Inspection methods

Affected unit Affected equipment Affected material prevention Appearance

NDT DT

a) Graphitization is a change in the microstructure of certain carbon steels and

0.5Mo steels after long-term operation in the 800F to 1100F (427C to 593C)
range that may cause a loss in strength, ductility, and/or creep resistance. b) At Some grades of carbon steel and 0.5Mo
elevated temperatures, the carbide phases in these steels are unstable and may steels
decompose into graphite nodules. This decomposition is known as
graphitization
 Inspection methods
Affected unit Affected equipment Affected material prevention Appearance
 Damage due to loss of
Mechanisms Description of Damage loss of material property

damage mechanism

corrosion

loss of fracture toughness

crack

Formation of a metallurgical phase known as sigma phase decompose

loss of strength

formation of stress
loss of ductility
deformation

wear
Damage due to loss of material property
0

Evidence of Damage
damage mode failure mode

pinhole leak smalll leak

general thinning
large leak rupture

localized thinning pinhole leak smalll leak

transgranular

intergranular

scale formation

brittle fracture thermo mechanical fatigue creep

ductile fracture fatigue

cavitation oxidation

fretting

erosion
Affected Units Affected Equipment Affected Materials
 Critical Factors

caused by reactions

constituents of process streams

additives to process streams

contaminants in process streams

metal made up of

caused by temeratures

caused by sress
 Prevention / Mitigation

catalyst/neutraliser/inhibitor

micro structure

low temperatures/ambient/high temperatures

residual stress////cyclic stress

 a) Graphitization is a change in the microstructure of certain carbon steels and
0.5Mo steels after long-term operation in the 800F to 1100F (427C to 593C)
range that may cause a loss in strength, ductility, and/or creep resistance.
Metallurgical Failure b) At elevated temperatures, the carbide phases in these steels are unstable and
may decompose into graphite nodules. This decomposition is known as
graphitization.

Spheroidization is a change in the microstructure of steels after exposure in the

850F to 1400F range, where the carbide phases in carbon steels are unstable
and may agglomerate from their normal plate-like form to a spheroidal form, or
decompose from small, finely dispersed carbides in low alloy steels like 1Cr-0.5Mo to large
agglomerated carbides. Spheroidization may cause a loss in strength and/or creep
resistance.

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 650F to 1070F.
This change causes an upward shift in the ductile-to-brittle transition
loss of ductility
temperature as measured by Charpy impact testing. Although the loss of
toughness is not evident at operating temperature, equipment that is temper
embrittled may be susceptible to brittle fracture during start-up and shutdown

Strain aging is a form of damage found mostly in older vintage carbon steels and C-
0.5 Mo low alloy steels under the combined effects of deformation and aging at an
intermediate temperature. This results in an increase in hardness and strength with a
reduction in ductility and toughness.
 Advanced stages of damage Advanced stages of damage
Initial stage Damage

NDT DT NDT DT
Evidence of graphitization is most
effectively evaluated through
Advanced stages of damage
removal of full thickness samples Advanced stages of damage
related to loss in creep strength
Damage due to graphitization is for examination using related to loss in strength include
may include
not visible or readily apparent metallographic techniques. surface breaking cracks or creep
microfissuring/microvoid
Damage may occur midwall so that deformation that may be difficult
formation, subsurface cracking or
a) Spheroidization is not visible surface connected cracking. field replicas may be inadequate. to detect.
or readily apparent and can
only be observed through
metallography. b) In the case of the 5% to 9% Spheroidization can only be found
CrMo alloys, spheroidization is through field metallography or
The pearlitic phase undergoes
removal of samples for
a time dependant the process of transforming the
metallographic observation. A
transformation from partial to carbides from their original
reduction in tensile strength
complete finely dispersed morphology to and/or hardness may indicate a
spheroidization (Figure 43 large agglomerated carbides. spheroidized microstructure
and Figure 44).

a) A common method of
monitoring is to install blocks of
b) Temper embrittlement can be original heats of the alloy steel
identified by an upward shift in the material inside the reactor.
ductile-to-brittle transition Samples are periodically removed
temperature measured in a Charpy from these blocks for impact
a) Temper embrittlement is a
V-notch impact test, as compared testing to monitor/establish the
metallurgical change that is not
to the non-embrittled or de- ductile-brittle transition
readily apparent and can be
embrittled material (Figure 4-5). temperature. The test blocks
confirmed through impact testing.
Another important characteristic of should be strategically located
Damage due to temper
temper embrittlement is that there near the top and bottom of the
embrittlement may result in
is no effect on the upper shelf reactor to make sure that the test
catastrophic brittle fracture.
energy. material is exposed to both inlet
c) SEM fractographs of severely and outlet conditions.
temper embrittled material show b) Process conditions should be
primarily intergranular cracking monitored to ensure that a proper
due to impurity segregation at pressurization sequence is followed
grain boundaries. to help prevent brittle fracture due
to temper embrittlement.

Strain aging can result in the

formation of brittle cracks that are
revealed through detailed
Inspection and monitoring are not
metallurgical analyses, but
used to control strain aging.
damage most likely will not be
identified as strain aging until
fracture has already occurred.
a) Primarily hot-wall piping and equipment in the FCC, catalytic reforming b) Bainitic grades are less susceptible than coarse pearlitic grades.
and coker units. c) Few failures directly attributable to e) Where concentrated eyebrow graphitization occurs along heat-affected
graphitization have been reported in the refining industry. zones, the creep rupture strength may be drastically lowered. Slight to
d) Several serious cases of graphitization have occurred in the reactors moderate amounts of graphite along the heat-affected zones do not
Some grades of carbon steel and 0.5Mo
and piping of fluid catalytic cracking units, as well as with carbon steel appear to significantly lower room or high-temperature properties.
steels
furnace tubes in a thermal cracking unit and the failure of seal welds at the f) Graphitization seldom occurs on boiling surface tubing but did occur
bottom tube sheet of a vertical waste heat boiler in a fluid catalytic cracker. in low alloy C-0.5Mo tubes and headers during the 1940s. Economizer
A graphitization failure was reported in the long seam weld of a C-0.5Mo tubing, steam piping and other equipment that operates in the range of
catalytic reformer reactor/interheater line. temperatures of 850F to 1025F is more likely to suffer
a) Spheroidization can occur in piping and equipment aftergraphitization.
exposure to
temperatures above 850F All commonly used grades of carbon steel
c) Spheroidization affects hot wall piping and equipment in the FCC,
The loss in strength may be as high as about 30% but failure is not likely and low alloy steels including C-0.5Mo,1Cr-
catalytic reforming and coker units. Fired heater tubes in boilers or process
to occur except under very high applied stresses, in areas of stress Mo,1.25Cr-
units may be affected by a loss in creep strength, but equipment, in
concentration, or in combination with other damage mechanisms. 0.5Mo, 2.25Cr-1Mo, 3Cr-1Mo, 5Cr-0.5Mo,
general, is seldom renewed or repaired because of spheroidization
b) The loss in strength is usually accompanied by an increase in ductility and 9Cr-1Mo steels.
which allows for deformation at stress concentrations.

a) Primarily 2.25Cr-1Mo low alloy steel,

3Cr-1Mo (to a lesser extent), and the high-
strength low alloy Cr-Mo-V rotor steels.
b) Older generation 2.25Cr-1Mo materials
a) Temper embrittlement occurs in a variety of process units after long
manufactured prior to 1972 may be
term exposure to temperatures above 650F (343C). It should be noted
particularly susceptible.
that there have been very few industry failures related directly to temper
Some high strength low alloy steels are
embrittlement.
also susceptible.
b) Equipment susceptible to temper embrittlement is most often found in
c) The C-0.5Mo, 1Cr-0.5Mo and 1.25Cr-
hydroprocessing units,
0.5Mo alloy steels are not significantly
particularly reactors, hot feed/effluent exchanger components, and hot
affected by temper embrittlement.
HP separators. Other units with the potential for temper embrittlement
However, other high temperature damage
include catalytic reforming units (reactors and exchangers), FCC reactors,
mechanisms promote metallurgical
coker and visbreaking units.
changes that can alter the toughness or
c) Welds in these alloys are often more susceptible than the base metal
high temperature ductility of these
and should be evaluated.
materials. Refer to API 934-C and API 934-
D for additional information.
d) Weld materials are generally more
affected than todays low-impurity base
materials.

Mostly older (pre-1980s) carbon steels

with a large grain size and C-0.5 Mo low
alloy steel.
a) The most important factors that affect graphitization are the chemistry, stress, temperature, and time of
exposure.
b) In general, graphitization is not commonly observed. Some steels are much more susceptible to
graphitization than others, but exactly what causes some steels to graphitize while others are
resistant is not well understood. It was originally thought that silicon and aluminum content played a major role
but it has been shown that they have negligible influence on graphitization.
c) Graphitization has been found in low alloy C-Mo steels with up to 1% Mo. The addition of about 0.7%
chromium has been found to eliminate graphitization.
d) Temperature has an important effect on the rate of graphitization. Below 800F (427C), the rate is
extremely slow. The rate increases with increasing temperature.
e) There are two general types of graphitization. First is random graphitization in which the graphite nodules
are distributed randomly throughout the steel. While this type of graphitization may lower the room-temperature
tensile strength, it does not usually lower the creep resistance.

f) The second and more damaging type of graphitization results in chains or local planes of concentrated
graphite nodules. This form of graphitization can result in a significant reduction in load bearing capability while
increasing the potential for brittle fracture along this plane. The two forms of this type of graphitization are weld
heat-affected zone graphitization and non-weld graphitization.
1) Weld heat-affected zone graphitization is most frequently found in the heat-affected zone adjacent to welds
in a narrow band, corresponding to the low temperature edge of the heat- affected zone. In multipass welded
butt joints, these zones overlap each other, covering the entire cross-section. Graphite nodules can form at the
low temperature edge of these heat-affected
exposure zones, resulting in a band
areofcritical
weak factors.
graphite extending across the
a) Metal chemistry, microstructure, time, and temperature
section. Because of its appearance, this graphite formation within heat-affected
b) The rate of spheroidization depends on the temperature and initial microstructure. zones is called eyebrowcan occur
Spheroidization
graphitization.
in a few hours at 1300F (552C), but may take several years at 850F (454C).
2) Non-weld steels
c) Annealed graphitization
are moreisresistant
a form oftolocalized graphitization
spheroidization that sometimes
than normalized steels.occurs along planes
Coarse-grained of localized
steels are more
yielding in steel. It also occurs in a chain-like manner in regions that have experienced
resistant than fine-grained. Fine grained silicon-killed steels are more resistant than significant plastic
deformation as a result of cold working operations or bending.
aluminum-killed.
g) The extent and degree of graphitization is usually reported in a qualitative fashion (none, slight, moderate,
severe). Although it is difficult to predict the rate at which it forms, severe heat-affected zone graphitization can
develop in as little as five years at service temperatures above 1000F .Very slight graphitization would be
expected to be found after 30 to 40 years at 850F, Time-Temperature-Transformation curves for heat-affected
zone graphitization can be
found in Reference 2.

a) Alloy steel composition, thermal history, metal temperature and exposure time are critical factors.
b) Susceptibility to temper embrittlement is largely determined by the presence of the alloying elements
manganese and silicon, and the tramp elements phosphorus, tin, antimony, and arsenic. The strength level and
heat treatment/fabrication history should also be considered.
c) Temper embrittlement of 2.25Cr-1Mo steels develops more quickly at 900F (482C) than in the 800F to
850F (427C to 440C) range, but the damage is more severe after long-term exposure at 850F (440C).
d) Some embrittlement can occur during fabrication heat treatments, but most of the damage occurs over
many years of service in the embrittling temperature range.
e) This form of damage will significantly reduce the structural integrity of a component containing a crack-like
flaw. An evaluation of the materials toughness may be required depending on the flaw type, the severity of the
environment, and the operating conditions, particularly in hydrogen service.

a) Steel composition and manufacturing process determine steel susceptibility.

b) Steels manufactured by the Bessemer or open hearth process contain higher levels of critical
impurity elements than newer steels manufactured by the Basic Oxygen Furnace (BOF) process.
c) In general, steels made by BOF and fully killed with aluminum will not be susceptible. The effect is found in
rimmed and capped steels with higher levels of nitrogen and carbon, but not in the modern fully killed carbon
steels manufactured to a fine grain practice.
d) Strain aging effects are observed in materials that have been cold worked and placed into service at
intermediate temperatures without stress relieving.
e) Strain aging is a major concern for equipment that contains cracks. If susceptible materials are plastically
deformed and exposed to intermediate temperatures, the zone of deformed material may
become hardened and less ductile. This phenomenon has been associated with several vessels that
have failed by brittle fracture.
f) The pressurization sequence versus temperature is a critical issue to prevent brittle fracture of susceptible
materials.
g) Strain aging can also occur when welding in the vicinity of cracks and notches in a susceptible material.
Graphitization can be prevented by using chromium containing low alloy steels for long-term operation above
800F.

Spheroidization
a) is difficult to prevent except by minimizing long-term exposure to elevated temperatures.
Existing Materials
1) Temper embrittlement cannot be prevented if the material contains critical levels of the embrittling
impurity elements and is exposed in the embrittling temperature range.
2) To minimize the possibility of brittle fracture during startup and shutdown, many refiners use a
pressurization sequence to limit system pressure to about 25 percent of the maximum design pressure for
temperatures below a Minimum Pressurization Temperature (MPT). Note that MPT is not a single point but
rather a pressure-temperature envelope which defines safe operating conditions to minimize the likelihood of
brittle fracture.
3) MPTs generally range from 350oF (171oC) for the earliest, most highly temper embrittled steels, down
to 125oF (52oC) or lower for newer, temper embrittlement resistant steels (as required to also minimize
effects of hydrogen embrittlement).
4) If weld repairs are required, the effects of temper embrittlement can be temporarily reversed (de-
embrittled) by heating at 1150F (620C) for two hours per inch of thickness, and rapidly cooling to room
temperature. It is important to note that re-embrittlement will occur over time if the material is re-exposed
to the embrittling temperature range.
b) New Materials
1) The best way to minimize the likelihood and extent of temper embrittlement is to limit the acceptance
levels of manganese, silicon, phosphorus, tin, antimony, and arsenic in the base metal and welding
consumables. In addition, strength levels and PWHT procedures should be specified and carefully controlled.
2) A common way to minimize temper embrittlement is to limit the "J*" Factor for base metal and the "X"
Factor for weld metal, based on material composition as follows:
J* = (Si + Mn) x (P + Sn) x 104 \'7belements in wt%\'7d

X = (10P + 5Sb + 4Sn + As)/100 \'7belements in ppm\'7d

3) Typical J* and X factors used for 2.25 Cr steel are a maximum of 100 and 15, respectively. Studies have
also shown that limiting the (P + Sn) to less than 0.01% is sufficient to minimize temper embrittlement
because
a) Strain (Si + Mn)
aging control
is not the rate
an issue of embrittlement.
for newer steels that contain low levels of interstitial impurity elements and
4) A newer
sufficient and less
aluminum widely used
(>0.015 wt%)factor called
to fully the Equivalent
deoxidize the steel.Phosphorus content has been developed for
base metal
b) For olderand weld metal
equipment, and care
extra is defined
shouldasbefollows
taken is togiven
avoidby:
the potentially damaging effects of strain aging
byP avoiding
= C + Mnstressing
+ (Mo Cr) or /3 + Si / 4 +equipment
pressurizing 3.5 x [(10 until
x P +the(5 metal
x Sb) + (4 x Sn) + reaches
temperature As) \'7belements
an in wt%\'7d
5)acceptable
Expert metallurgical
level whereadvice should
the risk be solicited
of brittle fracturetois determine
low. Refer acceptable
to curve Acomposition,
in UCS 66 oftoughness
the ASMEand
strength levels,VIII,
Code Section as well as appropriate
Division welding, fabricating
I for pressurization temperatures and of heat treating
vessels procedures
susceptible for new
to strain loweffects.
aging alloy
steel heavy wall
c) Applying PWHTequipment and lowofalloy
to weld repairs equipment
susceptible operating
materials will in the temper
eliminate the embrittlement
effects of strainand/or
aging.creep
range
Where PWHT is not possible, buttering should be considered to minimize welding on old material
under restraint.
885F (475C) embrittlement is a loss in toughness due to a metallurgical change
that can occur in alloys containing a ferrite phase, as a result of exposure in the
temperature range 600F to1000F (316C to 540C).

Formation of a metallurgical phase known as sigma phase can result in a

loss of fracture toughness in some stainless steels as a result of high
temperature exposure.

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.
 samples removed from service is
metallurgical
of highchange
restraint.that is not
the most positive indicator of a
readily
c) Testsapparent
performed withon
problem.
sigmatized 300 Seriesbe
metallography but can SS a)b)Physical
Most casestesting of samples
of embrittlement
confirmed
(304H)through
samples bend
from orFCC
impact removed from service is the
are found in the form of cracking
testing (Figure
regenerator internals4-6).have most positive indicator of a
during turnarounds, or during
b) The existence
shown that even with of 885F
10% problem.
startup or shutdown when the
embrittlement
sigma can
formation, be
theidentified
Charpy by b)isMost cases
a) Cracks material below aboutof200F
an increase in will typically
hardness be
in affected
impact
straight,toughness was 39 and
non-branching, ft-lbs embrittlement
(93C) and theare effects
found ofin the
areas.
largely (53 J)
devoid at form of cracking in
embrittlement areboth
Failure during bendoftesting
any or
1200F (649C). wrought mostanddetrimental.
cast (welded)
associated
impact testing plastic deformation
of samples removed
d) For the 10% sigmatized c) An during
metals increase in hardness isor
turnarounds,
from servicefine
(although is the most
shear positive
lips may
specimen, the the
values another
a) method
Inspection is of shutdown
notevaluating
normally
indicator
be foundofalong885F freeranged
embrittlement.
edge of during startup or
885F embrittlement.
from 0% ductility at room used
when the material is fracture.
to mitigate brittle below
the fracture, or localized
temperature to 100% b) Susceptible vessels should
about 500F
necking around the crack
at 1200F (649C). be(260C)
inspected
andfor pre-existing
(Figure 4-12 to Figure Thus,
4-16). the effects of
although the impact toughness flaws/defects.
embrittlement are most
b) Microscopically, the fracture
is reduced
surface at willhigh temperature,
be composed pronounced.
largely of cleavage,the with limited
specimens broke in a
intergranular cracking and100%
very
ductile fashion, indicating
little microvoid coalescence. that
the wrought material is still
suitable at operating
temperatures. See Figures 4-7
to 4-11.
e) Cast austenitic stainless
steels typically have high
ferrite/sigma content (up to
40%) and may have very poor
high temperature ductility.
 a) Equipment
are exposed to themanufactured to the ASME
embrittling temperature Boiler and Pressure Vessel
range.
Code, Section
b) Most refining companies limit theVIII,
use Division
of ferritic1,
stainless steels to non-
pressure
priorboundary
to the December 1987 Addenda, were made with limited
applications because of this damage
restrictions on notch mechanism.
toughness for
c) vessels
Commonoperating
examples at include fractionator
cold temperatures. traysHowever,
and internals
this in highnot
does a) 400 Series SS (e.g., 405, 409, 410,
temperature vesselsmean used in FCC, crude, vacuum
that all vessels fabricated and coker units. Typical a) 300 Series SS430
410S, wrought metals, weld
and 446).
failures include cracking when attempting to weld or to
prior to this date will be subject to brittle fracture. Many designers metal, and castings.
b) Duplex Cast 300
stainless steels such Series SS
as Alloys
a) Common
straighten
specifiedbent, examples
upset tower
supplemental include
trays
impact ofstainless
Type onsteel
tests409 and cyclones,
410
equipment thatpiping
material (occurs
was including the 2304
2205, HK andandHP alloys are
2507
ductwork
often and valves
with vacuum tower in high temperature
intended to be in cold service. FCC Regenerator service. especially susceptible to sigma
trays
b) of this material).
b) 300 Series
Equipment SS weld
made tooverlays
the same and tube-to-tubesheet
code after this date wereattachment
subject formation because of their high (10% to
d) Other examples weldsincludecan
duplex
be stainless steel
embrittled heat exchanger tubes
during 40%) ferrite content.
to the requirements of UCS 66
and otherPWHTcomponents exposed
treatment of theto temperatures
underlying abovebase
CrMo 600F (316C) for
metal. b) The 400 Series SS and other ferritic
extended time periods.
(impact exemption curves).
c) Stainless steel heater tubes are susceptible and can be
c) Most processes run at elevated temperature so the main and martensitic
Carbon SS with
steels and 17% steels
low alloy Cr or more
are
embrittled.
concern is for brittle fracture during startup, shutdown, or are also susceptible (e.g., Types
of prime concern, particularly older 430
hydrotest/tightness testing. Thick wall equipment on any unit should steels. 400and 440).SS are also
Series
be considered. c) Duplex
susceptible. steels
stainless
d) Brittle fracture can also occur during an autorefrigeration event
in units processing light
hydrocarbons such as methane, ethane/ethylene,
propane/propylene, or butane. This includes
alkylation units, olefin units and polymer plants (polyethylene and
polypropylene). Storage
bullets/spheres for light hydrocarbons may also be susceptible.
e) Brittle fracture can occur during ambient temperature
hydrotesting due to high stresses and low toughness at the testing
temperature.
 b)
c) Increasing
Sigma phase amounts
occursof in
ferrite phase
ferritic increase
(Fe-Cr), susceptibility
martensitic to damage
(Fe-Cr), when(Fe-Cr-Ni)
austenitic operating in andtheduplex
high stainless
temperature
steelsrange
whenofexposed
concern. to A dramatic
temperaturesincrease in in
thethe ductile-to-brittle
range of 1000F to transition
1700Ftemperature will occur.
(538C to 927C).
c) A primary consideration
Embrittlement canisresult
operating time at temperature
by holding within or cooling within through
the critical
thetemperature
transformationrange.range.
Damage
d) Sigmais cumulative
forms most and resultsfrom
rapidly from the
the ferrite
precipitation
phaseofthatan embrittling
exists in 300 intermetallic
Series SSphase that occurs
and duplex most
SS weld
readily at approximately
deposits. It can also885F
form (475C).
in the 300 Additional
Seriestime is required
SS base metalto(austenite
reach maximumphase) but usually more
embrittlement at temperatures above or below 885F (475C). For example, many thousands of
slowly.
hours
e) The 300 Series SS can exhibit about 10% to 15%(316C).
may be required to cause embrittlement at 600F sigma phase. Cast austenitic stainless steels can
d) Since
a)885oF
For aembrittlement
material containing a flaw, develop considerably
brittle fracture can occur.more sigma. are three important factors: 1)
can occur in a relatively short period of time,Following
it is often assumed that
The Materialmaterials
fracture that
toughness (resistance f)
totemperatures
crack like flaws)
susceptible have been exposed to in theas measured
700F in a(371C
to 1000F Charpyto
Formation
impact test;of sigma phase in austenitic stainless steels can also occur in a few hours, as evidenced by
538C) range are affected.
theThe
2)
e) known
The size,tendency
effect shape and
on toughnessforstress
sigma to form if an
is notconcentration
pronounced at austenitic
effect of a stainless
the operating flaw; steel isbut
temperature, subjected to aatpost
is significant lowerweld heat
temperatures
3) The amount experienced
of residualduring
andplant treatment
shutdowns,
applied stresses at 1275F
startups
on theor (690C).
upsets.
flaw.
b) g) The tensile
f) Embrittlement
Susceptibility and
can
to yield
result
brittle strength
from tempering
fracture mayof sigmatized
at increased
be stainless
higher temperatures steels
or byincreases
by the presence holding slightly
within
of embrittling compared
or cooling
phases. with
through the
solution
transformation annealed
range. material. This increase in strength is accompanied
c) Steel cleanliness and grain size have a significant influence on toughness and resistance to brittle by a reduction in ductility
fracture.(measured by percent elongation and reduction in area) and a slight increase in hardness.
h) Stainless steels with
d) Thicker material sigma
sections can
also havenormally withstand
a lower resistancenormal operating
to brittle stresses,
fracture but upon
due to higher cooling to
constraint
temperatures below about 500F (260C)
which increases triaxial stresses at the crack tip. may show a complete lack of fracture toughness as
measured in a Charpy impact test. Laboratory tests of embrittled weld metal have shown
e) In most cases, brittle fracture occurs only at temperatures below the Charpy impact transition a complete
lack oftransition
temperature (or ductile-to-brittle fracture toughness below
temperature), the1000F
point at(538C)
which the toughness of the
material drops off sharply. i)
The metallurgical change is actually the precipitation of a hard, brittle intermetallic compound that
can also render the material more susceptible to intergranular corrosion. The precipitation rate
increases with increasing chromium and molybdenum content.
a) The best way to prevent 885F embrittlement is to use low ferrite or non-ferritic alloys, or to avoid
exposing the susceptible
a) The best material
way to prevent to the
sigma embrittling
phase range.
embrittlement is to use alloys that are resistant to sigma
b) It is possible formation
to minimizeortheto effects of embrittlement
avoid exposing through
the material tomodifications in the
the embrittling chemical
range.
a)composition
For new of the alloy,
equipment, however,
brittle resistant
fracture is material
best may
prevented notbyalways
using be readily
materials
b) The lack of fracture ductility at room temperature indicates that care should be available in most
specifically designed
taken for
to avoid
commercial
low forms.
temperature operation including upset and autorefrigeration events. Materials
application of high stresses to sigmatized materials during shutdown, as a brittle fracture could with controlled
c) 885F embrittlement
chemical composition, is special
reversible by treatment
heat heat treatment
andto dissolve
impact precipitates,
test verificationfollowed
may be byrequired.
rapid cooling.
Refer
result.
The de-embrittling heat treatment to UCS temperature is typically
66 in Section VIII 1100F
of the ASME (593C) or
BPV Code.higher and may not be
c) The 300 Series SS can be de-sigmatized by solution annealing at 1950F (1066C) for four
practical for many equipment items. If the de-embrittled component is exposed to the same
b) Brittle fracture
hours is an
followed byevent
a water driven
quench. damage
However, mechanism.
this is notFor existing
practical formaterials, where the right
most equipment.
service conditions it will re-embrittle faster than it did initially.
combination
d) Sigma phase of stress,
in weldsmaterial
can be toughness
minimized and flaw size govern
by controlling thethe
ferrite in probability
range of of
5%the
to event,
9% for an
Type
engineering study can be performed in accordance 347 with API 579-1/ASME FFS-1 , Section 3, Level 1
and somewhat less ferrite for Type 304. The weld or 2.metal ferrite content should be limited to the
c) Preventative
stated maximum measures to minimize
to minimize the potential
sigma formation forservice
during brittle fracture in existing
or fabrication, equipment
and must are
meet the
limited to controlling the operating conditions (pressure, temperature), minimizing
stated minimum in order to minimize hot short cracking during welding. pressure at
e) For stainless steel weld overlay cladambient
Cr-Mo components, the exposure time to PWHT
temperatures duringtemperatures
startup and shutdown,
should be and periodic
limited inspection
wherever at high stress locations.
possible.
d) Some reduction in the likelihood of a brittle fracture may be achieved by:
1) Performing a post weld heat treatment (PWHT) on the vessel if it was not originally done during
manufacturing; or if the vessel has been weld repaired/modified while in service without the
subsequent PWHT.
2) Perform a warm pre-stress hydrotest followed by a lower temperature hydrotest to extend the
Minimum Safe Operating Temperature (MSOT) envelope.
 Mechanisms Description of Damage Affected Units

a) Primarily hot-wall piping and equipment in the FCC, catalytic reforming

and coker units. c) Few failures directly attributable to
graphitization have been reported in the refining industry.
Strain aging is a form of damage found mostly in older vintage carbon steels
d) Several serious cases of graphitization have occurred in the reactors
and C-0.5 Mo low alloy steels under the combined effects of deformation and
Metallurgical Failure and piping of fluid catalytic cracking units, as well as with carbon steel
aging at an intermediate temperature. This results in an increase in hardness
furnace tubes in a thermal cracking unit and the failure of seal welds at the
and strength with a reduction in ductility and toughness.
bottom tube sheet of a vertical waste heat boiler in a fluid catalytic cracker.
A graphitization failure was reported in the long seam weld of a C-0.5Mo
catalytic reformer reactor/interheater line.

Spheroidization is a change in the microstructure of steels after exposure in

the 850F to 1400F range, where the carbide phases in carbon steels are c) Spheroidization affects hot wall piping and equipment in the FCC,
unstable and may agglomerate from their normal plate-like form to a catalytic reforming and coker units. Fired heater tubes in boilers or process
spheroidal form, or from small, finely dispersed carbides in low alloy steels units may be affected by a loss in creep strength, but equipment, in
like 1Cr-0.5Mo to large agglomerated carbides. Spheroidization may cause a general, is seldom renewed or repaired because of spheroidization
loss in strength and/or creep resistance.
 Affected Equipment Affected Materials

Strain aging is most likely to occur in thick wall vessels manufactured from
Mostly older (pre-1980s) carbon steels
susceptible materials that have not been stress relieved.
with a large grain size and C-0.5 Mo low
alloy steel.

a) Spheroidization can occur in piping and equipment after exposure to

temperatures above 850F All commonly used grades of carbon steel
The loss in strength may be as high as about 30% but failure is not likely and low alloy steels including C-0.5Mo,1Cr-
to occur except under very high applied stresses, in areas of stress Mo,1.25Cr-
concentration, or in combination with other damage mechanisms. 0.5Mo, 2.25Cr-1Mo, 3Cr-1Mo, 5Cr-0.5Mo,
b) The loss in strength is usually accompanied by an increase in ductility and 9Cr-1Mo steels.
which allows for deformation at stress concentrations.
 Critical Factors

a) Steel composition and manufacturing process determine steel susceptibility.

b) Steels manufactured by the Bessemer or open hearth process contain higher levels of critical impurity
elements than newer steels manufactured by the Basic Oxygen Furnace (BOF) process.
c) In general, steels made by BOF and fully killed with aluminum will not be susceptible. The effect is found in
rimmed and capped steels with higher levels of nitrogen and carbon, but not in the modern fully killed carbon
steels manufactured to a fine grain practice.
d) Strain aging effects are observed in materials that have been cold worked and placed into service at
intermediate temperatures without stress relieving.
e) Strain aging is a major concern for equipment that contains cracks. If susceptible materials are plastically
deformed and exposed to intermediate temperatures, the zone of deformed material may become hardened and
less ductile. This phenomenon has been associated with several vessels that have failed by brittle fracture.
f) The pressurization sequence versus temperature is a critical issue to prevent brittle fracture of susceptible
materials.
g) Strain aging can also occur when welding in the vicinity of cracks and notches in a susceptible material.

a) Metal chemistry, microstructure, exposure time, and temperature are critical factors.
b) The rate of spheroidization depends on the temperature and initial microstructure. Spheroidization can occur
in a few hours at 1300F (552C), but may take several years at 850F (454C).
c) Annealed steels are more resistant to spheroidization than normalized steels. Coarse-grained steels are more
resistant than fine-grained. Fine grained silicon-killed steels are more resistant than
aluminum-killed.
 Prevention / Mitigation Appearance or Morphology of Damage

Initial stage Damage

a) Strain aging is not an issue for newer steels that contain low levels of interstitial impurity elements and
sufficient aluminum (>0.015 wt%) to fully deoxidize the steel.
b) For older equipment, extra care should be taken to avoid the potentially damaging effects of strain aging
Strain aging can result in the formation of brittle cracks that
by avoiding stressing or pressurizing equipment until the metal temperature reaches an acceptable level
are revealed through detailed metallurgical analyses, but
where the risk of brittle fracture is low. Refer to curve A in UCS 66 of the ASME Code Section VIII, Division
damage most likely will not be identified as strain aging until
I for pressurization temperatures of vessels susceptible to strain aging effects.
fracture has already occurred.
c) Applying PWHT to weld repairs of susceptible materials will eliminate the effects of strain aging. Where
PWHT is not possible, buttering should be considered to minimize welding on old material under restraint.

a) Spheroidization is not visible or readily apparent and

can only be observed through metallography.
The pearlitic phase undergoes a time dependant
Spheroidization is difficult to prevent except by minimizing long-term exposure to elevated temperatures. transformation from partial to complete
spheroidization (Figure 43 and Figure 44).
ce or Morphology of Damage Inspection and Monitoring

Advanced stages of damage Evidence of Damage Advanced stages of damage

Inspection and monitoring are not used to control strain aging.

b) In the case of the 5% to 9% CrMo alloys,

Spheroidization can only be found through field metallography or removal
spheroidization is the process of transforming the
of samples for metallographic observation. A reduction in tensile strength
carbides from their original finely dispersed
and/or hardness may indicate a spheroidized microstructure
morphology to large agglomerated carbides.
 a) Temper embrittlement occurs in a variety of process units after long
term exposure to temperatures above 650F (343C). It should be noted
that there have been very few industry failures related directly to temper
Temper embrittlement is the reduction in toughness due to a metallurgical
embrittlement.
change that can occur in some low alloy steels as a result of long term
b) Equipment susceptible to temper embrittlement is most often found in
exposure in the temperature range of about 650F to 1070F.
hydroprocessing units,
This change causes an upward shift in the ductile-to-brittle transition
particularly reactors, hot feed/effluent exchanger components, and hot
temperature as measured by Charpy impact testing. Although the loss of
HP separators. Other units with the potential for temper embrittlement
toughness is not evident at operating temperature, equipment that is temper
include catalytic reforming units (reactors and exchangers), FCC reactors,
embrittled may be susceptible to brittle fracture during start-up and
coker and visbreaking units.
shutdown
c) Welds in these alloys are often more susceptible than the base metal
and should be evaluated.
a) Primarily 2.25Cr-1Mo low alloy steel,
3Cr-1Mo (to a lesser extent), and the high-
strength low alloy Cr-Mo-V rotor steels.
b) Older generation 2.25Cr-1Mo materials
manufactured prior to 1972 may be
particularly susceptible.
Some high strength low alloy steels are
also susceptible.
c) The C-0.5Mo, 1Cr-0.5Mo and 1.25Cr-
0.5Mo alloy steels are not significantly
affected by temper embrittlement.
However, other high temperature damage
mechanisms promote metallurgical
changes that can alter the toughness or
high temperature ductility of these
materials. Refer to API 934-C and API 934-
D for additional information.
d) Weld materials are generally more
affected than todays low-impurity base
materials.
a) Alloy steel composition, thermal history, metal temperature and exposure time are critical factors.
b) Susceptibility to temper embrittlement is largely determined by the presence of the alloying elements
manganese and silicon, and the tramp elements phosphorus, tin, antimony, and arsenic. The strength level and
heat treatment/fabrication history should also be considered.
c) Temper embrittlement of 2.25Cr-1Mo steels develops more quickly at 900F (482C) than in the 800F to
850F (427C to 440C) range, but the damage is more severe after long-term exposure at 850F (440C).
d) Some embrittlement can occur during fabrication heat treatments, but most of the damage occurs over
many years of service in the embrittling temperature range.
e) This form of damage will significantly reduce the structural integrity of a component containing a crack-like
flaw. An evaluation of the materials toughness may be required depending on the flaw type, the severity of the
environment, and the operating conditions, particularly in hydrogen service.
 1) Temper embrittlement cannot be prevented if the material contains critical levels of the embrittling
impurity elements and is exposed in the embrittling temperature range.
2) To minimize the possibility of brittle fracture during startup and shutdown, many refiners use a
pressurization sequence to limit system pressure to about 25 percent of the maximum design pressure for
temperatures below a Minimum Pressurization Temperature (MPT). Note that MPT is not a single point but
rather a pressure-temperature envelope which defines safe operating conditions to minimize the likelihood of
brittle fracture.
3) MPTs generally range from 350oF (171oC) for the earliest, most highly temper embrittled steels, down
to 125oF (52oC) or lower for newer, temper embrittlement resistant steels (as required to also minimize
effects of hydrogen embrittlement).
4) If weld repairs are required, the effects of temper embrittlement can be temporarily reversed (de-
embrittled) by heating at 1150F (620C) for two hours per inch of thickness, and rapidly cooling to room
temperature. It is important to note that re-embrittlement will occur over time if the material is re-exposed
to the embrittling temperature range.
b) New Materials a) Temper embrittlement is a metallurgical change that is not
1) The best way to minimize the likelihood and extent of temper embrittlement is to limit the acceptance readily apparent and can be confirmed through impact
levels of manganese, silicon, phosphorus, tin, antimony, and arsenic in the base metal and welding testing. Damage due to temper embrittlement may result in
consumables. In addition, strength levels and PWHT procedures should be specified and carefully controlled. catastrophic brittle fracture.
2) A common way to minimize temper embrittlement is to limit the "J*" Factor for base metal and the "X"
Factor for weld metal, based on material composition as follows:
J* = (Si + Mn) x (P + Sn) x 104 \'7belements in wt%\'7d

X = (10P + 5Sb + 4Sn + As)/100 \'7belements in ppm\'7d

3) Typical J* and X factors used for 2.25 Cr steel are a maximum of 100 and 15, respectively. Studies have
also shown that limiting the (P + Sn) to less than 0.01% is sufficient to minimize temper embrittlement
because (Si + Mn) control the rate of embrittlement.
4) A newer and less widely used factor called the Equivalent Phosphorus content has been developed for
base metal and weld metal and is defined as follows is given by:
P = C + Mn + (Mo Cr) /3 + Si / 4 + 3.5 x [(10 x P + (5 x Sb) + (4 x Sn) + As) \'7belements in wt%\'7d
5) Expert metallurgical advice should be solicited to determine acceptable composition, toughness and
strength levels, as well as appropriate welding, fabricating and heat treating procedures for new low alloy
steel heavy wall equipment and low alloy equipment operating in the temper embrittlement and/or creep
range
 a) A common method of monitoring is to install blocks of original heats of
b) Temper embrittlement can be identified by an upward
the alloy steel material inside the reactor. Samples are periodically
shift in the ductile-to-brittle transition temperature measured
removed from these blocks for impact testing to monitor/establish the
in a Charpy V-notch impact test, as compared to the non-
ductile-brittle transition temperature. The test blocks should be
embrittled or de-embrittled material (Figure 4-5). Another
strategically located near the top and bottom of the reactor to make sure
important characteristic of temper embrittlement is that
that the test material is exposed to both inlet and outlet conditions.
there is no effect on the upper shelf energy.
b) Process conditions should be monitored to ensure that a proper
c) SEM fractographs of severely temper embrittled material
pressurization sequence is followed to help prevent brittle fracture due to
show primarily intergranular cracking due to impurity
temper embrittlement.
segregation at grain boundaries.