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Electrochemical Methods for

Corrosion Research
Topics

Short introduction: Metrohm Autolab


Main directions in corrosion research
Basic theoretical background
Electrochemical techniques used in
corrosion research
Metrohm Autolab

1984, Utrecht University: computer


controlled potentiostat/galvanostat
1986: Eco Chemie spin off created
1999: Joined the Metrohm group
2009: Changed the name to Metrohm
Autolab
Metrohm Autolab

Still based in Utrecht


42 employees
Develops and produces all the
instruments and the software
ISO 9001 certified company
Metrohm Group
International presence
Why measure corrosion
with electrochemistry?
Why corrosion
measurements & research?

Loss due to corrosion: >3% of GDP


Huge environmental impact
Safety issues
What is corrosion?

Corrosion is the act or process of


destroying a metal or alloy gradually,
especially by oxidation or (electro)
chemical action

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

looking into corrosion mechanism


Galvanic corrosion
Pitting corrosion
Crevice corrosion
Stress corrosion
Intergranular corrosion
High temperature corrosion, etc
Corrosion protection aspects

looking into corrosion protection


Passivation
Metalic coatings
Organic coatings
Corrosion resistant alloys
Corrosion inhibitors
Corrosion environment

looking into influence of an


environment on corrosion
Atmosferic corrosion (air)
Marine corrosion (sea water)
Oil (oil pipes)
High temperature (cooling systems)
Biocorrosion (medical implants), etc
Uniform Corrosion
Pitting Corrosion
Pitting corrosion is a localized form of
corrosion usually associated with
formation of pits in the presence of
chloride.
Crevice Corrosion
Crevice corrosion is a localized form of
corrosion usually associated with a
stagnant solution on the micro-
environmental level.
Deposition corrosion
From deposition of mud, slurries, sludges
Filiform corrosion
Filiform corrosion is a product on a
surface of a metal coated with paint
and coating with humid atmosphere
Coating degradation
Galvanic Corrosion
less noble metal anode corrodes
faster
more noble cathode corrodes
slower
Stress corrosion cracking
Mechanical stress combined with
corrosive attack can lead to a mechanism
known as stress corrosion cracking.
Microbiologically Induced
Corrosion (MIC)
Typical research directions
in 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

Metal protection: Coating / pain studies


Engine liquid cooling corrosion
Break fluid corrosion
Specific corrosion aspects:

Archeological and historical artifacts:


cleaning and protection
Food industry: coated tinplated packaging
control
Biofuel: corrosion resistance and ageing
studies
Medical: bones and dental implant studies
Basic Theoretical Aspects
in Corrosion
Electrochemical Corrosion
Ion conduction (electrolyte)

M2+ 2H+ H2
Anode reaction Cathode reaction

M 2e -

Electron conduction (metal)


Electrode potential

Potential of a metal M immersed in


Mn+ containing solution vs a reference

e- exchange occurs at interface


between metal and solution
Electrode potential
Noble metal (Au,Pt) Non-Noble metal (Zn, Fe)
_ _
+ _ _ + +
+
_ _ +
+
+ _ _ + _ _
+ _ _ +

+ _ _ + + _ _ +
+ _ _ +

+ _ _ + +
+
_ _ +
+
+ _ _ + _ _
+ _ _ +
+ +

M unwilling to M easily release


release ions, high ions, low electrode
electrode potential potential
Electrode potential

Standard potential
Galvanic series
Standard potential

Potential vs SHE
Equilibrium assumed
Activity=1, T=25 C
Reactions written as cathodic
reactions
Standard potential

Electrode reaction Std. potential Electrode reaction Std. potential

Au3+ + 3e- Au +1.42V Cd2+ + 2e- Cd -0.40V


O2+4H++4e- 2H2O +1.23V Fe2+ + 2e- Fe -0.44V
Pt2+ +2e- Pt +1.20V Cr3+ + 3e- Cr -0.74V
Ag+ + e- Ag +0.80V Zn2+ + 2e- Zn -0.76V
Fe3+ + e- Fe2+ +0.77V Ti2+ + 2e- Ti -1.63V
Cu2+ + 2e- Cu +0.34V Al3+ + 3e- Al -1.66V
2H+ + 2e- H2 0.00V Mg2+ + 2e- Mg -2.36V
Pb2+ + 2e- Pb -0.13V Na+ + e- Na -2.71V
Ni2+ + 2e- Ni -0.25V Ca2+ + 2e- Ca -2.76V
Galvanic series

Specific for a real environment


Possibility of passivation is taken ito
account
More practical
Galvanic series in seawater

Metal/alloy Electrode potential Metal/alloy Electrode potential

Gold +0.42V Lead -0.31V


Silver +0.19V Steel -0.46V
Stainless steel +0.09V Cadmium -0.49V
(18/8), passive Aluminum -0.51V
Cooper +0.02V Galvanized steel -0.81V
Tin -0.26V Zinc -0.86V
Stainless steel -0.29V Magnesium -1.36V
(18/8), active
Quantitative aspects

Thermodynamic
Nernst equation, Pourbaix diagram

Kinetic
Butler-Volmer equation, Faradays
law, Corrosion rate
Thermodynamic aspects
Thermodynamic aspects

Always at equilibrium (!)

red ox +ne-
Thermodynamic aspects

Nernsts equation - variation of the


equilibrium potential (E) with the activity of
involved species
Thermodynamic aspects
Pourbaix diagram (of Cr)
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

Deviation from equilibrium

polarization (overvoltage)
= E E0
Kinetic aspects

At equilibrium: =0,
ic=ia=i0
Total net current = 0

Deviation from equilibrium:


0, icia
Total net current 0
Kinetic aspects
Anodic Cathodic
polarization polarization

ia ia

i i

ic ic

Total net current 0


Kinetic aspects

Buttler-Volmer equation - Relation


between current density and potential for a
kinetically controlled reaction

Anodic current Cathodic current


density density
Kinetic aspects

High anodic overvoltage: >, =0.5

where are the Tafel constants


Kinetic aspects

High cathodic overvoltage: <, =0.5

where are the Tafel constants


Kinetic aspects

Faradays law - link between (anodic)


current density and corrosion rate
m- metal disolution rate
ia,M - anodic current density for
metal disolution (A/cm2)
F - Faradays constant (96500
C/mol)
n - no. of electrons involved in
the anodic reaction
Autolab Instruments
in Corrosion Research
Autolab Instruments
in Corrosion Research
The N series of PGSTATs

Three models available

PGSTAT128N PGSTAT302N PGSTAT100N


12 V / 800 mA 30 V / 2 A 100 V / 250 mA
Compact design

Potentiostat/Galvanostat with USB


Compact design at entry level price

PGSTAT204 PGSTAT101
20 V / 400 mA 10 V / 100 mA
Autolab PGSTAT302F

Switchable floating/non-floating PGSTAT


Which compliance voltage?
Control
amplifier Electrochemical
cell
Ce

VCe= -VWe RRs +RRp


Re

RRp
Rs
Voltage
follower Cdl
Rp
S

VCe= -1 100 +1000


We
1000
Current
follower Apply 1 V
VCe= -1.1 Voltage at CE
Which compliance voltage?

1st Example:
LOW resistance solution 100
HIGH polarization resistance 1M

VCe= -VWe RRs +RRp VCe= -1 100 +1M


1M
RRp

VCe= -1.0001
Which compliance voltage?

2nd Example:
HIGH resistance solution 30K
LOW polarization resistance 100

VCe= -VWe RRs +RRp


VCe= -1 30K +100
RRp 100
VCe= -301V
Which compliance voltage?

3rd Example:
HIGH resistance solution 30K
HIGH polarization resistance 10K

VCe= -VWe RRs +RRp VCe= -1 30K +10K


RRp 10K

VCe= -4V
MODULES
for corrosion applications:

FRA32M
ECN
MUX-MULTI4 or MUX-SCNR16
BOOSTER 10/20A
pX1000 monitoring pH and T
EQCM
ACCESSORIES:

References and counters electrodes


Corrosion cell (1L or 400ml)
Flat cell
Normal Metrohm cells
Faraday cage
1 liter Corrosion cell

Sample size:
14mm diameter
3mm thickness
Flat cell

Sample size:
55-85 mm diameter
up to 5 mm
thickness
Optional Instrumentations

RDE (Rotating disc electrode)

SECM ( Scanning Electro Chemical


Microscope)

Thermostatic bath (CPT measurement)


RDE (Rotating Disk Electrode)

100 to 10000 rpm


Hg Contact
Software or Manual Control
Scanning Electro Chemical
Microscope
Electrochemical Techniques
Used in Corrosion Research
Techniques

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

For materials without PAINT or COATINGS

Iron, steel, stainless steel, Aluminium,


Titanium, Cupper, Tin, Zinc and Alloys

Galvanic deposition process, metal


finishing control and surface treatment
process
Linear polarization
Linear polarization

Widely used in corrosion studies


Information on
Corrosion potential
Polarization resistance
Exchange current (density)
Corrosion rate
Linear polarization
Calculation of Polarization
Resistance Iron screw in seawater

Corrosion rate analysis


30u

20u

10u

Polarisation curve

i/A
0

around OCP -10u

-20u

-30u
-0.60 -0.55 -0.50 -0.45 -0.40 -0.35 -0.30 -0.25 -0.20 -0.15

E/ V

Determination of polarization resistance


from reciprocal of slope of LSV around Ecorr
Corrosion rate analysis

Corrosion rate, Tafel slope: calculates


the Tafel slope and provides an
estimation of Rp and the exchange
current density
Corrosion rate analysis

Corrosion rate, fit: more accurate


determination of parameters by fitting
the Butler-Volmer equation to the
experimental data set
Corrosion rate analysis
Example: influence of
inhibitors 0
10

-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

Link between the Pourbaix diagram and


the Evans plot
Influence of Cl- on Corrosion of
Iron 10
-2

-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

-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0


E (vs Hg 2 SO4 ), V
RDE & NOVA Inhibitors test
Electrochemical noise (ECN)
Electrochemical noise (ECN)
measurements

Non-invasive method
Statistical approach to corrosion
No external perturbation applied
Current is monitored through a Zero
Resistance Ammeter (ZRA)
ECN - data evaluation

EN analyzed by computing the spectral


density of the measured data
Transform time domain information to
frequency domain spectrum (FFT)
Different windowing functions are available
in the software: Square, Bartlett, Hanning,
Hamming, Blackman
ECN - data evaluation
Example: influence of the
electrolyte
Al rods in
NaCl 1mol

Al rods in
NaOH 0.5mol
Example: value of slope of
the current noise vs time

Most probable Most probable Most probable


shape of pits shape of pits shape of pits
when k = 1 when k = 1/2 when k = 3/2
Electrochemical impedance
spectroscopy (EIS)
Electrochemical impedance
spectroscopy (EIS)

Study of the variation of the impedance


of an electrochemical system with the
frequency of a small-amplitude AC
perturbation
WHY Electrochemical
impedance spectroscopy?

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

NOT STAND ALONE

INTERPRETATION OF THE DATA


SOMETIMES DIFFICULT
Electrochemical Impedance:
- Materials with paints and coatings

- Iron in concrete

- Special alloys

- Galvanic deposition

- Insulation control
EIS Basics

EIS is a transfer function between


AC potential and AC current
Z()
et e sin t it i sin t

e sin t sin t
Z Z0
i sin t sin t
EIS Basics

it i sin t

et e sin t

The current response


leads or lags the voltage
by a phase angle
EIS Basics: complex number

It is common practice to express Z as a


complex function

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

Z() Z'() j Z"()

Total impedance Real component Imaginary component


EIS Basics: data presentation

Nyquist

High frequency limit Low frequency limit


EIS Basics: data presentation

Bode presentation
Plot of |Z| vs log F and vs log F
Phase angle

j( )
Z() Z e

Total impedance Modulus


EIS Basics: data presentation

Bode presentation
EIS in Corrosion

Powerful technique for coating studies


Recording raw data useful for assuring
right measurement conditions
Fit and simulation estimates the
quality/type of coating

!! Knowledge of the system is required !!


EIS Coating on steel
RE
CE
3 electrode setup
NaCl Z measured
between RE and WE

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

Iron dissolves forming a pit


EIS Coating with blisters

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

Eduardo Homem de Siqueira Cavalcanti INT Instituto


Z' Nacional de Tecnologia Corrosion division
Special applications
in Corrosion Research
Critical Pitting Temperature
Critical Pitting temperature
Principle
ASTM G 150 -99 (reapproved 2004)
Critical Pitting Temperature

Measures the temperature when the


pitting starts/occurs
Chrono amperometric measurement
combined with a temperature ramp
Critical Pitting Temperature

Temperature is software controlled


using a thermostatic bath
T sensor in the measurement cell
T measurements with pX1000
Critical Pitting Temperature
Critical Pitting Temperature

Polarization resistance measurement

304 steel recorded at 25C and 60C


Critical Pitting Temperature

CPT measurement at different potentials

100 mV above the OCP 50mV above the OCP


Cyclic Thermammetry
Cyclic Thermammetry

Can be used in corrosion studies in


aggressive systems
In passive system to enhances the
passivity of metals under certain
conditions.
Can be used in different applications like
fuel cell or electrocatalysis.
Cyclic Thermammetry
Corrosion rate of Titanium alloy after
three thermal cycle of passivation
decrease by 75%
Applications on heat exchanger, cooling
system for power plants, Turbines
Cyclic Thermammetry
experiments
Temperature cycle from 30C to 70C
Applied +230 +170 +100 mV vs Time

+230 mV

+170mV

+100 mV
H permeation experiment
H permeation experiment

The problem: presence of Hydrogen in the


metal structure leads to a reduction in
plasticity of the metal/alloy, embrittlement

Research: study the effect of Hydrogen


permeation on metal properties
H permeation experiment

H is transported through a metal sample


2 cells separated by the sample
Induction side: H insertion in the
sample by controlling the current
Extraction side: detection of the H, by
measuring the current density
H permeation experiment
Experiment possible only by using 2
floating potentiostats (302F)
H permeation experiment
H permeation experiment
Other applications for
PGSTAT302F
Mimic the natural process

Electrochemical cell for


evaluation of corrosive soil
and trapped water

WE: Grounded metal sample


tribocorrosion cell setup
Friction device

CE RE WE (sample) - grounded
Corrosion in high pressure
and high temperature
autoclave

www.cormet.fi
Summary

Electrochemistry is a powerful technique


used in all branches of corrosion research
Using electrochemistry in corrosion
research will reduce the time of
experiments/trials
ASTM methods available for different
corrosion tests
www.metrohm-autolab.com

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