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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-Cr-Mo)
(Chlorimets)

Dilute sulfuric acid

Lead

No

Environment

Proper material

Nonstaining atmospheric
exposure
Distilled water

Aluminium

Titanium

Hot strong oxidizing


solution
Ultimate resistance

Tantalum

10

Concentrated sulfuric acid

Steel

7
8

Tin

NORSOK

NORSOK

NORSOK

NORSOK

NORSOK

Table 5 - Materials selection for sub-sea production and flowline systems

Table 5 - Materials selection for sub-sea production and flowline systems

Table 5 - Materials selection for sub-sea production and flowline systems

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 corrosion
resistance.

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 23%.
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 1618%) 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 microtunnels
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, SO2, 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.