Korosi

Johny
y Wahyuadi
y Soedarsono

Departemen Metalurgi dan Material FTUI

What is Corrosion?
Reaction of a metal with its
environment
Aqueous corrosion
„ reaction with water (usually containing
dissolved ions)
High temperature oxidation
„ reaction with oxygen at high temperature
High temperature corrosion
„ reaction with other gases

1
Examples of Corrosion
Rusting of steel
„ corrosion product (rust) is solid but not
protective
Reaction of aluminium with water
„ corrosion product is insoluble in water, so
may be protective
Burning of magnesium in air
„ high temperature oxidation

“R st Never
“Rust Ne e Sleep”

Kerugian Akibat Korosi

Sekitar 1 – 5 % dari Pendapatan

Domestik Nasional / Gross Domestic
Product (GDP).

Amerika Serikat pada tahun 1998

kerugian akibat korosi adalah sebesar
US $ 276 Milyar yang merupakan 3,15
% dari GDP

2
Penyebab Besarnya Biaya Korosi

Disain yang berlebihan (Corrosion

allowance yang terlalu besar)
Kehilangan produksi (shutdowns)
Kerusakan komponen
Biaya pemeliharaan
Kontaminasi terhadap produk
Kerusakan lingkungan

Data Kerugian Beberapa Negara

Akibat Korosi
No Sektor Industri / Negara Kerugian (US $)

1 Industri pesawat terbang (USA) 13 M / tahun

2 Pesawat militer (USA) 3 M/ tahun

3 Pesawat (tidak bisa terbang) 100.000 / hari

4 Angkatan Udara dan Laut (Australia) 50 juta / tahun

5 Otomotif (Finlandia) 300 Juta / tahun

6 Otomotif (USA) 0,25 % GNP tahun 1998

7 Menara Eiffel (Perancis) 40 juta / 7 tahun

8 Minyak dan gas (AGIP) 0,40 / barrel produksi tahun 1999

9 Minyak dan Gas (Laut Utara) 60% biaya pemeliharaan tahun 1999

10 Swiss 3 – 5 % GNP

80 % kerusakan material pada

industri minyak dan gas diakibatkan
oleh korosi (US $ Milyar)

1.4
7 3.7 Eksplorasi
Refining
Pipa transmisi
Distribusi gas
0.9 Transport
7 Penyimpanan
5

3
Problem Keselamatan dan
Lingkungan Akibat Korosi

Pengangkutan maupun penanganan

bahan beracun dan berbahaya yang
menggunakan material / logam

Kontaminasi pada pipa saluran air

minum atau industri makanan.

Contoh Kerugian Akibat

Terjadinya Korosi

Kejadian tahun 1987 di Minnesota dimana

korosi selektif pada lasan pipa bahan bakar
mengakibatkan terjadinya kebakaran dengan
korban tewas 2 orang

Korosi pada pipa uap Pembangkit Listrik

Nuklir di Virginia dimana terjadi korosi dan
erosi, uap panasnya mengakibatkan 8 orang
meninggal dunia.

Strategi Untuk Penghematan

Biaya Korosi (Save 25 – 30 %)

Kepedulian semua pihak terhadap korosi

Merubah salah persepsi bahwa korosi tidak
bisa diatasi
Perubahan kebijakan perusahaan dengan
menerapkan management korosi
Peningkatan pendidikan baik pendidikan
terstruktur maupun training untuk para staf

4
 Peningkatan keahlian disain yang tepat
Peningkatan metode pengkajian dan prediksi
umur pakai bahan / material
Pengembangan teknologi pencegahan korosi
melalui penelitian, pengembangan dan
implementasi

Examples of Corrosion
Rusting of steel
„ corrosion product (rust) is solid but not
protective
Reaction of aluminium with water
„ corrosion product is insoluble in water, so
may be protective
Burning of magnesium in air
„ high temperature oxidation

5
Prinsip Korosi :
534 W
Kec Korosi : mpy =
DAT
W: berat
be at yang
ang hilang (mg)
D: berat jenis logam ( g/cm3)
A : luas permukaan (inch2)
T : waktu (jam)

Aspek Elektrokimia
Reaksi elektrokimia
Polarisasi
Pasivasi

Aspek Lingkungan :
P
Pengaruh
h oksigen
k i dan
d hidrogen
hid
Pengaruh kecepatan
Pengaruh Temperatur
Pengaruh Konsentrasi Korosi
Pengaruh Galvanik

Aspek Metalurgi
Sifat logam
Masalah ekonomi
Inspeksi
Peralatan inspeksi

6
Material :
Logam / paduan
Polimer / plastik
Keramik /non logam
Sifat logam Korosi

Batas butir, energi , mudah terkorosi (intergranular,

pitting)
Laku mekanik tegangan dalam / tegangan
sisa (SCC)
Faktor yang mempengaruhi sifat korosi :
Tegangan
Konsentrasi Hidrogen / Oksigen
Homogenitas kimia (impurities, segregasi dll) dan fisik
(roughness, scale, kotor dll)
Protective film (pasivasi, lapisan oksida)
impermeable, kuat, tidak mudah retak, adhesi, mudah
terbentuk)

Pengaruh unsur paduan terhadap korosi

Stabilitas alpha (Cr, Si, Mo, W dll.)
Stabilitas gamma (Cu, Ni, Mn, Co dll)
Pembentuk karbida (Fe, Mn, Nb, Ti dll)
Menurunkan titik eutectoid ( Mn, V, Ta, W dll)
Tahan korosi (Cr
(Cr, Ni
Ni, Mo
Mo, Ti
Ti, Nb
Nb, Mn
Mn, Cu
Cu, Si)

Produk korosi tidak mudah larut

Pasivasi
stabilitas karbida

Korosi di atmosfer dan air laut

Korosi atmosferik disebabkan :
Gas oksigen
Uap air
Pengotor
Pengaruh atmosfer (kering, lembab, laut, tropis,
pedesaan, kota, industri)

Korosi lingkungan laut :

pH
Oksigen
Kecepatan gerak air laut
Temperatur
Biota laut (biofouling / pelekatan material, over
loaded)

7
Biota laut :
Bernacles (menimbulkan celah akan mempercepat
korosi)
Sebagai penghalang / turbulensi lokal
Mampu menembus lapisan pelindung
Bakteri pereduksi sulfat (menghasilkan asam sulfat)

Lingkungan laut :
Daerah percikan (serangan korosi sangat kuat,
kuat no
fouling)
Daerah Pasang (fouling mulai ada, air laut jenuh
udara)
Daerah laut dangkal (air laut jenuh oksigen,
pengotor, fouling, gerakan arus)
Laut dalam (korosi karena pengaruh oksigen, chlor
dll)
Daerah lumpur (komplex, korosi agak rendah /
oksigen terbatas)

8
 Corrosion of Zinc in Acid

Zinc dissolves with hydrogen evolution

Zn + 2HCl → ZnCl2 + H2
™Zinc known as a base or active metal

One atom
plusoftwo
zinc metal
molecules
reacts toofform
hydrogen
one molecule
plus of molecule
zinc chloride
to one
chloride (hydrochloric
goes acid) of hydrogen gas

Corrosion of Platinum in Acid

Platinum does not react with acids

Platinum is known as a noble metal

9
Connection of Platinum to Zinc
Zinc
Zinc andand platinum
platinum not
electrons current
connected, no flows
reaction
and hydrogen is evolved
on platinum
on platinum

Z
Zn Pt

HCl

Zn Zn2+→+ 2e
Zn +→2HCl -
ZnCl 2 + H2 2H+ + 2e- → H2
metal→
metal metal→ions
+ acid hydrogen ions + electrons → hydrogen gas
salt++electrons
hydrogen

Connection of Platinum to Zinc

Zn + 2HCl → ZnCl2 + H2
But we can separate metal dissolution
and hydrogen
h d ogen evolution
e ol tion
Zn → Zn2+ + 2e-
2H+ + 2e- → H2
These are known as electrochemical
One
oneatom of zinc metal
reactions zinc ion in two electrons in the metal
solution
Reactions that involve both
chemical change and the
transfer of charge

Electrodes

Electrodes are pieces of metal on which

an electrochemical reaction is occurring
An aanode
ode iss a
an e
electrode
ect ode o
on which
c a
an
anodic or oxidation reaction is occurring
A cathode is an electrode on which a
cathodic or reduction reaction is
occurring

10
Anodic Reactions

Examples
Zn → Zn2+ + 2e- zinc corrosion
Fe → Fe + 2e
2+ - iron corrosion
Al → Al3+ + 3e- aluminium corrosion
Fe → Fe + e
2+ 3+ - ferrous ion
oxidation
H2 → 2H+ + 2e- hydrogen oxidation
2H2O → O2 + 4H + 4e + - oxygen
evolution

Cathodic Reactions

Examples
O2 + 2H2O + 4e- → 4OH-
oxygen reduction
2H2O + 2e- → H2 + 2OH- hydrogen
evolution
Cu2+ + 2e- → Cu copper plating
Fe + e → Fe
3+ - 2+ ferric ion
reduction
Reduction reactions

Corrosion of zinc in acid

When zinc is placed in acid the metal

will start to dissolve and hydrogen will
start to be liberated according to the
potential of the metal
Consider the anodic zinc dissolution
reaction
Zn → Zn2+ + 2e-

11
How Fast will Corrosion
Occur?
Corrosion kinetics
„ Concerned with the rates of corrosion
reactions
Mixed potential theory:
„ The corrosion potential will be that potential
at which the sum of all anodic (positive)
and cathodic (negative) currents on the
electrode is zero
Polarization
„ The change in potential that is caused by

12
Types of Polarization
Activation Polarization
„ The polarization necessary for the
electrochemical reaction to go at the given
rate
„ Given by Tafel’s Law:

E = potential at current i
Eo = potential at current io
b = Tafel slope

E-log i and Evans Diagrams

Plot E against |i|,thethen activation
logio for
Eo and
polarization gives
cathodic a straight line
reaction
Anodic reaction, Tafel slope
Mixed equilibrium
p Eis
Tafel slope corr and
occurs icorr for
Cathodic
expressed
when the
sum reaction,
reaction
as
of
Electrode Potential

positive corrosion reaction

mV Tafel
all currents slope is
perisdecade
zero
Eo and io for the negative
of current
anodic reaction
mV

log (-i2) - log (-i1)

log |current|

Concentration Polarization

Additional polarization caused by drop in

concentration of a reactant at the
electrode surface
As concentration falls, more polarization is
needed to make the current flow
Eventually, no more current can flow
because no more reactant can reach the
metal, and a limiting current is reached

13
Concentration Polarization
Oxygen reduction is often affected by
concentration polarization
Rate of cathodic oxygen
Rate of cathodic
reduction oxygen
without
Electrode Potential

reduction
concentration with
polarization
Limiting current
concentration density -
polarization
rate of reaction limited by
availability of oxygen at
the metal surface

log |current density|

Resistance Polarization
If there is a resistance between the
anode and the cathode in a cell, then
the current flowing through that
resistance will cause a potential drop
given by Ohm’s Law:
V = IR
This is important for paint films and for
high resistance solutions

Resistance Polarization
Resistance Polarization
causes potential of anode
and cathode to differ due
to potential drop across
ential

solution, hence corrosion

current is reduced
Electrode Pote

log |current density|

14
Passivation
When a passive film is formed, this
causes a marked drop in current density
due to the resistance of the film and its
effect as a barrier to diffusion
This effect is seen on the anodic curve

Passivation
When aRapidThe rate
stable of corrosion
passive film will be
rate of cathodic
has formed, critically affected
has by the
reactionthe leads current
to passivation,
Lower
low rate cathodic
of thecurve
a steady,
and low value
rate of-cathodic
corrosion
ential

Butcurrent
Current
reaction
passive it mayfallsalso
leads as lead
to the
density to and
low
passive
activity,
Very slow cathodic reaction
rate of corrosion?
l film
Active corrosion gives normal d starts
high rate torate
llowof form
t off -corrosion
corrosion the i
Electrode Pote

leads tto
activation polarizationactive-passive transition

log |current density|

Polarization Curves
Iron in hydrochloric acid
ntial
Electrode Poten

Anodic iron dissolution

Cathodic hydrogen evolution

log |current density|

15
Polarization Curves
Iron in sulphuric acid
ntial

Anodic iron dissolution ((with

Electrode Poten

active-passive
Oxygen evolutiontransition)
on passive
film (or transpassive corrosion
Cathodic
as metalhydrogen evolution
is oxidised to a
higher oxidation state)

log |current density|

Effect of pH on reaction rate

Consider hydrogen evolution reaction

2H+ + 2e- → H2
The concentration of hydrogen ions will
influence the rate of the reaction
As the hydrogen ion concentration is
increased (i.e. the solution made more
acid), so the rate of the reaction
increases
Similarly the potential will influence the
ti th ti th

Effect of pH and potential on rate

of hydrogen evolution

Slower

Potential

Faster

pH

16
Effect of pH on reaction rate

On platinum no metal dissolution will

occur, but to balance the charge a
reaction which creates electrons must
occur
If the solution contains dissolved
hydrogen, the reverse of the hydrogen
evolution reaction can occur:
H2 → 2H+ + 2e-

Effect of pH on reaction rate

H2 → 2H+ + 2e-

This reaction will go faster in alkaline

solution (since H+ will be removed by H+
+ OH- → H2O)

This reaction will go faster at more

positive potentials (because electrons
will be removed from metal)

Effect of pH and potential on rate

of hydrogen oxidation

Oxidation
Faster Reduction
Slower
Potential

Oxidation
Slower Reduction Rates equal
Faster Electrochemical
Equilibrium
pH

17
The Nernst equation

2H+ + 2e- = H2
The Nernst equation gives

For 1 atm. hydrogen gas

The Pourbaix (E-pH) Diagram

2H2O = O2 + 4H+ + 4e-
2.0 Equilibrium potential
1.6
Ofalls as pH increases
2 is stable
1.2 2H+ + 2e- = H2
0.8 Equilibrium
al

potential
t ti l falls
f ll as
Potentia

0.4 H2O is stable

pH increases
0.0
-0.4
-0.8
-1.2 H2 is stable
pH = - log [H+]
-1.6
0 7 14

Pourbaix Diagram Corrosion

for Zinc
possible with
2.0 oxygen
1.6 reduction
Corrosion Corrosion is
1.2 possible, but likely
Corrrosion

possible with
Passivity

0.8 to be stifled by solid

y gZn(OH)
hydrogen ( )
al

2
C
Corrosion
i
Potentia

0.4 evolution corrosion

stable
i product
d t
ZnO22-
0.0 Corrosion requires
Corrosion
solid is
Zn2+ stable
strong oxidising stable in
-0.4 thermodynamically
solution
in solution agent
impossible
-0.8
-1.2 Immunity
Zn metal stable
-1.6
0 7 14

18
 Pourbaix Diagram for Gold
2.0
1.6 C Passivity
1.2 C
0.8
al
Potentia

0.4
Gold Gold
metalcan’t corrode
stable
0.0 with oxygen reduction
Immunity
-0.4 or hydrogen evolution
-0.8
-1.2
-1.6
0 7 14

Pourbaix Diagram for Iron

2.0 Will iron
WillWill
ironiron
corrode
1.6
corrode
Yes - therein
is a
corrode 1.2in
in alkaline reasonably wide
0.8
Fe 3+
acid?
range
g of p potentials
neutral waters?
solution?
al
Potentia

0.4 Fe oxides where hydrogen

Yes - although iron can
0.0 stable can be evolved and
form an oxide in neutral 2+ iron dissolved
Fe stable
solution, it tends-0.4
not to
form directly -0.8
on the
No - iron forms a solid
metal, as oxide -1.2
the potential Fe metal stable
at all potentials,
is too low, therefore
will itpassivate
and-1.6 is
not protective. 0 7 14

Pourbaix diagram for

Aluminium
1.2
0.8
0.4
0.0
al
Potentia

-0.4
-0.8 Al3+
Al2O3
-1.2 AlO2-
-1.6
-2.0 Al
-2.4
0 7 14

19
Limitations of Pourbaix
Diagrams
Tell us what can happen, not
necessarily what will happen
No information on rate of reaction
Can only be plotted for pure metals and
simple solutions, not for alloys

Sources of Localized Corrosion

Environment
„ oxygen concentration
„ chloride ion concentration
„ pH
„ flow rate

Sources of Localized Corrosion

Material
„ segregation
„ inclusions
„ different phases
„ grain boundaries

20
 Sources of Localized Corrosion

Mechanical
„ static stress
„ fluctuatingg stress

Galvanic Corrosion

Conventional
Electrons current

2+ 2+
FeFe
Fe Cu
O2
O2

Table 1
Galvanic
Standard emf series
Corrosion
Table 2 Galvanic Series in Seawater
Reaction Eo at 25oC,
(V vs NHE)
↑
3+
Au-Au +1.498 Platinum
•The
Pt-Pt2+ galvanic series. •TheGold
+1.2 Noble or emf, or electrochemical
•Ordered by observed series.
+
Ag-Ag +0.799 cathodic Silver
•Note
Hg-Hg 2+ that some+0.788alloys can 18-8 Mo stainless steel (passive)
behaviour
2
in service •Ordered by standard
appear twice according to
2+
Cu-Cu +0.337 Nickel (passive)
•Allows for corrosion q Cupronickels
equilibrium
p p
potential
((60-90 Cu,, 40-10 Ni))
whether
h+ th th
they are active
ti or
products
H2-H 0.000 •Assumes
Copper activity of solution
passive Nickel (active)
•Can
Ni-Ni2+ be defined for alloys species
-0.250 is one
18-8 Mo stainless steel (active)
•Different
Fe-Fe2+ for every
-0.440 •DoesSteelnot allow for protective
or iron
3+
environment
Cr-Cr -0.744 corrosion products
2024 aluminium (4.5 Cu, 1.5 Mg, 0.6 Mn)
Zn-Zn2+ -0.763 Cadmium
Al-Al3+
-1.662 Active or •Cannot be defined
Commercially pure aluminium for alloys
(1100)
Mg-Mg2+ -2.363 anodic Zinc
Na-Na+ -2.714 ↓ Magnesium and magnesium alloys
After de Bethune and Loud from INCO test results

21
 Galvanic Corrosion

Important factors in galvanic corrosion

„ relative areas of anode and cathode
„ difference in p
potential between anode and
cathode
„ effect of anodic polarization on anode
(some may passivate)

Galvanic Corrosion - Questions

Which is better, a steel bolt in a brass

structure, or a brass bolt in a steel
structure?
The steel will be the anode, so a small
steel bolt in a large brass structure will
suffer severe galvanic corrosion. A
brass bolt will be protected by the steel
structur

Which is better?

Brass bolt in a steel structure Steel bolt in a brass structure

Small brass cathode Small steel anode

will cause small
increase in corrosion of
steel structure. Bolt
will be protected from
corrosion by coupling
to steel
will suffer large
increase in corrosion
due to coupling with
brass structure.

22
 What should we paint?
A milk cooler has an
inner liner of stainless
steel, and an outer
casing of mild steel.
Chilled brine is used
between the steel and
stainless steel to cool
the milk.
This would be a very bad idea
Corrosion
as of the in
any pin-holes mild
the paint
steel isact
would occurring -
as the anode, with the
would
full areaitofbethe
a good idea steel as
stainless
to paint
the the inside of
cathode.
the mild steel casing?

Galvanic Corrosion in Alloys

Galvanic corrosion can occur between
different phases in an alloy
This is especially important when one of
the phases is much more active as a
cathode,
th d e.g.:
„ Cu-containing precipitates in aluminium
alloys – initiate pitting corrosion
„ Fe and Cu impurities in commercial zinc
– cause a large increase in corrosion rate
compared to pure zinc

Differential Aeration
2.0
Conventional
1.6 Aerated Deaerated
Electrons
current 1.2 3+alkaline pH goes acid by
pH goesFe
0.8
by Fe2+ + H2O → FeOH+ +
ential

O2 + 2H2O + 4e- → H+
0.4
4OH+ Fe oxides
Steel p
passivates Steel corrodes
Pote

Fe2+
Fe2+ O2 00
0.0 stable
actively
Fe
Fe2+ Fe -0.4 Fe2+ stable
O2
-0.8
-1.2 Fe metal stable
-1.6
0 7 14
pH

23
Crevice Corrosion
O2 Metal

O Hydrolysis
Cr2 3+ Cr3+is a reaction with
Metal
water, in this case
2Cr3+ + 6H2O → Cr2O3 +
Active corrosion
6H+ is
1 Oxygen is consumed incorrosion
crevice byoccurring
slow passive
in thecorrosion
absence of an oxide film
2 Passive corrosion continues, and pH falls by Cr3+ hydroly

3 Passive film breaks down in acid and rapid active corrosi

starts
4 The active corrosion causes even stronger acidification a
stabilises the crevice corrosion

Crevice Corrosion

Pitting corrosion
on free surface
Crevice
corrosion under
washers

Pitting
Cl- Cl-
O2 O2

Cr3+ Cr3+ e
e

Otherpresence
Inside
The anions
the growing
(e.g. - and
of chloride
OH
pit the is 2-
hydrolysis
SO
important,
4 ) can
of
as3+it lowers
inhibit
Cr allows athe
pitting, pHpHof and
either about 1 to be
breaks
by buffering down the
the pH
achieved
passive
in (HCl
the pitfilm.
or by is acathodic
The strong
causing theacid, and
oxygen
precipitation
does notfilm
reduction
of a salt associate) and the metal
reaction continues outside the
chlorides
pit are very soluble

24
Mechanical Aspects of
Corrosion
Static stress
„ stress-corrosion cracking
„ hydrogen
y g embrittlement
„ liquid metal embrittlement
Dynamic stress
„ corrosion fatigue
„ fretting corrosion

The Effect of Stress and Strain

on Corrosion
Stress per se does not affect corrosion
processes much
Plastic strain can have a large effect:
„ increased dislocation density
„ rupture of passive films

Stress-Corrosion Cracking
Cracking of a metal under the combined
effects of a static stress and a specific
chemical environment
Several possible mechanisms, still not
fully understood
Cause of major industrial costs and
safety hazards

25
 Stress-Corrosion Cracking
Mechanisms
„ Anodic dissolution
„ y g embrittlement
Hydrogen
„ Film-induced cleavage

Anodic Dissolution

1 The walls and tip of the crack are

passive
2 The passive film at the crack tip is ruptured by the
plastic
3 strain, andtip
The crack active corrosion occurs
repassivates
4 Go back to 1

Film-Induced Cleavage

1 The walls and tip of the crack are covered by a brittle

film
2 (either
The filmanatoxide film or
the crack tipaisde-alloyed layer)
ruptured by the plastic
strain
3 The brittle crack continues into the metal
4 The crack is blunted by plastic strain

26
 Hydrogen Embrittlement
H H H H
H HH
H

1 Hydrogen produced by the cathodic reaction

2 Hydrogen diffuses to region of tri-axial tensile stress

3 ahead of the
Hydrogen crackbrittle fracture
causes
4 Crack blunts by plastic deformation as it runs out of
hydrogen

Hydrogen Embrittlement

sources of hydrogen
„ welding
„ electroplating
p g
„ contact with gaseous hydrogen
„ corrosion, especially in the presence of
sulphides
higher strength materials are more
susceptible to hydrogen embrittlement

Hydrogen Induced Cracking

Internal cracking of lower strength

steels (e.g. pipeline steels) due to high
pressure hydrogen collecting at
inclusions.

27
Hydrogen Cracking

Internal cracking of steels at higher

temperatures due to reaction of
dissolved hydrogen with carbon to form
methane

Stress Corrosion Cracking

Systems
Brass and ammonia (often in local
atmospheres).
Austenitic stainless steels and chloride
solutions (70oC).
Carbon steels in caustic, carbonate/
bicarbonate, nitrate and phosphate.
High strength aluminium alloys in water
or water vapour.

Control of Stress-Corrosion
Remove stress (often difficult, especially
for residual stresses)
Avoid the necessary environment
Apply electrochemical protection where
possible
Use a different material
Live with it

28
Liquid Metal Embrittlement

Liquid metals can permeate down grain

boundaries and cause intergranular
cracking:
„ mercury on brass and aluminium alloys
„ liquid zinc on stainless steel

Corrosion Fatigue

Metal fatigue results in crack

propagation due to a cyclic stress
Corrosion makes both crack initiation
and propagation easier

Fretting Corrosion

Rubbing of two metals removes oxide

film and allows oxidation
Theeooxide
de may
ay a
also
so act as a
an ab
abrasive
as e
Prevention of relative motion and
allowing larger relative movement may
prevent the problem

29
Characteristics of Pitting
Corrosion
the alloy is passive
„ pitting requires a passive external surface
that can provide a high potential to cause
the current to flow into the pit; if the
external surface is active, this driving force
is not available
„ thus carbon steel will only pit if the solution
tends to passivate it (e.g. alkaline
solutions), it won’t pit if it is corroding
generally (e.g. neutral salt solutions)

Characteristics of Pitting
Corrosion
passivity broken down locally, usually
by chloride
„ the cause of the initiation of pitting
p g
corrosion is still not entirely clear, but it
involves a very small pit nucleus that
grows over periods of the order of seconds

Characteristics of Pitting
Corrosion
pits become more stable as they
become larger
„ for veryy small p
pits the acidityy will be
neutralised by diffusion into the bulk
solution very easily
„ as the pits get larger the diffusion
distances increase, and it gets harder for
the acidity to diffuse away

30
Characteristics of Pitting
Corrosion
small pits are often stabilised by a film
of oxide or metal that partially covers
the entrance
„ this allows pits that would not otherwise be
stable to continue growing (these are
known as metastable pits)

Characteristics of Pitting
Corrosion
pitting becomes more likely as the
potential becomes more positive
„ this p
provides a greater
g driving
g force for the
corrosion process, and helps to stabilise
the metastable pits

Management
Stainless steels
of Pitting
„ Pitting breakdown potential (that potential
above which the anodic current starts to
increase); lower pitting potential implies
greater susceptibility
„ C iti l pitting
Critical itti temperature
t t (CPT
(CPT,
temperature at which pitting is observed in
aggressive conditions); lower CPT implies
greater susceptibility
„ Pitting Resistance Equivalent (formula
based on composition e.g. Cr + 3Mo + 30
N) gives ranking of alloys

31
 Management of Pitting
Pit growth tends to follow a law of the
form
depth = constant x timen
where n is between 0.3 and 0.5
Pitting is a statistical process, and can
be modelled by extreme value statistics

Dealloying

Alloy containing one noble element and

one base element (e.g. brass, Cu + Zn)
Base element can dissolve leaving a
matrix of the noble element
„ dezincification of brass
„ graphitization of grey cast iron
Causes loss of mechanical strength
without obvious change in shape

Dealloying

‘Plug-type’ dealloying of a brass tube

32
Intergranular When
Corrosion
stainless steel is heated to
about
650oC, Cr carbides form at the grain
boundaries

C CrCr C
Cr Cr C
C

Because of its high diffusion rate,

carbon canIf diffuse
the grain boundary
a long way toCr concentration
falls low enough
However,
form the precipitate (below
chromium about
can only9%),
diffuse
then it willdistance,
a short no longerand
remain passive,
this reduces
andthegrain
matrix boundary corrosion
concentration of will
occur
chromium at the grain boundary

Intergranular Corrosion
When grain boundary chromium carbide
precipitation has occurred, the stainless
steel is said to be sensitised.
Sensitisation frequently occurs in the
heat-affected zone during welding, and
the resultant corrosion is called weld
decay.

Intergranular Corrosion
- Weld Decay of Stainless
Steel

33
Solving Weld Decay
Use a low carbon grade of stainless
steel
Use a stabilised grade of steel, which
includes a strong carbide-forming
element (Nb or Ti) to lock up the
carbon
For existing components that have been
sensitised, heat treat to re-dissolve the
carbides (but this is very difficult in
practice)

Flow Effects

Flow can
„ increase transport of oxygen to the metal
surface (may help to passivate)
„ increase the rate of dissolution of corrosion
product films
„ mechanically remove oxides
Terminology is poorly-defined, and
often contradictory

Erosion Corrosion
Corrosion accelerated by impact by
solid particles
These may remove metal, or they may
just remove oxide and allow metal to
corrode more quickly

34
Impingement
Corrosion rate increased by the impact
of turbulent eddies on the metal surface
These locally remove the corrosion
product by rapid dissolution, and allow
rapid active corrosion
Characterised by ‘horseshoe-shaped
pits’

Cavitation
High velocity flow leads to pressure
falling below zero at points of highest
flow
Vapour bubbles form in these regions
as the liquid is ‘pulled apart’
When the pressure increases again the
collapse of the vapour bubbles creates
an intense shockwave that removes
metal or oxide from the surface

Flow Effects

35
Terima Kasih

36