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CORROSION

CONTROL
MATERIAL

SELECTION
ALTERATION OF ENVIRONMENT
PROPER DESIGN
CATHODIC PROTECTION
ANODIC PROTECTION
COATINGS & WRAPPING

(1) MATERIAL SELECTION


(selection of proper material for a
particular corrosive service)
Metallic

[metal and alloy]

Nonmetallic [rubbers (natural and synthetic),


plastics, ceramics, carbon and graphite, and
wood]

Metals and Alloys


No

Environment

Proper material

Nitric acid

Stainless steels

Caustic

Nickel and nickel


alloys

Hydrofluoric acid

Monel (Ni-Cu)

Hot hydrochloric
acid

Hastelloys (Ni-CrMo) (Chlorimets)

Dilute sulfuric acid Lead

No
6

Environment
Nonstaining
atmospheric
exposure

Proper material
Aluminium

7
8

Distilled water
Hot strong oxidizing
solution

Tin
Titanium

9
10

Ultimate resistance
Concentrated
sulfuric acid

Tantalum
Steel

Stainless steels are


iron base alloys that
contain a minimum
of approximately
11% Cr, the amount
needed to prevent
the formation of rust
in unpolluted
atmosphere.

Dissolution rate, cm/sec

E.g : Stainless
Steels

wt.% Cr

Alloying elements of stainless steel


:

Other than Ni, Cr and C, the following alloying elements


may also present in stainless steel: Mo, N, Si, Mn, Cu,
Ti, Nb, Ta and/or W.

Main alloying elements (Cr, Ni and C):


1. Chromium
Minimum concentration of Cr in a
stainless steel is 12-14wt.%
Structure : BCC (ferrite forming element)
* Note that the affinity of Cr to form Cr-carbides is
very
high. Chromium carbide formation along grain
boundaries may induce intergranular corrosion.

Binary diagram of Fe-Cr


Sigma phase
formation which
is initially formed
at grain
boundaries has to
be avoided
because it will
increase
hardness,
decrease ductility
and notch
toughness as well
as reduce

2. Nickel
Structure: FCC (austenite forming
element/stabilize austenitic structure)
Added to produce austenitic or duplex stainless
steels. These materials possess excellent
ductility, formability and toughness as well as
weld-ability.
Nickel improves mechanical properties of
stainless steels servicing at high temperatures.
Nickel increases aqueous corrosion resistance of
materials.

Ternary diagram of Fe-Cr-Ni at 6500 and 10000C

AISI : American Iron and Steel Institute

Anodic polarization curves of Cr, Ni and Fe in 1 N


H2SO4 solution

Influence of Cr on corrosion resistance of iron


base alloy

Influence of Ni on corrosion resistance of iron base alloy

Influence of Cr on
iron base alloy
containing 8.39.8wt.%Ni

3. Carbon
Very strong austenite forming element (30x
more effective than Ni). I.e. if austenitic
stainless steel 18Cr-8Ni contains 0.007%C,
its structure will convert to ferritic structure.
However the concentration of carbon is
usually limited to 0.08%C (normal
stainless steels) and 0.03%C (low carbon
stainless steels to avoid sensitization during
welding).

Minor alloying
elements :

Manganese
Austenitic forming element. When necessary can be
used to substitute Ni. Concentration of Mn in stainless
steel is usually 2-3%.

Molybdenum
Ferritic forming element. Added to increase pitting
corrosion resistance of stainless steel (2-4%).
Molybdenum addition has to be followed by decreasing
chromium concentration (i.e. in 18-8SS has to be
decreased down to 16-18%) and increasing nickel
concentration (i.e. has to be increased up to 10-14%).
Improves mechanical properties of stainless steel at
high temperature. Increase aqueous corrosion
resistance of material exposed in reducing acid.

Tungsten
Is added to increase the strength and toughness of
martensitic stainless steel.

Nitrogen (up to 0.25%)


Stabilize austenitic structure. Increases strength and
corrosion resistance. Increases weld ability of
duplex SS.

Titanium, Niobium and Tantalum


To stabilize stainless steel by reducing susceptibility
of the material to intergranular corrosion. Ti
addition > 5x%C. Ta+Nb addition > 10x%C.

Copper
Is added to increase corrosion resistance of
stainless steel exposed in environment containing
sulfuric acid.

Silicon
Reduce susceptibility of SS to pitting and crevice
corrosion as well as SCC.

Influence of alloying elements on


pitting corrosion resistance of
stainless steels

Influence of alloying elements on


crevice corrosion resistance of
stainless steels

Influence of alloying elements


on SCC resistance of stainless
steels

Five basic types of stainless


steels :

Austenitic - Susceptible to SCC. Can be hardened by


only by cold working. Good toughness and
formability, easily to be welded and high corrosion
resistance. Nonmagnetic except after excess cold
working due to martensitic formation.
Martensitic - Application: when high mechanical
strength and wear resistance combined with some
degree of corrosion resistance are required. Typical
application include steam turbine blades, valves body
and seats, bolts and screws, springs, knives, surgical
instruments, and chemical engineering equipment.
Ferritic - Higher resistance to SCC than austenitic SS.
Tend to be notch sensitive and are susceptible to
embrittlement during welding. Not recommended for
service above 3000C because they will loss their
room temperature ductility.

Duplex (austenitic + ferritic) has enhanced


resistance to SCC with corrosion resistance performance
similar to AISI 316 SS. Has higher tensile strengths than
the austenitic type, are slightly less easy to form and
have weld ability similar to the austenitic stainless steel.
Can be considered as combining many of the best
features of both the austenitic and ferritic types. Suffer a
loss impact strength if held for extended periods at high
temperatures above 3000C.

Precipitation hardening - Have the highest strength


but require proper heat-treatment to develop the correct
combination of strength and corrosion resistance. To be
used for specialized application where high strength
together with good corrosion resistance is required.

Stress Corrosion Cracking of Stainless


Steel

Stress corrosion cracking (SCC) is defined as


crack nucleation and propagation in stainless
steel caused by synergistic action of tensile
stress, either constant or slightly changing with
time, together with crack tip chemical reactions
or other environment-induced crack tip effect.

SCC failure is a brittle failure at relatively low


constant tensile stress of an alloy exposed in a
specific corrosive environment.

However the final fracture because of overload of


remaining load-bearing section is no longer SCC.

Three

conditions must be present


simultaneously to produce SCC:
- a critical environment
- a susceptible alloy
- some component of tensile
stress

Pure metals are more


resistance to SCC but not
immune and susceptibility
increases with strength

Tensile stress
is below yield
point
Tensile
stress

Corrosive
environment is
often specific to
the alloy system

Susceptible
material

Corrosive
environment

Stress
corrosion
cracking

Typical micro cracks formed during


SCC of sensitized AISI 304 SS

Surface morphology

Example of crack propagation during


transgranular stress corrosion cracking (TGSCC)
brass

Example of crack
propagation during
intergranular stress
corrosion cracking
(IGSCC) ASTM A245
carbon steel

Fracture surface of
intergranular SCC on
carbon steel in hot nitric
solution

Fracture surface of
transgranular SCC on
austenitic stainless steel in
hot chloride solution

Fracture surface due


to intergranular SCC

Fracture surface due to


local stress has reached
its tensile strength value
on the remaining section

Electrochemical effect

pitting
Zone 1

cracking
zones

passive

Usual region for


TGSCC, mostly is
initiated by pitting
corrosion
(transgranular cracking
propagation needs
higher energy)

Zone 2

active

Usual region for IGSCC,


SCC usually occurs where
the passive film is
relatively weak

Note that non-susceptible alloy-environment


combinations, will not crack the alloy even if held in
one of the potential zones.
Temperature and solution composition (including
pH, dissolved oxidizers, aggressive ions and
inhibitors or passivators) can modify the anodic
polarization behavior to permit SCC.
Susceptibility to SCC cannot be predicted solely
from the anodic polarization curve.

Models of stress corrosion


cracking
Slip

step dissolution model


Discontinuous intergranular crack growth
Crack nucleation by rows of corrosion
micro-tunnels
Absorption induced cleavage
Surface mobility (atoms migrate out of
the crack tips)
Hydrogen embrittlementHIC

Control/prevention :
Reduce

applied stress level


Remove residual tensile stress (internal
stress)
Lowering oxidizing agent and/or critical
species from the environment
Add inhibitor
Use more resistant alloys
Cathodic protection

Alteration of Environment

Typical changes in medium are :


Lowering temperature but there are cases
where increasing T decreases attack. E.g hot,
fresh or salt water is raised to boiling T and
result in decreasing O2 solubility with T.

Decreasing velocity exception ; metals &


alloys that passivate (e.g stainless steel)
generally have better resistance to flowing
mediums than stagnant. Avoid very high
velocity because of erosion-corrosion effects.

Removing oxygen or oxidizers e.g boiler


feedwater was deaerated by passing it thru a
large mass of scrap steel. Modern practice
vacuum treatment, inert gas sparging, or thru the
use of oxygen scavengers. However, not
recommended for active-passive metals or alloys.
These materials require oxidizers to form
protective oxide films.

Changing concentration higher


concentration of acid has higher amount of active
species (H ions). However, for materials that
exhibit passivity, effect is normally negligible.

Environment factors
affecting corrosion design
:
Dust particles and man-made pollution CO,
NO, methane, etc.
Temperature high T & high humidity
accelerates corrosion.
Rainfall excess washes corrosive materials
and debris but scarce may leave water
droplets.
Proximity to sea
Air pollution NaCl, SO 2, sulfurous acid, etc.

Humidity cause condensation.

Design Dos & Donts

Wall thickness allowance to accommodate for


corrosion effect.
Avoid excessive mechanical stresses and stress
concentrations in components exposed to corrosive
mediums. Esp when using materials susceptible to SCC.
Avoid galvanic contact / electrical contact between
dissimilar metals to prevent galvanic corrosion.
Avoid sharp bends in piping systems when high
velocities and/or solid in suspension are involved
erosion corrosion.
Avoid crevices e.g weld rather than rivet tanks and
other containers, proper trimming of gasket, etc.

Avoid sharp corners paint tends to be thinner at


sharp corners and often starts to fail.
Provide for easy drainage (esp tanks) avoid
remaining liquids collect at bottom. E.g steel is
resistant against concentrated sulfuric acid. But if
remaining liquid is exposed to air, acid tend to absorb
moisture, resulting in dilution and rapid attack occurs.
Avoid hot spots during heat transfer operations
localized heating and high corrosion rates. Hot spots
also tend to produce stresses SCC failures.
Design to exclude air except for active-passive
metals and alloys coz they require O2 for protective
films.
Most general rule : AVOID HETEROGENEITY!!!

Protective Coatings /
Wrapping
Provide barrier between metal and environment.

Coatings may act as sacrificial anode or release


substance that inhibit corrosive attack on substrate.
Metal coatings :
Noble silver, copper, nickel, Cr, Sn, Pb on steel.
Should be free of pores/discontinuity coz creates
small anode-large cathode leading to rapid attack
at the damaged areas.
Sacrificial Zn, Al, Cd on steel. Exposed substrate
will be cathodic & will be protected.
Application hot dipping, flame spraying,
cladding, electroplating, vapor deposition, etc.

Surface modification to structure or composition by


use of directed energy or particle beams. E.g ion
implantation and laser processing.
Inorganic coating : cement coatings, glass coatings,
ceramic coatings, chemical conversion coatings.
Chemical conversion anodizing, phosphatizing, oxide
coating, chromate.
Organic coating : paints, lacquers, varnishes. Coating
liquid generally consists of solvent, resin and pigment.
The resin provides chemical and corrosion resistance,
and pigments may also have corrosion inhibition
functions.

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