Beruflich Dokumente
Kultur Dokumente
Abstract
This section gives basic metallurgical information for Chevron engineers and
inspectors supporting upstream operations, pipelines, refineries, and chemical
plants.
Contents Page
310 Introduction
amount the hinged hammer travels after impact. The results of these tests correlate
reasonably well with the notch toughness.
Inclusions. Nonmetallic material contained in a solid metal.
Induction bending. The use of electric induction to heat a material to a high
temperature so it can be bent without introducing a significant amount of residual
stress in the material when it is cooled to room temperature.
Killed steel. Steel that has had silicon and sometimes aluminum added during the
melt to reduce oxygen so that the bubbling from carbon dioxide evolution is
stopped. This improves notch toughness. If only enough silicon is added to partially
stop bubbling the steel, the steel is referred to as semi-killed. Semi-killing gives
greater ingot yield but poorer impact properties than fully killed steel.
Martensite. The hard brittle structure formed by rapidly cooling steel from high
temperatures.
Modulus of elasticity. The relation between stress and strain in the elastic range.
MDMT (Minimum design metal temperature). The lowest temperature a piece of
equipment can safely be operated at without concern about brittle fracture.
Microstructure. The structure of a material revealed by viewing a polished and
etched metal under the microscope.
Normalizing. Heating a steel to a temperature high enough so that fine grains are
formed in the high temperature phase, and then cooling the steel rapidly enough so
that the fine grains are maintained, but not so rapidly that structures such as marten-
site are formed.
Notch toughness. The ability of a material to deform in the presence of a notch or
defect under tensile stress without failure below the tensile strength.
Pearlite. A structure seen in steel at high magnification that consists of alternate
layers of ferrite and iron carbide (cementite). Pearlite is formed by slow cooling
from elevated temperatures.
Precipitation hardening. Hardening (strengthening) of a material by heating in a
temperature range where a second phase precipitates.
Quench hardening. In steel, rapid cooling from elevated temperatures to form a
hard, brittle structure.
Quenched and tempered. In steel, having heated in an intermediate temperature
range to recover toughness while retaining the strength of the quenched material.
Recrystallization. Heating in a temperature range where fine grains form. The
formation of strain free grains results from cold worked material or a change in
crystal structure at high temperature.
Residual stress. The stress left in a material after all loads are removed. Commonly
caused by welding or cold working.
Sigma phase embrittlement. The formation phase called sigma at high tempera-
ture in alloys containing iron and chromium. This phase tends to make a material
brittle at room temperature and slightly above.
Spheroidizing. In steel, the causing of iron carbide to form spheres as a result of
exposure to high temperatures.
Strain, elastic. The change in dimensions under load that is recovered after removal
of the load.
Strain, plastic. The change in dimensions under load that is permanent after the
load is removed.
Strain hardening. The increase in hardness (strength) as a result of permanent
deformation.
Stress relief. Heating a material to a temperature, holding it at that temperature for a
length of time, then followed by slow cooling so that most of the residual stresses
are removed.
Temper. See quenched and tempered.
Temper embrittlement. Heating of steel, most commonly Cr - Mo steel, in a range
where undesirable impurities diffuse to the grain boundaries causing a lost in tough-
ness at room temperature and slightly above.
Transition Temperature. The temperature where the fracture surface of an impact
test specimen is brittle and half ductile. Thus, the material is considered resistant
(but not immune) to brittle fracture above this temperature and not resistant to brittle
fracture below.
Ultimate tensile strength. The stress at which a material will fracture in a ductile
manner under a short-term load.
Upper Shelf in impact strength tests. The temperature range where the fracture
surface of an impact test specimen is fully ductile. Thus, the material is considered
immune to brittle fracture in this range. Conversely, the Lower Shelf is the tempera-
ture range where the fracture surface is completely brittle. Thus, the material is
considered brittle in this range.
Yield strength. The maximum stress a material can withstand without significant
permanent deformation.
Crystalline Structure
All metals have crystalline structures. The photomicrograph in Figure 300-1 illus-
trates the crystalline structure (microstructure) typical of carbon steels. The figure
shows the irregular detail, texture, and variation in individual grains that are each
separated by the irregular lines (grain boundaries). While crystals are regular in
atomic structure, grains are crystals with irregular boundaries resulting when the
growth of each is impacted by the growth of other grains, randomly precipitating as
the liquid freezes to a crystalline solid. Grain boundaries frequently become impor-
tant to metallurgists diagnosing problems because of both the physical and chem-
ical discontinuities at the boundaries. In addition, atomic irregularities within the
crystals can be significant, but usually they have their greatest effect on the macro-
scopic properties of particular metals.
Chemical Composition
Virtually all metals used in our business are solutions or mixtures of several
elements. Solution implies that the atoms are evenly distributed throughout the
metal while the phases in a metal are not usually evenly distributed. Many metals
exist in different phases at different temperatures, some with mixed phases.
For example, the most common material we use is carbon steel, a solution of iron,
carbon, and frequently minor percentages of other elements such as manganese and
molybdenum. Most steels also have trace amounts of several of the following: phos-
phorous, sulfur, silicon, copper, nickel, aluminum, chromium, vanadium, colum-
bium, titanium. Carbon steel also contains a mixture of phases, with a separate
phase of non-dissolved iron carbide. Figure 300-2 shows the chemistry for some
typical steel grades used in industry pressure vessel shells.
Fig. 300-2 Chemical Requirements (from ASTM A 516 (p.248, ASTM Vol. 01.04, 1998 Standard) (Copyright ASTM.
Reprinted with permission.)
Composition, %
Grade 55 Grade 50 Grade 65 Grade 70
Elements [Grade 380] [Grade 415] [Grade 450] [Grade 485]
Carbon, max(1):
1/2 in. [12.5 mm] and under 0.18 0.21 0.24 0.27
Over 1/2 in. to 2 in. [12.5 to 50 mm], incl 0.20 0.23 0.26 0.28
Over 2 in. to 4 in. [50 to 100 mm], incl 0.22 0.25 0.28 0.30
Over 4 to 8 in. [100 to 200 mm], incl 0.24 0.27 0.29 0.31
Over 8 in. [200 mm] 0.26 0.27 0.29 0.31
Manganese:
1/2 in. [12.5] and under:
Heat analysis(2) 0.60-0.90 0.60-0.90 0.85-1.20 0.85-1.20
Product analysis(2) 0.55-0.98 0.55-0.98 0.79-1.30 0.79-1.30
Over 1/2 in [12.5]:
Heat analysis 0.60-1.20 0.85-1.20 0.85-1.20 0.85-1.20
Product analysis 0.55-1.30 0.79-1.30 0.79-1.30 0.79-1.30
Phosphorus, max(1) 0.035 0.035 0.035 0.035
(1)
Sulfur, max 0.035 0.035 0.035 0.035
Silicon:
Heat analysis 0.15-0.40 0.15-0.40 0.15-0.40 0.15-0.40
Product analysis 0.13-0.45 0.13-0.45 0.13-0.45 0.13-0.45
(1) Applies to both heat and product analyses.
(2) Grade 60 plates 1/2 in. [12.5 mm] and under in thickness may have 0.85-1.20% manganese on heat analysis, and 0.79-1.30% manganese
on product analysis.
Other commonly used alloys have unique properties due to chemistry and the pres-
ence of other phases. The particular chemistry or phase distribution in an alloy gives
it the ability to resist particular corrosion mechanisms or high temperature effects in
various applications. Common alloys include low alloy steels (low chrome-molyb-
denum carbon steels), stainless steels, copper alloys, and high chrome and nickel
alloys. Occasionally, titanium and other unique materials are used in alloys. By far,
the most common metals used in the petrochemical industry are carbon and stain-
less steels.
Phase
The primary phases in carbon steel and stainless steel are ferrite or austenite. The
atoms in a ferrite phase are arranged in a regular pattern called a body centered
cubic structure shown in Figure 300-3. The atoms in the austenite phase are
arranged in another regular pattern called face centered cubic shown in
Figure 300-4. These terms are of both practical and theoretical importance. Carbon
steel is predominately ferrite (with some iron carbide) while many commonly used
stainless steels (300 series) are austenitic (or at least mostly austenitic) at ambient
and normal operating temperatures. Ferritic materials are magnetic, and austenitic
are not (thus a magnet is often used to distinguish between ferritic and austenitic
materials).
Fig. 300-3 Ferrite Phase (Body Centered Cubic) (From Fig. 300-4 Austenite Phase (Face-Centered Cubic)
Structure and Properties of Engineering (From Structure and Properties of Engi-
Materials, Fourth Edition, 1977, McGraw- neering Materials, Fourth Edition, 1977,
Hill Book Company. Used with permission.) McGraw-Hill Book Company. Used with
permission)
Cast Irons
Cast irons-mostly iron with typically a few percent of carbon-are even less expen-
sive than carbon steel. However, the high level of carbon is in the form of graphite
flakes or nodules. These nodules essentially cause the material to behave as if it
were full of small cracks, and so it is very brittle. Particularly for fire safety reasons,
we therefore rarely use cast irons except for water service.
315 Some Features of the Most Commonly Used Pressure Vessel Steels
SA-516 Grade 70 and SA-285 Grade C are the two most widely used plate steels for
pressure vessels. SA-285 is not made to fine grain practice and can have compara-
tively poor toughness, so its use is generally limited to lower pressure and thinner
wall vessels up to " thick. SA-516 Gr. 70 has better fracture toughness, particu-
larly in heavy sections, since it is made to fine grain practice and is required to have
a normalizing heat treatment if thicker than 1". For this reason, today SA-516
Gr.70 is the workhorse steel used for most moderate and high pressure services
where section thickness is greater than ".
SA-201 and SA-212 plate steels were commonly used prior to 1968, when they
were replaced by SA-515 and SA-516 specifications. The SA-201 Grades A & B
had minimum tensile strengths of 55 ksi and 60 ksi, and the SA-212 Grades A & B
had minimum tensile strengths of 65 and 70 ksi. SA-212 had slightly higher limits
for carbon content and a lower ductility requirement to accommodate its higher
strength. SA-201 and SA-212 could either be ordered for low temperature service
(meaning fine grain practice and probably a normalizing heat treatment) or for high
temperature service (meaning coarse grain practice for better high temperature
strength, but lower toughness). Since SA-201 and SA-212 steels may have either
high or low fracture toughness, Chevron assigns them to Curve A of ASME Section
VIII Division I, Figure UCS-66 unless we know enough about the production and
heat treatment history to be confident of their toughness. Pressure vessels made
from these steels often have higher minimum pressurization temperatures than most
modern vessels.
The modern equivalent specifications are organized differently. SA-515 and SA-516
both have four grades: 55, 60, 65, and 70 ksi minimum tensile strengths. SA-515
steel is made to coarse grain practice, whereas SA-516 is made to fine grain
practice and is given a normalizing heat treatment if thicker than 1". The finer
grain size of SA-516 gives it much better toughness than SA-515 at any given
strength level and plate thickness. The coarser grain size of SA-515 may theoreti-
cally give it better high temperature strength, but in practice the ASME allowable
stresses for SA-515 and SA-516 are the same. Consequently, SA-515 is seldom used
today in petrochemical services.
Occasionally we find pressure vessel steels designated as Code Case 1280, which
is equivalent to SA-516 Grade 70, or Code Case 1256, which is equivalent to
SA-442. These code cases predated the establishment of the now equivalent ASME
specifications, and were in use for only a short period.
1960s and earlier vintage specifications often refer to the terms firebox quality
(FBX) or flange quality steel. Firebox quality steels required more testing, tighter
control of chemistry, and slightly higher ductility. Therefore, firebox quality steels
were generally used for pressure vessels.
Nozzles in carbon steel pressure vessels are typically made from SA-105 forgings or
from SA-106 seamless pipe. There has been little change in these specifications
over the years.
Iron-Carbon Diagram
The Iron-Carbon Phase diagram (Figure 300-5) is of particular use to experienced
inspectors and experienced plant engineers concerned with damage mechanisms
occurring in their plants. At the far left of the diagram we see the stable phase is
ferrite. However, less than 0.02% of carbon is soluble in the ferrite phase. There-
fore, carbon exists in two different forms in the steel: first, a small amount is
dissolved in the atomic (crystalline) structure, being finely dispersed. The remainder
of the carbon is combined with iron in the form of a separate phase called iron
carbide. Iron carbide is a very hard, very strong material.
The combination of ferrite and cementite typically forms pearlite. Figure 300-6, a
high magnification photo of a carbon steel, shows the white grains of ferrite. The
darker material is the carbide, cementite. For these steels, the cementite often forms
a long rod-like shape. These patches of alternating cementite and ferrite form what
is called pearlite.
Lets see what happens as we increase the temperature of a typical carbon steel, with
about 0.15% carbon. At most temperatures we deal with, the microstructure of the
steel is ferrite and pearlite. As you increase the temperature, the strength of the steel
decreases, but the microstructure of the steel does not change.
At 1100F, the yield strength of the steel is about 1/3 of what it was at 80F. That is
why, when we stress relieve carbon steel welds at 11001200F, we do not change
the steel microstructurally, but the metal can relax and lower the residual stresses
to about 1/3 of the 80F value.
As we go still higher in temperature, say a little above 1200F, we start to see a
microstructural change as the lamellar shape of the carbides in the pearlite become
rounded, or spheroidized. This permanently reduces the high temperature strength
(creep strength) of the material somewhat. Spheroidization is an indicator of the
metal becoming overheated and is actually a time-temperature phenomenon: the
lower the temperature, the longer the process takes. Some very old vessels oper-
ating at about 900F have developed spheroidized microstructures.
At still higher temperatures, we come to the lower critical temperature (Ac1) of
1330F. Here, the austenite phase starts to appear. Austenite is a high temperature
phase1, and it can dissolve much more carbon. The 1330F temperature is truly
critical to metallurgistsfor example, if there is a fire, we are often interested to
know if the steel got hotter than 1330F. Below 1330F, the steel may soften a little,
but will probably not suffer a severe consequence. If the steel gets hotter than
1330F, it may end up with a very mixed up microstructure, with poor properties,
depending upon how it is subsequently cooled.
For this 0.15% carbon steel we see that above about 1590F we are above the
upper critical temperature (Ac3). Here the carbon is completely dissolved. (If
you wish to gain the maximum hardness of a steel, you would raise its temperature
above this upper critical temperature to make sure all of the carbon was in solution,
1. For many of the stainless steels Chevron uses, austenite is the stable phase for all practical temperatures,
including room temperature. The 300-series stainless steels, such as Type 304 SS, are called austenitic stain-
less steels.
Ferrite
Pearlite
then cool it as rapidly as possible-quench it-to form the highest hardness possible
for that chemical composition).
Somewhat higher temperatures are used for annealing or normalizing. Normalizing
is typically done at about 1650F for carbon steel. Much higher temperatures are
used for forging, and the steel actually melts at about 2800F.
heat treatments. For example, when vessel plates are stacked on top of each other to
cool after the hot rolling process, the middle plates may have a slow cooled,
annealed type structure, while the top plate may have cooled rapidly enough to have
a much finer grain size. Also, if the steel is used in the as-rolled condition we
typically will not be able to predict the microstructure, because the steel can cool at
various rates as it is being rolled (flattened) into shape.
If having a fine grain size is important to us, then for extra cost (perhaps 1040%
extra for a typical carbon steel) we can require it be made to fine grained practice
(you may sometimes see the initials FGP on drawings). The steel maker will typi-
cally adjust the chemistry slightly (for example, adding aluminum) to make sure
fine grain size can be achieved with practical cooling rates, and almost always a
normalizing heat treatment will be done. This normalizing both makes the grain size
smaller, and it definitely makes the grain size more uniform. It is possible to
normalize (heat treat) the steel and gain some benefit, without the raw steel itself
being made to fine grain practice.
As the steel is first made, the nature of the cooling process tends to force impurities
to the center of the original cast ingot or slab. When the steel is flattened into the
shape for plates by the rollers in the rolling mill, the defects in the steel are squeezed
together and flattened into pancake shape defects, called inclusions. This is why
such defects are typically found in the middle of the plate thickness (or the middle
of the pipe wall, if it is large diameter pipe made from plate). These types of defects
are seen less frequently in seamless pipe.
remove oxygen. The silicon abruptly stops or kills the bubblinghence the name
killed steel. Steel makers can partly or fully deoxidize the steel. Examples of
semi-killed steel is A53 pipe and A285 plate2. Examples of fully killed steel are
A106 pipe and A516 plate.
Rimmed steels have no special deoxidationthe interior portion of the steel ingot
is full of gas pockets and impurities, and only the outer portion is used. Because of
this, rimmed steels are not used for modern vessels or piping.
Sulfur. Steel purity has greatly improved over the past few decades. The sulfur level
in 1990s steels is typically less than that in a typical 1970s material (often less than
0.010 wt.% today versus 0.025 wt.% in the 1970s).
319 Welding
Welding is a common and necessary process in both new construction and mainte-
nance. However, welding must be conducted within tightly controlled variables to
assure reliable joints. By its nature, welding involves changing from a solid to liquid
phase and back to solid. During this operation, the equipment may undergo changes
in its local chemistry as well as changes in the crystalline structure and mechanical
properties
Figure 300-8 is a sketch of typical microstructures at a butt weld of two plates, pipe
or vessel walls. This figure illustrates the various microstructures near the weld, all
resulting from different thermal histories. Note the difference in the structure as the
weld progresses from the previously liquefied zone through the heat affected zone
(HAZ) to the unaffected parent metal. The material affected by the welding process
has varying grain structures that affect strength, resistance to cracking, brittle
failure, and may have slightly different chemistry that affects mechanical properties
and resistance to corrosion. Common concerns are hard welds that are prone to
attack from dissolved sulfides in the process streams, or welds that contain so much
trapped hydrogen that they are prone to immediate or delayed cracking.
2. Why are not all materials fully killed? Primarily, because fully killing the steel reduces the amount of steel a
steel maker can get from a particular ingot.
The ferritic and martensitic stainless steels contain chromium, but little or no nickel.
They are not typically as corrosion resistant as the austenitic alloys, but have high
ambient temperature strength in addition to relatively good corrosion resistance.
Duplex stainless steels have a mixed austenitic and ferritic microstructure. The
duplex stainless steels are useful for their ability to withstand SCC in aqueous chlo-
ride services. They are typically used for piping and heat exchanger tubing in
aqueous chlorides where both corrosion and SCC resistance are needed.
A list of commonly-used stainless steels, their product form ASTM designations,
and brief descriptions of corrosion resistance and mechanical properties appear in
Figure 300-22 and Figure 300-23.
between about 800F and 1600F, so it is important that the annealing temperature
be sufficiently high, and that the subsequent cool down move rapidly through the
embrittling and carbide precipitation range. Use of L grades reduces the risk of
grain boundary carbide precipitation during heat treatment and therefore resists
sensitization.
Since rapid cooling may leave high residual stresses in the finished product, stress
relief at 1600F may be done following cooling to eliminate residual stresses. Stress
relief is especially important if the steel is to be used in a SCC environment.
Residual stress greatly increases the risk of stress-corrosion cracking of austenitic
stainless steels.
A stabilizing anneal may be given to Types 321 and 347 stainless steel. These
grades are known as stabilized grades because they contain elements (titanium in
the case of Type 321 and niobium in the case of Type 347) which form carbides that
are more stable than iron carbides.
Stabilized carbides are important when the steel is to be used at elevated tempera-
tures. This is because at about 700F and higher, the non-stabilized grades (such as
Types 304 and 316) are susceptible to intergranular precipitation of chromium
carbides (Cr23C6) which causes sensitization and can lead to intergranular cracking
and corrosion. By adding titanium (in the case of 321 stainless steel), titanium
carbides (TiC) are formed in the steel, rather than iron carbides. Titanium carbides
are more stable than iron carbides at elevated temperatures and do not transform to
grain boundary chromium carbides until at least 850F. For use in the 850900F
range, niobium (also called Cb) is added to form niobium carbides in 347 stainless
steel, which are stable at those temperatures.
The stabilizing anneal is performed at a temperature which is higher than the iron
carbide dissolution temperature but lower than the TiC (or NbC) dissolution temper-
ature, usually at 16001650F. By holding the steel at that temperature for four
hours, carbon in the steel reacts with either titanium or niobium, and little or no iron
carbide remains. Later, when the steel is used in elevated temperature service, there
are fewer iron carbides to transform to grain boundary chromium carbides, and so
the physical and mechanical properties are maintained even after years at elevated
service temperatures.
sion-resistant counterpart of martensitic low carbon steels. Due to its high strength,
however, it can yield very hard welds. For this reason the Type 410S (low carbon)
or Type 405 is typically chosen for welded construction if its strength is sufficient.
Heat Treatment of Ferritic and Martensitic Stainless Steels. The tensile strength
of martensitic stainless steels like Type 410 can exceed 300 ksi. The very high
strength and hardness makes these steels susceptible to stress-corrosion cracking in
wet H2S environments, so they must be chosen carefully in petrochemical applica-
tions. Only in cases where the process temperature is hot enough so that no liquid
water exists or where there is no H2S present should martensitic stainless steels be
considered.
If corrosion resistance is the primary need, and the strength of a martensitic struc-
ture is not necessary for a particular application, Type 410 can be tempered or
annealed. Tempering for several hours at 12001600F yields tempered martensite
which retains very high tensile strength, but is tougher and more ductile than
quenched martensite.
Annealing at 1600F followed by slow cooling coarsens and softens the martensite
enough that ductility can be raised from near zero to as high as 10% or so. Ferritic
steels can also be purchased in the annealed condition if corrosion resistance,
ductility, and toughness are required.
common Hastelloys we use; they have excellent resistance to corrosion in acids and
are immune to chloride SCC. Typical uses are tubes for heat exchanger bundles in
refinery and chemical plants where acids and chloride salts are likely.
Inconel 600, 601, and 625 contain 6075 wt.% nickel and 1520 wt.% chromium,
and up to 10 wt.% molybdenum; they are primarily used for high-temperature
strength and outstanding corrosion resistance. Incoloy alloys like 800 and 825 are
not technically considered nickel-based alloys because they are a mixture of about
equal parts of iron, chromium, and nickel (2040 wt.% each). These alloys can be
used in both corrosive aqueous environments and in high-temperature oxidation
applications.
Incoloy 800H is commonly used in high-temperature services in chemical plants,
where operating temperatures may exceed 1200F. Ethylene and styrene plants, in
particular, make use of Incoloy 800 and 800H pressure vessels, transfer piping, and
furnace tubes. Incoloy 800H is distinguished from Incoloy 800 for its minimum
carbon level of 0.04 wt.% and its high-temperature tensile strength. Whereas
Incoloy 800 has excellent corrosion and SCC resistance in aqueous chlorides, the
extra carbon in Incoloy 800H allows it to be used for Code pressure vessels and
piping as high as 1650F.
A major caution with Incoloy 800H is that it sensitizes to a very great degree; there-
fore, we must avoid using the H grade for aqueous services. Even the standard
Incoloy 800 has become more susceptible to sensitization in recent years due to the
manufacturers trends to increasing the grain size. Contact a materials engineer if
you are dealing with these alloys. Incoloy 825 finds use in effluent air coolers where
ammonium chloride salts form which would typically cause cracking of lesser
austenitic stainless steels. The 825 grade is resistant to sensitization at elevated
temperatures due to titanium additions.
Brasses
Our largest use of copper alloys is for heat exchanger bundles. Admiralty brass is
the most commonly used of the copper alloys for heat exchanger tubing because of
its resistance to corrosion in water. A potential problem of brass is its susceptibility
to ammonia or sulfate stress corrosion cracking.
About 28 wt.% zinc and 1 wt.% tin are added to copper to make Admiralty brass. A
few variations of Admiralty brass are the arsenical, antimonial and phosphorized
inhibited Admiralty alloys. In these inhibited alloys, about 0.1 wt.% max. of
Bronzes
Bronzes are copper-based alloys which are alloyed with tin, aluminum, and/or
silicon, but with less zinc than the brass alloys. Due to their lower zinc content,
bronzes are not as susceptible to SCC as the brasses, but they are also not as corro-
sion resistant. For this reason, we do not use much bronze in Company applica-
tions. Where SCC and impingement resistance are needed in conjunction with
excellent corrosion resistance, we typically upgrade Admiralty brass by jumping
directly to copper-nickel alloys.
Copper-Nickel Alloys
The two common copper-nickel alloys which are used as upgrades for Admiralty
brass are 70-30 Cu-Ni and 90-10 Cu-Ni. The 70-30 alloy contains approxi-
mately 70 wt.% copper plus 30 wt.% nickel plus a small (<1 wt.%) iron addition.
The 90-10 alloy is about 89% copper plus 10% nickel plus 1 wt.% iron. Copper
nickel alloys are more resistant than Admiralty to wet acid corrosion. They also
resist ammonia and sulfate SCC.
Impingement attack is a scouring away of protective scales on soft copper alloys
due to contact with turbulent or high velocity fluid. Impingement attack can occur
on Admiralty brass in water streams where flow exceeds about 5 fps. In such cases,
upgrading to 90-10 or 70-30 may be necessary. The copper-nickel alloys generally
resist impingement attack to greater than 10-15 fps.
The nickel content of the copper-nickel alloys makes them more susceptible than
other copper alloys to corrosion in ammonium bisulfide and H2S environments.
Stainless steels and titanium alloys should be considered for upgrades to Admiralty
brass in sulfur-containing environments.
331 Spheroidization
Above about 1000F, carbides will agglomerate or spheroidize, and lose some of
their strengthening effect in carbon steels and low-alloy steels. Aside from some
reductions in ambient temperature strength, spheroidization can cause decreases in
creep and stress-rupture life, especially in furnace tubes which commonly run in the
spheroidizing temperature range.
332 Graphitization
Graphitization of carbon steels and carbon-molybdenum (C-Mo) steels can occur
after thousands of hours above 800F for carbon steel, and 850F for C-Mo.
Graphitization occurs most prominently in welds and weld heat affected zones
(HAZ), and results in the dissolution of iron carbides to iron and elemental carbon
(graphite). Linking together or alignment of graphite nodules and flakes causes
sharp decreases in ductility and toughness, which can make a material susceptible to
failure from mechanical and thermal shock. Graphitization is eliminated in low-
alloy steels by the addition of 0.5 wt.% or more of chromium.
elements which play the greatest role in temper embrittlement are antimony, tin,
phosphorus, and arsenic. In modern steel making practice, the levels of antimony
and arsenic in the steel should be zero. Tin and phosphorus, while usually present,
should be controlled to less than 0.01 wt.% to reduce the effects of TE.
Temper embrittlement is important in hydroprocessing reactors, since reactors are
typically fabricated from thick-walled 2Cr-1Mo in order to resist high-tempera-
ture hydrogen attack at temperatures in the 800F range. Thick-walled vessels are
more susceptible to brittle fracture even in the absence of temper embrittlement, so
concern is heightened when reactors operate in the embrittling range.
Concerns for in-service temper embrittlement cause us to warm these reactors
before pressurizing them. A minimum pressurizing temperature (MPT) is chosen for
each reactor depending on the performance of its fabrication heats to a step cooling
test. The step cooling test, developed by Chevron, is an accelerated temper
embrittlement test which predicts the amount of embrittlement which will occur in a
heat of steel after long service (100,000 hrs or more) in the embrittling temperature
range.
3. Often, creep embrittlement is most severe when small amounts of creep strain
occur over long periods of time. Therefore, it is more severe at the lower
temperatures in the creep range.
4. Creep embrittlement is characterized by the low stress rupture ductility.
5. Ambient temperature properties of the material may be little affected by creep
embrittlement.
6. Creep embrittlement, unlike some other forms of embrittlement, is not revers-
ible by heat treating the material.
From the description above we can see that we are vulnerable to this mechanism
when we deal with the low chrome alloys in the creep range. The problem tends to
show up near welds, particularly at the coarse Heat Affected Zones. Creep embrit-
tlement cracking has been a significant problem with Rheniformer reactors, particu-
larly at nozzles. It has also been reported at long seams of some high temperature
piping. In addition to the metallurgical factors noted above, ensuring smooth welds
is a significant help in avoiding creep embrittlement.
338 Creep
Another high-temperature degradation mechanism is creep. All metallic materials
including stainless steels, nickel alloys, titanium alloys, etc., are susceptible to
creep. As temperature rises, metals soften and lose some of their strength. This loss
of strength causes the material to stretch very slowly over long periods of time at
elevated temperature.
A typical creep curve is shown in Figure 300-10. Creep occurs in three distinct
stages. In the first stage, the amount of stretching is rather fast but does not last
long. In fact, many stainless steels undergo no Stage 1 creep at all. Most of the creep
life occurs in Stage 2 during which the material expands at a slow but steady rate. In
Stage 3, which is shorter than Stage 2, growth accelerates rapidly. If a material
enters Stage 3 creep, it can fail without warning and cause a catastrophic failure.
We use some materials at very high temperatures (especially furnace tube mate-
rials) with the knowledge that creep may occur, and that we must inspect at regular
intervals to determine if and when creep is occurring. It is then up to our best engi-
neering judgement to determine if the tubes can continue to operate in Stage 2 creep
until the next shutdown, or if there is a risk that they will enter Stage 3 creep and
fail before the next shutdown.
The life of a tube can be reduced significantly by what might appear to be only a
small increase in temperature. Creep life is typically reduced by half for each 25F
increase in temperature, so that a furnace tube which might last 10 years under
normal operating pressure at 1000F, will last only 2 years at 1050F.
The approximate temperature at which significant creep deformation begins to
occur for some alloys is shown in Figure 300-11. Further discussion of creep is
contained in the Fired Heater and Waste Heat Recovery Manual. The Appendix of
the Fired Heater and Waste Heat Recovery Manual contains API Recommended
Practice RP 530, Calculation of Heater Tube Thickness in Petroleum Refineries,
which can assist the engineer in choosing furnace tube metallurgy and predicting
remaining furnace tube service life as a function of stress and temperature.
At about ambient temperature and below, carbon steel, low alloy steels, and some
stainless steels undergo a ductile-to-brittle transformation. If the material is highly
stressed while in the brittle condition, it may suffer a brittle fracture. With a ductile
fracture, the metal stretches substantially and often the equipment will leak, but not
fracture violently. However, a brittle fracture fails suddenly, without warning, and
with a large, immediate, release of energy.
This section outlines the basics of brittle fracture, then details the process Chevron
and the industry uses to avoid brittle fracture of pressure vessels, piping and tanks:
The basics:
lists the major factors causing brittle fracture
defines the terminology of Minimum Design Metal Temperature and
related concepts
outlines the concept of staying below certain pressures when at cold
temperatures
summarizes the development of the industry brittle fracture guidelines, to
help give perspective as to where all the various Code, industry, and
Chevron standards fit in
Setting MDMTs for New Equipment:
Briefly explains the process for establishing safe limits for new equipment
Notes the temperature maps for helping establish Critical Exposure
Temperatures
Helpful Definitions
It will be useful to first clarify some terminology:
Minimum Design Metal Temperature (MDMT): This is defined in the ASME
Code (Section VIII Div. 1, UG-20) as the lowest (temperature) expected in
service. Consideration shall include the lowest operating temperature, operational
upsets, autorefrigeration, atmospheric temperature, and any other sources of
cooling.
terminology, we would say that the Minimum Pressurizing Temperature for this
piece of equipment is 70F.
Chevron and industry practice is to avoid pressurizing equipment whenever the
equipment is below the MDMT (or the MPT). The specific rules are:
For Division 1 vessels built before 1999: stay below 40% of the Maximum
Allowable Working Pressure whenever you are below the MDMT.
For Division 1 vessels built in 1999 and later: stay below 35% of the Maximum
Allowable Pressure whenever you are below the MDMT.
For Division 2 vessels: stay below 25% of the Design Pressure whenever you
are below the MDMT.
For piping (ASME/ANSI B 31.3 Code) stay below 40% of the Design Pressure
whenever you are below the MDMT.
For tanks, applied stress is a function of fill height rather than internal pres-
sure. As explained below, the methodology for determining MDMT's is the
same, using exemption curves found in API Standard 650.
Although the wording is different, each of the guidelines above ends up requiring
you stay below about the same 8 ksi level any time you are below the Minimum
Design Metal Temperature. Some of the RP-579 wording is also a little different,
but again RP-579 leads to the same results.
Historical Perspective
The paragraphs below summarize the development of the industry brittle fracture
guidelines, to help give perspective as to where all the various Code, industry, and
Chevron standards fit in.
Prior to the 1960s, the Code did not address testing requirements for operating down
to -20F. In the 1960s, the Division 2 of Section VIII introduced the first exemp-
tion curves, in which impact testing was required of materials, unless they were
exempted by the material curves in that Code.
From 1969 to 1982, Chevron developed proprietary exemption curves for equip-
ment constructed to Section VIII, Division 1, though this was not required by the
Code. In 1983 the Chevron curves were revised.
From 1987 to today, the Section VIII Division 1 code has included exemption
curves. These were compiled from the Division 2 curves, an API document
(API 650), the British Standard 5500 curves, the Chevron proprietary curves, and
two other major users. It is unclear as to the original basis for the Division 2 curves.
For some years the Codes were inconsistent in the curves they used for setting
MDMTs, but in recent years they have essentially standardized on the same curves.
In 1990 the API issued Recommended Practice 920, Prevention of Brittle Fracture
of Pressure Vessels. This document pertained to both new and existing vessels, and
it specifically dealt with the issue that many existing vessels successfully operate
although they would not meet the current guidelines for avoiding brittle fracture.
In the mid-1990s the ASME Code B31.3 issued the first exemption curves for
piping. Prior to this time, all piping was considered suitable down to -20F. (Even
now, the ASME Section VIII pressure vessel code assumes all piping components of
pressure vessels to have the same properties, so there is still some inconsistency).
In the late 1990s, a major industry-wide Fitness For Service effort was started to
give a more rigorous, formal, and industry-standardized basis for how to deal with
equipment which is in service, with defects. The (very large) resource document for
this effort is API Recommended Practice 579, which is expected to be issued in
2000. API RP 579 will supersede the previous API RP 920 document. RP 579 uses
and extends current Code methodology, and in turn the ASME will adopt the
RP 579 methodology when it issues its Post Construction Code (coming some
years in the future).
The terminology Critical Exposure Temperature and Minimum Allowable
Temperature comes from RP 579. RP 579 does not use the traditional Chevron
wording of Minimum Pressurizing Temperature. We are adopting the RP 579
methodology, which is consistent with our past practice. We are also adopting the
RP 579 terminology, but for those who are used to thinking in terms of Minimum
Pressurizing Temperatures we will also use that term.
As noted below, it is our position that when the Minimum Design Metal Tempera-
ture (or MPs) have been calculated using the older Chevron guidelines, those calcu-
lations are still valid today, even when in some cases the current curves may be
somewhat more conservative. Any new MDMTs (or MPTs) should be calculated
using the current Code curves, except for the few cases where our guidelines are
more conservative.
Actually, in the latest editions of the Codes, these curves are almost identical.
Figure 300-14 on page 300-45 can also be used for existing equipment.
The basic methodology for determining the MDMT is rather simple:
1. From the appropriate exemption curve, note the Minimum Design Metal
Temperature for that particular material and thickness.
2. Repeat step (1) separately for every component of the vessel (heads, shell,
nozzles, etc.).
3. Take the highest (most conservative) MDMT of all the components as the
MDMT for the entire vessel.
Some special notes:
For any alloy (non-carbon steel) vessel, always consult a materials engi-
neer in setting the MDMT. Alloy materials can embrittle in some services,
and the MDMT set by the fabricator may not be adequate for the long term. See
also the discussion below in Section 345.
For Division 1 vessels, the MDMT for all B16.5 flanges is set at -20F, while
the nuts are set at -50F.
The Division 1 exemption curves extend all the way to six inches; but even
when the base metal is exempt, the welds of that material must be impact tested
if the material is thicker than 4 inches.
For Division 1 vessels, the Welding Procedure Qualification must generally be
impact tested if the base metals require impact testing. (See paragraph UCS-67
for more details.)
For Division 2 vessels, there are special rules for some alloy materials (para-
graph AM-213), but just follow the advice above to always consult a mate-
rials engineer when dealing with an alloy vessel.
Chevron has more conservative requirements for MDMTs of a few specific
materials. See Section 344.
Tanks
The methodology for tanks is much the same. Refer to the set of tank exemption
curves in API Standard 650, Welded Steel Tanks for Oil Storage and also to
Chevrons Tank Manual.
300 Metallurgy
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300 Metallurgy Corrosion Prevention and Metallurgy Manual
If the MDMT of the suppliers standard material is greater than what we want for
our particular location, our options are:
1. Upgrade the material to one which will meet our desired MDMTs
2. Charpy impact test the material at the desired MDMTs. The test requirements
are spelled out in the relevant Code. Note that while the testing itself (Charpy
impact testing) is inexpensive, the supplier may increase the cost of the mate-
rial for fear of not passing the test.
3. Accept the higher MDMT and put in engineering controls, such as establishing
Minimum Pressuring Temperature limits to ensure that the material is not
significantly stressed whenever it is colder than the MDMT (see example on
page 300-35.
The Chevron representative must advise the supplier where Chevron requires more
conservative treatment in selecting MDMTs for a few specific materials. This is
explained in Section 344.
Chevron Exceptions
All grades of SA-285 and SA-515 steels thicker than " should go on Curve A,
not Curve B. The Codes assign the higher strength Grade C of SA-285, and Grades
65 and 70 of SA-515, to the most conservative Curve A. Chevron agrees, but
lacking any additional data we assign all grades of these materials to Curve A, while
the Code allows SA-285 Grades A and B, and SA-515 Grade 60 to be on curve B.
Specifically, we say SA-285 and SA-515 steels thicker than " should be assigned
to Curve A. Our logic is that since the SA-285 may be a semi-killed steel, and SA-
515 is a coarse-grained material, the toughness characteristics do not warrant the
more conservative curve (at least for relatively thick sections) unless we can see
supporting data.
SA-106 and SA-53 pipe thicker than " should go on Curve A, not Curve B,
unless normalized. SA-106 and SA-53 pipe can have coarse grain and quite poor
toughness properties, particularly if they are thick. Often this thick pipe is used in
high pressure and critical services. Therefore, we assign the material to the more
conservative curve (at least for relatively thick sections) unless we can see
supporting data.
For obsolete materials, refer to Section 346. Because the Codes address only
new equipment, they do not refer to some older materials that are no longer
specified, but which we still have in our plants. Section 346 assigns these older
materials to the appropriate curves.
High Alloys
Under special circumstances 300-series and 400-series stainless steel can suffer very
severe in-service embrittlement (so called sigmatization and 885 embrittlement
respectively). For Chevron, these materials rarely limit Minimum Design Metal
Temperatures, because the sigmatization embrittlement does not occur until above
1100F; and we avoid using the 400-series stainless steels in pressure-containing
applications precisely because of the embrittlement problems. Other high alloys,
such as the Incoloys, can also experience various embrittlement mechanisms.
Low Alloys
Low alloys (1Cr, 1.25Cr, 2.25Cr, and 5Cr) are subject to temper embrittlement if
they are exposed to temperatures above about (conservatively) 650F. This subject
is discussed in more detail in Section 333, but the net effect is that the ductile-to-
brittle transition temperature increases. That is, the equipment will be brittle at
higher temperatures than when it was new.
An outline of how we deal with the 1Cr, 1.25Cr, and 2.25Cr materials is given
below. The 5Cr material is not used for vessels, and we have not encountered any
practical embrittlement problems of 5Cr piping (there are rare instances of 5Cr
furnace tube embrittlement).
1Cr and 1.25 Cr-0.5Mo Pressure Vessels. In-service embrittlement of these
vessels is covered in more detail in a 1990 memorandum3. Our guidelines for estab-
lishing MDMTs for these vessels are:
For normalized and tempered 1Cr or 1.25Cr steels operating above 750F, use
Curve A of the Code exemption curves (Division 1 or 2).
For annealed 1Cr or 1.25Cr steels operating at any temperature, also use
Curve A (Division 1 or 2).
3. Minimum Pressurizing Temperatures for Vessels Made of 1Cr-0.5Mo and 1.25Cr-0.5Mo Steels, 1/16/1990,
MEE file 47.50.01, 45.70.04
4. Two useful summaries are: Minimum Pressurizing Temperature for 2.25Cr-1Mo Hydrotreater Reactors,
September 9, 1983, MEE file 45.70.04; and Minimum Pressurizing Temperature Class I 2.25Cr-1Mo Steels,
December 15, 1988, MEE file 45.70.04.
Level 1 Analysis
Fig. 300-14 Minimum Allowable Metal Temperature for Pressurization of Equipment Without Impact Testing (Cour-
tesy of ASME and Courtesy of American Petroleum Institute)
Notes:
1. Curves A through D define material specification classes in accordance with Table 3.313.4.
2. Equipment whose CET is above the appropriate material curve is exempt from further brittle fracture assessment.
3. This figure is from paragraph UCS-66 of the ASME Code Section VIII, Division 1, and API RP-579.
4. Curve A intersects the y-axis at -8C (18F), Curve B intersects the y-axis at -29 (-20F), and Curves C and D intersect the y-axis at -48C (-
53F).
5. These curves can also be used to evaluate piping components designed to ASME 1331.3. In this case, Curve B should be shifted to the
right so that 1.27 mm (0.5 in.) corresponds to a temperature of -29C (-20F). To account for this shift in an assessment, an effective
governing thickness equal to the actual governing thickness minus 2.69 mm (0.106 in.) can be used to determine the MAT.
for flat heads or tubesheets, the thinner of the two parts joined or the compo-
nent thickness divided by four, whichever is larger. See Figure 300-17 (D and E)
and Figure 300-18 (F).
The governing thickness of a casting shall be its largest nominal thickness, and the
governing thickness of nonwelded parts, such as bolted flanges, tubesheets, and flat
heads, is the component thickness divided by four. See Figure 300-17 (D).
well below freezing, should consider reviewing their systems. Contact MEE for
help.
2. For temperatures above about 750F for low alloy piping (1Cr, 1.25Cr, 2.25Cr)
we must consider the effects of temper embrittlement. See the comments above
in Section 345.
3. For pump cases, valves, and other cast components, Chevron has historically
not been concerned with determining an MDMT/MAT. Because these compo-
nents are typically highly over-designed, stress levels are not high enough to
lead to brittle fracture. At this time, we would recommend against determining
MDMTs for such components. We will revisit this issue if the industry should
take another approach in the future.
Some Comments for Tanks. Use API Standard 650 and the Tank Manual (along
with API RP 579) for guidance in establishing MDMTs for tanks. The methodology
is the same, but the curves and some of the materials employed are different. If the
tank material is unknown, then API RP 579 provides some help in that we can
consider the tank safe to use at any temperature for metal thicknesses less than 0.5".
Also, metal temperatures above 60F are safe regardless of the thickness. For tanks
with metal temperatures less than 60F, and thicknesses greater than 0.5", contact
MEE for help. Also contact MEE for help with atmospheric or low pressure tanks
dealing with a refrigerated product.
Level 2 Assessments (These are from RP 579, Contact MEE for help)
Pressure Vessels, Method A: This method takes advantage of the fact that if the
operating pressures/stresses are well below the design values, then the risk of brittle
fracture is much less. The method in effect involves calculating the ratio of the
actual vs. the design stresses, then going to a curve to gain reductions of as much as
100F or even more in the MDMT/MAT. The ASME Code Divisions 1 and 2 use the
same methodology for new construction.
347 Autorefrigeration
One must consider the potential for autorefrigeration occurring either during opera-
tion or as a result of equipment failure. The effect of autorefrigeration depends upon
the state of the process fluid; for example, the vessel contains all gas (typically little
effect), all liquid (typically large effect), or a mixture. The effect also depends upon
how the vessel may be vented. Autorefrigeration, caused by depressurization, may
also occur in a flowing system with a flashing liquid. As the pressure decreases, the
temperature will follow the vapor pressure curve.
In recent years, at least one catastrophic failure occurred when a unit processing
LPG suddenly depressured, causing the equipment to cool. The equipment did not
fail upon the initial event, because the pressure was low as the contents vented.
However, the unit was repressurized while the equipment was still coldat that
point the equipment failed.
Autorefrigeration is not considered as stressful to the equipment as is continuous
operation at cold temperatures. This is due to the principle explained above: if you
are below 8 ksi stress, you will not have brittle fracture. Therefore, it is not realistic
(nor often economic) to select the materials based upon the coldest temperature the
equipment could possibly reach under autorefrigeration (at near zero pressure).
Instead, for ASME Section VIII Division I vessels we would typically consider the
temperature of the vessel contents when the vessel is at 40% of the Maximum
Allowable Working Pressure.
When dealing with autorefrigeration, as with brittle fracture in general, it is the
metal temperature that is important. In some cases this can help give us an extra
margin of safety, but a more careful thermal analysis of the cooling effects would be
required.
If a review of operating facilities determines that some equipment may be subject to
temperatures below the MDMT while above 40% of the MAWP, we urge that CRTC
be contacted for a closer review. In some cases a Level 3 analysis may be
neededthis analysis determines what flaw sizes could be tolerated under autore-
frigeration conditions. The final step of such an analysis would be to assure (typi-
cally by thorough nondestructive examination) that no such flaws exist, nor could
they reasonably occur before the next inspection interval.
Fig. 300-19 Hydrotest Pressures for ASME Carbon Steel and Low-Alloy Pipe Classes
Against Blind Flanges vs. Against Blocked-in Valves
Standard ASME Carbon Steel / Low-Alloy Hydrotest Pressure
Pipe Class By Flange Rating Against Blocked-in Valves
150 psig 425 psig 350 psig
300 1100 750
600 2175 1000
900 3250 2200
1500 5400 3600
2500 9000 6000
Note CAUTION! Often high pressure flanges do not limit the hydrotest. Be sure
the pipe wall is sufficient.
Curve A.) Using Figure 300-15, for a 9/16" (0.5625") thick section on Curve A, we
can read on the Y-axis of the plot an MDMT for this vessel of 40F.
The curves thus allow us to assume that there are no heats of A285 Grade C steel
which would be at risk of brittle fracture above 40F as long as the wall thickness is
only 9/16". If the wall thickness of the same vessel was 2", the MDMT would rise
to nearly 100F. At that thickness, the vessel would be susceptible to brittle fracture
up to 100F.
If this drum was located at Hawaii Refinery, where the critical exposure tempera-
ture (CET) exceeds 40F, this exercise would show that no risk of brittle fracture
exists with the vessel, and that no special start-up and shutdown precautions are
warranted at that location. On the other hand, if the drum was located in El Paso,
where the lowest one-day mean temperature is about 10F, (see Figure 300-13), a
risk of brittle fracture would exist. In the El Paso location, when the ambient
temperature during start-up or shutdown was less than 40F, the internal drum pres-
sure should be kept below 65 psig, which is 40% of the MAWP of 163 psig.
For overseas locations where historical weather information is not available, care
will be required to keep pressure below 40% of MAWP (or 25% for Division 2
vessels) whenever ambient temperatures are near MDMT. For locations shown on
the map in Figure 300-13, the same care is required, but the map can serve as a
guide to alert the operator when a problem with brittle fracture may exist.
Example 2: Assume the Same Vessel was Fabricated from Different Material
Suppose the same vessel as in Example 1 was fabricated from grade A516 Grade 60
steel. In that case, Curve C would be used for the MDMT determination. For the
9/16" thick drum fabricated from SA516 Grade 60, the MDMT is -30F. With this
material, even the El Paso location would have no concern about brittle fracture
with this drum.
This example shows that for some locations, use of a tougher steel allows a vessel to
be run immediately at 100% of MAWP on cold start-up, rather than at 40% of
MAWP, which can save valuable time. Conversely, if during fabrication of the
vessel, the steel had been Charpy Impact tested at 10F, and passed the tests in accor-
dance with UG-84 of ASME Section VIII, Division 1 (or AM0211 of Section VIII,
Division 2 for Div. 2 vessels), then the vessel could be assumed to be immune to
brittle fracture under all weather conditions at the El Paso location.
Typically, for a colder location, either a tougher steel will be used or Charpy impact
testing will be done at the lowest one-day mean temperature for the location, so that
start-up and shutdown schedules are not affected by the concern for MDMT.
Example 3: A Heat Exchanger
Assume that the shell material is SA516, Grade 70 carbon steel. The nominal thick-
ness, and assumed governing thickness, of the shell is ". It has double butt longitu-
dinal and girth weld seams. The channel forging is SA105, Grade II carbon steel.
The governing thickness of the channel is 4". The nonwelded tubesheet is 6" thick
SA105, Grade II carbon steel. The governing thickness of this nonwelded tubesheet
is 1" (6" divided by four).
Baffle and partition plate materials and thicknesses are not considered. It is
Chevrons philosophy that non-pressure containing components and welds should
not enter into MDMT determinations.
For the channel forging and tubesheet, it is possible that the materials were
purchased in the normalized condition; however, there is no proof of such on the
U-1 Form. Unless proof of normalizing can be found on available mill certificates
for this exchanger, the channel and tubesheet must be assumed to be not normal-
ized. In that case, the channel forging (SA105, Grade II steel) goes on Curve A.
With a weld thickness of 4", the MDMT for the channel forging (using
Figure 300-14 is 118F.
The SA516, Grade 70 carbon steel (non-normalized) shell goes on Curve B. With a
thickness of " governing thickness, the MDMT for the shell is -5F.
The tubesheet is SA105, Grade II with governing thickness of 1". The MDMT for
the tubesheet is 85F.
The MDMT for the exchanger is chosen to match the highest MDMT for any one
component. In this case, it is 118F. The internal pressure in the exchanger should
be kept at 440 psig or below (40% of the 1100 psig MAWP) when the metal temper-
ature is below 118F.
is more conservative. From Figure 300-14, for 0.937" thick material on Curve A,
the MDMT is 65F.
The piping in question should not be allowed to operate at a pressure higher than
40% of MAWP (or design pressure) at a temperature below 65F.
You can use a material that does not have an endurance limit under cyclic loading
conditions only if the number of cycles is limited to test data indications of what it
can withstand without fracture. This is called the fatigue limit. Figure 300-21 is a
schematic illustration of fatigue curves on a plot of stress versus number of cycles,
showing both fatigue limits and endurance limits.
Fig. 300-21 Schematic Illustration of the Fatigue Behavior of Ferrous and Non Ferrous Alloys
Stress relieving a structure does not usually affect fatigue life; however, shot
peening a part to put residual compressive stresses on the surface increases fatigue
life.
Following are some common locations where fatigue failures occur in our facilities:
Heat Exchangers
Tube vibration as a result of flow patterns is a common cause of fatigue fail-
ures. Many such failures have occurred on alloy tubes, which are usually
purchased with thinner wall thickness. Failures typically initiate at tube-to-tube
sheet joints or baffles. Fatigue failures, although rare, can be found in the
middle between two baffles. There are also typical patterns on the tube sheet
layout, depending on the baffle location and other factors, where fatigue fail-
ures occur.
Branch and Screwed Connections
Because failure of valved branch connections on large lines is common in refin-
eries, such connections should be designed properly and regularly inspected.
Screwed connections on cyclic service should be seal-welded, and valves at
branch connections should be bridge-weldedsee Section 600 of the Piping
Manual.
Reciprocating Pumps and Compressors
Reciprocating pumps and compressors are significant sources of alternating
stresses and, therefore, a common area for fatigue to develop.
40-18
Ni Resist Sour Water, A436
Caustic
300 Metallurgy
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Fig. 300-22 Common Chevron Refinery Alloy Material Specifications and Applications (Adapted from the Richmond Refinery Materials Engineering Web Site)
Chevron Corporation
300 Metallurgy
February 2000
300 Metallurgy
Transfer
February 2000
Fig. 300-22 Common Chevron Refinery Alloy Material Specifications and Applications (Adapted from the Richmond Refinery Materials Engineering Web Site)
Chevron Corporation
300 Metallurgy
February 2000
Fig. 300-22 Common Chevron Refinery Alloy Material Specifications and Applications (Adapted from the Richmond Refinery Materials Engineering Web Site)
Chevron Corporation
acid, BFW
Chemicals,
low tempera-
ture sulfur,
sulfidation,
ammonium
bisulfide, high
temperature.
2205 Duplex Chloride, H2S UNS S32205 A240 A790 A182, A815 A789
Stainless environments UNS S31803
Steel (preferred),
UNS S32205
(acceptable)
2507 Duplex Chloride, H2S UNS S32750 A240 A790 A182, A815 A789
300 Metallurgy
February 2000
rine
Alloy 600 UNS N06600 B168 B517 (welded) B166 (bars) B163, B167
B167 (Seam- B366 (seamless)
less) B564 (Forg- B516 (Welded
ings) Tube)
Alloy 625 High tempera- UNS N06625 B168 B444 (Seam- B446 B444 (seam- B494
ture, High B443 less Tube) B626 less)
hydrogen, B705 (Welded) B622 (tubing)
High chloride B564 (Forg-
ings)
B574 (Rod)
Alloy High tempera- UNS N08800, B409 B407 (Seam- B366 B163, B407
800/H/HT (Fe- ture hydrogen N08810, less) (seamless)
300 Metallurgy
B408
February 2000
Hastelloy C- Acid UNS N10002 B575 (C-22 & B619 (Welded) B366 B626B622 A494
276 UNS N10276 C-276 B622 (Seam- B574 (Rod) (Seamless) Gr.Cw-12MW
(UNS N06022) less) B564 (Forg- B619 (Welded)
ings)
Admiralty General UNS C44300 B171 (A. B, C) B111 (A. B, C) B584
Brass (Inhib- steam and (Arsenic),
ited) cooling water C44400 (Anti-
service, to mony),C44500
140F (Phosphorus)
70-30 Cu-Ni Slightly higher (UNS C71500) B171 B466 B111
temp steam
and cooling
water service,
>140F.
300 Metallurgy
February 2000
Note that Section 315 further discusses the most common ASTM grades of carbon steel, including obsolete grades still
300-65
300 Metallurgy
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300 Metallurgy Corrosion Prevention and Metallurgy Manual
Fig. 300-23 Corrosion Resistance and Mechanical Properties for Common Steel Product Forms (1)
Ambient Temp. Yield &
Typical Alloy Typical Chemistry Tensile Strengths Comments
Low and Fe-1Mn-0.2C Y = 25-40 ksi Adequate strength and corrosion resistance for many
Medium Carbon UTS = 50-80 ksi applications.
Steels
Low-Alloys 1Cr-Mo; Y = 25-60 ksi Strength and creep resistance > 900F.
2Cr-1Mo; UTS = 60-110 ksi Hydrogen attack resistance > 450F.
9Cr-1Mo H2S resistance to 650F for the higher Cr alloys.
5Cr-Mo
12-Chrome 12-13Cr Y = 40-100 ksi Very high hardness and strength.
(e.g., 410) and 17Cr-4Ni UTS = 60-200 ksi H2S resistance to 800F.
17-4PH Susceptible to sulfide stress cracking.
304SS, 304L, 18Cr-8Ni Y = 25-40 ksi Good high temperature corrosion resistance. Weld
304H UTS = 65-80 ksi with L grade.
H2S resistance > 800F; H2/H2S > 550F.
304H has creep resistance to 1500F.
All sensitize after long-term service above 700F.
316SS, 316L, 18Cr-12Ni-2Mo Y = 25-40 ksi Better aqueous corrosion resistance than 18-8SS.,
317SS, 317L (317/L: 3%Mo) UTS = 70-90 ksi Type 317 resists naphthenic acid corrosion.
All will sensitize after long-term service above 700F.
321SS, 347SS 18Cr-10Ni Y = 25-40 ksi Stabilized grades can be welded without
UTS = 70-90 ksi sensitization.
Type 321 will not sensitize below about 850F.
Type 347 will not sensitize below about 900F.
Alloy 20 20Cr-33Ni-2Mo-3.5Cu Y = 35-50 ksi Acid corrosion resistance especially sulfuric. May
(Cb3 adds <1% Nb) UTS = 80-95 ksi contain Cb for sensitization resistance (Alloy 20Cb3).
Cast pump cases in sulfuric acid plants.
Incoloy 825 21Cr-42Ni-3Mo-2.3Cu- Y = 35-45 ksi Corrosion and SCC resistant.
1Ti UTS = 85-95 ksi Will not sensitize on welding or in operation.
For effluent air coolers in aqueous NH4Cl.
Inconel 625 21Cr-61Ni-9Mo-4Nb- Y = 60-80 ksi Excellent in strong acids.
4Fe UTS = 120-140 ksi High temp. strength and oxidation resistance.
Hastelloy 15Cr-57Ni-15Mo-4V- Y = 40-190 ksi Excellent in strong acids (esp. hydrochloric, nitric,
C-276 5.5Fe UTS = 100-200 ksi and sulfuric) and in acids contaminated with
chlorides.
Resists SCC and pitting in severe environments.
Monel 66Ni-31Cu Y = 25-35 ksi Best for hydrofluoric acid.
UTS = 60-80 ksi
Titanium Grades 2, 7, 12 Y = 40-60 ksi Seawater exchangers and aqueous streams
UTS = 50-70 ksi containing H2S and chlorides.
(1) Also see Appendix A of the Welding Manual.
Fig. 300-24 Conversion Table for Hardness Numbers for Steel (Non-austenitic)Approximate (1 of 2)
Fig. 300-24 Conversion Table for Hardness Numbers for Steel (Non-austenitic)Approximate (2 of 2)
Fig. 300-25 Temperature Color Scale Courtesy of Tempil Division, Air Liquide America Corp.
(This Scale is in color (and easier to read) on the website: http://chevron.com/MEE/Metallurgy/)
370 References
1. C. D. Buscemi and G. B. Kohut, Brittle Fracture and MPT Determination for
Upstream Equipment, CRTC Upstream Portfolio Item PFS-19 memo 9/22/97.
2. C. D. Buscemi, et. al., Temper Embrittlement in 2- Cr-1Mo Steels After
75,000-Hour Isothermal Aging, Journal of Engineering Materials and
Technology, July 1991, vol. 113, p. 329.
3. R. A. Flinn and P. K. Trojan, Engineering Materials and Their Applications,
Houghton Mifflin Company, Boston, second edition, 1981.
4. R. M. Brick, et. al., Structure and Properties of Engineering Materials,
McGraw-Hill Company, New York, fourth edition, 1977.
5. R. W. Hertzberg, Deformation and Fracture Mechanics of Engineering
Materials, John Wiley & Sons Company, New York, second edition, 1983.
6. W. T. Lankford, et.al, The Making, Shaping and Treating of Steel, ed. U.S. Steel
Company with Association of Iron and Steel Engineers (AISE), 10th edition,
1985.
7. Properties and Selection: Irons and Steels, Metals Handbook, Volume 1,
American Society for Metals (ASM), Metals Park, OH, first printing 1978.
8. Properties and Selection: Stainless Steels, Tool Materials, and Special-Purpose
Metals, Metals Handbook, Volume 3, American Society for Metals (ASM),
Metals Park, OH, first printing 1978.
9. Heat Treatment, Metals Handbook, Volume 4, American Society for Metals
(ASM), Metals Park, OH, first printing 1978.
10. Source Book on Copper and Copper Alloys, American Society for Metals
(ASM), Metals Park, OH, first printing 1979.
11. API Recommended Practice 941, Steels for Hydrogen Service at Elevated
Temperatures and Pressures in Petroleum Refineries and Petrochemical Plants,
fifth edition, 1997.
12. Pressure Vessel Manual, Section 500 Materials, Volume 1, Engineering Guide-
lines, Chevron.
13. Welding Manual, Section 100 Welding Fundamentals, Chevron.
14. Welding Manual, Section 300 Welding Practices, Chevron.
15. Fired Heater and Waste Heat Boiler Manual, Section 700 Materials, Chevron.
16. API RP 579, Recommended Practice for Fitness-For-Service, Section 3,
Assessment of Equipment for Brittle Fracture (Final Draft - Revision 33).