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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

1 Nitric acid Stainless steels


2 Caustic Nickel and nickel
alloys
3 Hydrofluoric acid Monel (Ni-Cu)
4 Hot hydrochloric Hastelloys (Ni-Cr-
acid Mo) (Chlorimets)
5 Dilute sulfuric acid Lead
No Environment Proper material
6 Nonstaining Aluminium
atmospheric exposure

7 Distilled water Tin


8 Hot strong oxidizing Titanium
solution
9 Ultimate resistance Tantalum
10 Concentrated sulfuric Steel
acid
E.g : Stainless
Steels

Stainless steels are


iron base alloys that

Dissolution rate, cm/sec


contain a minimum of
approximately 11%
Cr, the amount
needed to prevent the
formation of rust in
unpolluted
atmosphere.
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 8.3-
9.8wt.%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
Tensile stress immune and susceptibility
is below yield increases with strength
point

Susceptible
Tensile
material
stress

Stress
Corrosive corrosion
Corrosive environment
environment is cracking
often specific to
the alloy system
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 Fracture surface due to
intergranular SCC local stress has reached its
tensile strength value on the
remaining section
Electrochemical effect
Usual region for TGSCC,
mostly is initiated by
pitting pitting corrosion
Zone 1
(transgranular cracking
propagation needs higher
energy)
cracking passive
zones

Zone 2
Usual region for IGSCC,
active 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 embrittlement→HIC
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, SO2, sulfurous acid, etc.

 Humidity – cause condensation.


Design Do’s & Don’ts
 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.