Materials Selection

for Corrosion Prevention

(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

3

No
6

7
8
9
10

Environment
Nonstaining
atmospheric
exposure
Distilled water

Proper material
Aluminium

Hot strong oxidizing

solution
Ultimate resistance

Titanium

Concentrated
sulfuric acid

Tin

Tantalum
Steel
4

NORSOK

NORSOK

NORSOK

NORSOK

NORSOK

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

11

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

12

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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

15

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
16
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 17reduce
corrosion

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

AISI : American Iron and Steel Institute

19

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

H2SO4 solution

20

Influence of Cr on corrosion resistance of iron

base alloy

21

Influence of Ni on corrosion resistance of iron base alloy

22

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

23

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).
24

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
25
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.

26

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.

27

Influence of alloying elements on

pitting corrosion resistance of
stainless steels

28

Influence of alloying elements on

crevice corrosion resistance of
stainless steels

29

Influence of alloying elements

on SCC resistance of stainless
steels

30

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 3000C31 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
32
corrosion resistance. To be used for specialized
application where high strength together with

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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.
41

 Three

conditions must be present

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

42

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

43

Typical micro cracks formed during

SCC of sensitized AISI 304 SS

Surface morphology
44

Example of crack propagation during

transgranular stress corrosion cracking (TGSCC)
brass

45

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

46

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
47

Fracture surface due

to intergranular SCC

Fracture surface due to

local stress has reached
its tensile strength value
on the remaining section
48

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
49

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.

50

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
51

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
52

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.
53

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
54
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 , sulfurous acid,
2
etc.

55

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
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and other containers, proper trimming of gasket,

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.
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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,
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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
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corrosion inhibition functions.

VALVE BODIES (ALLOY STEEL)

ADEQUATE FOR BENIGN SERVICE LOW CO2
WELDABLE
CRITICAL SEALING AREAS NEED TO HAVE ALLOY
625 OVERLAY

GOOD TOUGHNESS
SOME LOW ALLOY MATERIALS HAVE LOW
HARDENABILITY

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NACE REQUIREMENTS

HARDNESS OF LOW ALLOY MATERIALS LIMITED TO HRC 22

MAXIMUM
NICKEL CONTENT IS LIMITED TO 1.0 PERCENT MAX FOR LOW
ALLOY MATERIALS
NACE MR0175 (ISO 15156) COVERS METALLIC MATERIALS
REQUIREMENT FOR RESISTANCE TO SULFIDE STRESS
CRACKING (SCC)
STANDARD IS NOT INTENDED AS DESIGN SPECIFICATION
EACH TYPE OF MATERIAL HAS SPECIFIC HEAT TREATMENT
REQUIREMENTS SUCH AS ONE OF THE FOLLOWING:
HOT ROLLED
ANNEALED
NORMALIZED
NORMALIZED, AUSTENITIZED, QUENCHED AND TEMPERED
AUSTENITIZED, QUENCHED AND TEMPERED

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API MATERIAL CLASS REQUIREMENTS

CRA (Corrosion Resistant Alloy) = Any one or Sum of Co, Cr, Mo, Ni, and Ti exceeds 50
percent
Wellhead equipment to satisfy the above API corrosive requirements can be group as follows:
Low alloy
Stainless Steel
Combination of the above
Duplex stainless steels
CRAs
Each of these alloys has successfully been used for subsea wellhead application but all have
some type of environmental limitations.
62

API 6A AND 17D

- SPECIFY STRENGTH LEVELS FOR VARIOUS PRESSURE
-

LEVELS
FOR PRESSURE LEVELS UP TO AND INCLUDING 10.000 PSI,
YIELD STRENGTH OF 60,000 PSI MINIMUM

- FOR PRESSURE LEVELS EXCEEDING 10,000 PSI, YIELD

-

STRENGTH OF 75,000 PSI MINIMUM

SPECIFY PSL (PRODUCT SPECIFICATION LEVELS ) PSL 1-4
PSL LEVELS ARE QUALITY RELATED
SPECIFIES IMPACT REQUIREMENTS FOR SUBSEA
EQUIPMENT TEST TEMPERATURE IS 0 DEGREES F

- TEST COUPON SIZE ( 4-INCH X 4-INCH CROSS-SECTION)

63

MATERIALS FOR SEAWATER INJECTION

FACTORS:
TEMPERATURE
CHLORINE LEVEL
PITTING RESISTANCE EQUIVALENT (PRE) OF MATERIALS
OXYGEN CONTENT
CANDIDATE MATERIALS:
PRE>40 FOR MATERIALS FOR USE IN AERATED
SEAWATER
LOWER PRE WITH LOWER OXYGEN

64

MATERIALS SELECTION CONSIDERATIONS

INCLUDE

COMPOSITION OF PRODUCED FLUIDS IN CONTACT WITH VALVE

BODY AND INTERNAL PARTS
SERVICE TEMPERATURE
PRESSURE RANGES
GALVANIC EFFECTS DUE TO CONTACT BETWEEN DIFFERENT
MAERIALS
CREVICE CORROSION RESISTANCE AT SEAL AND FLANGE FACES
WEAR AND GALLING RESISTANCE FOR MOVING PARTS
TEMPERATURE AND CHEMICAL RESISTANCE FOR NON-METALLIC
MATERIALS
CP ON METALS
EFFECTIVENESS OF COATINGS USED ON MATERIALS
WELDABILITY FOR WELD OVERLAY
MATERIAL AVAILABILITY AND COST
COMPATIBILITY OF MATERIALS WITH INJECTED FLUIDS

65

STAINLESS STEEL 410

GOOD CORROSION RESISTANCE FOR MANY APPLICATIONS

LOW TOUGHNESS IN WROUGHT CONDITION
LOW TOUGHNESS IN WELDED CONDTIONS
CRITICAL SEALING AREAS NEED ALLOY 625 OVERLAY
STAINLESS F6NM

SOMEWHAT BETTER CORROSION RESISTANCE THAN 410 SS

GOOD WELDABILITY
GOOD TOUGHNESS IN LOW TEMPERATURES
CRITICAL SEALING AREAS NEED ALLOY 625 OVERLAY
GOOD HARDENABILITY

66

NICKEL ALLOYS
EXCELLENT CORROSION RESISTANCE IN SUBSEA AND
PRODUCED FLUID ENVIRONMENTS

DIFFICULT IN MACHINING
EXPENSIVE
DIFFICULTIES FOR WELD REPAIR IN AGED CONDITION
CRITICAL SEALING SURFACES DO NOT REQUIRE
OVERLAY

LARGE COMPONENTS REQUIRE LONG LEAD TIME

PROCUREMENT

NO API 6A OR 17D ENVIRONMENTAL LIMITS

67

DUPLEX STAINLESS STEELS

GOOD CORROSION RESISTANCE IN MOST PRODUCED

FLUIDS
MORE RESISTANT TO STRESS CORROSION CRACKING IN
CHLORIDE ENVIRONMENTS THAN AUSTENITIC SS
GOOD WELDABILITY FOR STANDARD DUPLEX (2205)
WELDING ISSUES WITH SUPER DUPLEX (2507)
GOOD WELDABILITY WITH HEAT INPUT CONTROL
GOOD TOUGHNESS
EXHIBIT PROBLEMS WHEN HEAT TREATED IN LARGE
SECTIONS
MAY EXHIBIT HYDROGEN EMBRITTLEMENT WITH CP
LIMITED IN H2S SERVICE
68

MATERIAL LIMITS FOR PRODUCTION

EQUIPMENT
Alloy

H2S

CO2

Chlorides

Low Temp

Alloy Steel

Unlimited

Low

Limited

Unlimited

410 SS

Traces

Unlimited

Limited

Limited

F6NM

Limits

Unlimited

Limited

Unlimited

Duplex

Depending of Cl & H2S

Yes

Unlimited

No limits

Nickel Alloys

No Limits

No Limits

No Limits

No limits

Alloy + Selective Clad

Yes

Limits

Yes

Few limits

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MISCELLANEOUS MATERIALS

STAINLESS (3XX)
COPPER BASE
6 MO
13 CR
NITRONIC (50 OR 60)
PRECIPITATION HARDENED (A286, 925, 718, 625+)
ULTRAHIGH STRENGTH (MP35N)

70

PITTING RESISTANCE EQUIVALENT (PRE)

VS
CRITICAL CREVICE/PITTING TEMPERATURE

Pitting Resistance Equivalent (PRE) = %Cr + 3.3(%Mo) + 16(%N)

71

CREVICE CORROSION
-

Narrow spaces between metal-to-metal components

Attack occurs in small volumes of stagnant solution
Occurs under bolt heads and gaskets
Crevice can occur in absence of pitting for marginally
pitting resistant alloys

- Crevice sequence includes depletion of oxygen in

crevice, followed by chloride ion concentration and
increase in acidity within crevice

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FASTENERS
Common low alloy steel bolting materials include either ASTM A193

Grade B7 or A320 Grade L7

These materials are not corrosion resistant and require CP if not
coated
If coating is used, electrical continuity is required between bolt and
assembly for CP performance
Each bolt must be connected to CP system
Low alloy bolting may be used on CRA type flanges if connected to
CP
CRA type bolting is preferred if flanges are CRA type material
Low alloy bolting can result in hydrogen embrittlement from CP
system. Hardness should be limited to HRC 34
Typical CRA type bolting include A453, 718, 925, 625 and Alloy K500

73

PITTING CORROSION
Extreme localized form of corrosion that results in holes in the metal
Characterized by attacks at small discrete areas
Small on the surface but may have larger cross sectional area

deeper inside the metal

Pits are considered self-forming crevices
Pits usually grow in the direction of gravity
Pits develop and grow downward from horizontal surfaces
Associated with stagnant conditions such as liquid in a tank or liquid
trapped low in the component
Ordinary steels are more resistant to pitting than most stainless
steel
Attack occurs in acidic solutions containing chlorides

74

CHEMICAL INJECTION FLUIDS

PARAFFIN INHIBITORS
ASPHALTENE DISPERSANT
ASPHALTENE SOLVENT TOLUENE
SCALE INHIBITORS
CORROSION INHIBITORS
BIOCIDES
ALL CHEMICAL INJECTION FLUIDS HAVE PROPRIETARY
ADDITIVES THAT MAY AFFECT CERTAIN MATERIALS
COMPATIBILITY DATA IS REQUIRED FOR METALLIC AND NONMETALLIC MATERIALS

75

FLUID COMPATIBILITY
PART: TUBING HEAD BODY
MATERIAL: (ALLOY BODY)
EXPOSED COMPATIABLE
PARAFFINNO N/A
INHIBITOR

NO OK

ASPHALTENE NONE N/A

DISPERSANTNONE
ASPHALTENE SOLVENT NONE N/A
HYDRATE INHIBITOR NONE N/A
CONTROL FLUIDS

NONE N/A

PRODUCTION FLUIDS

NONE N/A

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SPECIAL CONSIDERATION FOR SUBSEA

APPLICATIONS (CP & HE)
MATERIAL

CP NEEDED

SUSCEPTIBLE TO HE

316 SS
YES
NO
17-4 PH YES
YES
2205 DUPLEX YES
YES
A286 ASTM A453 YES
NO
X-750 YES
YES
MONEL K-500 YES
YES
2507 DUPLEX TEMP RELATED
ALLOY 625
NO RARELY
ALLOY 718
NO RARELY

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PRICE

78

Terima
Kasih
79