Metalurgia PDF

300 Metallurgy
Author: E.H. (Ned) Niccolls
Abstract
This section gives basic metallurgical information for Chevron engineers and
inspectors supporting upstream operations, pipelines, refineries, and chemical
plants.
Contents Page
310 Introduction 300-3

311 Metallurgy in Chevrons Business
312 Glossary of Commonly Used Metallurgical Terms
313 Nature of Metals
314 Types of Steel Chevron Uses
315 Some Features of the Most Commonly Used Pressure Vessel Steels
316 Heat Treating Steels
317 Steel Making and Equipment Reliability
318 Metal Properties
319 Welding
320 Detailed Information on Higher Alloys 300-20
321 Stainless Steels
322 Nickel-Based Alloys
323 Titanium Alloys
324 Copper Alloys
330 High Temperature Degradation Mechanisms 300-27
331 Spheroidization
332 Graphitization
333 Temper Embrittlement
334 Creep Embrittlement
Chevron Corporation 300-1 February 2000

300 Metallurgy Corrosion Prevention and Metallurgy Manual
335 Sigma Phase Embrittlement of Stainless Steels (Sigmatization)

336 885F Embrittlement of Ferritic Stainless Steels
337 Embrittlement Mechanisms in Nickel-Based Alloys
338 Creep
340 Avoiding Low Temperature Problems-Brittle Fracture 300-32
341 How To Use This Section
342 The Basics
343 Setting MDMTs For New Equipment
344 Special Chevron Criteria
345 Setting MDMTs For Equipment Subject To In-Service Embrittlement
346 Setting MATs for Existing Equipment
347 Autorefrigeration
348 Notes on Hydrotest
349 Worked Examples
350 Fatigue and Thermal Fatigue 300-55
351 Endurance and Fatigue Limit
352 Factors Affecting Fatigue Life
360 Reference Tables 300-58
370 References 300-70
February 2000 300-2 Chevron Corporation

Corrosion Prevention and Metallurgy Manual 300 Metallurgy
310 Introduction
311 Metallurgy in Chevrons Business

The performance of materials plays a critical role in maintaining operations which
in turn impacts the Companys financial performance. Most pressure-containing
materials used in producing, pipeline, refining and transportation operations are
made of metal.
Metallurgy is fairly complex and usually best left to specialists. However, a working
knowledge of metallurgy (as described in this section) will be helpful in the
following situations:
Troubleshooting routine problems, bad actors or unexpected equipment fail-
ures.
Specifying appropriate and necessary requirements for welding, heat treating of
welds, details in forming operations, etc., in work orders and project specifica-
tions to assure reliable welds and other fabrication details.
Assuring appropriate and cost effective choices of materials for new or replace-
ment equipment. These decisions should be based on an engineering analysis of
service life, maintenance costs vs. initial capital cost, and made after consulta-
tion with a specialist when appropriate.
Understanding when the mechanical integrity of in-service equipment may
have been affected by events causing the metal to exceed its design limitations,
such as overheating from fires, exothermic reactions, mechanical friction, etc.
Knowing when metallurgical issues need to be further analyzed; getting
specialist counsel at appropriate times to assure safe, reliable facilities to
support operations.
312 Glossary of Commonly Used Metallurgical Terms

This section explains words and phrases frequently used in metallurgy. Throughout
Section 300, words in italics indicate that you can find their definitions here.
Alpha phase. The primary phase of metals. In steel, the primary phase is ferrite.
Annealing. Heating a material to a high enough temperature so that on slow cooling
the material is soft, ductile and free from residual stress.
Austenite. The predominant high temperature (face centered cubic) phase in steel
that is relatively stable at room temperature in 300 series stainless steels.
Bainite. An intermediate structure between pearlite and martensite. Bainite is the
common structure found in Cr-Mo reactor steels.
Brittle Fracture. Fracture of metal at relatively low stress levels without signifi-
cant deformation.

Carbide precipitation. The combination of carbon with a metallic element to form

a compound. In stainless steel, carbide precipitation can happen at elevated tempera-
tures (including during welding), particularly at grain boundaries. Carbide precipita-
tion can result in degradation of stress corrosion, cracking resistance or strength.
Cold working. Permanent time-dependent deformation at a temperature where it
will strengthen a material and reduce its ductility. Sometimes referred to as work
hardening or strain hardening.
Creep. Permanent deformation of a material under load at high temperature (>
the melting temperature).
Crystallization. The separation of the solid phase from the liquid phase. Incor-
rectly used to describe a fatigue failure. A fatigue failure is not crystallization
because the failed metal is crystalline before it fails.
Delta phase. In steel, the high temperature body centered cubic phase. Sometimes
referred to as delta ferrite.
Embrittlement. Severe loss of resistance to brittle fracture due to a chemical or
mechanical property change.
Fatigue. Failure of a material due to exposure to cyclic stresses below the tensile
strength.
Ferrite. The major (body centered cubic) phase in steel comprised of iron and
carbon plus some trace elements.
Free machining. A property of a material due to the introduction of an ingredient
that makes machining easier and causes machining chips to break off easily. In
steels, the most common way to make them free machining is to add a significant
amount of sulfur to the steel.
Gamma phase. In steel and stainless steel, the gamma phase is the austenitic phase
Graphitization. Decay of carbides to carbon and iron in steel at elevated tempera-
tures causing a loss in strength.
Hardenability. The ability of a material to strengthen upon rapid quenching from
elevated temperatures.
Heat affected zone (HAZ). The area next to a weld that is not melted but has a
change in properties from the heat of welding.
Hot shortness. Brittleness of a metal at hot forming temperatures. In steel this is
usually caused by high sulfur content.
Hydrogen embrittlement. Loss of ductility due to the absorption of hydrogen in
the metal.
Impact test. A test to determine the resistance of a material to an impact load. The
most commonly used test is the Charpy impact test where a notched specimen is hit
with a hinged hammer and the impact strength is inversely proportional to the

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.
313 Nature of Metals

This section describes the nature of metals their crystalline structure, chemical
composition, and phase all of which add to the complexity of working with
metals. These variables must be managed to assure reliable operating equipment, as
they all affect critical properties such as strength, hardness, weldability and resis-
tance to fracture.

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.
Fig. 300-1 Photograph of a Magnified Surface of Carbon Steel
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.
This combination of chemistry and the presence of different phases (discussed

below) become important as the metals are formed, welded, heat treated, exposed to
corrosive environments, and exposed to different temperatures in service.
All these variables impact material properties such as strength, toughness, and
ductility. Although steel is very common, it is a surprisingly complex material due
to different phases and properties that can be obtained by variations in chemistry
and heat treatment.

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)

314 Types of Steel Chevron Uses

Carbon Steel
Carbon steel is by far the most commonly used material in Chevron. Carbon steel is
essentially all iron, with a small amount (up to a few tenths of one percent) of
carbon. Carbon steel is relatively inexpensive, easy to weld, and a forgiving mate-
rial: its properties are predictable, it rarely fails without warning, and it is strong in
service below 1000F. However, mild carbon steel is normally limited to 800F
because of degradation (called graphitization) due to the breakdown of iron carbide
after long periods at elevated temperatures. (See Section 332 for further discussion
of graphitization.) Further, at 950F, carbon steel is subject to excessive oxidation
when exposed to air.
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.
Low to Medium Alloys

To increase strength and corrosion resistance at higher temperatures, one percent to
nine percent chromium is added to carbon steel, often with a little molybdenum.
This combination forms a class of materials that we loosely term low to medium
alloys. These alloys cost several times more than carbon steel, and more care must
be taken in welding (they virtually always require heat treating after welding).
The low alloy materials (chrome-moly alloys) may form the bainite or marten-
site microstructures as they cool during the initial manufacture of the steel (or,
during welding). These microstructures have high strength (are very hard, often the
equivalent of more than 400 BHN) but their toughness is very poor. Fortunately, by
heat treating the material in the range of 13001400F (tempering), the toughness
can be increased dramatically while still maintaining a high strength level-an excel-
lent combination. For this reason, low alloy materials such as 2.25Cr-1Mo are used
in our high pressure heavy wall equipment, such as hydroprocessing reactors.
Usually these materials are used in the Quenched and Tempered (Q&T) Condi-
tion. (See Section 316 for a discussion on heat treating.)
A potential problem with such alloys is that they are not as forgiving if exposed to
temperature excursions. For example, in a fire the carbon steel components are
rarely damaged by overheating, or by the rapid quenching from fire water. In
contrast, the low alloy components might soften (held at high temperatures for too
long, they lose too much strength by becoming overtempered), or harden (due to
reformation of the very high hardness bainite or martensite microstructures from the
quenching action of fire water).

Stainless Steels and Nonferrous Materials

Above 1112% chrome, the alloys form the general class of stainless steels. As a
very rough general rule, the more money you are willing to spend in adding more
alloy (more chrome, nickel, molybdenum) the more enhanced corrosion resistance
and/or high temperature resistance you can achieve. A steel with more alloy than
iron (for example, the nickel-based Inconels or Hastelloys) is a member of the
nonferrous class of materials. Other nonferrous materials used occasionally by
Chevron include titanium, aluminum, and a few copper-based alloys. (Aluminum is
often not very expensive, but it has poor fire resistance.)
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,

Fig. 300-5 Heat Treating Temperatures in Relation to the Iron-Carbon Diagram
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.

Fig. 300-6 Mixed Ferrite-Pearlite Microstructure
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.
316 Heat Treating Steels

Steels have a wide range of properties, depending upon how they were formed in
the mill, and then fabricated into the final product. Virtually all steels start life
when the mill heats them above approximately 1650F to develop the high tempera-
ture austenite phase. Upon cooling, the austenite transforms to the stable lower-
temperature ferrite phase structure.
Heat Treatment. As carbon steel cools from liquid, it transforms its crystalline
structure. More importantly, as carbon steel cools below 1330F (721C), it can
form a number of different arrangement and types of phases with various iron
carbide content and distributions, depending on carbon content and cooling rate.
Heat treatment variations such as quenching, annealing, etc. are all chosen by metal-
lurgists to give specific and predictable properties.
Since desired properties are often mutually exclusive, treatment becomes a
balancing act to achieve optimal properties for the specific application. The prac-
tical aspect of this is to be aware that carbon steel, a common material, can be
altered during fabrication, subsequent heat-treating and welding operations. The
same basic principles apply to alloys in fact, many alloys are even more respon-
sive to heat treatment practices.
Typical considerations when heat treating and welding include the following:
Mechanical strength is very important in many machinery applications.
Weldability is important in vessels, tanks, and piping where shop and field
fabrication are common.

Resistance to brittle fracture (toughness) is critical in low temperature applica-

tions, thick wall materials, and services that become saturated with hydrogen.
Ductile (not hard) steels and welded areas are needed in services subject to wet,
sour service.
Note Refer to procedures in the Welding Manual and get expert counsel when
appropriate to help assure mechanical integrity regarding heat treating and welding
operations.
Metal Grain Size and Heat Treatment. In the next section, we note how the size
of the grains of the metal affects metal properties. The heat treatment of the metal
determines the grain size.
The following steps would be used to increase the grain size:
use a higher austenitizing temperature (a typical austenitizing temperature
would be approximately 1650F)
hold the austenitizing treatment longer, to allow more time for the grains to
grow
slowly cool the steel
Large grain size improves some high temperature strength properties (creep), but as
noted below, in most cases a fine grain size is what we really want. To achieve a
finer grain size, we would control the austenitizing temperature and time and rapidly
cool the steel.
Cooling Rates: Annealing, Normalizing, and Quenching. A steel is annealed by
slowly cooling it from the austenitizing temperature typically by leaving the steel
in the turned-off heat treating furnace. A moderately fast cooling rate is achieved by
normalizing the steel, whereby the steel is cooled in air from the austenitizing
temperature. A very fast cooling rate is obtained by dipping the steel or spraying it
with oil this very rapid cooling is called quenching.
Quenching the steel produces high strength and hardness, but also high residual
stress and poor toughness. (See Section 318 for definitions.) Therefore, for many
applications, the steel is given a follow-up heat treatment at 1000 - 1400F,
depending upon the steel or alloy. This is called tempering. Tempering reduces
strength somewhat, but it greatly improves the ductility and toughness of the steel.
Done correctly, the quench and tempering process (Q&T) can produce steels with
an excellent combination of strength and toughness.
317 Steel Making and Equipment Reliability

For virtually all of our steel componentswhether it is downhole tubing, line pipe,
pressure vessel plates, or plant pipingwe seek the optimum combination of high
strength, high toughness, and low price. Both strength and toughness are found in a
steel with relatively small grain size, and with minimal defects.
For most process piping applications, and for many pressure vessel applications, the
annealed steel is good enough. If we do not specify a particular heat treatment (or
the ASTM specification does not call it out for us), we may actually get a range of

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.
318 Metal Properties

Metal properties affect the fitness of each piece of equipment to perform its opera-
tion safely and dependably. Metals are the primary materials in equipment such as
pressure vessels, piping, machinery, tanks, furnaces, platforms, structures, bolting,
etc.
These properties include:
Tensile strength. The limit of the materials ability to carry stress (loads) without
failure.
Yield strength. The limit of the materials ability to carry stress (loads) without
significant deformation.
Strain. The amount a material deforms compared to its original dimensions. Elastic
strain is recovered when the stress is removed and the material returns to its orig-
inal dimension; plastic strain results in a permanent deformation. See Figure 300-7.
Ductility. The ability to deform under stress.
Toughness. The ability of a material to resist brittle fracture in the presence of a
notch. Usually measured by impact testing. (See Brittleness, below.)
Hardness. Resistance to surface penetration. In general, the harder the material, the
more resistance to wear.

Fig. 300-7 Stress vs. Elongation Chart
Thermal stability. The ability to operate without internal metallurgical changes.

Examples are resistance to temper embrittlement in high temperature reactors and
resistance to sigma phase formation in austenitic stainless steel furnace tubes.
Resistance to corrosion. The ability to operate in various chemical environments
without decay of the metal.
Resistance to creep. the ability to operate under stress at high temperature without
significant permanent deformation (important in furnace tubes and other high
temperature applications.)
Brittleness. The tendency to shatter under load without much strain.
Weldability. The ability to be welded without resulting defects such as cracking or
excessive hardness (frequently leading to subsequent cracking).
Fatigue resistance. The ability to resist cyclic loads without failure.

Controlling Metallurgical Properties

Rules of thumb.
1. Strength and toughness tend to be incompatible. Higher strength materials are
usually less tough, and more brittle. The exception is that decreasing the grain
size increases both strength and toughness.
2. Strength and hardness are closely related. High hardness materials are strong
(and less tough, i.e., more brittle).
As the following examples illustrate, managing metallurgy is an exercise in
balancing the various properties to assure performance. Many desirable properties
are just not possible with any one material, so applications are compromises to
cover all the design requirements. For example, strength is important in nearly all
applications, but very strong steel may be too hard, and consequently too brittle to
be used in low temperature services.
Common tools used to manage properties include:
Chemistry. Usually controlled by choosing an appropriate ASTM standard for
the metal. Materials selection is usually done by specialists, and not discussed
further here. Chemistry is also controlled in the selection of various welding
consumables (rod, wire). See the Welding Manual, and consult a specialist if in
doubt.
Heat treating. Commonly specified in ASTM metallurgy standards for stan-
dard materials for plate, piping, etc., and also controlled in shop and field fabri-
cation.
Welding specifications. See Section 319. Also see the Welding Manual, and
consult a specialist if in doubt.
Operating limits. Metals must be operated within design conditions to avoid
excessive corrosive attack if process compositions exceed limits or if tempera-
ture limits are exceeded. Operating metals within design conditions avoids
short term loss of strength or long term affects such as creep.
Cold working. Occasionally there are limits on bending or other forming to
prevent excessive hardening or susceptibility to stress corrosion cracking from
cold working.
Stress Relieving. Heating to remove residual stress due to welding or cold
working.
Postweld heat treatment (PWHT). PWHT after welding may be specified to
restore mechanical properties, reduce hardness, increase resistance to brittle
fracture, reduce the risk of stress corrosion cracking, or relieve residual
stresses. PWHT is an important and common procedure specified after shop
and field welding. It adds to the cost, and frequently significantly so, particu-
larly for field welds in piping systems. PWHT and other heat treating opera-
tions are covered thoroughly in the Welding Manual, Section 150.

Improving Metal Properties

All steels start out as cast ingots, or as continuously cast slabs of material, as the
material is cooled from its original molten state. In some cases, the steels are used as
cast. Cast steels are much less brittle than cast irons, but for improved properties the
steel is most often worked to at least some degree. Three methods of working
the steel are rolling, forging, and drawing.
Rolling the steel into flat plates forces shut many of the defects or gaps in the
material, thereby increasing the soundness of the material. Rolling also can help
break apart large grains, and make the material somewhat more homogenous.
Forging the steel-quite literally, hammering the steel into shape using very large
hammers and dies-similarly closes up defects and improves the properties.
Drawing the material-in which the steel is pushed over a mandrel to form a
tubular shape for tubing or pipe-again helps improve the product, although typi-
cally such material has been fairly heavily worked before it gets to the drawing
mandrels.
Special Care for Thick Metals

Above we noted the advantages of working the material by rolling, forging, etc.
One of the problems with thick materials is that often they have not been rolled as
much, or forged as much, as the thinner material, so they tend to have more defects
and less homogeneous properties. (For our purposes, we consider thick materials
to be more than about 1.5 inches thick.)
Another problem for thick materials is that it often is difficult for the material to
have the optimum heat treating conditions throughout its thickness. Like a thick
steak cooking on the grill, the middle may tend to be a bit raw.
It is for these reasons that you will often see Chevron or industry specifications call
for metallurgical samples (especially toughness samples) taken at the T posi-
tion (that is, at half-way through the thickness, in the middle). This is also one
reason why some specific low alloy materials are used for thick equipment. As in
the case of the 2.25Cr-1Mo steel noted above, such materials are designed to be able
to through-harden effectively even if the vessel wall is many inches thick.
Two low alloy materials to watch out for in thick sections are the C-0.5Mo mate-
rial, and the 1.25Cr material (especially the higher strength Class 2 version). In
addition to the general problems noted above for all thick materials, these materials
are known to have particular problems maintaining good toughness. In any event, it
is always a good idea to obtain metallurgical consultation for any thick material.
Steel Purity Affects Mechanical Properties

Impuritiesprimarily oxygen and sulfurcan greatly reduce the mechanical prop-
erties of the steel. The toughness (that is, the resistance to fracturesee
Section 340) is particularly sensitive to impurities.
Oxygen. Over the years, the steel makers have become increasingly skilled at deox-
idation practices. They add silicon to the violently boiling liquid steel primarily to

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.
320 Detailed Information on Higher Alloys
321 Stainless Steels

There are four major categories of stainless steels: austenitic, martensitic, ferritic,
and duplex. We use the austenitic stainless steels the most, for their high-tempera-
ture sulfidation and oxidation resistance and their resistance to aqueous corrosion.
The major drawback of austenitic stainless steels is their tendency to undergo stress-
corrosion cracking in aqueous chlorides above about 140F. Austenitic stainless
steels are extremely versatile, and are used for piping, pressure vessels, weld
overlay, and heat exchanger tubing. The austenitic steels contain chromium and
nickel as alloying elements.
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.

Fig. 300-8 Grain/Phase Diagram (Courtesy of Butterworth Heinemann Publishers)
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.
Austenitic Stainless Steels

Austenitic stainless steels contain significant amounts of chromium (1626 wt.%)
and nickel (820 wt.%). The nickel causes these alloys to retain an austenitic micro-
structure as they cool. Most common in this group are the 300-series stainless steels,
such as Types 304, 304L, 316, 316L, 321, and 347. The primary advantages of these
steels are their high-temperature strength, oxidation and sulfidation resistance, and

their resistance to corrosion in many aqueous environments. Above about 1000F,

this class of steel surpasses all others for strength and creep resistance. In most high-
temperature services we encounter, austenitic stainless steels are chosen for their
ability to resist corrosion by H2S and H2-H2S mixtures at elevated temperatures.
The austenitic stainless steels are susceptible to stress-corrosion cracking (SCC) in
aqueous chloride-containing environments. They should not be used in chloride-
containing water above 140F. Section 420 of this manual gives more detail
regarding SCC.
The least expensive, but also the least corrosion resistant of the 300-series stainless
steels is Type 304 which contains only 8 wt.% nickel. For most corrosive aqueous
environments, Types 316, 316L, 321, or 347 will be used; these contain 1012 wt.%
nickel.
Types 304 and 316 are susceptible to intergranular corrosion and cracking if welded
and placed in corrosive aqueous environments, due to a phenomenon called sensiti-
zation. For welded equipment and piping, Chevron uses only the low-carbon
L-grades, like Types 304L and 316L, or the stabilized grades, like Types 321 and
347. For use at temperatures above 700F, Type 321 is used. For services above
800F, Type 347 is used. Refer to Section 410 for more information regarding sensi-
tization.
The carbon added to austenitic stainless steels imparts some strength but not as
much as in carbon and low-alloy steels due to the austenitic grain structure. Like-
wise, austenitic stainless steels are not hardenable through heat treatment. For the
L grades, such as 304L and 316L, carbon is intentionally left out (less than
0.03 wt.%) to reduce the susceptibility of the alloy to sensitization and intergranular
corrosion.
In a few cases where corrosion resistance and elevated temperature strength is
needed simultaneously, high-carbon austenitic stainless steels may be used. Stain-
less steel grades to which at least 0.04 wt.% carbon has been intentionally added are
also known as H grades (such as Type 304H) to distinguish them for their strength
in high-temperature service.
The strength of Type 304H versus that for 304L is about the same at room tempera-
ture, but at higher temperatures the Type 304L loses strength much more rapidly
than does the 304H. The ASME Code allows 304H to be used to 1500F but 304L
to be used only to 800850F.
Heat Treatment of Austenitic Stainless Steels. Austenitic stainless steels cannot
be hardened by heat treatment but can be hardened by cold working. Depending on
the required service then, they are typically purchased one of two ways: either cold
worked for maximum strength, or annealed for maximum resistance to corrosion
and stress corrosion cracking (SCC).
Annealing is done by holding the stainless steel at about 1900F for an hour per
inch of thickness. For Types 316 and 317, which contain higher nickel content,
annealing is typically done 100200F higher. Carbide precipitates and deleterious
brittle phases (sigma) can form in austenitic stainless steels at temperatures

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.
Ferritic and Martensitic Stainless Steels

Stainless steels that contain similar amounts of chromium to the austenitic stainless
steels, but little or no nickel, transform to ferritic and/or martensitic structures upon
cooling. Ferritic and martensitic stainless steels contain less than 2.5 wt.% nickel,
and may contain none. Chromium (1225 wt.%) is added for corrosion resistance.
Upon cooling from the high-temperature austenitic structure, these steels transform
to either ferrite or martensite depending on carbon content.
The most common types used in the petrochemical industry are the 12-chrome
martensitic Types 410 and ferritic Type 405 stainless steels. The two have very
similar corrosion resistance and are commonly used for cladding and internals for
vessels in purely H2S service above 450F. Owing to its martensitic structure, Type
410 is much harder and stronger than Type 405, and can be thought of as the corro-

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.
Duplex Stainless Steels

A common grade of duplex stainless steel for petrochemical services is Alloy 2205.
It contains 22 wt.% chromium, 5.5 wt.% nickel, and 3 wt.% molybdenum. The
intermediate nickel content causes the microstructure to be a mixture of ferritic
phases and austenitic phases. Since the ferritic phases are not susceptible to chlo-
ride stress-corrosion cracking, they act as barriers to crack propagation. Molyb-
denum increases the pitting resistance of the alloy; that, in addition to its good
corrosion resistance and its ability to withstand cracking, makes the duplex stain-
less steels a good choice for heat exchanger bundles where SCC and corrosion resis-
tance are needed above 140F in the presence of chlorides.
More information on duplex stainless steels will be added to the next revision of this
section.
322 Nickel-Based Alloys

Aside from the carbon steels, low-alloy steels, and stainless steels, the other major
structural alloys we use in the petrochemical industry are the nickel-based alloys.
This group of alloys contains Monels, Hastelloys, and Inconels. For our purposes
we also include Incoloys in this category.
Monel alloys are mixtures of mostly nickel (66 wt.%) and copper (31 wt.%). Monel
is used primarily for resistance to acids, and especially for resistance to corrosion by
hydrofluoric acid (HF).
Hastelloys typically contain at least 40 wt.% nickel and appreciable quantities
(1025 wt.%) of chromium and molybdenum. Hastelloy B and C are the most

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.
Heat Treatment of Nickel-Based Alloys

Like carbon and low alloy steels and stainless steels, nickel-based alloys can be
annealed in order to soften them and make then more formable and machineable.
Annealing is typically done at very high temperatures but for short times. Tempera-
tures of 16002200F are common depending on the alloy. In order to avoid
oxidizing the annealed part, the anneal may be done in a reducing environment and
will typically last only 1030 minutes. Annealing results in a completely recrystal-
lized and homogenized grain structure.
If annealing is carried out for several hours, carbides and secondary phases will
dissolve back into solution. This treatment is described as solution annealing. Solu-
tion annealing homogenizes the part and results in an extremely soft material which
can be subsequently reheated (aged) at lower temperatures to yield specific mechan-
ical properties. Age hardening typically consists of a series of hold times (usually
several hours or longer) at progressively cooler temperatures from about 1400F
down to 1100F. The age hardening treatment precipitates strengthening carbides
and intermetallic phases.

323 Titanium Alloys

Our use of titanium is mostly limited to heat exchanger bundles and tubesheets
where numerous corrosion mechanisms are at work and no other material has suffi-
cient corrosion resistance. Although expensive, titanium bundles have been found to
be cost effective in FCC overhead streams, where chloride pitting and cracking, and
ammonium bisulfide corrosion can occur simultaneously. Titanium is also used for
bundles and tubesheets in seawater coolers in refineries and on offshore platforms
where the exchanger sees seawater on one side and corrosion from hot aqueous
chlorides and/or sour water on the other.
We commonly use three grades of titanium alloys. Ti Grade 2 is commercially pure,
with at least 98.885 wt.% titanium. Ti Grade 7 contains 0.120.25 wt.% palladium.
Ti Grade 7 has the greatest pitting resistance of the three Ti alloys we use, but it is
the most expensive. Both Grades 2 and 7 have 40 ksi minimum yield strength and
50 ksi minimum tensile strength at ambient temperature.
Ti Grade 12 is the strongest. Grade 12 contains 0.8 wt.% nickel and 0.3 wt.%
molybdenum, and has 55 ksi minimum yield strength and 70 ksi minimum tensile
strength.
High-strength structural grades of titanium which contain aluminum, vanadium,
chromium, and molybdenum are also available, but they are primarily used for
aircraft, aerospace, and military applications. These structural alloys of titanium are
classified as alpha, beta, or alpha-beta alloys depending on their microstructures but
we will not discuss them further here because of their limited use in our industry.
324 Copper Alloys

The copper alloys Chevron uses the most are:
Brass primarily copper and zinc
Bronze primarily copper and tin
Copper Nickel primarily copper and nickel
As noted below, the copper alloys have good corrosion resistance to water, but they
are relatively weak and have very poor fire resistance. See Section 215 for a more
complete description of the corrosion resistance and potential problems with these
alloys.
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

arsenic, antimony, or phosphorus are added to the alloy to prevent dezincification in

hot water. Dezincification is localized corrosion of zinc phases in the alloy, which
can leave exchanger tubes porous and brittle. Arsenical Admiralty is the most effec-
tive, and the most used by Chevron.
Tubesheets of similar copper alloys are highly recommended for use with copper
alloy tubes, although carbon steel tubesheets can be used in less severe environ-
ments (low chloride content and cool temperatures). Naval rolled brass (copper plus
about 35 wt.% zinc and 1 wt.% tin) is the most common tubesheet material for use
with Admiralty tubes.
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.
330 High Temperature Degradation Mechanisms

This section describes the most common ways the metals we use can be damaged
when exposed to high temperatures, with or without stress being applied. An addi-
tional damage mechanismhigh temperature hydrogen attackinvolves tempera-
ture and hydrogen, and is covered in Section 440 of this manual.
All but one of the damage mechanisms listed in Figure 300-9 below are only active
on one type of metal, or family of metals. However, all of these metals (in fact, all
materials) are subject to the creep damage mechanism.

Fig. 300-9 Susceptibility of Metal Types to Damage Mechanisms

Damage Mechanism Metal Type Susceptible to Damage
Spheriodization Carbon steel and low-alloy steels
Graphitization Carbon and C-0.5Mo steels
Temper embrittlement Low-alloy steels
Creep embrittlement Low alloy steels
Sigmitization Austenitic stainless steels (primarily)
885F embrittlement Ferritic stainless steels (primarily)
Intermetallic embrittlement of nickel alloys Nickel alloys
Creep All metals
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.
333 Temper Embrittlement

Both 1Cr-Mo and 2Cr-1Mo exhibit an increase in ductile-to-brittle transition
temperature (DBTT) after long-time service in the range 6501100F. This is known
as temper embrittlement (TE). Temper embrittlement can cause these alloys to lose
significant toughness, so that they may fracture in a brittle manner even at elevated
temperatures, in some cases up to 350F. The 2Cr-1Mo alloy exhibits far greater
increases in DBTT than 1Cr-Mo, and for most of our applications temper embrit-
tlement is only a concern with 2Cr-1Mo.
Embrittlement is due to segregation of impurity elements to grain boundaries, which
causes the fracture path to change from transgranular to intergranular. The worst
temperature for embrittlement is about 850F. Welds and weld heat affected zones
are most severely affected by TE, followed by plates and forgings. The tramp

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.
334 Creep Embrittlement

This damage occurs in the temperature range of about 9001100F and involves the
low alloy chrome-molybdenum steels, particularly 1Cr and 1.25Cr alloys. As the
name implies, it occurs in the creep range of these alloys (see the description of
creep in Section 338). Essentially the same or related mechanisms sometimes have
the names stress rupture cracking, reheat cracking, or strain aging.
As discussed in Section 338, when materials are exposed to temperatures in the
creep range under stress, they will slowly stretch or deform, until eventually they
fail by creep cracking. A unique feature of creep embrittlement is that the material
cracks or ruptures with very little deformation.
In terms of the microstructure of the material, the form of damage is low ductility
intergranular fracturecracking along the grain boundaries of the material. Creep
embrittlement occurs when the grains of the material are substantially harder
(stronger) than the grain boundaries. This is caused by precipitation of molyb-
denum carbides in the grains (which strengthens the grains), or segregation of minor
elements or impurities in the grain boundaries which weakens the grain boundaries-
or both.
Creep embrittlement has the following characteristics:
1. Creep embrittlement is more severe for higher tensile strength materials, partic-
ularly above 110 ksi.
2. Susceptibility of a material to creep embrittlement depends upon grain size and
type of microstructure, in addition to the chemistry effects noted above. A
coarse grained material is more susceptible than a fine grained one.

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.
335 Sigma Phase Embrittlement of Stainless Steels (Sigmatization)

Holding austenitic and ferritic stainless steels within the temperature range
11001800F allows formation of a brittle intermetallic sigma phase (). Sigma
phase formation results in significant reductions in ductility at temperatures below
500F. At elevated temperatures, adequate toughness and ductility usually remain.
During plant start-up and shutdown, however, reduced ambient temperature
ductility can cause mechanical and thermal shock failures.
Aside from the formation of sigma phase during high-temperature operation, welds
can become sigmatized during post-weld heat treatment. In order to reduce the risk
of sigmatization in austenitic stainless steel welds, the ferrite content of the welds is
limited by Chevron specifications to the range 310%.
Estimated ferrite content of solidified weld metal may be determined from chem-
ical composition of weld consumables using diagrams known as Schaeffler or
DeLong diagrams. A ferritescope can also measure ferrite by determining the
magnetic response of the weld, since ferrite is magnetic while austenite is not.
Consult the Welding Manual for more information concerning welding of austenitic
and ferritic stainless steels and determination of ferrite content in welds.
336 885F Embrittlement of Ferritic Stainless Steels

Heat treatment of ferritic or martensitic stainless steels must avoid slow cooling
through the 7001000F temperature range due to the formation of brittle phases.
The phenomenon is known as 885F embrittlement and results from the formation
of brittle intermetallic chromium-nickel phases known as alpha-prime ('). The
885F embrittlement problem is a major reason why Chevron does not use the
ferritic or martensitic (400 series) stainless steels for high temperature piping or
furnace tube applications.

337 Embrittlement Mechanisms in Nickel-Based Alloys

Thousands of hours of service at temperatures in the 10001400F range can cause
embrittlement of nickel-based alloys due to formation of brittle intermetallic phases.
High-carbon Incoloy 800HT is especially susceptible to embrittlement. Failures of
embrittled Incoloy 800HT have occurred in chemical plant services where oper-
ating temperature routinely reaches 10001200F. The embrittlement is due to
precipitation and coarsening of brittle grain boundary phases containing nickel,
aluminum, and titanium. Embrittlement is manifested by grain boundary cracking,
near zero creep ductility, and inability to perform weld repair without cracking.
Use of these alloys in oxidizing environments complicates the problem because the
same process that causes the precipitation of grain boundary phases dilutes chro-
mium there and reduces local oxidation resistance. Failures due to stress-assisted
grain boundary oxidation (SAGBO) are notable for their oxidized and cracked grain
boundaries, while the remainders of the grains appear unaffected. Consult a metal-
lurgist when nickel-based alloys are to be used in very high temperature services.
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,

Fig. 300-10 Typical Creep Curve
which can assist the engineer in choosing furnace tube metallurgy and predicting
remaining furnace tube service life as a function of stress and temperature.
Fig. 300-11 Typical Temperatures at Which Significant Creep Deformation Occurs*

Material Typical Temperature for Creep
Carbon Steel 800F
2Cr-1 Mo 900F
9Cr-1 Mo 950F
T347SS 1100F
* Be careful - if stresses are high, significant creep can occur at lower temperatures.
340 Avoiding Low Temperature Problems-Brittle Fracture

Sections 341 and 342 are useful to all readers. The rest of Section 340 is for senior
inspectors and senior plant engineers.
341 How To Use This Section

While brittle fracture of pressure equipment is rare, there have still been occasional
cases in our industry in recent years (see Figure 300-12 below). Because brittle frac-
ture of pressure equipment is usually catastrophic, the subject warrants our careful
attention.

Fig. 300-12 Piece of Fractured Clear Creek LPG Vessel
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

Special Chevron Criteria:

Identifies the few specific materials and details where we believe current
industry guidelines are inappropriate or insufficient
Notes that these criteria apply to both new and existing equipment
Setting MDMTs for Equipment Subject to In-Service Embrittlement
Identifies which materials are subject to this embrittlement
Provides guidelines for adjusting the MDMT to accommodate this embrit-
tlement
Setting MDMTs for Existing Equipment:
Provides a step-by-step process for establishing a MDMT for existing
equipment
Autorefrigeration:
Briefly reviews the concept of autorefrigeration
Explains how to select materials to take into account autorefrigeration
Outlines some options in dealing with possible autorefrigeration effects in
existing pressure equipment
342 The Basics

Major Factors Causing Brittle Fracture
Avoiding brittle fracture involves dealing with some basic facts:
1. Carbon steels and low alloy steels become more brittle at lower temperatures.
2. The thicker the steel, the more brittle it behaves.
3. The higher the stress, the more susceptible we are to brittle fracture.
4. The more brittle the material, the smaller the flaw size we can tolerate without
causing a brittle fracture.
5. Some alloy steels can become embrittled in service, and require special
consideration.
In our discussion below, we shall see how each of these factors comes into play.
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.

Critical Exposure Temperature (CET): The CET is terminology used by API

Recommended Practice 579 (see Historical Perspective below). It is determined
from the anticipated process and atmospheric conditions, and is defined as ...the
lowest metal temperature derived from either the operating or atmospheric condi-
tions. As explained in more detail below, the CET is the lowest metal temperature
the equipment will see when under significant stress. Significant stress in most
cases is taken as 8 ksi.
Minimum Allowable Temperature (MAT): RP 579 defines this as the permis-
sible lower metal temperature limit for a given material at a specified thickness
based upon its resistance to brittle fracture. The MAT is derived from mechanical
design information, materials specifications and/or materials data.
In simple language, the CET is the lowest temperature we expect the equipment to
see, and the MAT is the lowest temperature which the equipment material can safely
handle. We want to make sure the CET is always above the MAT.
Minimum Pressurizing Temperature (MPT): Chevron has used this terminology
for many years, but it is not found in the Code or RP 579. It means essentially the
same as MDMT or MAT.
Staying Below Certain Pressures When at Cold Temperatures

The Minimum Design Metal Temperature or the Minimum Allowable Temperature
for any particular piece of equipment is the lowest temperature at which we know it
has good resistance to fracture. The Critical Exposure Temperature is more closely
related to the operation of that piece of equipment.
Every new piece of equipment must have a Minimum Design Metal Temperature.
As explained below, it is determined by the manufacturer, based on the mechanical
and materials data for that piece of equipment. The manufacturer should document
it on the U-1 form, and we should record it on our Safety Instruction Sheets.
As explained in more detail below, either the Critical Exposure Temperature or the
Minimum Allowable Temperature can be one temperature at a particular pressure,
or can be a set of temperatures over a range of pressures. In setting the CET for
vessels and piping, we must consider both atmospheric and process conditions,
including the lowest one-day mean atmospheric temperatures, the lowest tempera-
ture under normal operating conditions, startup, shutdown and upset conditions,
future hydrotests, possible autorefrigeration, and shock chilling.
Typically a project or plant will establish a Critical Exposure Temperature that is
realistic for their climate and process, and then ensure that the Minimum Design
Metal Temperatures of the equipment are below the CET. In some cases this is not
practical for all pieces of equipment.
For example - suppose the MDMT for a thick vessel is 70F, but we know that in
the winter months the actual metal temperature may go down to, say, 30F during a
shutdown. For such a case we take advantage of the fact that at low enough stress
(below 8 ksi) our risk of brittle fracture is negligible, even if the material is brittle.
In this case, we must ensure that the vessel is not stressed above 8 ksi (general
membrane stress) any time the metal temperature is below 70F. In past Chevron

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.
A Caution Regarding the Rules for Pressurizing Equipment

Above we noted that we must not pressure Division 1 vessels above 40% or 35% of
their MAWP whenever they are below the MDMT, depending upon when the vessel
was built. More precisely, this depends upon which edition of the Code was used.
These rules are based on staying below about 8 ksi membrane stress. In 1999 the
ASME Code increased the allowable stresses for Division 1 vessels (effectively
allowing thinner vessels).This means that to stay below the safe stress while cold,
we must reduce the pressure by the same amount.
343 Setting MDMTs For New Equipment

Determining the MDMT for Pressure Vessels and Piping
For new equipment the manufacturer should determine the MDMT. For ASME
Code vessels and piping, the MDMT is determined from exemption curves given
in the Code. These are:
For Div. 1 vessels, ASME Section VIII Div. 1 Figure UCS-66 and its notes
For Div. 2 vessels, ASME Section VIII Div. 2 Figure AM-218.1 and its notes
For process plant piping, ASME/ANSI 31.3 Figure 323.2.2 and its notes

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.
Advising Suppliers on Desired MDMTs for Chevron Projects

Typically the Chevron representative will tell the supplier the desired MDMT's for
the equipment, based upon the geographic location of the equipment. Often the
desired temperature is equal to the lowest one-day mean temperature for the
specific location. For locations in the contiguous U.S. and Southern Canada, those
low one-day means are shown on the map given in Figure 300-13 (reprinted from
API Standard 650, Welded Steel Tanks for Oil Storage).

Fig. 300-13 Isothermal Lines of Lowest One-Day Mean Temperatures (API Standard 650, Welded Steel Tanks for Oil Storage)
Chevron Corporation
Corrosion Prevention and Metallurgy Manual

300-39
300 Metallurgy
February 2000
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.
344 Special Chevron Criteria

With very few exceptions, Chevron follows the Code requirements for determining
the MDMTs and whether or not materials must be impact tested. The few excep-
tions are due to our belief that the Code is not conservative enough for a few
materials.
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.

Selection of MDMT for Vessel and Piping Supports

The vessel support or skirt where it immediately attaches to the vessel is subject to
essentially the same temperature as the vessel shell. A failure in that attachment
could propagate into the vessel shell and threaten the reliability of the vessel itself.
Therefore, our Chevron pressure vessel specifications call for skirts and other vessel
supports to be suitable for the same Minimum Design Metal Temperature as the
vessel.
Saddle-type supports of horizontal vessels are less critical. For new equipment it is
still generally good practice to have them meet the same Minimum Design Metal
Temperature criteria as the vessel.
Piping supports do not have any special criteria. We are not aware that brittle frac-
ture emanating from piping supports has been an issue in the industry.
345 Setting MDMTs For Equipment Subject To In-Service Embrittlement

Please contact a materials engineer whenever the potential for in-service embrittle-
ment is encounteredessentially, whenever dealing with alloy vessels.
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).

For normalized, or normalized and tempered, 1Cr or 1.25Cr steels operating

below 750F, use Curve B (Division 1 or 2).
2.25Cr-1Mo Pressure Vessels. Ever since the problem of temper embrittlement of
low alloy steels was first recognized in the late 1960's and 1970's, particularly of
2.25Cr hydroprocessing vessels, there have been numerous studies and memoranda
issued on the subject4. Our guidelines for establishing MDMTs for these vessels are:
For 2.25Cr-1Mo Class 2 higher strength steels (typically Code Division 2)
steels, typically used for large hydroprocessing reactors and vessels, each vessel
should already have an MDMT (MPT) already assigned which takes into
account that particular vessels' vintage and metallurgy. Contact CRTC Mate-
rials and Equipment Engineering if you cannot find such documentation.
For 2.25Cr-1Mo Class 1 lower strength steels (typically Code Division 1)
steels, vessel MDMTs (MPTs) are set at either 160F (for steels purchased prior
to 1983, which were not screened for susceptibility to temper embrittlement), or
at 120F (for steels purchased for the 1983 RLOP project or later, which did
undergo temper embrittlement screening).
1Cr, 1.25Cr, and 2.25Cr Piping. For temperatures above about 750F for low
alloy piping (1Cr, 1.25Cr, 2.25Cr), we must consider the potential effects of temper
embrittlement, as we do for the vessels. The ASME VIII Code allows essentially all
pipe material to be on Curve B, while the ASME/ANSI B31.3 assigns a blanket -
20F to such low alloy materials (such as SA-335 Gr P22, 2.25Cr-1Mo). Please
contact CRTC Materials and Equipment Engineering for guidance in setting
MDMTs of alloy piping operating above 750F.
In truth, we have not made special precautions for such alloy piping in the past. The
reasons we have not had problems are most likely because:
1. The piping is unlikely to see low temperatures while under stress-for example,
the process of heating the reactors to meet the MDMT requirements for a
hydroprocessing vessel would be more than adequate to protect the piping in
the same circuit, and
2. The piping alloys should not temper embrittle to nearly the same degree as the
high strength (especially quench and tempered) vessel materials.
Nevertheless, for 1Cr, 1.25Cr and 2.25Cr piping operating above 750F we should
follow the same guidelines as outlined for pressure vessels above.
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.

346 Setting MATs for Existing Equipment

Pressure Vessels and Piping
This section guides field personnel in determining the Critical Exposure Tempera-
tures and Minimum Allowable Temperatures (equivalent to MPTs) for an existing
pressure vessel or piping system. Tanks follow a very similar methodology which is
described below.
Information needed to assess your equipment includes:
operating pressure and maximum allowable working pressure,
normal operating and design temperatures,
materials of construction, including the specific grades of steel (e.g., A516
Grade 70),
as-fabricated or current wall thickness of each component,
thickness of welds (best found on fabrication drawings),
history of weld repairs and alterations,
heat treatment history (was the material specially heat treated, such as normal-
ized? Were the welds postweld heat treated)?
Type of process fluid (e.g., can the fluid induce autorefrigeration of the vessel?
See Section 347.
Lowest one-day mean temperature at the equipment location
(e.g., Figure 300-13).
For vessels, much of this information can be found on the U-1 Form Manufac-
turers Data Report.
Level 1, Level 2, and Level 3 Brittle Fracture Assessments

The (to be published) API RP 579 gives procedures for assessing pressure vessels,
piping, and tanks which are labeled Level 1, Level 2, and Level 3. Field
personnel should be familiar with the Level 1 requirements described below. A
Level 1 assessment relies either on having Charpy impact test results for the partic-
ular steel used, or on the use of industry accepted impact test exemption curves for
the general grade of steel used.
If a pressure vessel fails a Level 1 assessment (that is, the assessment finds that the
vessel could be subject to temperatures below the MDMT), then a Level 2 assess-
ment may be done. Some aspects of a Level 2 assessment are briefly outlined below.
If a vessel fails a Level 2 assessment, a Level 3 assessment can be made which
would use sophisticated fracture mechanics and risk analyses performed on a case
by case basis. We recommend consulting with MEE for help with Level 2 or Level 3
assessments.

Level 1 Analysis
Step 1. Check for an existing MDMT.

The first step is to find out if the equipment manufacturer has already specified the
MDMT. This information should be on the Chevron Safety Instruction Sheetif it
is not, be sure to add it when you complete work! The information may (should)
also be found on the U-1 Form (Manufacturers data sheet), on the vessel name-
plate, or on the manufacturer's fabrication drawings. If you are uncertain how a
MDMT was determined, you should recalculate it, or ask MEE for help.
Step 2. Use Charpy Impact Test Exemption Curves to Determine an MAT

Based on Material and Thickness.
If no MDMT was found in Step 1, you can determine the MAT using the ASME
Code exemption curves. The intent of the curves is to provide a temperature above
which we can have confidence that all heats of a particular grade and thickness of
steel will have enough toughness that the steel can be used at full pressure (100% of
MAWP) without risk of brittle fracture. Very roughly, we can expect the curves to
represent about 15 ft-lbs or better of charpy impact toughness, although this may not
be strictly true in all cases.
The curves found in the various pressure vessel and piping codes are essentially the
same. The draft API RP 579 uses one set of curves for all vessels and piping, and
we will adopt the same approach here. Figure 300-14 gives the exemption curves.
Note that this set of curves may be used for both Division 1 and 2 pressure vessels.
By tweaking Curve B a bit, it is also used for piping (see note 5 in Figure 300-14).
As explained below, tanks use somewhat different curves.
Figure 300-15 tells which materials go on the different curves. In almost all cases,
the Chevron assignment of materials is the same as the Codes/RP 579. However, as
explained in Section 353, in a few cases we are more conservative than the
Codes/RP 579. Also, the Codes/RP 579 do not reference some of the obsolete
materials still found in our plants. In Figure 300-15 we have assigned these old
materials to the appropriate curves.
For welded assemblies comprised of more than two components (such as a nozzle-
to-shell joint with a reinforcing pad), determine the governing thickness and permis-
sible MDMT for each of the individual joints of the welded assembly, and use the
warmest (most conservative) of the MDMTs as the permissible MDMT of the
entire assembly.
How to Determine the Governing Thickness.. In using the exemption curves,
we need to know the thickness of the component. The governing thickness (tg) is
defined in API RP 579 and the Code as follows:
for butt joints, except those in flat heads and tubesheets, the nominal thickness
of the welded joint. See Figure 300-16(A).
for corner, fillet, or lap welded joints, including attachments, the thinner of the
two parts joined. See Figure 300-16 (B) and Figure 300-17 (C).

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).

Fig. 300-15 Assignment of Materials to the Curves in Figure 300-14 (1 of 2)

Curve Material (1, 2, 6)
A 1. All carbon and all low alloy steel plates, structural shapes and bars not listed in Curves B, C, and D below.
2. SA-216 Grades WCB and WCC if normalized and tempered or water-quenched and tempered
SA-217 Grade WC6 if normalized and tempered or water-quenched and tempered.
3. The following specifications for obsolete materials are also included in Curve A: A7, A10, A30, A70, A113, A149, A150 (3).
4. The following specifications for obsolete materials are also included in Curve A: S1, S2, S25, S26, S27 (4)
5. A201 and A212 unless it can be established that the steel was produced by a fine-grain practice (5).
6. SA-285 through SA-515, all grades, in thicknesses greater than "
7. SA-53 through SA-106 pipe in thicknesses greater than "
B 1. SA-216 Grades WCA if normalized and tempered or water-quenched and tempered
SA-216 Grades WCB and WCC for thicknesses not exceeding 2 inches if produced to a fine grain practice and water
quenched and tempered
SA-217 Grade WC9 if normalized and tempered
SA-285 Grades A and B (note: See Item 6 above, for Chevron restrictions greater than ")
SA-414 Grade A
SA-442 Grade 55 >1in. if not to fine grain practice and normalized
SA-442 Grade 60 if not to fine grain practice and normalized
SA-515 Grades 55 and 60 (note: See Item 4, above, for Chevron restrictions greater than ")
SA-516 Grades 65 and 70 if not normalized
SA-612 if not normalized
SA-662 Grade B if not normalized
Code Case 1256 (equivalent to SA-442) if not normalized
Code Case 1280 (equivalent to SA516) if not normalized
2. Except for cast steels, all materials of Curve A if produced to fine grain practice and normalized which are not listed for Curve
C and D below
3. All pipe, fittings, forgings, and tubing not listed for Curves C and D below; (note: see Item 7 above for Chevron restrictions of
A-53/A-106 pipe greater than ")
4. Parts permitted from ASME Code Section VIII, Division 1, paragraph UG-11 shall be included in Curve B even when fabri-
cated from plate that otherwise would be assigned to a different curve.
5. A201 and A212 if it can be established that the steel was produced by a fine-grain practice.
C 1. SA-182 Grades 21 and 22 if normalized and tempered

SA-302 Grades C and D
SA-336 Grades F21 and 22 if normalized and tempered
SA-387 Grades 21 and 22 if normalized and tempered
SA-442 Grades 55 <1in. if not to fine grain practice and normalized
SA-516 Grades 55 and 60 if not normalized
SA-533 Grades B and C
SA-662 Grade A
2. All material of Curve B if produced to fine grain practice and normalized and not listed for Curve D below

Fig. 300-15 Assignment of Materials to the Curves in Figure 300-14 (2 of 2)

Curve Material (1, 2, 6)
D SA-203
SA-442 if to fine grain practice and normalized
SA-508 Class 1
SA-516 if normalized
SA-524 Classes 1 and 2
SA-537 Classes 1 and 2
SA-738 Grade A
Code Case 1256 (equivalent to SA-442) if normalized
Code Case 1280 (equivalent to SA-442) if normalized
Notes:
1. When a material class or grade is not shown, all classes or grades are included.
2. The following apply to all material assignment notes
Cooling rates faster than those obtained in air, followed by tempering, as permitted by the material specification, are considered to be
equivalent to normalizing and tempering heat treatments.
Fine grain practice is defined as the procedures necessary to obtain a fine austenitic grain size as described in SA-20.
3. The first edition of the API Code for Unfired Pressure Vessels (discontinued in 1956) included these ASTM carbon steel plate specifica-
tions. These specifications were variously designated for structural steel for bridges, locomotives, and rail cars or for boilers and firebox
steel for locomotives and stationary service. ASTM A 149 and A 150 were applicable to high-tensile-strength carbon steel plates for pres-
sure vessels.
4. The 1934 edition of Section VIII of the ASME Code listed a series of ASME steel specifications, including S1 and S2 for forge welding; S26
and S27 for carbon steel plates; and S25 for open-hearth iron. The titles of some of these specifications are similar to the ASTM specifica-
tions listed in the 1934 edition of the API Code for Unfired Pressure Vessels.
5. These two steels were replaced in strength grades by the four grades specified in ASTM A 515 and the four grades specified in ASTM
A 516. Steel in accordance with ASTM A 212 was made only in strength grades the same as Grades 65 and 70 and has accounted for
several known brittle failures. Steels in conformance with ASTM A 201 and A 212 should be assigned to Curve A unless it can be estab-
lished that the steel was produced by fine-grain practice, which may have enhanced the toughness properties.
6. No attempt has been made to make a list of obsolete specifications for tubes, pipes, forgings, bars and castings. Unless specific informa-
tion to the contrary is available, all of these product forms should be assigned to Curve A.
7. These assignments are from the draft of API Recommended Practice 579, except the items in italics are Chevron modifications.
Division 1 Vessels may be allowed a reduction in the MDMT. For Division 1

vessels fabricated from P1 Group No. 1, or P1 Group No. 2 Code steels, you may
reduce the MDMT by 30F if the steel was postweld heat treated and the governing
thickness is less than or equal to 1.5". This is allowed because vast experience with
PWHTd vessels has shown that they are far less susceptible to brittle fracture than
non-PWHTd vessels. (The code requires PWHT for thicknesses greater than 1.5",
so this additional credit for non-required PWHT is not available for thicker
vessels.)
Some Comments for Piping Systems. For establishing MDMTs of piping systems,
three aspects are worth considering:
1. For thicknesses less than " we generally have not made an effort to go back
and establish MDMTs for existing systems. This decision is based upon the
excellent experience we have had with piping systems. However, operating
facilities in cold climates (which can see temperatures significantly below
freezing), or those that operate systems which can see process temperatures

Fig. 300-16 Typical Vessel Details Showing the Governing Thicknesses (1 of 3)

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.

Pressure Vessels, Method B: For both Division 1 and 2 vessels, a reduction in

MDMT can be taken based upon a combination of the actual metal temperature
during a hydrotest, and the ratio of the operating pressure to the hydrotest pressure.
Pressure Vessels, Method C: This is essentially a grandfather set of guidelines to
consider a vessel safe for continued use based upon past experience operating at low
temperatures (there is no Code equivalent, because the Code is only for new
construction).
Piping, Method A: This method uses the same methodology as described for
vessels, Method A above.
Piping, Method B: Seamless piping can be considered suitable to as low as -50F
(or possibly even lower), if a series of guideline questions can be answered satisfac-
torily, with special emphasis to avoid shock chilling (very rapid cooling of the
metal).
Tanks: A Level 2 assessment for tanks involves answering a series of questions (a
decision tree), including such factors as past operating conditions in some cases, to
determine the suitability for future service.
Level 3 Assessments (From RP 579, Contact MEE for help)

Level 3 assessments of pressure vessels, piping, and tanks are done on a case-by-
case basis. They typically involve specialists from several disciplines including
process, materials, mechanical, and inspection. Often stresses are analyzed using
advanced techniques such as finite element analysis, and considering localized and
transient conditions. Normally a maximum expected flaw size must be determined.
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.
348 Notes on Hydrotest

Effects of MDMT on Hydrotesting of Pressure Vessels and Tanks
Hydrotesting of Pressure Vessels. In general, hydrotest of existing equipment may
be required following: alterations or major repairs, re-rating that increases the
equipments design pressure or temperature, determination of significant wall thick-
ness loss due to corrosion, etc. If it is determined by the field engineer that a
hydrotest is required on existing equipment, it is imperative that the hydrotest be
done at a warm enough temperature to avoid the risk of brittle fracture.
ASME Code guidelines suggest that the mean metal temperature of equipment
during hydrotest be at least 30F warmer than the MDMT for the vessel. This added
measure of safety is due to the fact that the hydrotest exposes the vessel to higher
than design pressure (1.50 times MAWP for Section VIII, Division 1 vessels, and
1.25 times Design Pressure for Division 2 vessels), during which the risk of brittle
fracture is increased. The mean metal temperature is typically controlled by control-
ling the temperature of the hydrotest water.
Chevron practice agrees with the added 30F margin, except when it would cause
the hydrotest to be done at hotter than 120F. We avoid hydrotesting with water
warmer than 120F to limit the chance for burns to personnel in the event of a leak
or rupture. If there is a conflict between keeping the hydrotest temperature cooler
than 120F, but warmer than 30F above the MDMT, a materials engineer should be
consulted.
If at all possible, hydrotest should be done against blinded flanges, not against
blocked valves. Hydrotest pressure shall be limited to a lower value against
blocked-in valves than against blind flanges. Figure 300-19 lists hydrotest pressures
for ASME carbon steel and low-alloy pipe classes against blind flanges vs. against
blocked-in valves.
Note Hydrotest pressures are lower for stainless steels than for carbon and
low-alloy steels.

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.
Hydrotesting of Tanks. Hydrotesting of existing tanks is covered by API Standard

653 Tank Inspection, Repair, Alteration, and Reconstruction. Tanks which have
undergone major repairs or alterations, such as cutting, adding, removal or replace-
ment of a major portion of the shell, the annular plate ring, the concrete ring wall,
the shell plates below the design liquid level, or the shell-to-bottom weld, may be
subject to hydrotesting before being placed back in service. Refer to API 653 for
more information.
Although the Standard does not suggest that the hydrotest temperature exceed the
MDMT, wherever possible the hydrotest water should be warmed above the MDMT
to avoid brittle fracture. Warming above MDMT is not as critical for tanks as for
pressure vessels, since tanks are not typically pressured any higher during hydrotest
than during normal operation. As with the pressure vessel testing, hydrotest water
would be kept to a maximum of 120F, if possible, to avoid danger to personnel
from leaking water.
349 Worked Examples

Equipment Fabricated to ASME Code Section VIII, Division 1
Note For Division 2 equipment, contact a metallurgist for help.
Example 1: K.O. Drum
Suppose the shell and heads are all SA285 Grade C carbon steel with nominal thick-
ness of 9/16" and they are double butt welded. Barring any unusual weld details or
thick reinforcing pads, the governing thickness for both the shell and the heads is
assumed to be 9/16" (equal to the welded nominal thickness). In the absence of
fabrication drawings, this assumption should be checked by field inspection. From
Figure 300-15, we see that A-285 Grade C steel is assigned to Curve A. (Because
Grade C of SA-285 is not specifically listed, you must assume it is assigned to

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.
Equipment Fabricated to API Standard 650

The following is an example of how to determine MDMT for piping using
ASME/ANSI B31.3:
Example 1: What is the MDMT for non-normalized 24" Schedule 60, A106 carbon
steel pipe?
The thickness of 24" Schedule 60 pipe is nominally 0.968". Since the pipe is not
normalized, Chevron takes exception to ASME/ANSI rules and uses Curve A (not
curve B) to determine MDMT. Figure 300-14 shows that for material on Curve A
which is 0.968" thick, the MDMT is 68F.
With this MDMT, the piping in question should not be allowed to operate at a pres-
sure higher than 40% of MAWP at a temperature below 68F. Typically, MAWP for
the piping will be the same as design pressure.
Example 2: What is the MDMT for 8" Standard weight, A106 carbon steel pipe?
The thickness of 8" Standard weight pipe is nominally 0.322". No MDMT calcula-
tion is necessary since the pipe is <3/4" thick.
Example 3: What is the MDMT for 18" Schedule 80 pipe of unknown grade, but
with chemistry and mechanical properties which match API 5L Grades X-52 and
X-56?
The nominal thickness of 18" Schedule 80 pipe is 0.937". Figure 300-15 shows that
for X grades of API 5L material, Curve B can be used to determine MDMT if it is
known that the steel is normalized or quenched and tempered (Q&T). In this case,
since we do not know the steel heat treatment, we are forced to use Curve A, which

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.
350 Fatigue and Thermal Fatigue

Fatigue is one of the most common type of mechanical failure mechanisms. It
occurs when cyclic stress causes a crack to initiate and then propagate.
The source of fatigue stress can be mechanical (e.g., vibration of a pipe attached to a
compressor) or thermal (e.g., cyclic heating of a restrained part). Fatigue is usually
divided into two types-high-stress/low-cycle (<~103 cycles) and low-stress/high-
cycle (>~103 cycles).
Thermal fatigue is often high stress/low cycle fatigue. Much of the fatigue life is
used up in the crack initiation; after cracks form, crack growth can be relatively fast.
This type of fatigue results in multiple initiation sites, which can join randomly to
form the main crack. This crack appearance, often referred to as craze cracking, is
shown in Figure 300-20.
Fig. 300-20 Craze Cracking
351 Endurance and Fatigue Limit

Carbon, low alloy steels and titanium have endurance limitsa cyclic stress below
which fatigue failure does not occur. The limit is about half the tensile strength.
Conversely, 300 Series stainless steels, aluminum, copper, and nickel alloys do not
have an endurance limit; given enough cycles, such materials eventually fail at any
cyclic stress range.

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
352 Factors Affecting Fatigue Life

Stress concentration is an important factor in fatigue. Notches at sharp corners (such
as shaft keyways) and rough weld surfaces, for example, greatly shorten fatigue life.
Conversely, using generous radii in corners and grinding rough weld surfaces
smooth can greatly increase fatigue life. The fact that the fatigue limit is about half
the tensile strength would indicate that the higher the strength, the higher the fatigue
strength. However, this assumption is true only for polished specimens. Because
most structures have notches, there is rarely any advantage in using a higher
strength material to solve a fatigue problem. The best solution to fatigue is proper
design. Fatigue is not a metallurgical problem.
In other parts of this manual we discuss the various effects of hydrogen upon
metals. One of the effects is to increase the tendency of cracks to grow. Therefore, it
should be no surprise that fatigue cracks grow faster when the metal is exposed to
hydrogen. What can be surprising is how much effect the hydrogen can have, even
under low temperature and low pressure hydrogen conditions.
Certainly the message is that in almost all cases, if we find a crack in hydrogen plus
fatigue service, we need to remove it-regardless of the size of the crack. This mech-
anism also explains why it is so important to pay attention to details like bridge
welding piping connections. In the 1960s and early 1970s we learned these lessons
the hard way by having many small diameter piping failures in the early Isomax
plants, especially around the reciprocating hydrogen booster compressors.

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.

360 Reference Tables
Chevron Corporation

Fig. 300-22 Common Chevron Refinery Alloy Material Specifications and Applications (Adapted from the Richmond Refinery Materials Engineering Web Site)
(1 of 8)
Forgings
& Fittings
Process Envi- Richmond Common UNS (Includes Tubes
Alloy Type ronments Pipe Class Equivalent Plate Pipe Bars) (Heat Exchgr) Castings
Gray Cast Iron Fresh Water, Depends on A48
Cooling grade A126
Water, BFW,
A278
A351, A352 -
Code
Ductile Cast Depends on A395
Iron grade A536 Gr. 60-
300-58
40-18
Ni Resist Sour Water, A436
Caustic
300 Metallurgy
February 2000
Chevron Corporation

(2 of 8)
Forgings
& Fittings
Code Carbon General AA6,AA7, Depends on A285 Gr. C A53 A234-WPB A161-LC, C-1/2 A27
Steel Hydrocarbon, AA9, ABO, grade and (UNS K0281 A106 A181 Mo A216-WCB
steam and AB1, AB2, product form. A515 A179 (Smls, (UNS J03002)
water service, AB4, AB6, A333 A105
A516 Cold Drawn) - - WCA, -WCC
to 800F, w/ H2, AB7, AB8, A671 acidic svc.,
w/H2S, cyclic, AF1, AF2, AF3, A352
A672 UNS K03503
MEA, Caustic, AF4, AF5, AF6,
Sulfuric >85% AF7, AF8, AF9, A691 A192 (Smls, Hi
AF10, AF11, Press) -
AG2, AJ1, Boiler, UNS
AJ2, AJ4, K01201
AK1, AL1, A214 (ERW) -
300-59
BB1, BF1, non-acidic

BJ2, BL1, DK1, svc., UNS
DK2, DK4, K01807
DL1, DL4, DP1,
DP2, DP4,
DP5, DR1, DR4
Non-Code Depends on A36 (UNS A120 A27
Carbon Steel grade and K02600) API 5L
(Structural) product form. A131 A134 EFW
A283 A135 ERW
High Str. Steel Depends on A537, A737
grade.
Tank General Depends on A36, A131,
300 Metallurgy
February 2000
Hydrocarbon grade. A283, A285,

steam and A516, A573
water service
Chevron Corporation

(3 of 8)
Forgings
& Fittings
C-1/2 Mo Formerly used A204 Gr. A - C A335-P1 A182-F1 A161-T1 A217-WCI
Steel in High A302 A672 Gr. C A234-WP1 A209-T1 (UNS A356 Gr. 2
temperature K11522)
H2 A336 Gr. F1
A250
A692
1 Cr - Mo High tempera- A387-12
ture H2,
Oxidation
1 CR-1/2 Mo High tempera- RG1, RG4, A387-11 A335-P11 A182-F11 A199-T11 A217-WC6
ture H2, RK1, RK2, RK3, A234-WP11 (UNS K11597) A356 Gr. 6
300-60
Oxidation, H2 RK4, RL1, RL2, A213-T11

w/ HC, H2 RP3, RP4, RR4 A336-F11 A389 Gr. C23
(UNS K11597)
w/LPG, A541 Cl 11c
A200-T11
Steam
2 Cr - 1 Mo High tempera- SP4, SR4 A387-22 A335-P22 A182-F22 A199-T22 A217-WC9
ture H2, A234- A213-T22 A356 Gr. 10
Oxidation, H2 WP22A336- A200-T22
w/ HC F22
A541 Cl 22b
5 Cr - Mo High tempera- TF1, TF2 A387-5 A335-P5 A182-F5 A199-T5 A217-C5, C-12
ture H2, Sulfi- A234-WP5 A213-T5 (UNS
dation, HC, K21590)
Furnace
A200-T5
300 Metallurgy
Transfer
February 2000
Chevron Corporation

(4 of 8)
Forgings
& Fittings
7 Cr 1 Mo High tempera- A387-9 A335-P7 A182-F7 A199-T7 A217-C
ture H2, Sulfi- A234-WP7 A213-T7
dation
A200-T7
9 Cr - 1 Mo High tempera- A387-9 A335-P9 A182-F9 A199-T9 A217-C12
ture H2, Sulfi- A234-WP9 A213-T9
dation,
Furnace A200-T9
Tubes
12 Cr Sulfidation UNS S04100 A240-405, 410, (Commonly A182-F6 A268-TP406, A487-Gr CA15
410S manufac- A479-405, 410 (UNS type B-D
300-61
A176-410 tured from 410S (bars) 41500) A487-CA6NM

sheet or plate)
A217-CA15
A743-CA15
A743-CA6MM
300 Metallurgy
February 2000
Chevron Corporation

(5 of 8)
Forgings
& Fittings
18 Cr - 8 Ni Demineral- GB!, GB6, Depends on A240-3XX A312-3XX A182-F3XX A213-TP3XX A351 CF3,
(3XX Series ized Water, GB7, GF1, GF6, alloy (and A167-3XX A358-3XX A403-WP3XX A271-TP3XX CF3A, CF3M,
Stainless) Lean/Rich GJ1, GJ6, product form) CF8
(flashing) GM1, GP6, A743 CF3,
DEA, H2 w/ GQ6, JB3, JF1, CF3A
HC, JF2, JK3, KF1,
Napthenic, KF2, KK4, KL4, A744 CF3,
Acid, Dilute KL5, KP4, KP5, CF3A
Phosphoric KR4, KR5, KR6,
Acid Weak to
strong acids,
Dilute Sulfuric
300-62
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
Stainless environments UNS S32750

Steel
Chevron Corporation

(6 of 8)
Forgings
& Fittings
Super Stain- UNS N08367 B688 B675 B676 A744 CN3MN,
less Steel UNS J94651
AL6XN
Alloy 20 Cb-3 Dilute Sulfuric MB2 (UNS N08020) B-463 B464 B462 (forg- B468 (Welded A351-CN7M,
acid B474 (EFW) ings) Tube) UNS N08007
B472, B473
(bars)
Monel 400 Acid Environ- UB2, UB6 UNS04400 B127 B165 B164 B163- A494 Gr M . . .
ments HCl, B564 (Forg- B165
HF, and ings)
Caustic, Chlo-
300-63
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
32Ni-21Cr) N08811 B514 (Welded) B515 (welded)

B464 (Forg-
ings)
Chevron Corporation

(7 of 8)
Forgings
& Fittings
Alloy 825 High velocity, XP6, XR6 UNS NO8825 B424 B423 (Seam- B366 B163
high pres- less) B425 B423 (Seam-
sure, high B-468 less)
temperature B564 (Forg-
ammonium B705 (welded) ings) B-468
bisulfide, Sour B704
Water.
HP Modified, Hydrogen A297
HK-40 furnace tubes,
furnace tube
hangers
300-64
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
90-10 Cu-Ni Seawater, UNS 70600

steam
Chevron Corporation

(8 of 8)
Forgings
& Fittings
Titanium H2S, waste Gr. 2 UNS B265 Gr. 1, 2, B337 Gr. 1, 2, B381 F-1, 2 B338 Gr. 1, 2, B367
Alloys water treater R50400 12 12 12
HEX <180F Gr. 12 UNS
R53400
AISI 4130
AISI 4140 A193 B7, B7M
(bolts)
AISI 4340
Note that Section 315 further discusses the most common ASTM grades of carbon steel, including obsolete grades still
300-65
commonly found in our facilities.
300 Metallurgy
February 2000
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)
Conversion To Rockwell C Conversion To Rockwell B

Tensile Tensile
Rockwell Brinell Strength Rockwell Brinell Strength
C Vickers Hard- (approx.) B Vickers Hard- (approx.)
Hardness(1) Hardness(1) ness(1),(2) 1000 psi(3) Hardness(1) Hardness(1) ness(1),(2) 1000 psi(3)
68 940 100 240 240 116
67 900 99 234 234 114
66 865 98 228 228 111
65 832 97 222 222 107
64 800 96 216 216 105
63 772 95 210 210 101
62 746 94 205 205 100
61 720 93 200 200 98
60 697 92 195 195 95
59 674 91 190 190 92
58 653 90 185 185 90
57 633 89 180 180 88
56 613 88 176 176 84
55 595 87 172 172 83
54 577 86 169 169 82
53 560 85 165 165 80
52 544 500 265 84 162 162 79
51 528 487 83 159 159 78
50 513 475 252 82 156 156 76
49 498 464 245 81 153 153 75
48 484 451 236 80 150 150 73
47 471 442 229 79 147 147 72
46 458 432 225 78 144 144 71
45 446 421 216 77 141 141
44 434 409 76 139 139
43 423 400 201 75 137 137 67
42 412 390 192 74 135 135
41 402 381 73 132 132
40 392 371 72 130 130 65
39 382 362 177 71 127 127

Fig. 300-24 Conversion Table for Hardness Numbers for Steel (Non-austenitic)Approximate (2 of 2)
Conversion To Rockwell C Conversion To Rockwell B

Tensile Tensile
Rockwell Brinell Strength Rockwell Brinell Strength
C Vickers Hard- (approx.) B Vickers Hard- (approx.)
Hardness(1) Hardness(1) ness(1),(2) 1000 psi(3) Hardness(1) Hardness(1) ness(1),(2) 1000 psi(3)
38 372 353 172 70 125 125 63
37 363 344 166 69 123 123
36 354 336 68 121 121 60
35 345 327 157 67 119 119
34 336 319 66 117 117
33 327 311 149 65 116 116 58
32 318 301 146 64 114 114
31 310 294 142 63 112 112
30 302 286 138 62 110 110 56
29 294 279 135 61 108 108
28 286 271 131 60 107 107
27 279 264 127
26 272 258
25 266 253
24 260 247 120
23 254 243 116
22 248 237 114
21 243 231 110
20 238 226 108
(1) ASTM E140-86, Standard Hardness Conversion Tables for Metals
(2) The Brinell hardness numbers in boldface type are outside the range recommended for Brinell hardness testing in 3.2.2 of ASTM Test
Method E10.
(3) Tensile strength values given are approximate, and are provided for general reference only.

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).

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300 Metallurgy

Author: E.H. (Ned) Niccolls

310 Introduction 300-3

Chevron Corporation 300-1 February 2000

335 Sigma Phase Embrittlement of Stainless Steels (Sigmatization)

February 2000 300-2 Chevron Corporation

311 Metallurgy in Chevrons Business

312 Glossary of Commonly Used Metallurgical Terms

Chevron Corporation 300-3 February 2000

Carbide precipitation. The combination of carbon with a metallic element to form

February 2000 300-4 Chevron Corporation

Chevron Corporation 300-5 February 2000

313 Nature of Metals

February 2000 300-6 Chevron Corporation

Fig. 300-1 Photograph of a Magnified Surface of Carbon Steel

Chevron Corporation 300-7 February 2000

This combination of chemistry and the presence of different phases (discussed

February 2000 300-8 Chevron Corporation

Chevron Corporation 300-9 February 2000

314 Types of Steel Chevron Uses

Low to Medium Alloys

February 2000 300-10 Chevron Corporation

Stainless Steels and Nonferrous Materials

Chevron Corporation 300-11 February 2000

February 2000 300-12 Chevron Corporation

Fig. 300-5 Heat Treating Temperatures in Relation to the Iron-Carbon Diagram

Chevron Corporation 300-13 February 2000

Fig. 300-6 Mixed Ferrite-Pearlite Microstructure

316 Heat Treating Steels

February 2000 300-14 Chevron Corporation

Resistance to brittle fracture (toughness) is critical in low temperature applica-

317 Steel Making and Equipment Reliability

Chevron Corporation 300-15 February 2000

318 Metal Properties

February 2000 300-16 Chevron Corporation

Fig. 300-7 Stress vs. Elongation Chart

Thermal stability. The ability to operate without internal metallurgical changes.

Chevron Corporation 300-17 February 2000

Controlling Metallurgical Properties

February 2000 300-18 Chevron Corporation

Improving Metal Properties

Special Care for Thick Metals

Steel Purity Affects Mechanical Properties

Chevron Corporation 300-19 February 2000

320 Detailed Information on Higher Alloys

321 Stainless Steels

February 2000 300-20 Chevron Corporation

Fig. 300-8 Grain/Phase Diagram (Courtesy of Butterworth Heinemann Publishers)

Austenitic Stainless Steels

Chevron Corporation 300-21 February 2000

their resistance to corrosion in many aqueous environments. Above about 1000F,

February 2000 300-22 Chevron Corporation

Ferritic and Martensitic Stainless Steels

Chevron Corporation 300-23 February 2000

Duplex Stainless Steels

322 Nickel-Based Alloys

February 2000 300-24 Chevron Corporation

Heat Treatment of Nickel-Based Alloys

Chevron Corporation 300-25 February 2000

323 Titanium Alloys

324 Copper Alloys

February 2000 300-26 Chevron Corporation

arsenic, antimony, or phosphorus are added to the alloy to prevent dezincification in