Korosi dan Pencegahan

Prof. Dr. Ir. Johny Wahyuadi Soedarsono, DEA

Departemen Metalurgi dan Material FTUI
2008
Completing the Materials Cycle




What is Corrosion?
Metals made by smelting
(reduction of ore)

Metals in air want to return to
their oxidized state

Corrosion is a natural process!
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
Corrosion Cycle
Iron Ore Fe
2
O
3
Blast Furnace Reduction to Fe

Steelmaking Furnace

Structural Steel

Oxidation of Fe Rust - Fe
2
O
3
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
Examples of Corrosion

Korosi yang terjadi pada Pipe Line
Figure : Three types of
oxides may form,
depending on the
volume ratio between
the metal and the
oxide:
(a) magnesium produces a
porous oxide film,
(b) aluminum forms a
protective, adherent,
nonporous oxide film,
and
(c) iron forms an oxide film
that spills off the
surface and provides
poor protection.
2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning

is a trademark used herein under license.

Rust Never 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

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 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
3.7
7
5
0.9
7
Eksplorasi
Refining
Pipa transmisi
Distribusi gas
Transport
Penyimpanan
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 Korosi
Kejadian tahun 1987 di Minnesota
korosi selektif pada lasan pipa bahan
bakar, terjadi kebakaran korban
tewas 2 orang

Korosi pipa uap Pembangkit Listrik
Nuklir di Virginia, terjadi korosi dan
erosi, uap panas mengakibatkan 8
orang meninggal dunia.
Strategi Untuk Penghematan Biaya
Korosi (Save 25 30 %)
Kepedulian semua pihak terhadap
korosi
Merubah persepsi korosi tidak bisa
diatasi
Perubahan kebijakan perusahaan
menerapkan management korosi
Peningkatan pendidikan, pendidikan
terstruktur maupun training untuk
para staf
Peningkatan keahlian disain
Peningkatan pengkajian dan prediksi umur
pakai bahan / material
Pengembangan teknologi pencegahan
korosi melalui penelitian, pengembangan
dan implementasi

Mekanisme Korosi :

Korosi : peristiwa elektrokimia antara
logam dengan lingkungannya, syarat
terjadinya :
anoda, terjadi reaksi oksidasi,
katoda, terjadi reaksi reduksi,
elektrolit, penghantar arus listrik,
ada hubungan anoda dengan katoda.

Mekanisme korosi : ada beda
potensial
Contoh Zn dlm asam, potensial
Zn lebih rendah dari potensial
H
2
.
Zn Zn
2+
+ 2e
-


pada permukaan logam
membentuk gas H
2
.
2H
+
+ 2e
-
H
2

Reaksi umum :

Anoda : M M
n+
+ ne
-


Katoda :
evolusi hidrogen (asam): 2H
+
+ 2e
-
H
2


reduksi air (netral/basa): H
2
O + 2e
-
H
2
+ 2 OH
-


reduksi oksigen (asam) :O
2
+ 4H
+
+ 2e
-
2 H
2
O

Reduksi oksigen (netral/basa) :O
2
+ 2 H
2
O + 4e- 4OH
-

2
0
0
3

B
r
o
o
k
s
/
C
o
l
e
,

a

d
i
v
i
s
i
o
n

o
f

T
h
o
m
s
o
n

L
e
a
r
n
i
n
g
,

I
n
c
.


T
h
o
m
s
o
n

L
e
a
r
n
i
n
g

i
s

a

t
r
a
d
e
m
a
r
k

u
s
e
d

h
e
r
e
i
n

u
n
d
e
r

l
i
c
e
n
s
e
.

Figure The half-cell used
to measured the electrode
potential of copper under
standard conditions. The
electrode potential of
copper is the potential
difference between it and
the standard hydrogen
electrode in an open
circuit. Since E
0
is great
than zero, copper is
cathodic compared with
the hydrogen electrode.
Crystal Structure of Metals
Crystal Structure of Metals
Atoms arrange themselves into
various orderly configuration, called
crystals.
The arrangement of the atoms in
the crystal is called crystalline
structure.
The smallest group of atoms
showing the characteristic lattice
structure of a particular metal is
known as a unit cell.

A
o
A
d
force
die
blank
force
Forging
(wrenches, crankshafts)
FORMING
Drawing
(rods, wire, tubing)
often at
elev. T
Rolling
(I-beams, rails)
Extrusion
(rods, tubing)
tensile
force
A
o
A
d
die
die
METAL FABRICATION METHODS-I

2
0
0
3

B
r
o
o
k
s
/
C
o
l
e
,

a

d
i
v
i
s
i
o
n

o
f

T
h
o
m
s
o
n

L
e
a
r
n
i
n
g
,

I
n
c
.


T
h
o
m
s
o
n

L
e
a
r
n
i
n
g

i
s

a

t
r
a
d
e
m
a
r
k

u
s
e
d

h
e
r
e
i
n

u
n
d
e
r

l
i
c
e
n
s
e
.

Figure The Fe-Fe
3
C
phase diagram ( a
portion of the Fe-C
diagram). The vertical
line at 6.67% C is the
stoichiometric
compound Fe
3
C.
A phase diagram, also called equilibrium diagram or a constitutional diagram,
graphically illustrates the relationships among temperature, composition, and the
phases present in a particular alloy system.
400 C

1400
C
1200
C
1000
C
800
C
600 C
1600
C
Fe 1% C 2% C 3% C 4% C 5% C 6% C 6.70% C
L

o
o
Steel Cast
Iron
Pure Metal Solidification
Temperature remains
constant while grains
grow.

Some metals undergo
allotropic transformation
in solid state.

For example on cooling
bcc o-iron changes to
fcc -iron at 1400 C,
which again to bcc o-
iron at 906 C.
Crystal Nucleation and Growth
Nucleation and Grain Growth
Nucleation;
Homogeneous nucleation: very pure metal, substantial
undercooling (0.2Tm)
Heterogeneous nucleation: nucleation agents (5C
undercooling)
Grain growth
Planar: pure metal
Dendritic: solid solution
Grain size
depends on number of nuclei and cooling rate.

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning

is a trademark used herein under license.

Figure 11.17 The evolution of the microstructure of
hypoeutectoid and hypereutectoid steels during cooling. In
relationship to the Fe-Fe
3
C phase diagram.
Figure 11.16 Growth and structure of pearlite: (a)
redistribution of carbon and iron, and (b)
photomicrograph of the pearlite lamellae (2000).
(From ASM Handbook, Vol. 7, (1972), ASM
International, Materials Park, OH 44073.)
Figure : Example of microgalvanic cells in two-phase alloys:
(a) In steel, ferrite is anodic to cementite.
(b) In austenitic stainless steel, precipitation of chromium carbide
makes the low Cr austenite in the grain boundaries anodic.
2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning

is a trademark used herein under

license.
Figure 7.20 The structure and properties surrounding a fusion weld in
a cold-worked metal. Note: only the right-hand side of the heat-
affected zone is marked on the diagram. Note the loss in strength
caused by recrystallization and grain growth in the heat-affected zone
2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning

is a trademark used herein under

license.
Figure 7.21 During hot working, the elongated anisotropic
grains immediately recrystallize. If the hot-working
temperature is properly controlled, the final hot-worked
grain size can be very fine
Differential Aeration
Fe
O
2

Fe
2+

Fe
Fe
2+

O
2

Electrons
Conventional
current
Fe
2+

Aerated Deaerated
pH goes acid by
Fe
2+
+ H
2
O FeOH
+
+
H
+

pH goes alkaline
by
O
2
+ 2H
2
O + 4e
-

4OH
+

Steel corrodes
actively
Steel passivates
7 14
P
o
t
e
n
t
i
a
l

2.0
1.6
0.8
1.2
-0.4
0.4
0.0
-1.6
-0.8
-1.2
0
Fe metal stable
Fe
3+

Fe oxides
stable
Fe
2+
stable
pH
2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning

is a trademark used herein under license.

Figure : Concentration cells:
(a) Corrosion occurs beneath a water droplet on a steel plate
due to low oxygen concentration in the water.
(b) Corrosion occurs at the tip of a crevice because of limited
access to oxygen.
2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning

is a trademark used herein under license.

Figure 22.8 Examples of stress cells. (a) Cold work required to
bend a steel bar introduces high residual stresses at the bend,
which then is anodic and corrodes. (b) Because grain
boundaries have a high energy, they are anodic and corrode.
2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning

is a trademark used herein under license.

Figure : Concentration cells:
(a) Corrosion occurs beneath a water droplet on a steel plate
due to low oxygen concentration in the water.
(b) Corrosion occurs at the tip of a crevice because of limited
access to oxygen.

2
0
0
3

B
r
o
o
k
s
/
C
o
l
e
,

a

d
i
v
i
s
i
o
n

o
f

T
h
o
m
s
o
n

L
e
a
r
n
i
n
g
,

I
n
c
.


T
h
o
m
s
o
n

L
e
a
r
n
i
n
g

i
s

a

t
r
a
d
e
m
a
r
k

u
s
e
d

h
e
r
e
i
n

u
n
d
e
r

l
i
c
e
n
s
e
.

Figure 22.10 (a) Bacterial
cells growing in a colony
(x2700). (b) Formation of
a tubercule and a pit
under a biological colony.
2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning

is a trademark used herein under license.

Figure 22.11 Alternative methods for joining two pieces of
steel: (a) Fasteners may produce a concentration cell, (b)
brazing or soldering may produce a composition cell, and (c)
welding with a filler metal that matches the base metal may
avoid the formation of galvanic cells (for Example 22.8)
Galvanic Corrosion
Table 1 Standard emf series Table 2 Galvanic Series in Seawater
Reaction E
o
at 25
o
C,
(V vs NHE)
Au-Au
3+
Pt-Pt
2+
Ag-Ag
+
Hg-Hg
2
2+
Cu-Cu
2+
H
2
-H
+
Ni-Ni
2+
Fe-Fe
2+
Cr-Cr
3+
Zn-Zn
2+
Al-Al
3+
Mg-Mg
2+
Na-Na
+
+1.498
+1.2
+0.799
+0.788
+0.337
0.000
-0.250
-0.440
-0.744
-0.763
-1.662
-2.363
-2.714
|
Noble or
cathodic
Active or
anodic
+
Platinum
Gold
Silver
18-8 Mo stainless steel (passive)
Nickel (passive)
Cupronickels (60-90 Cu, 40-10 Ni)
Copper
Nickel (active)
18-8 Mo stainless steel (active)
Steel or iron
2024 aluminium (4.5 Cu, 1.5 Mg, 0.6 Mn)
Cadmium
Commercially pure aluminium (1100)
Zinc
Magnesium and magnesium alloys
After de Bethune and Loud from INCO test results
Which is better?
Brass bolt in a steel structure Steel bolt in a brass structure
Small brass cathode
will cause small
increase in corrosion of
steel structure. Bolt
will be protected from
corrosion by coupling
to steel
Small steel anode
will suffer large
increase in corrosion
due to coupling with
brass structure.
2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning

is a trademark used herein under license.

Figure 22.12 Zinc-plated steel and tin-plated steel are
protected differently. Zinc protects steel even when the
coating is scratched, since zinc is anodic to steel. Tin does
not protect steel when the coating is disrupted, since steel is
anodic with respect to tin.
2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning

is a trademark used herein under license.

Figure : Cathodic protection of a buried steel pipeline:
(a) A sacrificial magnesium anode assures that the galvanic
cell makes the pipeline the cathode.
(b) An impressed voltage between a scrap iron auxiliary anode
and the pipeline assures that the pipeline is the cathode.
Relevant Rusting
Results
Unprotected iron in agar media
Relevant Rusting
Results
Iron wrapped with
zinc wire
Iron wrapped with
copper wire
Material :
Logam / paduan
Polimer / plastik
Keramik /non logam

Sifat logam, Korosi
Batas butir, energi tinggi, 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, Ni, Mo, Ti, Nb, Mn, 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)
Biota laut :
Bernacles (menimbulkan celah, mempercepat
korosi)
Sebagai penghalang / turbulensi lokal
Mampu menembus lapisan pelindung
Bakteri pereduksi sulfat (menghasilkan asam sulfat)

Lingkungan laut :
Daerah percikan (serangan korosi sangat 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)
Corrosion of Zinc in Acid
Zinc dissolves with hydrogen
evolution
Zn + 2HCl ZnCl
2
+ H
2


Zinc known as a base or active metal
One atom of zinc metal
plus two molecules of hydrogen
chloride (hydrochloric acid)
reacts to form
goes to
one molecule of zinc chloride
plus one molecule of hydrogen gas
Corrosion of Platinum in Acid
Platinum does not react with acids
Platinum is known as a noble metal
Connection of Platinum to Zinc
Zn



Pt



HCl
Zinc and platinum not
connected, no reaction
on platinum
Zinc and platinum
connected, current flows
and hydrogen is evolved
on platinum
Zn + 2HCl ZnCl
2
+ H
2
metal + acid salt + hydrogen
Zn Zn
2+
+ 2e
-

metal metal ions + electrons
2H
+
+ 2e
-
H
2
hydrogen ions + electrons hydrogen gas
electrons
Connection of Platinum to Zinc
Zn + 2HCl ZnCl
2
+ H
2

But we can separate metal
dissolution and hydrogen evolution
Zn Zn
2+
+ 2e
-


Reactions that involve both
chemical change and the
transfer of charge
2H
+
+ 2e
-
H
2

These are known as electrochemical
reactions
One atom of zinc metal
one zinc ion in solution
two electrons in the metal
Electrodes
Electrodes are pieces of metal on
which an electrochemical reaction is
occurring
An anode is an electrode on which an
anodic or oxidation reaction is
occurring
A cathode is an electrode on which a
cathodic or reduction reaction is
occurring
Anodic Reactions
Examples
Zn Zn
2+
+ 2e
-
zinc corrosion
Fe Fe
2+
+ 2e
-
iron corrosion

Al Al
3+
+ 3e
-
aluminium corrosion


Fe
2+
Fe
3+
+ e
-
ferrous ion oxidation

H
2
2H
+
+ 2e
-
hydrogen oxidation


2H
2
O O
2
+ 4H
+
+ 4e
-
oxygen
evolution

Oxidation reactions
Produce electrons
Cathodic Reactions
Examples
O
2
+ 2H
2
O + 4e
-
4OH
-
oxygen reduction

2H
2
O + 2e
-
H
2
+ 2OH
-
hydrogen evolution

Cu
2+
+ 2e
-
Cu (copper plating)
Fe
3+
+ e
-
Fe
2+
(Ferric ion reduction)
Reduction reactions
Consume electrons
Effect of pH on reaction rate
Consider hydrogen evolution reaction :
2H
+
+ 2e
-
H
2

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
reaction - the more negative the
potential the faster the reaction
Effect of pH and potential on rate
of hydrogen evolution
pH
Potential
Faster
Slower
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:
H
2
2H
+
+ 2e
-
Effect of pH on reaction rate
H
2
2H
+
+ 2e
-

This reaction will go faster in alkaline
solution (since H
+
will be removed by
H
+
+ OH
-
H
2
O)

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
pH
Potential
Oxidation
Faster
Oxidation
Slower
Reduction
Faster
Reduction
Slower
Rates equal
Electrochemical
Equilibrium
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 Zn
2+
+ 2e
-
Polarisasi
Logam dlm lar setimbang, reaksi anodik dan katodik

Tidak dalam kesetimbangan, selisihnya : overpotensial (q) atau
polarisasi

Klasifikasi :
Polarisasi aktivasi : terdiri dari 3 tahapan utama.
Pertama : H+ + e- H ads
Kedua : H ads + H ads H2
Ketiga : gelembung H2


Hubungan antara polarisasi / overpotensial dengan laju reaksi


untuk polarisasi anodik, dan polarisasi katodiknya adalah :


i0 : exchange current density,
|a dan |c tetapan anoda dan katoda Tafel.
o
a
a a
i
i
log | q =
o
c
c c
i
i
log | q =
Kurva Tafel

Kecepatan korosi material dalam mpy (mils per year; 1 mil =
0,001 inchi),



di mana : D = densitas (g/cm3)
icor = rapat arus korosi (A/cm2)
M = berat ekivalen (g/mol.equ)
D
M i
129 , 0 mpy
cor
=
Polarisasi konsentrasi
akibat kecepatan reaksi terhadap
koefisien difusi ion terlarut (Dz) dan
konsentrasinya dlm larutan (CB).
Hubungan koefisien difusi, konsentrasi
larutan dengan kecepatan reaksi
disebut rapat arus batas (iL) :


o : ketebalan gradien konsentrasi dlm lar.

Jika tanpa polarisasi aktivasi, polarisasi
konsentrasi :

R : konstanta gas (8,314 J/mol.K)
T : temperatur absolut (273 K)
o
B z
L
nFC D
i =
|
|
.
|

\
|
=
L
k
i
i
1 log
nF
RT
2,3 q
Passivation
definisi sebagai sebuah bentuk
ketahanan korosi akibat
pembentukan lapisan pelindung

Jika lapisan pelindung terbentuk, hal
ini akan menyebabkan rapat arus
turun akibat tahanan lapisan film
dan pengaruh lapisan difusi
Kurva disolusi anodik dari logam aktif-pasif
Passivation
log |current density|
E
l
e
c
t
r
o
d
e

P
o
t
e
n
t
i
a
l

Active corrosion gives normal
activation polarization
Current falls as the passive
film starts to form - the
active-passive transition
When a stable passive film
has formed, the current has
a steady, low value - the
passive current density
The rate of corrosion will be
critically affected by the
cathodic curve
Rapid rate of cathodic
reaction leads to passivation,
and low rate of corrosion
Lower rate of cathodic
reaction leads to activity, and
high rate of corrosion
But it may also lead to low
rate of corrosion?
Very slow cathodic reaction
leads to low rate of corrosion
The Pourbaix (E-pH) Diagram
P
o
t
e
n
t
i
a
l

H
2
O is stable
H
2
is stable
7 14
pH = - log [H
+
]
2H
+
+ 2e
-
= H
2

Equilibrium
potential falls as
pH increases
2.0
1.6
0.8
1.2
-0.4
0.4
0.0
-1.6
-0.8
-1.2
0
2H
2
O = O
2
+ 4H
+
+ 4e
-
Equilibrium potential
falls as pH increases
O
2
is stable
Pitting Resistance Index
Pitting
P
o
t
e
n
t
i
a
l

7 14
2.0
1.6
0.8
1.2
-0.4
0.4
0.0
-1.6
-0.8
-1.2
0
Pourbaix Diagram for Zinc
Zn metal stable
Zn
2+
stable
in solution
Zn(OH)
2

stable
solid
ZnO
2
2-

stable in
solution
Corrosion
C
o
r
r
o
s
i
o
n

Immunity
P
a
s
s
i
v
i
t
y

Corrosion
possible with
oxygen
reduction
Corrosion
possible with
hydrogen
evolution
Corrosion requires
strong oxidising
agent
Corrosion is
thermodynamically
impossible
Corrosion is
possible, but likely
to be stifled by solid
corrosion product
Pourbaix Diagram for Gold
P
o
t
e
n
t
i
a
l

7 14
2.0
1.6
0.8
1.2
-0.4
0.4
0.0
-1.6
-0.8
-1.2
0
Gold metal stable
Immunity
C
C
Passivity
Gold cant corrode
with oxygen reduction
or hydrogen evolution
Pourbaix Diagram for Iron
P
o
t
e
n
t
i
a
l

7 14
2.0
1.6
0.8
1.2
-0.4
0.4
0.0
-1.6
-0.8
-1.2
0
Fe metal stable
Fe
3+

Fe oxides
stable
Will iron
corrode in
acid?
Fe
2+
stable
Yes - there is a
reasonably wide
range of potentials
where hydrogen
can be evolved and
iron dissolved
Will iron
corrode in
neutral waters?
Yes - although iron can
form an oxide in neutral
solution, it tends not to
form directly on the
metal, as the potential
is too low, therefore it is
not protective.
Will iron corrode
in alkaline
solution?
No - iron forms a solid
oxide at all potentials,
and will passivate
Pourbaix diagram for Aluminium
P
o
t
e
n
t
i
a
l

7 14
1.2
0.8
0.0
0.4
-1.2
-0.4
-0.8
-2.4
-1.6
-2.0
0
Al
Al
3+

Al
2
O
3

AlO
2
-

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
Bentuk korosi
Sources of Localized Corrosion
Environment
oxygen concentration
chloride ion concentration
pH
flow rate
Sources of Localized Corrosion
Material
segregation
inclusions
different phases
grain boundaries
Sources of Localized Corrosion
Mechanical
static stress
fluctuating stress
Bentuk-bentuk korosi sumuran :

(a) narrow,deep, (b )eliptical, (c) wide, shallow, (d)
subsurface, (e) undercutting, (f) horizontal, (g) vertical

Gambar Skematis proses pertumbuhan
pit pada besi

Contoh : Produk yang terkorosi merata
Galvanic Corrosion
Fe
O
2

Cu
Fe
2+

Electrons
Conventional
current
Fe
2+

O
2

Galvanic Corrosion
Important factors in galvanic
corrosion
relative areas of anode and cathode
difference in potential between anode
and cathode
effect of anodic polarization on anode
(some may passivate)
Crevice Corrosion
Metal
O
2

O
2

Cr
3+

1 Oxygen is consumed in crevice by slow passive corrosion
Metal
2 Passive corrosion continues, and pH falls by Cr
3+
hydrolysis
3 Passive film breaks down in acid and rapid active corrosion
starts
Active corrosion is
corrosion occurring in the
absence of an oxide film
Cr
3+

Hydrolysis is a reaction with
water, in this case
2Cr
3+
+ 6H
2
O Cr
2
O
3
+
6H
+

4 The active corrosion causes even stronger acidification and
stabilises the crevice corrosion
Crevice Corrosion
Crevice
corrosion under
washers
Pitting corrosion
on free surface
Gambar 1. Tahap awal korosi celah
2. Tahap lanjut
1 2
Other anions (e.g. OH
-
and SO
4
2-
) can
inhibit pitting, either by buffering the pH
in the pit or by causing the precipitation
of a salt film
Pitting
O
2
O
2

Cr
3+
Cr
3+

Inside the growing pit the hydrolysis of
Cr
3+
lowers the pH and breaks down the
passive film. The cathodic oxygen
reduction reaction continues outside the
pit
e
e
Cl
-

Cl
-

The presence of chloride is important,
as it allows a pH of about 1 to be
achieved (HCl is a strong acid, and
does not associate) and the metal
chlorides are very soluble
Mechanical Aspects of Corrosion
Static stress
stress-corrosion cracking
hydrogen 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
Stress-Corrosion Cracking
Mechanisms
Anodic dissolution
Hydrogen embrittlement
Film-induced cleavage
Dealloying
Plug-type dealloying of a brass tube
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.

2
0
0
3

B
r
o
o
k
s
/
C
o
l
e
,

a

d
i
v
i
s
i
o
n

o
f

T
h
o
m
s
o
n

L
e
a
r
n
i
n
g
,

I
n
c
.


T
h
o
m
s
o
n

L
e
a
r
n
i
n
g

i
s

a

t
r
a
d
e
m
a
r
k

u
s
e
d

h
e
r
e
i
n

u
n
d
e
r

l
i
c
e
n
s
e
.

Figure 22.15 The
peak temperature
surrounding a
stainless-steel weld
and the sensitized
structure produced
when the weld
slowly cools (for
Example 22.10)
Figure 22.14 (a) Intergranular
corrosion takes place in austenitic
stainless steel. (b) Slow cooling
permits chromium carbides to
precipitate at grain boundaries.
(c) A quench anneal to dissolve
the carbides may prevent
intergranular corrosion.
Concentration of
Cr decreases near
the precipitates
Cr
23
C
6
Grain boundaries will be depleted in Cr and will corrode
Intergranular Corrosion
When stainless steel is heated to
about 650
o
C, Cr carbides form at
the grain boundaries
C
C
C
C
Because of its high diffusion
rate, carbon can diffuse a
long way to form the
precipitate
However, chromium can only diffuse
a short distance, and this reduces the
matrix concentration of chromium at
the grain boundary
Cr
Cr
Cr
Cr
If the grain boundary Cr oncentration falls low enough
(below about 9%), then it will no longer remain passive, and
grain boundary corrosion will occur
Gambar Mekanisme korosi erosi oleh partikel padat
Flow Effects
Perhitungan kecepatan korosi



W = massa yang hilang (mg)
D = densitas (g/cm3)
A = luas permukaan (in2)
T = waktu penetrasi (jam)

DAT
W 534
mpy =
Corrosion Rates
Nomograph for Calculation of Corrosion Rate
Parameter Air Sedimen Baku
1. Kation
- Kalsium - Besi
- Magnesium - Barium
- Natrium - Strontium
2. Anion
- Klorida - Karbonat dan Bikarbonat
- Sulfat
3. Sifat-Sifat Fisik
- pH - Temperatur
- TDS - Oksigen terlarut
- Alkalinitas - Karbon Dioksida terlarut
Parameter Air Sedimen Baku
Kalsium (Ca
2+
) : Sebagai unsur utama pada oilfield brines dan
dapat berperan sebagai pembentuk endapan.
pH : Kelarutan senyawa CaCO3 dan besi sangat tergantung pada
besarnya pH.
TDS : Jumlah total zat yang larut dalam air (kation dan anion).
Alkalinitas : Ditandai dengan kehadiran ion HCO
3
-
, CO
3
2-
dan OH
-








Temperatur : Berpengaruh terhadap kecenderungan
pembentukan endapan, pH dan kelarutan gas di dalam air serta
berat jenis air itu sendiri.
pH Ion Penyebab Alkalinitas
9,6 - 14 OH
-
dan CO
3
2-

8,3 - 9,6 HCO
3
-
dan CO
3
2-
4,5 - 8,3 HCO
3
-
Indeks Korosifitas
1. Langelier (LI)
LI = pH - pH
s
2. Ryznar (RI)
RI = 2pH
s
- pH

pH
s
= (9,3 + A + B) - (C + D)
Dimana:
A = (log TDS (mg/L atau ppm) - 1)/10
B = -13,12 log (T (C)+ 273) + 34,55
C = log (Ca
2+
(mg/L atau ppm)) - 0,4
D = log (alkalinitas (mg/L atau ppm))


Kriteria Sifat Korosifitas

Interpretasi LI:
LI > 0 Air akan membentuk endapan
LI = 0 Air bersifat netral
LI < 0 Air bersifat korosif
Interpretasi RI:
RI < 5,5 Heavy scale akan terbentuk
5,5 < RI < 6,2 Endapan akan terbentuk
6,2 < RI < 6,8 Air bersifat netral
6,8 < RI < 8,5 Air bersifat korosif
RI > 8,5 Air bersifat sangat korosif
Dealing with Corrosion
There are many ways to prevent or
minimize corrosion damage.

Alloying
Coating - metallic
Coating organic
Electrochemical
Inhibitors

Steel Alloying to Provide
Corrosion Resistance
Add >11% Cr (stainless steel)

Add >2% Mo to stainless (resist
pitting)

Add Si, P, Cu, Cr ( and others) to
obtain weathering steel
Metallic Coatings
Widely used to protect steel and
to make other metals more
attractive
Zn and Zn alloys on steel:
Galvanizing
Al on steel: Aluminizing
Ni + Cr on steel, brass or zinc to
give a bright finish
Cu + Ni + Cr also used for bright
finish
Organic Coatings - Paint
Barrier layer to keep water
away

Adhesion is key to success

Susceptible to thermal
damage

Susceptible to UV damage
Inhibitors - Additions to the electrolyte that
preferentially migrate to the anode or cathode,
cause polarization, and reduce the rate of
corrosion.

Sacrificial anode - Cathodic protection by which a
more anodic material is connected electrically to
the material to be protected. The anode corrodes
to protect the desired material.

Passivation - Producing strong anodic polarization
by causing a protective coating to form on the
anode surface and to thereby interrupt the electric
circuit.
Protection Against Electrochemical Corrosion
Inhibitor
Inhibitor senyawa kimia
ditambahkan dalam jumlah kecil
Interface inhibisi : interaksi inhibitor
dengan permukaan logam membentuk
lapisan tipis (presipitasi).
Interphase inhibisi : yaitu modifikasi
lingkungan yang korosif , misal :
penangkapan oksigen, netralisasi gas
yang bersifat asam, pengaturan pH dan
lain sebagainya.
Mekanisme
mekanisme inhibitor
dibedakan 4 jenis :
1. Oxidizer
2. Oxygen scavengers
3. Precipitation
inhibitors
4. Adsorpsion inhibitor


Corrosion Inhibitors
Used in water systems:
Automotive cooling systems
Cooling towers
Boilers, especially high pressure
steam
Temporary preservatives for metals
Volatile corrosion inhibitors
Paints and primers
Pencegahan dan perlindungan korosi
Perlindungan katodik
1. Arus tanding (impressed current)



2. Anoda korban (sacrificed anode)
Kriteria material anoda korban

logam aktif dengan potensial korosi lebih
kecil/negatif dari potensial korosi yang
diproteksi
potensial korosi harus mampu melawan
hambatan elektrolit
polarisasinya rendah,
tidak dalam kondisi pasif pada lingkungan
kerja
efisiensi tinggi
nilai ekonomis tinggi.
Kriteria Proteksi Katodik
Kriteria proteksi NACE Standard RP 0169-83:
potensial terukur terhadap Cu/CuSO4
maksimal 850 mV (untuk baja),
polarisasi katodik lebih dari 300 mV aktif
terhadap potensial korosi struktur (dengan
faktor IRO),
polarisasi katodik lebih dari 100 mV aktif
terhadap potensial korosi struktur (tanpa
faktor IRO),
besar potensial polarisasi katodik
berdasarkan sifat yang diinginkan menurut
kurva Tafel (E-log I), dan
arus proteksi yang mencapai struktur
merupakan nilai bersih.
Terima Kasih