Presented by Iwan Susanto, Ph.

Mechanical Engineering Department

Politeknik Negeri Jakarta Created by Dr. Vika Rizkia
 Natural Gas Pipeline Rupture and Fire
Near Carlsbad, New Mexico, 19 August 2000
 The deterioration of materials by chemical
interaction with their environment. The term
corrosion is sometimes also applied to the Rusting conversion of iron in to
degradation of plastics, concrete and wood, but its oxide (Fe2O3 Heamatite)
generally refers to metals. The most widely used
metal is iron (usually as steel) and the following Tarnishing silver is converted in
discussion is mainly related to its corrosion. its sulfide (Ag2S –Silver glance)

Conversion of copper in to its

green colored carbonate
(malachite)
 Any spontaneous reaction in the universe is associated with a lowering in the free energy of the
system. All metals except the noble metals have free energies greater than their compounds. So
they tend to become their compounds through the process of corrosion.

Except noble metal, all metals are unstable to varying degrees in a terrestrial atmosphere. The
most widely used metals, namely, Iron, aluminium, copper, nickel, silver and alloys of these metals
all decay and lose good mechanical properties

The surfaces of all metals (except gold) in air are covered with oxide films. When such a metal is
immersed in an aqueous solution, the oxide film tends to dissolve. If the solution is acidic, the
oxide film may dissolve completely leaving a bare metal surface, which is said to be in the active
state. In near-neutral solutions, the solubility of the oxide will be much lower than in acid solution
and the extent of dissolution will tent to be smaller.

If the near-neutral solution contains inhibiting anions, this dissolution of the oxide film may be
suppressed and the oxide film stabilized to form a passivating oxide film which can effectively
prevent the corrosion of the metal, which is then in the passive state.
When the oxide-free surface of a metal becomes exposed to the solution, positively charged
metal ions tend to pass from the metal into the solution, leaving electrons behind on the
metal, i.e.

M Mn+ + ne- (1)

Atom in the metal surface ion in solution electron(s) in metal

The accumulation of negative charge on the metal due to the residual electrons leads to an
increase in the potential difference between the metal and the solution. This potential
difference is called the electrode potential which thus becomes more negative. This change
in the potential tends to retard the dissolution of metal ions but to encourage the
deposition of dissolved metal ions from the solution on to the metal

0 RT
E r,Mn+/M = E Mn+/M + ln a M n+
nF
Continuation of the dissolution and deposition of metal ions would
result in the metal reaching a stable potential such that the rate of
dissolution becomes equal to the rate of deposition. This potential
is termed the reversible potential Er and its value depends on the
concentration of dissolved metal ions and the standard reversible
potential Eo for unit activity of dissolved metal Ions, aM n+, i.e.,

Mn+ + ne- M (2)

 In acid solutions, electrons can react with hydrogen ions, adsorbed on the metal
surface from the solution, to produce hydrogen gas.

2H + + 2e- H2 (3)
adsorbed on metal surface in metal gas

The occurrence of reaction (3) permits the continued passage of an equivalent quantity
of metal ions into solution, leading to corrosion of the metal. Reaction (3) is also
reversible and has a reversible potential given by

P 1/2
0 RT H2
E = E - ln
r, H+/H2 H+/H2
nF a H+
In neutral solutions, the concentration of hydrogen ions is too low to
allow reaction (3) to proceed at a significant rate, but electrons in the
metal can react with oxygen molecules, adsorbed on the metal
surface from air dissolved in the solution, to produce hydroxyl ions

O2 + 2H2O + 4 e- 4OH- (4)

Adsorbed on metal surface in metal in solution

P4 -
RT OH
E = E0 - ln
r, O2 / OH - O2 / OH
-
4F P O2
Dalam larutan asam, dengan konsentrasi ion
hidrogen (H) tinggi

Dalam larutan asam dengan oksigen terlarut

Dalam larutan netral dengan oksigen terlarut

Dalam larutan yang memiliki ion multivalensi

Dalam larutan dimana logam terreduksi total

For corrosion to take place, the
formation of a corrosion cell is
essentially comprised of the
following four components.
Anode
An anode is an electrode through which electric current flows in to a polarized electrical device

Cathode
One of the two electrodes in an electrolytic cell represented as a positive terminal of a cell. Reduction
takes place at the cathode and electrons are consumed.

Electrolyte

It is the electrically conducting solution (e.g. salt solution) that must be present for corrosion to occur.
Note that pure water is a bad conductor of electricity. Positive electricity passes from anode to cathode
through the electrolyte as cations, e.g. Zn++ ions dissolve from a zinc anode and thus carry positive
current away from it, through the aqueous electrolyte

Metallic Path

The two electrodes are connected externally by a metallic conductor. In the metallic conductor,
'conventional' current flows from (+) to (—) which is really electrons flowing from (—) to (+). Metals
provide a path for the flow of conventional current which is actually passage of electrons in the
opposite direction
Conventional current flows from anode (—) to cathode (+) as Zn++ ions
through the solution. The current is carried by these positive charged ions.
The circuit is completed by passage of electrons from the anode (—) to
the cathode (+) through the external metallic wire circuit (outer current)
Most common – i.e. steel exposed to
environment
Uniform in nature – leaves scale or deposit
over entire exposed area – this is called rust
which is really iron-oxide – Fe(OH)3 or Fe2O3
Fairly predictable and therefore the effects can
be minimized!
Prevented by
Removing electrolyte (i.e. lower relative
humidity below 30%)
Choose material that doesn’t rust in a
particular environment – look at
potential-pH diagram!
Add design “allowance” for rust
When two dissimilar metals are joined together and exposed, the more active of the two
metals corrode faster and the nobler metal is protected. This excess corrosion is due to
the galvanic current generated at the junction.
In metal salt – containing liquid
Steel screws and brass Steel screw in Mg
Prevention ?? Do not have the area of the more active
metal smaller than the area of the less
active metal.

If dissimilar metals are to be used,

insulate them

Use inhibitors in aqueous systems

whenever applicable
Intensive localized corrosion within crevices & shielded
areas on metal surfaces. Small volumes of stagnant
corrosive caused by holes, gaskets, surface deposits, lap
joints

• Can be between metal surfaces or non-metal

surfaces in contact with metal.
• Very destructive since highly localized!
• How design around?
– Leak proof weld
– Better gasket design
– Avoid stagnant water

Terjadi akibat terdapat perbedaan konsentrasi ion atau gas terlarut (misal oksigen)
dalam larutan elektrolit antara dua logam yang sama. Korosi terjadi pada daerah
yang memiliki konsentrasi lebih rendah.
Good example – crevices and recesses or under deposits of dirt
or corrosion products where the solution is stagnet.
– Crevice must be wide enough to allow solution to penetrate yet
narrow enough for stagnancy (i.e. few thousandths of an inch).

Depending on the environment developed in the crevice and the nature of

the metal, the crevice corrosion can take a form of:

- pitting (i.e., formation of pits),

- filiform corrosion (this type of crevice corrosion that may occur on an
aluminium surface underneath an organic coating),
- intergrannular attack, or
- stress corrosion cracking.
KEY – In crevice there
are high
concentrations of H+
and Cl- ions which are
especially corrosive!
WHY? Low oxygen
levels (stagnant) means
ions have nothing to
react w/ except the
metal!!
Crevice corrosion between Rubber pads just accelerated
pipe and I-beam: the attack – why???
• Similar in chemistry to crevice corrosion except it happens in pits.
• Occurs in “pits” of metal surfaces where again, electrolyte is
aggressive (stagnant).
• More of a problem in stagnant solutions.
• Very destructive since highly localized – may go undetected until
failure occurs.
• Gravity causes pit to grow downward – corrosion rate can increase
with time
• A pit can be initiated by a localized surface
defect, scratch or slight variation in
composition.
• Stainless steels are especially susceptable to
this form of corrosion.
• Prevention?
– Material selection
– Avoid stagnant flow
– Alloy SS with about 2% molybdenum.
The grain boundaries in metals are more active than the grains because of segregation
of impurities and depletion of protective elements. So preferential attack along grain
boundaries occurs. e.g. weld decay in stainless steels
Cara mencegah :
1. Aplikasikan material pada temp dimana semua chromium carbide particles terlarut
2. Rendahkan kandungan karbon < 0.03 wt% C, sehingga pembentukan karbida
terminimalisir.
3. Tambahkan SS dengan logam Ni atau Ti yang memiliki kecenderungan
membentuk karbida lebih tinggi dari Cr, sehingga Cr akan tetap menjadi solid
solution (lapisan protektif).
Chloride Stress Corrosion Cracking
(SCC) adalah adalah retak-retak
yang disebabkan oleh adanya
tegangan tarik yang terus menerus
dalam medium korosif (pengaruh
ion Cl-).
Kondisi yang harus dipenuhi pada
Chloride Stress Corrorion Cracking;
 Ion Cl-
 Oksigen terlarut
 Tegangan pada logam
Diawali korosi pitting pada permukaan logam
Ion Cl- akan berikatan dengan atom logam
sehingga akan menguragi interaksi atom logam
dengan atom tetangganya
Adanya tegangan akan menyebabkan atom-
atom logam saling terpisah dan terjadi retak
awal pada daerah pitting
Untuk ion Cl- meskipun jumlahnya kecil,
katakanlah tingkatan ppm sudah cukup
memicu munculnya SCC
Pencegahan ??? Pemilihan material yg tahan/ imun
terhadap SCC. Type austenitic dan high
chromium content ferritic alloys rentan thd
SCC.

Modifikasi lingkungan. Lingkungan yang aggressive, misal

mengandung NaOH atau NaCl dengan konsentrasi tinggi,
ditambah adanya oxygen, akan mendorong terjadinya
SCC ini. Penambahan corrosion inhibitor bisa mengurangi
potensi ini.

Mengurangi tensile stress.

 Terkadang disebut sebagai hydrogen induced cracking dan hydrogen stress
cracking. Terjadi karena adanya reduksi ductility dan tensile strength ketika atom
hydrogen (H) masuk ke dalam logam.

Atom hidrogen berdifusi ke dalam logam. Di H2 atau CH4 kemudian menguap

dalam logam, mereka membentuk gas H2 meninggalkan lubang pada
atau berkombinasi dengan C (jika ada) logam, sehingga menyebabkan
membentuk CH4. stress concentration.

Tekanan H2 tinggi  dapat memutuskan ikatan

interatomik  terbentuk void  terbentuk blister 
blister muncul ke permukaan material dan
menyebabkan crack
Pencegahan ??? Menghilangkan sumber hidrogen, baik selama
proses metal forming, atau saat material
dipakai  supaya hidrogen tidak bisa penetrasi

Menghindari proteksi katodik / pelapisan

galvanis karena dapat menimbulkan
pembentukan hidrogen di permukaan logam

Pemberian unsur penghambat (inhibitor)

dengan membuat lapisan inert pada logam
an acceleration in the rate of corrosion attack
in metal due to the relative motion of a
corrosive fluid and a metal surface.

The increased turbulence caused by pitting on

the internal surfaces of a tube can result in
rapidly increasing erosion rates and eventually
a leak.

Erosion corrosion can also be aggravated by

faulty workmanship. For example, burrs left at
cut tube ends can upset smooth water flow,
cause localized turbulence and high flow
velocities, resulting in erosion corrosion. A
combination of erosion and corrosion can lead
to extremely high pitting rates.
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