coating
Ru
Cdl
Coating + pores
Steel
EIS Failing coating
Fitting?
EIS Failing coating
Fit result
EIS Coating with blisters
RE CE
Steel
WE
Corrosion example 4: Electron
transfer + mass transport
Fe Fe2+ + 2e-
O2 + 2H2O + 4e- 4OH-
Rust
Fe2+(aq) Fe3+(aq) + e-
EIS Coating with blisters
EIS Two layer coating
Electrolyte Re
Csf1
Rsf1
Surface
film 1
Rsf2
Surface film 2
Csf2 Cdl
Rct
Electrode
EIS Two layer coating
EIS - Inductance
EIS main possible plots
RQ
R(RC)
EIS main possible plots
R(Q[RW])
R(Q[R(RQ)])
Real example:
Real example:
PGSTAT100N Biodiesel analysis
Estimated C:5,6258 pF
Estimated R:10,135 G
+230 mV
+170mV
+100 mV
H permeation experiment
H permeation experiment
CE RE WE (sample) - grounded
Corrosion in high pressure
and high temperature
autoclave
www.cormet.fi
Summary