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Damage Mechanisms in the

Refinery and Petrochemical


Industry

Based on API RP 571

Mike Holland

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Course Outline
• Introduction
• Revision : Basic Steel Metallurgy
Stainless Steel Metallurgy
• Damage mechanisms –
metallurgical/environmental/mechanical
• Revision : Basic Corrosion Theory
• Damage mechanisms – Corrosion-related
• Review : Basic Refinery Processes
• Damage mechanisms – Refinery specific
• Concluding summary
• Multiple Choice Examination

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Introduction

• Scope – service-induced damage (not


fabrication flaws).
• Importance of thorough, accurate plant
failure investigations to assist with
appropriate mitigation actions.
• Increase awareness and understanding of
DM’s for better materials selection at
design stage.
• Relevance of DM identification and
monitoring to RBI and FFS studies.
• Organization and scope of API 571

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Outline of API 571
Organization
• Over 60 damage mechanisms
addressed in the following format :

• Description of Damage
• Affected Materials
• Critical Factors
• Affected Units or Equipment (also shown on
process flow diagrams for typical process units).
• Appearance or Morphology of Damage (with
pictures)
• Prevention/ Mitigation
• Inspection and Monitoring
• Related Mechanisms
• References

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What do we remember about

Basic Steel
Metallurgy ?

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Review of Steel Metallurgy
• Carbon steel – range of steels – C = 1.7% max.
• Greatest volume for construction :
– Low carbon steel < 0.14% C
– Mild steel 0.15 – 0.30% C

2 allotropes of Fe –BCC up to 910oC (Ferrite)


FCC 910 1410oC(Austenite)
BCC 1410 – 1535oC (MP)

Alloying with C changes 'transformation points'.


<0.02%C soluble in ferrite – remainder forms FeC
'Cementite'.

Combination of alternating ferrite and cementite


is called 'pearlite'.

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Iron – Carbon Phase Diagram

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Transformation of Austenite

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Typical Carbon Steel
Microstructure

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Effect of Carbon on Mechanical
Properties

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Heat Treatment

• Heat treatment substantially alters mechanical


properties.
• 'Normalizing' – heat to austenite range and air
cool (grain refinement).
• 'Annealing' –furnace cool from austenite range
(softening).
• 'Quenching' – rapid cooling from austenite range
by quenching in water / oil (hardening).
• 'Tempering' – re-heating to below Ac1 temp. after
quenching to improve toughness and soften.
• 'PWHT' – re-heating to below Ac1 after welding to
relieve residual stresses and soften HAZ

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Low to Medium Alloy Steels
• Additions primarily of - Cr up to 9%
- Mo up to 1%

• Increased mechanical strength


(particularly at elevated temperatures).

• Typically used for high temperature,


heavy wall pressure equipment.

• More difficult to weld – less forgiving


than mild steels.

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Any
Questions ?
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What do we remember about

Stainless Steels ?

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Basic Stainless Steel
Metallurgy
• At least 11 – 12% Cr.

• Inert, stable Cr2O3 surface film


confers 'stainless' property.

• Four major categories of S/S:


– Austenitic
– Ferritic
– Martensitic
– Duplex

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Iron-Chromium Phase Diagram

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Schaeffler Diagram (Cr-Ni
equivalents)

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Schaeffler Diagram (Cr-Ni
equivalents)

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Austenitic Stainless Steels (1)
• Typically contain 16-26% Cr and 8-20% Ni
(18/8).
• Ni causes these alloys to retain austenitic
microstructures, hence:
– No austenite → ferrite transition (not
hardenable other than by cold work).
– Non-magnetic.

Good high temp. strength, oxidation and


corrosion resistance.
Most common are '300' series S/S e.g.
304, 304L, 316, 316L, 321, 347.

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Austenitic Stainless Steels (2)

• Susceptible to inter-granular corrosion due to


'sensitization'.
• Caused by localised depletion of Cr due to Cr 23C6
formation at high temps. (e.g. weld HAZ).
• Prevented by use of low C 'L' grades (<0.03%C) to
limit Cr carbide formation.
• Also 'stabilized' grades 321 / 347 (Ti and Nb have
greater affinity for C than does Cr).
• High C 'H' grades (>0.04%C) used for high temp.
strength, e.g ASME allows 304H up to 815oC, but
304L only to 425-455oC.
• Highly susceptible to Cl-induced SCC at T>60oC

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Inter-granular HAZ Corrosion
(Due to too high C content)

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Inter-granular Corrosion due to
Sensitization

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Ferritic and Martensitic S/S
• Similar Cr to austenitic S/S but <2.5% Ni.
• On cooling, transform to ferrite or
martensite, depending on C content.
• Both are magnetic, most common types
are:
Martensitic – types 410, 420, 431, 440,
moderate carbon between 0.2-1.2%.
Hardenable by heat treatment.

Ferritic – types 405, 409, 430, low


carbon < 0.12%.
• Weldability :– Martensitic – poor
Ferritic – moderate to poor

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Duplex Stainless Steel

• Typically 18-26% Cr, 4-6.5% Ni, 2.5-3%


Mo, <0.03% C.
• Intermediate Ni content causes
microstructure to be mixture of ferrite
and austenite.
• Thus high resistance to Cl SCC.
• Weldability good.
• Strength very good, higher than
austenitic and ferritic S/S.

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Duplex Stainless Steel Micro

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Nominal Compositions of Common
Stainless Steels

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Any
Questions ?
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Damage Mechanisms

Associated with

Metallurgical,
Environmental
and Mechanical aspects

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Mechanical Fatigue

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Typical Fatigue 'Beachmarks'

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Description of Damage

• Cracking when a component is


exposed to cyclical stresses for an
extended period
• These stresses can arise from either
mechanical loading or thermal
cycling and are typically well below
the yield strength of the material
• Surface breaking and initiate at
stress concentrations

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Alexander Kielland Failure
Fatigue cracking in brace D6 of
Alexander L. Kielland platform
TECHNOLOGY

© Copyright TWI Ltd., 2000 Session 2/7

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Critical Factors: Mechanical
• F (geometry, welds, stress level, number of cycles,
and material properties (strength))
• Fatigue cracks initiate on the surface at notches or
stress raisers under cyclic loading
– Mechanical notches (sharp corners or grooves)
– Key holes on drive shafts of rotating equipment
– Quench nozzles
– Thread root notches
• Some materials such as titanium, carbon steel and
low alloy steel have an endurance limit. Limit
based on Tensile strength ~0.5
• SS and other materials that do not have an
endurance limit will have a fatigue limit defined by
the number of cycles at a given stress amplitude
• Welded structures have fatigue life insensitive to
material or strength

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Effect of Geometry and Stress on Fatigue
Fracture

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Effect of Weld Joint on Fatigue
Strength

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Affected Units: Mechanical

• Equipment in cyclical service due to


variable mechanical loading
• High pressure drop control valves or
steam reducing stations can cause serious
vibration problems in connected piping
• Small diameter piping that may see
vibration from adjacent equipment or wind
• Rotating shafts on centrifugal pumps or
compressors have stress concentrations
due to changes in radii and key ways

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Corrosion Fatigue
• Essentially similar to mechanical fatigue,
but accelerated by corrosive
environment.
• Unlike pure mechanical fatigue, no
fatigue limit load in corrosion-assisted
fatigue.
• Accelerated crack propagation due to:

– Inability of metal surface to develop protective


film under cyclic loading.
– Corrosion products intensify stress at crack tip
by 'wedging action'.

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Corrosion Fatigue Cracks on
Thick-Walled Header

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Effect of Environment on Fatigue crack
Propagation

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Thermal Fatigue

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Cause of Thermal Fatigue

• Thermal fatigue is the result of cyclic


stresses caused by variations in
temperature.
• Equivalent to low cycle fatigue,
resulting in fracture < 10 000 cycles.
• Pre-requisite is that thermal
expansion due to cyclic temp.
variations be constrained such that
the temp. gradients generate
thermal stresses.

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Critical Factors: Thermal
• F (magnitude of the temperature swing and the
frequency)
• Time to failure is a function of the magnitude of the
stress and the number of cycles
• Start-up and shutdown of equipment increase the
susceptibility to thermal fatigue
• No set limit on temperature swings; however, as a
practical rule, cracking may be suspected if the
temperature swings exceed about 95 oC
• Damage is also promoted by rapid changes in surface
temperature that result in a thermal gradient
through-wall or along the component
• Notches or nozzles act as constraint and subject to
cracking
• Some alloys better than other (those with low
coefficients of thermal expansion)

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Thermal Fatigue Cracking

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Influence of Weld on Cracking
Severity

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Cross-section Through Surface
'Craze Cracking'

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Affected Units: Thermal

• Mix points of hot and cold streams


(Hydro-cracker H2 injection points
and REAC water wash injection)
• Coke drum shell and skirts
• Boiler components
• Reformer MOV’s
• Coal gasification reactors

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Appearance or Morphology of
Damage
• Mechanical
– Distinctive fracture surface appearance
• 'beach marks' emanating from the crack initiation
site
• 'waves' of crack propagation that occur during every
cycle above the threshold
• Final overload area
– Surface initiating cracks - transgranular

• Thermal
– Surface initiating cracks - transgranular
– Generally dagger-shaped and oxide filled
– Can have elephant skin appearance ('craze
cracking')
– Cracks often at welds and attachments

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'Elephant Skin' Thermal Fatigue
Cracking of Boiler Tube

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Prevention/Mitigation
• Mechanical
– Design that uses correct material helps minimize stress
concentration (generous radius along edges and corners)
– Select a metal with a design fatigue life sufficient for its
intended cyclic service
– Brace small connections
– TIG wash fillet welds and grind welds flat

• Thermal
– Design and operate to minimize thermal stresses and
thermal cycling
– Reduce stress concentrators and blend grind weld profiles
– Controlled rates of heating and cooling during start-up and
shutdown
– Consideration of dissimilar material junctions
– Incorporate flexibility to accommodate differential expansion
– Use thermal sleeves

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Inspection and Monitoring

• Since cracking is surface connected,


VT, MT, PT, ACFM are appropriate.
• External SWUT.
• VT of small diameter piping to detect
oscillation or other cyclical movement
that could lead to cracking.
• Vibration monitoring of rotating
equipment to help detect shafts that
may be out of balance.

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Creep Rupture

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Description of Damage

• Creep is when metal components at


high temperatures continuously
deform at stresses below yield.

• Can result in deformation or


cracking.

• Damage may not initiate at surface.

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Boiler Tube Creep Failure

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Boiler Tube 'Fish Mouth' Creep
Failure

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Creep
The macro
‘Small fissure’ rupture

Oxidised bulge

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Critical Factors
• Strain rate is sensitive to both load and temp.
• 3 stages of creep – 'Primary', 'Secondary' and
'Tertiary'.
• Rule of thumb that strain rate doubles for an
increase of 12oC or an increase of 15% in stress
(i.e., remaining life is halved!).
• Temperature needs to be above a threshold
temperature, (generally T > 0.4Tm).
• LM Parameter correlates creep-rupture test
variables : LM = T(logRt + C).
• Usual design criteria are :
– Min. stress to rupture after 100 000 hrs @ design T
– Stress for creep strain of 1% in 10 000 hrs @design
T

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Strain v Time Creep Curves

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Threshold Temperatures for
Creep
Material Threshold Temperature

Carbon Steel 370ºC


C-1/2 Mo 400ºC
1 1/4Cr-1/2Mo 425ºC
2 1/4Cr-1Mo 425ºC
5Cr-1/2Mo 425ºC
9Cr-1Mo 425ºC
304H SS 480ºC
347H SS 540ºC

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Affected Units
• Any unit where equipment operates
above threshold temperature.
• Heater tubes and supports.
• Piping and equipment, such as hot-wall
catalytic reforming reactors and FCC
regen internals.
• Nozzles and tees with high strain
concentration in catalytic reformer units.
• Dissimilar metal welds (e.g., ferritic to
austenitic welds) may suffer creep
related damage at high temps. due to
differential thermal expansion stresses.

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Appearance or Morphology of
Damage
• Creep voids typically show up at the
grain boundaries and in later stages form
fissures and then cracks. Many alloys do
not void until late in life.
• Deformation and bulging is possible, but
the amount is highly dependent on the
material, temperature, and stress level.
• Cracks at constraint areas, such as
nozzles, tees, welds. Creep cracking,
once initiated, can progress rapidly.
• Cracks will mostly be inter-granular.

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Inter-granular Creep Fissuring

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Prevention/Mitigation

• During design, select appropriate material


and heat treatment.
• Control temperatures with temperature
measurements (thermocouples and IR).
• Inspect for flame impingement/hot spots
to prevent coking.
• Perform creep calculations per API 579
Part 10
• Observe deformation.
• Perform destructive tests to obtain
remaining life.

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Inspection and Monitoring

• VT and deformation measurements.


• PT, MT, UT angle beam for cracks at
welds.
• Metallographic replication.
• Destructive sampling for metallography
and creep testing.
• Fired heater tubes can be inspected by
automated crawler employing
simultaneous diametrical measurement
and UT/EC.

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Hydrogen Damage

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Description of Damage
• HTHA results from exposure to hydrogen
at elevated temperatures and pressures.
• H reacts with carbides in steel to form
methane, which can not diffuse out. The
loss of carbide causes an overall loss in
strength and methane causes internal
stress. Methane pressure builds up,
forming bubbles or cavities, micro-
fissures and finally fissures that combine
to form cracks.
• Failures occur when the cracks reduce the
load carrying ability of the component.

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Affected Materials

• CS
• C-0.5Mo
• 1Cr, 1.25Cr
• 2.25Cr, 5Cr

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Critical Factors
• For specific material, HTHA f(temperature/hydrogen
partial pressure/time/stress).
• Service exposure time is cumulative.
• Chemistry and microstructure important.
• Attack typically slow, appears to have incubation
period before properties are affected.
• 6th edition API RP 941 published in 2004. The curves
show a temperature/hydrogen partial pressure safe
operating envelope for carbon and low alloy steels
based on experience.
• Biggest problem has been with 0.5Mo alloys.
• 300 Series SS, as well as 5, 9 and 12Cr alloys, are not
susceptible to HTHA at conditions normally seen in
refinery units.

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API 941 'Nelson Curves'

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Affected Units

• Hydro-processing units, such as


hydro-treaters (desulphurizers) and
hydro-crackers, catalytic reformers.
• Hydrogen producing units and
hydrogen cleanup units, such as
pressure swing absorption units,
are all susceptible to HTHA.
• Boilers (tubes in very high pressure
steam service).

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Appearance or Morphology of
Damage
• Damage moves from ID through the wall.
• Early stages of voids are detectable with
high power metallography (SEM) 15,000X.
• Intermediate stages can be found with
high quality optical metallography ,
showing voids and decarburization.
• Advanced stages can be found by
metallography showing fissures.
• In rare cases blisters can be observed due
to accumulation of molecular methane.
• The damage is typically inter-granular,
adjacent to pearlite in CS.

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Early Stages of H2 Micro-fissuring
(SEM)

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Micro-fissuring and Internal
Decarburization due to HTHA

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Hydrogen Blisters

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Embrittlement Effect of High
Temperature Hydrogen Damage

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Hydrogen Damage
Effect on Mechanical Properties

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Prevention/Mitigation
• US practice uses alloy steels with Cr and Mo to increase
carbide stability and thus minimize methane formation.
• European practice keeps Cr and Mo to a minimum, and
adds other carbide stabilizing elements such as
tungsten and vanadium.
• Normal design practice is to add a safety factor of 20-
30oC when using the API RP 941 curves.
• There have been several failures of C-0.5Mo steels in
refinery service conditions that were previously
considered safe. C-0.5Mo steel has therefore been
removed from the main set of API RP 941 curves and
the material is not recommended for new construction
in hot hydrogen service.
• Cladding with 300 Series SS will reduce ppH 2 at the clad
interface, but most practice ensures that the base metal
has adequate resistance to the service conditions.

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Inspection and Monitoring
• Advanced stages of damage in many cases appear to
be localized, challenging the ability of inspection.
• Ultrasonic techniques (AUBT) consisting of a
combination of backscatter, velocity ratio, and other
spectral analyses have been the most successful in
finding fissuring and/or serious cracking.
• In-situ metallography can only detect micro-fissuring,
fissuring and decarburization near the surface. Most
equipment has decarburized surfaces due to the
various heat treatments used during fabrication.
• VT for blisters on ID, but HTHA does not always give
blisters.
• PT, WFMT, and RT severely limited in their ability to
detect anything except advanced stages of damage.
• AET has been used in a few cases, but not a proven
method for the detection of damage.

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Graphitization

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Description of Damage
• Graphitization is a change in
microstructure of certain C and C-
0.5Mo steels after long term
exposure in temp. range 440 –
590oC.
• Carbide phases are unstable and
decompose into graphite nodules.
• In general, this phenomenon is not
commonly observed.
• Few failures directly attributable to
graphitization have been reported in
the Refining industry.

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Examples of Severe Graphitization
CS and C-½Mo

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Spheroidization

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Description of Damage

• Spheroidization is a change in
microstructure of steels after long
term exposure in 440 – 760oC temp.
range.
• Carbide phases are unstable and
change from normal plate-like form
(pearlite) to finely dispersed or large
agglomerated carbides.
• Generally accompanied by some loss
in strength and increase in ductility.

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Critical Factors
• Metal temp., exposure time and
microstructure.
• Spheroidization can occur in a few
hours at 550oC but may take several
years at 440oC.
• Assessment of spheroidization is
sometimes useful to establish
probable exposure temperature of
fire-damaged equipment.
• All commonly used grades of carbon
steel and low alloy steels are
affected.

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Temper Embrittlement

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Description of Damage
• Temper embrittlement is the reduction in
toughness due to a metallurgical change
that can occur in some low alloy steels as a
result of long term exposure in the
temperature range of about 350oC to 600oC.
• This change causes an upward shift in the
ductile-to-brittle transition temperature as
measured by Charpy impact testing.
• The loss of toughness is not evident at
operating temperature.
• Temper embrittled equipment is susceptible
to brittle fracture during start-up or
shutdown.

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Temper Embrittlement DBTT
Shift

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Affected Materials
• Primarily 2.25Cr-1Mo low alloy steel, 3Cr-
1Mo (to a lesser extent), and the high-
strength low alloy Cr-Mo-V rotor steels.
• Older generation 2.25Cr-1Mo materials
manufactured prior to 1972 may be
particularly susceptible.
• Some high strength low alloy steels are
also susceptible.
• The C-0.5Mo and 1.25Cr-0.5Mo alloy steels
are only slightly susceptible to temper
embrittlement, but their toughness can
degrade due to other mechanisms.

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Critical Factors

• Temper embrittlement = f (alloy composition,


thermal history, metal temperature and exposure
time)
• Detrimental elements are manganese, silicon,
phosphorus, tin, antimony, and arsenic.
• Higher strength alloys are more affected.
• Temper embrittlement rate and degree for
2.25Cr-1Mo steel are a function of temperature.
• Hydrogen embrittlement is more severe for a
temper embrittled steel.
• Low temperature toughness is affected, whereas
no concern at operating temperatures.

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Affected Units
• Temper embrittlement occurs in a variety
of process units after a long term exposure
to the critical temperature range.
• Equipment susceptible to temper
embrittlement is most often found in
hydro-processing units, particularly
reactors, hot feed/effluent exchanger
components, and hot HP separators.
• Other units include catalytic reforming
units (reactors and exchangers), FCC
reactor piping and internals.
• Coker and Visbreaking units.

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Appearance of Morphology of
Damage
• Temper embrittlement is a metallurgical
change that is not readily apparent and
can only be confirmed through impact
testing.

• Temper embrittlement can be identified


by an upward shift in the ductile-to-
brittle transition temperature measured
in a Charpy V-notch impact test, as
compared to the non-embrittled or de-
embrittled material.

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Prevention/Mitigation
• Existing Materials: Nothing can be done to prevent a
susceptible material from temper embrittling.
– To minimize the possibility of brittle fracture during start-
up and shutdown, only partial pressurization until the
Minimum Pressurization Temperature (MPT); these range
from 170oC to 40oC based on generation of steel.
– The effects of temper embrittlement can be temporarily
reversed by heating at 620oC for several hours and rapid
cooling; however, re-embrittlement will occur over time.
• New Materials
– Control chemistry of new alloys and weld materials
– 'J*' Factor for base weld - J* = (Si + Mn) x (P + Sn) x 10
{elements in wt%}
– 'X' Factor for weld metal - X = (10P +5Sb + 4Sn + Az)/100
{elements in ppm}
– Typical J* and X factors used for 2.25 Cr steel are 100 and
15, respectively.

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Inspection and Monitoring
• There is no inspection for Temper
Embrittlement.
• Install surveillance blocks of original
heats of the alloy steel material inside
the reactor. Samples are periodically
removed for impact testing to monitor
progress of temper embrittlement.
• Process conditions should be monitored
to ensure that a proper pressurization
sequence is followed to help prevent
brittle fracture due to temper
embrittlement.

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475oC Embrittlement

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Description of Damage
• 475oC embrittlement is a loss in toughness
due to metallurgical change that can occur
in Fe-Cr-Ni alloys containing ferrite when
exposed to temps. In range 320 – 540 oC.

• Results from formation of brittle inter-


metallic Cr-Ni phases known as 'alpha
prime'.

• Affected materials are 400 series S/S,


Duplex S/S, and 300 series S/S if they
contain ferrite, e.g. castings, welds, weld
overlay.

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Critical Factors
• Type of alloy, amount of ferrite phase,
and operating temp.
• Increasing ferrite will increase
susceptibility to damage.
• Primary consideration is operating time
and temp. within the critical range.
• Precipitation of embrittling inter-metallic
phase occurs most readily at approx.
475oC.
• Additional time is required to reach max.
embrittlement at temps. above or below
475oC.

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Affected Units or Equipment
• Most refining companies limit the
use of ferritic S/S to non-pressure
boundary applications because of
this damage mechanism, e.g.
fractionator trays, internals of high
temp. vessels used in FCC, crude,
vacuum and coker units.

• 475oC embrittlement is a
metallurgical change, not readily
apparent, and can only be confirmed
by metallography or impact testing.

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Sigma Phase Embrittlement

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Description of Damage

• A loss of fracture toughness due to


the formation of a phase known as
'sigma phase' in some stainless
steels as a result of high
temperature exposure.
• Not obvious from a visual inspection.
• Can result in cracking.
• Toughness can be glass-like.
• Also affects the creep ductility.

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Affected Materials

• 300 Series SS wrought metals, weld


metal and castings
• Cast 300 Series SS - due to high
ferrite content (10-40%)
• HK and HP alloys
• 400 Series SS and other ferritic and
martensitic SS with 17% Cr or more
(e.g. Types 430 and 440)
• Duplex stainless steels

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Critical Factors
• Alloy composition, time, temperature, cold work.
• Sigma forms at exposure temperatures in the range of
540oC to 950oC. Can occur during cooling from HT.
• Sigma forms most rapidly from the ferrite phase that
exists in 300 Series SS and duplex SS weld deposits.
• Sigma can also form in the 300 Series SS base metal
(austenite phase) but usually more slowly.
• The 300 Series SS can exhibit about 10% to 15% sigma
phase. Cast austenitic stainless steels can develop
considerably more sigma.
• Tensile and yield strengths and hardness increase slightly
vs solution annealed and ductility decreases moderately.
• Toughness is decreased significantly, especially at temps.
below 260oC
• Metallurgical charge is precipitation of hard, brittle inter-
metallic compound

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Fe-Cr Phase Diagram

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Affected Units

• Common examples include stainless steel


cyclones, piping ductwork and valves in
high temperature FCC Regenerator service.
• 300 Series SS weld overlays and tube-to-
tube-sheet attachment welds can be
embrittled during PWHT of the underlying
Cr-Mo base metal.
• Stainless steel heater components are
susceptible.
• HK and HP alloys in hydrogen plants,
reformer furnaces.

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Appearance or Morphology of
Damage
• Sigma phase embrittlement is a
metallurgical change that is not readily
apparent, and can only be confirmed
through metallographic examination and
impact testing.
• Damage appears in the form of cracking,
particularly at welds or in areas of high
restraint.
• Special etchants are needed to confirm
sigma phase and can have blocky and
needle-like appearance.
• At room temperature impact energy may be
less than 8 Joules.

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Prevention/Mitigation
• Use alloys that are resistant to sigma formation.
• Avoid exposing the material to the embrittling range.
• Take care at shutdown with SS.
• 300 Series SS can be de-sigmatized by solution
annealing at 1065oC for four hours followed by a
water quench. However, this is not practical for most
equipment and sigma will reform.
• Sigma phase in welds can be minimized by
controlling ferrite in the range of 4 to 10% (minimum
to prevent hot shortness during welding).
• For stainless steel weld overlay clad Cr-Mo
components, the exposure time to PWHT
temperatures should be limited wherever possible.

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Inspection and Monitoring

• There is no inspection for Sigma phase


embrittlement.
• Sample removal and Charpy testing are
most common method to determine if a
sample is embrittled.
• Install surveillance blocks of original
heats of the alloy. Samples are
periodically removed for impact testing to
monitor progress of sigma embrittlement.
• Most cases of embrittlement are found in
the form of cracking during turnarounds,
or during start-up or shutdown.

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Brittle Fracture

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Description of Damage

• Brittle fracture is the sudden rapid


fracture under stress (residual or
applied) where the material
exhibits little or no evidence of
ductility or plastic deformation.

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Affected Materials

• Carbon steels, low alloy steels,


particularly older steels.
• 400 Series SS or duplex SS also
susceptible.
• 300 Series if embrittled.

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Critical Factors (1/2)
When the critical combination of 3 factors
is reached, brittle fracture can occur:
• Material fracture toughness (resistance
to crack-like flaws).
• The size, shape and location of a defect.
• The magnitude of residual and applied
stresses on the flaw.

The 'Triangle of Integrity'

KIc   a
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USS Schenectady

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Critical Factors (2/2)

• Susceptibility to brittle fracture may be


increased by presence of embrittling phases.
• Steel cleanliness and grain size have a
significant influence on toughness and
resistance to brittle fracture.
• Thicker material sections also have a lower
resistance to brittle fracture due to the
higher constraints from tri-axial stresses at
crack tips.
• In most cases, brittle fracture occurs at a
temperature below the ductile - brittle
transition temperature.

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Affected Units
• Any unit, although most units operate at
temperatures above brittle fracture
concern, low temp. processes and those
light hydrocarbons that can auto-
refrigerate are most susceptible.
• Most vulnerable at start-up and shutdown
and hydro-test.
• Equipment built after 1986 least
vulnerable (UCS-66).
• Thick wall equipment, spheres, bullets,
etc. more vulnerable.
• Warmer climates not exempt from failures.

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Appearance or Morphology of
Damage
• Cracks will typically be straight, non-
branching, and largely devoid of any
associated plastic deformation (No shear
lips or localized necking around the crack).
• Fracture surface may have a 'chevron'
appearance.
• Microscopically, the fracture surface has a
cleavage appearance (limited inter-
granular cracking and micro-void
coalescence).
• Typically found starting at welds.

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Brittle Fracture Failure
Cockenzie boiler drum
TECHNOLOGY

© Copyright TWI Ltd., 2000 Session 2/8

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Prevention/Mitigation (1/2)
• New equipment - brittle fracture prevented
by using materials specifically designed for
low temp. operation, including upset and
auto-refrigeration events. (Materials with
controlled chemical composition, special heat
treatment, and impact test verification may
be required.

• Brittle fracture is an 'event' driven damage


mechanism. For existing materials, where the
appropriate combination of stress, fracture
toughness and flaw size govern probability of
the event, can use API 579 level 1 or 2.

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Prevention / Mitigation (2/2)
• Preventative measures to minimize
potential for brittle fracture in
existing equipment are limited to
controlling operating pressure and
temp., and observing ambient temps.
during start-up and shut down.
• Some reduction in likelihood of brittle
fracture may be achieved by:-
– PWHT on vessel
– Ensure no cold temp. hydro-testing
undertaken (e.g. 'warm' pre-stress).

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Inspection and Monitoring

• Can’t inspect for brittle fracture,


although can:

– inspect susceptible equipment for


flaws.

– monitor the embrittlement potential of


the material by sample removal or
hardness tests.

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Any
Questions ?
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