Introduction

Welcome to the Damage Mechanisms unit of the Mechanical Integrity

Professional Initiative. Inside this unit, you will learn about the numerous damage
mechanisms that are relevant to the refining and petrochemical industries, as
well as some important concepts that will help you to understand why they occur
in the first place.

Much of the information found in this unit comes from API RP 571, Damage
Mechanisms Affecting Fixed Equipment in the Refining Industry. For the sake of
consistency, this unit uses many of the same conventions that are found in API
RP 571 such as damage mechanism groupings (e.g., Mechanical or Metallurgical
Failure Mechanisms, High Temperature Corrosion, etc.).

In fact, this unit may certainly be used as a study reference for those who are
interested in obtaining the API 571 certification. While it is not a replacement for
detailed training or the Recommended Practice itself, it may provide additional
context to help understand the API 571 body of knowledge.

Please note that this unit provides high level summaries of damage

mechanisms. We highly recommend that you refer to comprehensive references
such as API RP 571 to obtain a better understanding of each of the damage
mechanisms. Some of them are very complex and beyond the scope of this
project.

Exploring the Damage Mechanisms Unit

This unit contains 10 sections. The first two sections provide foundational
information that will lead to a better understanding of the damage mechanisms
themselves. We recommend that you start with these two sections before
exploring the different categories of damage mechanisms.
The damage mechanisms themselves (67 in total) are organized by category
first, and then alphabetically. Each damage mechanism may contain one or
more Important Concepts that provide information on why they occur in the first
place.

And finally, each section may contain some Additional Resources that enable

you to dig deeper into the topic.

What is a Damage Mechanism?

A damage mechanism is something that results in problems or failures with
process equipment. Damage mechanisms can range from corrosion, to cracking,
to heat damage, and everything in between.

API RP 571 (second edition) includes a variety of different damage mechanisms

that are known to affect the refining industry. The damage mechanisms are
grouped in the following categories:

 Mechanical or Metallurgical Failure Mechanisms

 Uniform or Localized Loss of Thickness
 High Temperature Corrosion
 Environment-Assisted Cracking
 Other Mechanisms

Why Understanding Damage Mechanisms is Important

API RP 584 (Integrity Operating Windows) puts it best:

In today’s operating environment, it is not enough to base future inspection plans

only on prior recorded/known history of equipment condition. A fundamental
understanding of the process/operating conditions and resulting damage
mechanisms are required in order to establish and maintain an inspection
program that yields the highest probability of detecting potential damage. [API
RP 584, 1st Edition, pp. vii]

Proper identification of damage mechanisms is important when:

 Implementing the API Inspection Codes (510, 570, and 653)

  Implementing API RP 584 (Integrity Operating Windows)
 Conducting risk-based inspection per API RP 580 or similar frameworks
 Performing fitness-for-service assessments

Damage mechanisms need to be understood and considered to determine

corrosion rates, location (general or local), and opportunities for mitigation.
 Crude Oil Refining Basics

Before diving into the specifics of the various damage mechanisms that are
prevalent in the refining industry, it is important to have a fundamental
understanding of how the crude oil refining process works. The journey from
pulling crude oil out of the ground to creating end products such as gasoline
involves numerous different manufacturing processes, each with their own
unique mechanical integrity concerns.

To begin with, consider crude oil: crude oils may look the same, but they are
not created equally. Some have more gasoline, more asphalt, more sulfur and
nitrogen, or more salt.

So, before even making its way into the refinery, the chemical makeup of crude
oil brings with it the potential for numerous damage mechanisms.

In a refinery, crude oil is sent through a series of process units in order to create
products such as gasoline, kerosene, diesel, naphtha, butanes, asphalt, and
many more intermediate and consumable products. The following sections will
provide brief overviews of some of the important process units found in refineries.

Crude Oil Distillation Unit

The very first process unit is the crude oil distillation unit, or crude unit.

Crude oil separation begins with washing the crude oil in the desalter. The
purpose of the desalter is to remove salt, sand, and silt from the crude. This is
the first step in refinery corrosion control.

Delayed Coker Unit

The purpose of the Delayed Coker is to thermally crack large hydrocarbon
molecules, such as asphalt, into smaller usable molecules like gasoline and
diesel. Coke drums that make up part of this process unit constantly cycle from
hot (900°F) to cold (100°F), allowing for the potential of various damage
mechanisms such as sulfidation, wet H2S, creep/stress rupture, thermal fatigue,
thermal shock, and corrosion under insulation.

Fluidized Catalytic Cracking Unit (FCCU)

Similar to the Delayed Coker, the FCCU (or “cat”) Unit cracks large hydrocarbon
molecules into smaller usable molecules. Damage and control issues in FCCU
design and operation include corrosive liquids and gases, erosive solids in the
form of catalyst, and high temperatures.

Hydrotreater
The purpose of hydrotreating is to remove sulfur compounds from hydrocarbon
molecules. To do so, hydrogen gas (H2) is injected in a Hydrotreater. At high
temperatures and pressure, the H2 combines with sulfur (S) compounds in the
hydrocarbon liquid to produce H2S (a gas). The H2S gas is then separated from
the liquid, leaving the liquid sulfur free. However, while removing the sulfur, the
hydrogen also combines with any nitrogen compounds that may exist to form
ammonia. The ammonia then combines with the H2S to form ammonium
bisulfide, a very corrosive compound.

Amine Unit
The purpose of the Amine Unit is to remove the H2S from sour gas, or
hydrocarbons which contain H2S. Sour gas can be collected from many different
refinery sources, such as the Crude Unit, Hydrotreaters, FCCU, among others.
The outputs of the Amine Unit are (1) “sweet” gas, free of H2S, which is then
further processed, as well as (2) H2S gas which is then sent to a Sulfur Unit.

There are two types of amine:

Rich amine has absorbed acid gases such as H2S and CO2. These gases make
it corrosive. Generally, rich amine occurs when the amine absorbs too much acid
gases, is heated at too high a temperature, and/or flows at too high a velocity.

Lean amine has been stripped of the acid gases.

In amine units, an amine molecule (a base) and an acid gas molecule (an acid)
are attracted to each other, forming an amine salt. That is how amine “treats” the
acid gases up to a certain concentration. However, heating the amine salt can
break it back to the acid gas molecule and the amine.

Alkylation Unit
The Alkylation Unit (“alky”) combines cracked gasses that come from either the
FCCU or Coker to form large gasoline molecules. This is done because cracked
gasses have low economic value, whereas alkylate is a very high octane
gasoline and has a high economic value.

Catalyst used in the Alkylation Unit can be either Sulfuric Acid or Hydrofluoric
(HF) Acid – they serve the same purpose.

Catalytic Reforming Unit

Catalytic reforming is a process that converts low octane naphtha into high
octane liquid. In doing so, the process separates hydrogen atoms from the
hydrocarbon molecules and produces very significant amounts of hydrogen gas
(H2) for use in a number of other processes involved in refining.
 Refinery Materials of Construction

Steel
Steel is an alloy that is primarily made up of iron and as a small percentage of
carbon. Many other alloying elements are used in steel, but iron and carbon are
the only elements found in all steel. The percentage of carbon in steel ranges
from just above 0% to approximately 2%. Most steels used in a refinery have
between 0.03% and 0.35% carbon.

As the carbon content of steel increases, so does strength, hardness, and

brittleness.

When steel is made, the iron dissolves the carbon. Approximately 2% carbon is
the most that can be dissolved in the iron. Eventually, as enough carbon is
added, the iron cannot dissolve all of it and some of the carbon precipitates out,
resulting in cast iron.

Cast iron is iron in which some of the carbon has precipitated out and appears as
flakes or little spheres. These flakes provide a cushioning effect for iron when it
receives high compression loads; however, they also make the material more
brittle than steel, have very poor strength when stretched in tension, and
encourage the formation and cracks.

Alloying Elements
Most steels contain other ingredients in addition to iron and carbon. These
ingredients are commonly called alloying elements. Most of these elements are
present in small amounts but they have a great effect on the properties of the
steel.

Metals can be selected because of advantageous mechanical, chemical, and

physical properties.
 Mechanical Properties Chemical/Physical Properties Fabrication Capa

Creep stability Corrosion resistance Castability

Ductility Oxidation resistance Formability
Elasticity Heat treatability
Hardness Machinability
Strength Weldability
Toughness

When compared to carbon steel, alloy steel is more expensive, contains more
alloying elements, and has more of the special properties in the table above.

Killed Steel
Killed steel is clean, meaning that it has minimal voids and inclusions. It is
produced while molten steel is still in the furnace. A deoxidizing agent is added to
remove gases, such as carbon dioxide, as it is being poured into the mold. The
result of killed steel is a product that has more uniform chemical composition and
properties. Killed steel has greater uniformity in resistance to corrosive attack.

Stress Relieving
Stress relieving is performed to relieve stresses that have been imparted to steel
due to forming, rolling, machining, or welding. The process involves heating the
steel to a pre-established temperature for a long enough time to reduce residual
stresses to an acceptable level. This is followed by slow cooling to avoid creation
of new stresses.

The amount of residual stress plays a critical role in determining the susceptibility
to many forms of stress corrosion cracking (SCC). Therefore, stress relieving can
be specified to improve a material’s resistance to a particular corrosion
mechanism.
 Damage Mechanism Basics

The damage mechanisms that follow use the same categorization as API RP 571
(Second Edition). The categories are:

 Mechanical or Metallurgical Failure Mechanisms

 Uniform or Localized Loss of Thickness
 High Temperature Corrosion
 Environment-Assisted Cracking
 Other Mechanisms

Damage mechanisms are listed in alphabetical order. You can quickly jump
between mechanisms by using the navigation sidebar after selecting a damage
mechanism category.
 Mechanical or Metallurgical Failure Mechanisms

885°F (475°C) Embrittlement

885 embrittlement a form of embrittlement that occurs from 600°F to 1000°F, but
most readily at a temperature of 885°F, hence the name. Affected materials
include 400 series of stainless steels, duplex stainless steels, and less commonly
in some 300 series stainless steels containing a metallurgical phase called
ferrite. This damage mechanism can occur in any unit where susceptible alloys
are exposed to the embrittling temperature range.

885 embrittlement is not easily detected or reported before failure. It can be

confirmed through bend or impact testing. Hardness tests that identify an
increase in hardness in affected areas may also give indications of 885
embrittlement.

This failure can be avoided by choosing the right materials for pressure
equipment. However, some types of trays and other non-pressure containing
hardware may be constructed of susceptible alloys and end up cracking during
repair or maintenance activities.

IMAGE GALLERY
Brittle Fracture
Brittle fracture is the sudden, very rapid fracture under residual and/or applied
stress where the material exhibits little or no evidence of ductility or plastic
degradation. Unlike most tensile failures, where the material plastically strains
under overload conditions and becomes thinner at the point of rupture, when a
piece of equipment suffers a brittle fracture, there is no thinning or necking down.
Rather, it breaks “like glass” without a warning, and may in fact fracture into
many pieces.

There are a number of key factors that combine to give rise to susceptibility to
brittle fracture. One of the most important factors is temperature. If the steel
temperature is below its brittle-to-ductile transition temperature, then it will be
susceptible to brittle fracture. Combined with a critical sized flaw and high stress
on that flaw (either applied or residual), then brittle fracture is likely.

The most susceptible materials are carbon and low alloy steels, but also include
the 400 series martensitic steels such as the 12 Cr varieties.

Affected units or equipment:

 Equipment manufactured prior to the December 1987 ASME Section VIII,

Div.1 code are susceptible.
 Most processes run at elevated temperatures, so the main concern for
brittle fracture is during startup, shutdown, and hydrotesting.
 Thick walled vessels should be considered.
 Brittle fracture can also occur during auto-refrigeration.

Brittle fracture is best prevented by using materials specifically designed for low
temperature operation including upset and auto-refrigeration events.

In existing equipment, preventative measures are limited to controlling operating

conditions, minimizing pressure at ambient temperatures during startup and
shutdown, and period inspection at high stress locations.

Inspection is not normally used to mitigate brittle fractures. Susceptible vessels

should be inspected for pre-existing flaws and defects.

IMAGE GALLERY
Cavitation
Cavitation is the sudden formation and immediate collapse of vapor or air
bubbles in a liquid stream when system pressure falls below the vapor pressure
of the liquid. The sudden collapse of these tiny bubbles generates enormous,
though tiny forces that mechanically erode metal. It affects copper, brass, cast
iron, carbon steel, low alloy steels, 300 and 400 series stainless steels. It occurs
in pumps and piping that are located downstream of orifices or control valves,
and it can be found in some restricted-flow passages.

Cavitation is characterized by sharp-edged pitting, but may also have a gouged

appearance in rotational components. Damage only occurs in localized low-
pressure zones.

Typically, the noise generated by cavitation is easily detectable and often sounds
like stones rattling around in a pump or valve. The key to mitigation of cavitation
is for operators to report such noise to engineers and inspectors so that steps
can be taken to mitigate the cause of cavitation.

As such, it is important for engineers and inspectors to let operators and

maintenance personnel know about cavitation and how damaging it can be if it is
not prevented.

In terms of inspection, acoustic monitoring of turbulent areas can be used to

detect characteristic sound frequencies. Visual inspection, UT, and RT can be
used to monitor for loss in thickness.

Creep and Stress Rupture

At high temperatures, metal slowly and continuously deforms under load. This
deformation is known as creep. The rate at which a material will creep is
dependent upon its strength, the stress imposed, and the operating temperature.

All metals and alloys are affected. The following table provides threshold
temperatures for various materials:

Material Threshold Temperature

 Carbon Steel 650 F (343 C)

C-0.5 Mo 700 F (371 C)

1.25 Cr-0.5 Mo 700 F (371 C)

2.25 Cr 750 F (399 C)

5 Cr 800 F (427 C)

9 Cr 800 F (427 C)

304 SS 800 F (427 C)

Nozzles and other components with high tri-axial loading on some catalytic
reformers have been susceptible to creep cracking and low creep ductility. While
furnace components, e.g. tubes, supports, hangers, etc. most commonly
experience creep damage, “cold-shell” designed equipment that is normally
protected by refractory can suffer “surprise” creep damage when the refractory
protection deteriorates. Dissimilar metal welds (DMW) are also susceptible to
creep damage (e.g. ferritic to austenitic welds) because of the high localized
stresses generated by differential thermal expansion.

The initial stages of creep can only be identified with a scanning electron
microscope (SEM). At temperatures well above the creep threshold, noticeable
deformation may be observed.

Since creep damage is irreversible, it is important to prevent it from occurring in

the first place by establishing adequate IOWs for any components operating in
the creep range, whereby operators should be required to make adjustments if
certain temperatures are reached.

Austenitic stainless steels, especially the “H” grades, may provide greater creep
resistance.

Inspection for creep damage requires a combination of techniques (UT, RT, EC,
dimensional measurements and replication). Destructive sampling and
metallographic examinations are used to confirm damage.

IMAGE GALLERY
 
Dissimilar Metal Weld Cracking
Dissimilar Metal Weld (DMW) Cracking is a fabrication issue that occurs at the
weld juncture where carbon steel or low alloy steels are welded to austenitic (300
series) stainless steels in high temperature applications. The most common
materials are ferritic steels (carbon steel and low alloy) that are welded to
austenitic stainless steel. Any material combinations that have widely differing
thermal expansion coefficients may be afflicted.

This type of cracking is most common when temperatures above 800F (425C)
are involved, such as FCCU reactor/regeneration systems, superheaters,
reheaters, fired heaters, and hydroprocess equipment.

Cracks form at the toe of the weld in the HAZ of the ferritic material.

The use of bolted joints, if possible, or nickel base filler materials helps to avoid
the DMW cracking problem.

Before critical dissimilar butt welds are put into service, consider 100% PT after
buttering and completion, 100% UT on the butter layer after PWHT, 100% RT,
100% UT, and Positive Materials Identification.

RT and UT shear wave inspection should be performed on dissimilar welds in

fired heater tubes.

Surface breaking cracks on the ID surface can be detected using WFMT or

external SWUT. 

Erosion/Erosion-Corrosion
The combination of erosion and corrosion on a metal surface, which is caused by
the rapid flow of turbulent liquids through piping, leads to Erosion-Corrosion.
Turbulence is often caused by pitting.
This damage mechanism occurs due to the speed of a moving liquid, as well as
its own corrosive properties. All metals, alloys, and refractories are affected. In
fact, all types of equipment exposed to moving fluids are subject to erosion
and erosion-corrosion.

The appearance of this damage mechanism comes in the form of pits, grooves,
gullies, waves, rounded holes, and valleys. These localized losses of thickness
often exhibit a directional pattern.

Erosion-Corrosion can be mitigated by reducing turbulence by streamlining

piping or slowing the speed of the liquid. Corrosion inhibitors or cathodic
protection may also be effective.

Visual examination of troublesome areas, as well as UT or RT can be used to

detect the extent of metal loss. Specialized corrosion coupons and on-line
corrosion monitoring electrical resistance probes have been used in some
applications. IR scans are used to detect refractory loss on stream.

Gaseous Oxygen-Enhanced Ignition and Combustion

Metals burn in enriched air (having greater than 25% oxygen). Spontaneous
oxygen fires may suddenly occur in such conditions, resulting in fires and
explosions.

Carbon steel and low alloy steels are flammable above 15 psig (0.103 Mpa).
Austenitic stainless steel can be used up to about 200 psig (1.38 Mpa). Cu alloys
(greater than 55% Cu) are very resistant, as is Alloy 400. Aluminum can be used,
but should be avoided because it burns quickly.

The easiest materials to ignite are plastics, rubber, and lubricants.

Any unit that uses oxygen or enriched air for combustion or other process
reasons is affected. These include Sulfur Recovery Units, Fluid Catalytic
Cracking Units, Gasification Units, and Partial Oxidation Units, among others.
To find signs of this damage mechanism, one should look for external heat
damage such as glowing pipe or heat tint. No inspection method will reliably
detect this sort of ignition/combustion.

In terms of mitigation, oxygen fires are not progressive or slowly-developing; they

occur very quickly. It is recommended to refer to the industry recommended
guidelines found in API RP 571 in order to learn the most effective prevention
and mitigation strategies.

Graphitization
Graphitization is not something that operators can do much about, and thankfully
it is not very common. It occurs when the microstructure of some grades of
carbon steel and low alloy steels breaks down after long exposure to elevated
temperatures, like in FCCUs. The carbide phases break down in temperature
ranges from 825 to 1300 F (440 - 590 C) and cause the metal to weaken and be
susceptible to cracking failures.

Graphitization damage is not visible and can only be observed with

metallographic examination. Mitigating graphitization begins with the proper
material selection is key to avoiding graphitization failures. Inspecting for
graphitization includes conducting a metallographic analysis of coupons cut from
the walls of susceptible equipment. This is effective in determining if
graphitization may be occurring. 

Mechanical Fatigue

Foundational Concepts

Fatigue

Mechanical fatigue (often referred to as “fatigue cracking”) is degradation that

occurs when a piece of equipment is exposed to cyclical stress for an extended
period of time. These stresses can arise from mechanical loading or thermal
cycling. Fatigue cracking can be thought of as an “overuse” of a part, resulting in
a break.

All alloys are affected, but stress levels and number of cycles required to cause
failure vary by material. Equipment that is affected by thermal cycling (e.g., coke
drums or auxiliary boilers) and equipment that is affected by mechanical loading
(e.g., pressure swing adsorbers, rotating shafts on centrifugal pumps.).

The best defense against fatigue cracking is good design that helps minimize
stress concentration of components that are in cyclic service. Fatigue cracks can
be detected with NDE techniques such as PT, MT, and SWUT. Visual testing of
small diameter piping can detect oscillation or other cyclical movements.
Vibration monitoring of rotating equipment may be used to detect shafts that are
out of balance.

Reheat Cracking
Reheat cracking (sometimes referred to as “stress relief cracking” or “stress
relaxation cracking”) is intergranular cracking that occurs in the heat affected
zone (HAZ) of welds or in the weld metal itself. Reheat cracking can either occur
during PWHT or in service at high temperature.

This damage mechanism is most likely to occur in heavy wall vessels in areas of
high restraint (e.g., nozzle welds and heavy wall piping). HSLA steels are very
susceptible to reheat cracking. 

Refractory Degradation
Refractories are used extensively in various units and processes. Refractory
materials such as insulating ceramic fibers, castables, refractory brick, and
plastic refractory, are susceptible to various forms of mechanical damage and
corrosion.

The key to mitigating refractory damage is the proper selection of refractory,

anchors, and fillers; as well as their proper installation. Inspecting for refractory
damage consists of performing visual inspection during shutdowns. Furthermore,
cold-wall equipment can be surveyed on-stream using IR to monitor for hot spots.

Short Term Overheating – Stress Rupture

Short Term Overheating (also referred to as Stress Rupture) occurs when
equipment, piping or furnace tubes that are designed to operate safely and
reliably in one temperature range are exposed to higher temperatures. At the
higher temperatures the metal is weaker and can only resist operating pressures
and stresses for a shorter period of time, sometimes only hours or minutes, if the
design temperature is significantly exceeded. Furnace tubes are the most
common types of equipment to suffer stress rupture from short term overheating.

Short Term Overheating can be prevented with careful operation,

instrumentation, inspection, and maintenance activities. These include routine IR
monitoring of susceptible equipment, heat sensitive paint on cold shell vessels,
furnace tube and vessel skin thermocouples, careful burner management of fired
heaters, and routine inspection and maintenance of refractory-lined equipment.

Sigma Phase Embrittlement

A metallurgical phase change occurs in some stainless steels when they are
heated above about 1000F (540C). That phase change results in a dramatic loss
of toughness, and therefore, can lead to brittle fracture of the “sigmatized”
equipment.

There’s no reasonable way to detect sigmatized stainless steels other than doing
impact testing or metallographic examination on failed equipment to verify what
caused the brittle cracking. The key to prevention of brittle cracking from sigma
phase is to select alloys that have less susceptibility to being sigmatized above
1000F, and with austenitic stainless steels that means careful ferrite control. 

Softening (Spheroidization)
Spheroidization occurs when carbon and low alloy steels are exposed to
temperatures in the range of 850F - 1400F (440C - 760C) where carbide phases
(the strengthening element of steels) become unstable and begin to
agglomerate, which then results in the loss of strength. It is not much of a threat
to pressure equipment, except in some unusual circumstances. Usually the loss
of strength is relatively minor, but under some high temperature conditions can
cause a 30% reduction in strength. However, that loss of strength usually results
in some reduction in design margin, which can sometimes be acceptable for
continued safe operation with appropriate fitness-for-service analysis.

Equipment that is susceptible to spheroidization include most vessels or piping

operating in the susceptible temperature range or that might be inadvertently
exposed to high temperatures because of operating malfunctions. Such
equipment includes furnace tubes, reactor/regeneration equipment in FCCUs, cat
reformers, cokers and hydroprocess reactors that might be exposed to
uncontrolled exothermic conditions (i.e.temperature runaways). Some steels are
more susceptible than others, including fine-grained steels versus course-
grained, aluminum-killed steels versus silicon-killed, and normalized steels
versus annealed.

Though the likelihood of spheroidization damage can be detected with standard

hardness testing looking for characteristic softening, spheroidization can only be
confirmed by taking samples for laboratory metallography or performing field
replication metallography for observation under microscopes.

Steam Blanketing
Steam-generating units, including fired boilers, waste heat exchangers in sulfur
plants, hydrogen reformers, and FCC units, can be affected by this type of
damage. Heat energy flowing through the wall of generating tubes results in the
formation of steam bubbles, which are swept away by moving fluid. When the
heat flow balance is disturbed, individual bubbles join to form a steam blanket.
Once the steam blanket forms, tube rupture can occur rapidly.

Prevention can be achieved with proper burner management and proper Boiler
Feed Water (BFW) treatment. 

Strain Aging
Strain aging occurs mostly in older vintage steels (carbon and low alloy) that
were common in older refineries. Decades ago, carbon steels were commonly
manufactured using processes that contained higher levels of critical impurity
elements than modern day steels, which are crafted with the Basic Oxygen
Furnace (BOF) process. Steels made by BOF that are fully killed are not
generally susceptible to Strain Aging.

What happens to the older steels is that they can undergo a form of precipitation-
hardening which increases their strength a bit, but more importantly results in
lower toughness. The lower toughness, in turn, could lead to brittle fracture when
associated with a critical defect of some sort. 

Temper Embrittlement
Temper embrittlement is a form of metallurgical degradation resulting from
exposure of susceptible low alloy steels to higher temperature ranges, usually in
service, but can occur to some extent even during heat treatment. Over a long
period of exposure to high temperatures, the material’s ductile/brittle transition
temperature decreases, meaning that it may become brittle at a lower
temperature.
If significant temper embrittlement has occurred, the equipment may be
susceptible to catastrophic brittle fracture. The low alloy steel most susceptible is
the 2.25Cr-1Mo steel, from which so much of the refining industry’s heavy wall
hydroprocess equipment is fabricated.

Certain low levels of “tramp” elements enhance the potential for temper
embrittlement. These elements, which include phosphorus, tin, antimony, and
arsenic, inadvertently make their way into steel during the steel making process
or through welding.

The best way to minimize the likelihood and extent of the so-called “tramp”
elements found in the base metal and welding consumables.

Temper embrittlement cannot be detected by normal inspection methods.

Toughness testing is the only conclusive way of determining the extent of
embrittlement. 

Thermal Fatigue

Foundational Concepts

Fatigue

Thermal Fatigue is caused by swings in temperature that create cyclic stresses.

In other words, repeated rises and falls in temperature of a component can result
in cracking damage. The more dramatic the temperature swings, and the more
frequent the number of cycles, the more likely that this damage mechanism will
result.

Some examples of situations that may give rise to thermal fatigue are:

 Equipment startup and shutdown

 Mix points of hot and cold streams such as hydrogen mix points in
hydroprocessing units
  Coke drum skirts, where stresses are promoted by a variation in
temperature between the drum and skirt 

Thermal Shock

Foundational Concepts

Fatigue

Thermal shock is a form of thermal fatigue cracking that can occur when high
and non-uniform thermal stresses develop over a relatively short period of time in
a piece of equipment.

Thermal shock failures usually involve sudden quenching of high temperature

equipment and furnace tubes with a relatively cooler liquid or saturated steam
containing some liquid, but not always. It can occur from sudden cooling of any
high temperature equipment, or sudden cooling of even lower temperature
equipment that causes it to suddenly be operating in a range in which it is now
brittle. Physical restraint of equipment that needs to grow as its temperature
increases or contract as its temperature decreases, will often produce
deformation or cracking failures.

The best way of avoiding unexpected thermal shock is to make sure that
operations and process engineers understand what can happen to equipment if
they suddenly chill it.

Vibration-Induced Fatigue

Foundational Concepts

Fatigue
Vibration Fatigue is a form of Mechanical Fatigue that is caused by dynamic
loading due to vibration, water hammer, or unstable fluid flow.

Typically the vibration is detectable or known to operators, so their knowledge of

the consequences of living with vibrations is key to prevention. Operators should
be encouraged to report vibrations to engineers and inspectors so that steps can
be taken to mitigate the cause of the vibration.

There are several design and operating steps that can be taken to minimize
vibration, and therefore prevent vibration fatigue failures. Often adding supports,
stiffening gussets, anchors, or dampeners can help. Sometimes shifting the
operating conditions of the machine is necessary.

Inspection cannot be relied upon to find vibration fatigue cracks before failure.
Though it is possible to find cracks with surface NDE techniques, most often the
time from cracking onset to failure is too short for inspection to be relied upon.
Therefore, operator knowledge is key to prevention.

Uniform or Localized Loss of Thickness

Amine Corrosion
Amine Corrosion occurs on carbon steel in amine treating processes. It is not
caused by the amine itself, but rather as a result of dissolved acid gases (CO2
and H2S), amine degradation products, Heat Stable Amine Salts, and other
contaminants. This damage mechanism can appear as either general uniform
thinning, localized corrosion, or localized underdeposit attack.
Ammonium Bisulfide Corrosion (Alkaline Sour Water)
This type of corrosion occurs in hydroprocessing reactor effluent streams and in
units handling alkaline sour water. Carbon steels are less resistant than 300
Series and duplex stainless steels, aluminum alloys, and nickel base alloys. The
more ammonium bisulfide (NH4HS), H2S partial pressure, velocity, the more
prone to Ammonium Bisulfide Corrosion a metal will be. Additional critical factors
that increase the likelihood of this corrosion are pH, temperature, and flow
distribution.

Ammonium Chloride Corrosion

When ammonia or amine chloride salts are present in a process stream,
Ammonium Chloride Corrosion may occur. The following units and equipment
are affected:

Crude Tower Overheads (tower tops, top trays, overhead piping, exchangers,
and top pumparound streams)

 Hydroprocessing (reactor effluent streams)

 Catalytic Reforming (reactor effluent streams and the H2 recycle system)
 FCCU and Coker (fractionator overheads and top pumparounds)

Aqueous Organic Acid Corrosion

Crude oil may contain some organic compounds that can decompose in the
crude furnace to form organic acids which condense in distillation tower
overhead systems. These acids may lead to this type of corrosion.

All carbon steels are affected; most other alloys that are typically used in crude
tower overhead systems are generally not affected.

Aqueous Organic Acid Corrosion in crude unit overhead systems can be

minimized with the injection of a chemical neutralizing additive. However,
frequent changes in crude blends must be paid attention to as they will require
different types or amounts of neutralizers.

Filming amines can also be used to prevent this type of corrosion so long as the
selected filming amine does not react with the organic acid. Filming amines are
not as effective as neutralization.

And finally, as with many other types of corrosion, upgrading to corrosion-

resistant alloys can prevent this type of corrosion. 

Atmospheric Corrosion
Atmospheric Corrosion refers to corrosion that affects equipment that is not
insulated and is exposed to moisture associated with atmospheric conditions
such as rain, condensation from humidity, marine spray, cooling tower mist,
industrial pollutants, etc.

Equipment located in dry or arid environments tend to have lower Atmospheric

Corrosion rates (<1 mpy) than equipment found in marine environments
(reaching up to 20 mpy).

As opposed to Corrosion Under Insulation, Atmospheric Corrosion is not hidden

underneath insulation materials and can be found with visual inspection.
Furthermore, if an equipment painting program is in place and up-to-date, the
corrosion becomes even easier to find visually. 

Boiler Water Condensate Corrosion

Boiler Water Condensate Corrosion occurs in boiler systems and condensate
return pipings. It primarily affects Carbon Steels, as well as some low alloy
steels, 300 Series SS, and copper based alloys.
This type of corrosion is usually the result of dissolved oxygen and carbon
dioxide. Critical factors are the concentration of dissolved gas, pH, temperature,
quality of the feedwater, and the specific feedwater treating system.

If the treatment system is effective, then a layer of iron oxide (magnetite) will
provide the protection needed to minimize boiler corrosion. If the treatment is not
effective or the quality varies from time to time then pitting type corrosion can
occur in the entire front end of the boiler, including the treating system,
deaerator, feed water lines, pumps, and preheat coils.

Higher pressure and temperature boiler systems tend to be more difficult to

control to the specifications required for minimizing this type of corrosion.
Chemical treatment for scale and deposit control must be tuned to coordinate
with the oxygen scavenger (typically sodium sulfite or hydrazine) and tuned for
the specific water quality and feedwater treating system. Routine water analysis
is the best monitoring tool to make sure that treatment systems are functioning
properly.

Caustic Corrosion
Caustic Corrosion is caused by the concentration of caustic or alkaline salts that
usually occur under evaporative or high heat transfer conditions. Carbon steels,
low alloy steels, and 300 Series steels are primarily affected.

The largest contributing factor to this type of corrosion is, as the name implies,
the presence of caustic (NaOH or KOH).

As with many other types of corrosion, the best prevention/mitigation strategies

are those that involve proper design.

CO2 Corrosion
Carbon dioxide (CO2) corrosion is most typically found in boiler condensate
return systems that are not adequately treated with corrosion inhibitors (typically
amines). Dissolved CO2 in condensate forms carbonic acid (H2CO3) which
corrodes steels and low alloys to form an iron carbonate scale.

Mitigation/prevention of this damage mechanism involves:

 Using corrosion inhibitors

 Using neutralizers (amines) to increase the pH level of condensate above
6
 Using 300 Series Stainless Steel

Water analysis is the best way to detect condensate problems that may lead to
leaks in condensate return systems. Radiography or ultrasonic thickness
measurements on the bottom of condensate piping and on the back side of
elbows or other areas of higher velocity and/or turbulence may also detect
localized thinning typical of condensate corrosion.

Cooling Water Corrosion

Cooling Water (CW) Corrosion is caused by dissolved salts, gasses, organic
compounds, or microbiological activity in water-cooled heat exchangers and
cooling towers. It is one of the oldest forms of corrosion in the refining industry,
yet it still poses challenges.

Cooling water corrosion and fouling are closely related and should be considered
together. Critical factors in controlling both include: process and CW
temperatures, heat flux, water velocity, type and quality of water (salt, brackish,
fresh) and type of cooling system. Increasing process side temperatures or
cooling water outlet temperatures typically will increase corrosion and fouling
rates. Generally, if the process side temperature is above 140F (60C), then
there’s a potential for scaling on the water side. With very few exceptions, the
CW needs to be on the tube side to minimize corrosion and fouling. Fluid velocity
in the tubes needs to be high enough to avoid dropping out deposits (typically
~3+fps) and low enough to avoid erosion-corrosion problems.
Corrosion in CW exchangers can manifest itself as general thinning, pitting,
stress corrosion cracking and microbiologically induced corrosion. Electric
resistance welded tubes will sometimes suffer localized weld attack, especially if
the CW quality is less than desirable.

Cooling water corrosion and fouling can be prevented by proper design,

operation, and chemical treatment of cooling water systems. 

Corrosion Under Insulation

Corrosion Under Insulation (CUI) is one of the most well-known phenomena in
the process industries, and yet it still makes up an inordinately large percentage
of global maintenance expenditures. CUI is a subject that is well-researched and
understood; extensive studies have been commissioned to determine the
causes, effects, prevention, and mitigation of CUI.

CUI is corrosion that occurs due to the presence of moisture on the external
surface of insulated or fireproofed equipment.

Any insulated piping or equipment is susceptible to CUI under the right

conditions. Some examples of situations that may give rise to CUI are:

 A facility being location: regions with high annual rainfall or humid

conditions are more prone to CUI than cooler, drier regions.
 Poor design or installation may allow water to become trapped.
 Inadequate design of insulation systems or improper selection of insulation
types.

Numerous mitigation and inspection approaches have been studied and

recommended, and are outside the scope of this summary. Refer to API RP
583, Corrosion Under Insulation and Fireproofing, for a thorough reference on
the design, maintenance, inspection, and mitigation practices for equipment that
is subject to CUI. 

IMAGE GALLERY
  

 
  

Dealloying
Dealloying, as the name implies, is corrosion that selectively removes specific
elements from an alloy. It may also be referred to by the element removed (e.g.
dezincification or dealuminification).

Alloys that are most commonly affected are copper alloys (brass, bronze, tin),
Alloy 400, and cast iron (refer to Graphitic Corrosion).

Dealloying of these alloys is influenced by temperature, degree of aeration, pH,

and time, although it is difficult to pinpoint exact conditions for each alloy. The
following table, found in API RP 571, provides common examples of where
dealloying has been found:

Alloy Environment Element Rem

Brasses (>15% Zn) * Many waters, especially stagnant Zinc (dezincif

conds.
 Gray Cast Iron Soils, many waters Iron (graphitic

Aluminum bronze (primarily w/> 8% HF acid, acids w/chloride ions, Aluminum

Al) seawater (dealuminifica

Silicon bronzes High-temp steam and acidic species Silicon (desili

Tin bronzes Hot brine or steam Tin (destanni

Copper nickels (70-30) High heat flux and low water velocity Nickel (denic

Monel Hydrofluoric and other acids Nickel (denic

* The extent of dezincification increases with increasing zinc content.

API RP 571 Table 4-7 – Combinations of Alloys and Environment Subject to

Dealloying.

Flue-Gas Dew-Point Corrosion

Most flue gases produced by the combustion of fuels contain contaminants that
can condense into sulfuric, sulfurous, or hydrochloric acid droplets. Flue Gas
Dew Point Corrosion occurs when these aggressive acids condense on carbon
and stainless steels in convection sections, flue ducts, and stacks. The amount of
contaminants in the fuel is directly correlated with the concentration of the acid
droplets, and therefore with the degree of corrosion.

There are several ways in which flue gas dew point corrosion can be avoided.
More resistant materials can be used in the construction of flues, which can
prevent corrosion. Also, limiting the number of contaminants in heater and boiler
fuels is another good way to prevent corrosion from occurring. Although, it should
be noted that the latter method is far more difficult to accomplish since most fuels
contain sulfur compounds and some are contaminated with chlorides. Another
way to prevent corrosion is to maintain the surface metal temperatures of
exposed equipment above the dew point. it is possible to protect cooler surfaces
by applying a coating that is resistant to the acidic condensate and will withstand
the temperatures to which it is exposed.

Inspection of this type of corrosion involves (1) UT for wall thickness

measurements to monitor wastage in economizer tubes, and (2) VT and PT to
detect stress corrosion cracking of 300 Series SS.

Galvanic Corrosion
Galvanic Corrosion refers to the accelerated corrosion of one metal when in
contact with another in a suitable electrolyte such as a moist or aqueous
environment. All metals, with the exception of the most noble, are affected. In
order for galvanic corrosion to occur, the following three conditions must be met:

1. An electrolyte (a fluid that can conduct a current) must be present.

2. Two different metals (known as the anode and the cathode) are in contact
with the electrolyte.
3. An electrical connection must exist between the anode and cathode.

The cathode is protected by sacrificial corrosion of the more active material (the
anode). The anode corrodes faster than it would if it were not connected to the
cathode through an electrolyte. If there is a large ratio of anode to cathode area,
the cathode will effectively be protected and the anode may not corrode at all.
Inversely, a small anode area and a large cathode area will result in rapid
corrosion.

Prevention of galvanic corrosion is achieved through proper design. Coatings

may also be helpful, but the more noble material should be coated.
Note: galvanic corrosion can also serve as a benefit when used purposefully –
cathodic protection with sacrificial anodes provides corrosion protection of one
metal by the preferential corrosion of another.

Graphitic Corrosion
Graphitic Corrosion is a form of dealloying that affects cast iron. Cast iron is
comprised of graphite and iron; over a long period of exposure to low pH and
stagnant conditions, the iron matrix of the cast iron is corroded, leaving only the
porous graphite.

This damage mechanism can occur in the presence of soft water, salt water,
mine water, dilute acids, and in underground piping and boiler feedwater
equipment.

Damage caused by graphitic corrosion can be general or localized. It may not be

noticeable upon visual inspection, but damaged areas will be soft and easily
gouged with hand tools. 

High Temp H2/H2S Corrosion

High Temperature H2/H2S Corrosion is a form of high temperature sulfidation
that occurs in piping and equipment in units where high temperature H2/H2S
streams are found. Such units include hydroprocessing units like desulfurizers,
hydrotreaters and hydrocracking units.

The major factors affecting this damage mechanism are temperature, the
presence of hydrogen, the concentration of H2S, and the alloy composition.

It can be prevented with proper materials selection – alloys with high chromium
content minimize the damage. More specifically, the 300 Series SS (304L, 316L,
321, and 347) are highly resistant.

Hydrochloric Acid (HCl) Corrosion

Hydrochloric Acid (HCl) Corrosion is a significant problem in many refining and
chemical process units, and often the materials solution to HCl corrosion is rather
expensive, since the lower cost, more available alloys are usually not resistant to
most concentrations of HCl. Typically process unit construction materials are
chosen to resist HCl when the designers know where HCl will be present in the
process, and at what temperature and concentration. The trouble comes when
low pH HCl fluids show up where they were not expected or process changes
occur causing unexpected HCl corrosion.

In the refining industry, the most common reason for HCl corrosion is dew point
formation in the overhead of distillation towers. Most crudes contain inorganic
salts that give rise to dew point HCl corrosion, and while effective desalting
removes the vast majority of these salts (thus reducing overhead corrosion), the
chlorides from those salts that are not removed often end up in the overhead
piping, exchangers and accumulator vessels as low pH corrosive water solutions.
Because of the mechanics/chemistry of dew point corrosion, the point where the
dew point first occurs in the overhead steams is normally the most corrosive and
lowest pH. If that point keeps shifting upstream or downstream (because of
process variations) from where it was expected by the plant designers, then
unexpected leaks can occur.

A similar phenomenon can occur at various mix points in process streams where
chloride contaminated streams are mixed with lower temperature, wet process
streams causing aggressive corrosion with hydrodynamic effects at the mix point
and just downstream of it. Another fairly common source of corrosion from
chlorides occurs in cat reforming units where chlorides are stripped from the
catalyst and then migrate downstream in recycle hydrogen streams. If chloride
beds/ treaters are not present or not maintained, then excessive chlorides can
break through and cause corrosion wherever the dew point is reached
downstream.
The refining industry has experienced a number of cases of severe corrosion
from organic chloride contamination of process crudes. These organic chlorides
are not effectively removed during normal desalting and often migrate
downstream to naphtha hydrotreaters (NHT), where they hydrolyze into low pH
streams that can cause corrosion rates into the 3-4 digit range, and leaks in
equipment within a very short period of time. Unfortunately, these organic
chlorides are not easily detected and are not revealed in typical crude assays.
But there are effective means to test for them and to monitor wash water pH in
NHT streams.

Prevention of HCl failures involves knowledge of where the low pH solutions are
likely to exist and selection of a number of potential mitigation strategies. These
strategies include choosing the right alloys to resist HCl corrosion, proper
neutralization and/or inhibitor injection, avoidance of oxygenates that can cause
corrosion of otherwise resistant high alloy materials, and installation and
maintenance of wash water systems and monitoring pH of water steams.

HCl corrosion can be both general and highly localized depending upon where a
dew point may be forming, where low pH solutions collect and the presence of
hydrodynamic effects.

Hydrofluoric (HF) Acid Corrosion

Hydrofluoric Alkylation (“HF Alky”) Units are usually carefully controlled in order
to avoid potential for a toxic hydrofluoric acid cloud after a leak. That said, HF
Alky Units also can have problems with process control that results in wet acid
carryover into carbon steel sections of the plant, which were never intended to be
exposed to HFA, resulting in corrosion and leaks. Whenever the temperature of
the acid phase exceeds 150 F or water content of the acid exceeds 3% (or some
combination thereof), there is the likelihood of higher corrosion rates on carbon
steel equipment. In areas prone to corrosion on carbon steel, Alloy 400 is widely
used with success, if oxygenates are minimized.

Carbon steel areas prone to corrosion include flange faces, deadlegs, overhead
systems, and some heat exchanger bundles. One of the interesting aspects of
HF Acid Corrosion on carbon steel is that corrosion rates can vary considerably
depending on the residual elements content of the steel. Some evidence exists
that the total % of Cu, Ni, and Cr need to be below 0.20% in order to avoid
accelerated corrosion of carbon steel in specific parts of the plant.

Refer to API RP 751 Safe Operation of HFA Alkylation Units for a more complete

reference on this damage mechanism.

Microbiologically Induced Corrosion (MIC)

Microbiologically Induced Corrosion (MIC) is caused by biological growth such as
bacteria, algae, or fungi, in water under low flow or stagnant conditions. It occurs
in cooling water systems, piping, vessels, and storage tank bottoms where the
conditions are conducive to it.

The following excerpt from A Framework for Conducting Analysis of

Microbiologically Influenced Corrosion Failures goes into further detail:

On wetted surfaces, microorganisms typically exist in a diverse biofilm that

consists of extracellular polymeric substances (EPS), various types of cells, and
organic and inorganic material. Biofilms formed by microorganisms create a
microenvironment on the metal surface that can differ significantly from the
overall environment, leading to local differences in electrochemical potential
resulting in corrosion. Microbial activities in biofilms can also facilitate corrosion
by producing corrosive metabolites (acids, elemental sulfur), changing the nature
or kinetics of rate controlling reactions, forming mineral scales, and direct uptake
of electrons from the steel surface.
Microorganisms and their activities are affected by many environmental factors,
including most prominently, temperature, salinity, oxygen concentration, pH, and
availability of nutrient compounds. Although most microorganisms can exist over
a range of these environmental conditions, they commonly have a set of
conditions at which growth is optimal. When conditions are unfavorable, cells
may become dormant or die, or transition to a spore form that can last a long
time until conditions once again become favorable for growth.

MIC manifests itself as pits that sometimes have subsurface “caverns” that are
larger than the pitted opening to the surface.

Naphthenic Acid Corrosion

Naphthenic Acid Corrosion (NAC) is associated with dry hydrocarbon streams
(no water phase). There are a variety of organic acids associated with
naphthenic acids in different crudes, and each can have a different impact on the
actual corrosion rates experienced. Though sulfur in crude promotes the
passivity and thus has an inhibiting effect on NAC, naphthenic acids remove the
protective sulfide scales, and typically result in a very localized type of corrosion,
which is difficult to find during external examinations of equipment. And though
NAC damage is typified by dozens of small localized “pock marks” and grooving
type corrosion surrounded by full thickness material, some lower alloys can
corrode by general thinning. Velocity and turbulence are big issues with regard to
NAC rates, including the flash zones of VFU’s, areas of two phase flow, weld
profile discontinuities, piping components, thermowells and pumps. Typically, the
higher the temperature of the hydrocarbon stream (up to 800 F [427 C]), the
more severe the NAC will be, up until the streams move into cat crackers and
hydroprocess units where the organic acids are destroyed.

Mitigation of the NAC is typically done in one of two ways or a combination of

them. Upgrading construction materials with increasing amounts of Molybdenum
is most effective, with type 316 and 317 stainless steels offering good resistance
under most circumstances where low alloy steels no longer offer cost effective
resistance. However, when conditions are particularly severe for NAC, upgrading
to 6% Mo alloys has provided resistance. The other main mitigation method is
crude and process cut blending to stay below a certain preset TAN in the crude
or process cut. Some companies have also tried NAC inhibitors. All of the known
mitigation strategies are pulled together in a model called CORAS, offered by
Shell Global Solutions to help find the most cost effective way to process high
TAN crudes.

Phenol (Carbolic Acid) Corrosion

When phenol is used as a solvent in plants to remove aromatic compounds from
lubricating oil feedstocks, Phenol Corrosion can occur. Materials affected, in
order of increasing resistance, are carbon steel, 304L, 316L, and Alloy C276.
This damage mechanism most commonly occurs in phenol extraction facilities in
lube plants.

As with many other damage mechanisms, the best prevention is to proactively

select proper materials and control of phenol solvent chemistry.

UT and RT can be used to monitor for thickness losses, and ER corrosion probes
and corrosion coupons have been used for corrosion monitoring.

Phosphoric Acid Corrosion

Corrosion from phosphoric acid is an issue that affects only a few processes in
the refining industry. It is largely associated with polymerization units using
phosphoric acid as a catalyst. Dry phosphoric acid catalyst is not corrosive to
carbon steel but that changes dramatically when free water is present. For nearly
all acidic corrosion, water content and temperatures are keys to understanding
how aggressive the corrosion is likely to be. Wet phosphoric acid can corrode
carbon steel at thousands of mils per year. Where water is present, upgrading to
304L, 316L, or Alloy 20 may be necessary largely depending on temperature.
Corrosion can often be found in dead zones and crevices where wet acid can
drop out. 

Soil Corrosion
Soil corrosion (also “underground corrosion”) is, as the name suggests, corrosion
caused by metals that are exposed to soils. It is well known and documented
since so many pipes and pipelines are buried underground, and nearly all
storage tanks rest on the soil. Soil corrosion rates can range from very low to
fairly aggressive, depending on the type of soil, the amount of moisture, soil
contamination, soil resistivity, drainage, and oxygen content.

Properly selected and applied coatings are key to soil corrosion control. A
combination of a well-designed and maintained Cathodic Protection system,
alongside good coatings, is the best way to control soil corrosion.

API 570, Piping Inspection Code, has an entire section devoted to the inspection
of buried piping. 

Sour Water Corrosion (Acidic)

Acidic sour water which contains H2S and a pH between 4.5 and 7.0 can result
in Acidic Sour Water Corrosion. It is a concern in FCCU overhead systems and
coker gas fractionation plants with high levels of H2S and low NH3 levels.

This damage mechanism primarily affects Carbon Steel, Stainless steel, copper,
and nickel-based alloys are resistant.

Sulfuric Acid Corrosion

Sulfuric Acid Corrosion of carbon steel and other alloys occurs when sulfuric acid
reacts with the iron in carbon steel to form ferrous sulfate (FeSO4). In the refining
industry, the most common place to experience this damage mechanism is in the
sulfuric acid alkylation units where process control or water contents of acids
deviates from design operation.
 High Temperature Corrosion

Carburization
Carburization occurs when carbon is absorbed into a material at high
temperature operating environments – typically temperatures above 1,100 F (593
C). Susceptible materials include carbon steel and low alloy steels, 300 and 400
Series stainless steels, cast stainless steels, some nickel base alloys, and
HK/HP alloys. In order for carburization to occur, these materials must have
exposure to a carburizing environment or carbonaceous material.

Carburization occurs most commonly in fired heater tubes but can also be found
elsewhere, so long as the conditions above are met.

Prevention of this damage mechanism comes down to alloy selection or reducing

the carbon activity in the environment through lower temperatures or higher
oxygen/sulfur partial pressures.

IMAGE GALLERY

Decarburization
Decarburization is the antithesis of carburization and rarely results in equipment
failure. However, surface decarburization is often a sign that something more
serious is going on, namely high temperature hydrogen attack (HTHA).
Decarburization can also be indicative of improper post weld heat treatment and
help identify equipment that is fire damaged, as hardness testing will reveal a
softening of the surface, indicative of loss of carbon (iron structure without carbon
is relatively soft compared to steels with carbides in their structure). 

Fuel Ash Corrosion

Fuel Ash Corrosion (or “catastrophic oxidation”) can occur when certain
contaminants are present in a high temperature environment, for example inside
furnace fireboxes. Those contaminants are typically vanadium pentoxide with
sulfur oxide or sodium sulfate. When these contaminants are present in the
combustion atmosphere, liquid slags can form on components operating above
1000F (538C) which can cause exceedingly high rates of corrosion (sometimes
up to 1000 mpy).

There are a variety of methods to reduce the risk of fuel ash corrosion, including:

 blending or changing fuel sources (minimizing the contaminants) and

operating equipment so that hot components are below the temperature
where molten deposits are formed
 Proper burner design and burner management to reduce flame
impingement and localized hot spots
 Firing with low excess oxygen or injecting special additives into the fuel, so
as to increase the melting point of slags.
 In some components such as tube hangers and supports, changing to a
50%Cr-50%Ni alloy such as Alloy 657 may minimize corrosion. 

Metal Dusting
Metal dusting is a severe form of carburization in which the extensive carbides
that form as a result of carburization lead to grains of metal falling out of the tube
or piping and being swept away by the process stream. This leaves a heavily
pitted looking structure along with thinning of the tube or pipe. Sometimes those
pits are still filled with a granular deposit of carbides that are easily chipped away
during inspection and testing. 

Nitriding
Above certain temperatures, process streams containing nitrogen compounds
such as ammonia or cyanides will form a hard, brittle surface layer on some
alloys – a metallurgical change known as Nitriding. Nitriding begins at
temperatures above 600 F (316 C) and becomes severe above 900 F (482 C).
Other critical factors are time, the partial pressure of nitrogen, and the alloy
composition.

Carbon steels, low alloy steels, and 300/400 Series SS are affected by Nitriding.
Alloys containing 30-80% nickel are more resistant. Therefore, mitigation may be
achieved by changing to alloys with higher nickel content where it makes
economic sense to do so. 

Oxidation
All metals oxidize, even at room temperature, and in many cases that slow
oxidation process actually protects the metal from rapid oxidation. Even rusting is
a low temperature oxidation process. But at higher temperatures, oxidation can
proceed fast enough to produce excessive scaling and thereby inhibit the
usefulness of steels and alloys at elevated temperatures. For carbon steel the
oxidation temperature limit is usually in the vicinity of 900F (482C) - 950F (510C)
range.

For higher temperature oxidation resistance, as well as strength, steels are

alloyed with chromium and molybdenum to increase their usefulness in high
temperature applications such as furnace tubes, furnace outlet piping, hot
hydroprocess equipment and catalytic reaction equipment.
Infrared thermography and surface thermocouples are two widely used methods
of monitoring for temperatures that may exceed design conditions of construction
materials. When high temperature oxidation failures do occur, it’s usually
because the excessive scaling or hot spots are not obvious. They may be on
furnace tubes that are not within sight of a furnace view port or may be occurring
underneath external insulation. Refractory linings can fail, causing steel pressure
retaining construction materials to be exposed to excessive temperatures. If the
OD is insulated, these excessive temperatures may not be apparent. 

Sulfidation
Sulfidation (or sulfidic corrosion) is corrosion that occurs with carbon steel and
other alloys as a result of the presence of sulfur compounds in high temperature
environments. It is a very common damage mechanism in the refining industry
and has been the cause of several high profile incidents.

Sulfidation is typically of concern in sour (high in hydrogen sulfide or other active

sulfur compounds) crude oil services starting at temperatures in the 500 F (260
C) range.

Common process units of concern are the crude, FCC, coker, vacuum,
visbreaker, and hydroprocessing units. Heaters fired with oil, gas, coke, and most
other sources of fuel may be affected depending on sulfur levels in the fuel.
Boilers and other high temperature equipment exposed to sour gases may also
be affected.

Sulfidation corrosion appears most often in the form of uniform thinning but may
also occur as localized corrosion or high velocity erosion-corrosion damage.

Industry failures from sulfidation have occurred, in large part, for one of three
reasons:
 1. Lack of adequate PMI, meaning that an inadvertent substitution of carbon
steel or lower chromium alloy caused a component to fail prematurely or
unexpectedly
2. Piping systems having a mixture of higher silicon containing steels
(“silicon-killed”) and lower silicon containing steels (“non-killed”).
3. Process Creep, or the gradual increase over time in hydrogen sulfide
content of process streams introduced by changing feedstocks.

Adequate PMI and MOC work processes can help to prevent unexpected piping
failures from sulfidation.
 Environment-Assisted Cracking

Amine Stress Corrosion Cracking

Foundational Concepts

Stress Corrosion Cracking

Amine Stress Corrosion Cracking (or, more commonly, “amine cracking”) is a

form of alkaline stress corrosion cracking that affects carbon and low alloy steels.
This damage mechanism is associated with lean amine, whereas cracking in rich
amine is actually wet H2S cracking.

Critical factors for this damage mechanism are the level of tensile stress (residual
stresses from welding, cold working, or fabrication that have not been removed
through proper PWHT), amine concentration, and temperature.

Amine cracking occurs in MEA and DEA services, but can also be found in
MDEA and DIPA. Cracking has occurred down to ambient temperatures with
some amines.

Equipment handling lean amine solutions that has not been stress-relieved or
may have been inadequately stress-relieved. This includes contactors,
absorbers, strippers, regenerators, and accumulators, as well as any equipment
that is subject to inadvertent amine carry over or steam cleaning in preparation
for maintenance.
Amine cracking propagates parallel to the weld in adjacent base metal but it can
also occur in the weld deposit or heat affected zone (HAZ). Cracks are similar in
appearance to those caused by wet H2S damage.

Post-weld heat treatment (PWHT) is an effective way to mitigate amine cracking.

Solid or clad stainless steel, alloy 400, or other corrosion resistant alloys can be
used in place of carbon steel to provide resistance to amine cracking. For crack
detection, performing WFMT, EC, RT, or ACFM is most effective. PT is not
effective. AET can be used for monitoring crack growth and locating growing
cracks.

Ammonia Stress Corrosion Cracking

Foundational Concepts

Stress Corrosion Cracking

Ammonia Stress Corrosion Cracking is a form of stress corrosion cracking that

commonly occurs in brass tubes in cooling water service that has been
contaminated with ammonia due to biological growths or other contamination.
This cracking can also occur when ammonia is intentionally added to process
streams as a neutralizer by someone unaware of its potential effect on brass
tubes. Brass condenser tubes can undergo brittle fracture if bent when significant
ammonia stress corrosion cracking is present.

Ammonia stress corrosion cracking can also affect carbon steel equipment, but
unlike the cracking mechanism on brass which occurs in an aqueous solution,
the cracking of steel equipment occurs in anhydrous ammonia. Systems with
air/oxygen contamination also tend to be particularly vulnerable to this issue.
Thankfully though, there are several ways in which ammonia stress corrosion
cracking can be prevented in steel equipment. First and foremost, systems that
have not undergone postweld heat treatment (PWHT) are much more
susceptible, thus proper PWHT is essential. Adding a very small amount of water
(0.2%) to the anhydrous ammonia can also inhibit the cracking of steel.

When inspecting for ammonia stress corrosion cracking in brass tubes, some of
the best techniques to involve the use of eddy current, such as pulsed eddy
current testing or eddy current array testing. To inspect for ammonia cracking in
steel tubes, wet fluorescent magnetic particle testing is best for where access to
the surface is available; when it’s not, shear wave ultrasonic testing tends to work
best.

Cupro-nickel alloys are usually not susceptible to ammonia stress corrosion

cracking, so if all else fails, upgrading to a new material is another form of
prevention. Austenitic stainless steels likewise are resistant to this form of
corrosion, so using them is another option.

Carbonate Stress Corrosion Cracking

Foundational Concepts

Stress Corrosion Cracking

Carbonate Stress Corrosion Cracking (“carbonate cracking”) is a form of alkaline

stress corrosion cracking that affects carbon and low alloy steels in “wet”
carbonate service. It often occurs more aggressively at higher pH and higher
concentrations of carbonate solutions.

Carbonate cracking requires the presence of water in order to form. Most failures
have occurred when the pH of the sour water ranges between 8 to 10. Some
amount of H2S may be present, although there is no established threshold
amount. Furthermore, Ammonia (NH3) raises the pH and therefore increases
cracking likelihood.
In FCCUs, higher levels of Feed Nitrogen and lower levels of Feed Sulfur are
associated with cracking susceptibility. In most cases, the Feed Nitrogen to
Sulfur ratio ranges from 0 to 70.

Carbonate cracking has been observed in the overhead system of FCCUs

(where water exists), in SWS strippers, and in Catacarb and CO2 removal
facilities of hydrogen manufacturing units. Cracks propagate parallel to the weld
in adjacent metal but can also occur in the weld deposit or HAZ. Cracks may be
mistaken for SSC or SOHIC, although they are usually further from the toe of the
weld and have multiple parallel cracks.

Effective PWHT is usually a good way to prevent Carbonate Cracking, but if it

isn’t done right with sufficient soak time and higher temperatures than normal,
then cracking may reappear in replacement equipment. Alloying up or applying
effective barrier coatings to protect the steel can also be effective. For crack
detection, performing WFMT or ACFM is most effective. PT is not effective. AET
can be used for monitoring crack growth and locating growing cracks. 

Caustic Stress Corrosion Cracking

Foundational Concepts

Stress Corrosion Cracking

Caustic Stress Corrosion Cracking is a form of alkaline stress corrosion cracking.

It is sometimes incorrectly referred to as Caustic Embrittlement; however, no
embrittlement is actually occurring with this damage mechanism. With caustic
stress corrosion cracking, cracks propagate parallel to the weld in the adjacent
base metal but can also occur in the weld deposit or HAZ

Caustic environments cause this type of cracking most commonly in weldments

because of high residual stresses, but base metals with high residual stresses
can also be affected. Affected materials include carbon steel, low alloy steel, and
austenitic stainless steel (nickel-based alloys are more resistant). Caustic stress
corrosion cracking can be found in piping and equipment that handles caustic,
including H2S and mercaptan removal units. It is also found in equipment that
uses caustic for neutralization in sulfuric acid alkylation units and HF alkylation
units.

For caustic stress corrosion cracking, proper PWHT of carbon steel, repair welds,
and internal and internal attachment welds is an effective way to prevent this
from occurring. For crack detection, performing WFMT, EC, RT, or ACFM is most
effective. PT is not effective. AET can be used for monitoring crack growth and
locating growing cracks.

Chloride Stress Corrosion Cracking

Foundational Concepts

Stress Corrosion Cracking

Chloride Stress Corrosion Cracking (Cl-SCC) is a type of Stress Corrosion

Cracking (SCC) and is one of the most well known forms of SCC in the refining
and chemical processing industries. It can be detrimental to austenitic stainless
steels, one of the main reasons these steels are not considered a cure-all for
corrosion problems. Damage due to Cl-SCC is easily identifiable by the telltale
spiderwebbed and lightning-array type network of highly branched cracks.

Despite the facts that we know much about this mechanism and there have been
many failures due to it in the past, it continues to plague the industry. This is
typically due to inadvertent contamination of equipment with chlorides that was
not anticipated by design engineers who are unaware of the potential
consequences of using austenitic stainless steels where chlorides may be
present.
Fortunately, catastrophic failures from Cl-SCC are rare because of the very high
toughness of stainless steel - although they can occur. The consequences from
most leaks tend to be economic in nature, although this can still be devastating to
some plants due to the high costs associated with replacing equipment.

 Chloride cracking of 300 series stainless steels continues to occur in a

number of places, including:
 Cracking from corrosion under insulation (CUI) which contains small
amounts of chloride or where chlorides are present in the atmosphere;
 When a process is inadvertently contaminated with chlorides by
unsuspecting people;
 Equipment that is is hydrotested with chloride contaminated water and left
to dry out (concentrating the chlorides into small pools of highly aggressive
salt solutions), which causes cracking on startup;
 Stainless steel deadlegs which collect chloride contaminated water;
 Instrument tubing that is normally not welded but contains high residual
stresses comes in contact with chloride contaminated atmospheres; and
 Stainless steel bellows which typically have high stress levels come in
contact with chloride contaminated environments especially during down
time.

IMAGE GALLERY

Corrosion Fatigue

Foundational Concepts
 Fatigue

Corrosion fatigue is closely related to mechanical and vibration fatigue cracking,

except that it is initiated and accelerated by a corrosion mechanism, especially
one that gives rise to pitting, from which cracks often initiate. But that corrosion
mechanism need not be very severe in order to give rise to corrosion fatigue. 

Ethanol Stress Corrosion Cracking

Foundational Concepts

Stress Corrosion Cracking

Ethanol SCC is caused by the combination of a fuel grade ethanol (FGE) and,
like all other forms of SCC, a tensile stress. This damage mechanism has been
discovered in carbon steel storage tanks, rack piping, and associated equipment,
and in FGE pipelines. It can be prevented or reduced through proper PWHT or
through the usage of coatings.

Hydrogen Embrittlement
Hydrogen embrittlement is a potential threat for most carbon steels and Cr-Mo
low-alloy steels exposed to services that can saturate the metal with atomic
hydrogen. Hydrogen embrittlement has been observed in some stainless steels
(400-series, precipitation hardening and duplex stainless steels, as well as in
severely cold worked austenitic alloys such as the 300-series stainless steels).
The affected metal, normally considered to be ductile, can fracture in a brittle
manner.

Hydrogen embrittlement is a very simple, yet often misunderstood, mechanism.

Atomic hydrogen is dissolved in the iron lattice taking up space. When the iron is
hot, and therefore more ductile, the hydrogen present does not cause a problem.
However, when the iron is cool, the hydrogen prevents the iron lattice from
moving. This is referred to as embrittlement. It is then de-embrittled when the iron
is heated and once again becomes ductile.

In general, hydrogen embrittlement is an insignificant threat for most services

and normally not a threat above about 300°F (150°C). However, embrittlement
may be a risk during shutdowns and downtime. During shutdowns, inspectors
should avoid activities such as hammer testing and using potentially embrittled
components for internal navigation. High strength low alloy bolting of trays and
tray supports are examples.

The primary mitigation measure for suspected hydrogen embrittlement is to

bake-out the hydrogen before initiating post-shutdown procedures.

IMAGE GALLERY

Hydrogen Stress Cracking - HF

Hydrogen stress cracking occurs when corrosion from acids like wet hydrogen
sulfide or hydrofluoric acid (HF) cause atomic hydrogen to penetrate hardened or
higher strength steels and cause stress cracking. Steel hardness, strength and
stresses present are the critical factors determining susceptibility. When
hydrogen stress cracking is a threat, equipment is often preheated and/or post
weld heat treated (PWHT) to reduce hardness and residual stress levels.

Because hydrogen stress cracking is nearly always a surface phenomena, most

any typical surface NDE is sufficient to find such cracking, and it’s not unusual for
the cracks to be clearly visible to the naked eye, especially those that are
transverse across a weld cap. Hardness testing can find welds and bolting
material that will likely be more susceptible to hydrogen stress cracking. 

Liquid Metal Embrittlement

Liquid Metal Embrittlement (LME), also referred to as Liquid Metal Cracking,
occurs when molten metals come in contact with susceptible materials. Cracking
rates can be exceedingly rapid and failure can occur within seconds. LME most
commonly afflicts austenitic stainless steels, but can afflict other copper, nickel,
and aluminum alloys. Damage resulting from LME appears as brittle cracks in an
otherwise ductile material.

During a fire, molten metals may drip onto a susceptible metal, leading to LME.
Liquid mercury contamination of some crude oils can also cause LMC in crude
overhead condensers as well as the overheads of depropanizers and
debutanizers. Mercury has also cracked aluminum core exchangers in ethylene
plants.

For mitigating LME, any stainless steel that will be used in furnaces or a
temperatures over about 780 F should not be allowed to come in contact with
anything that has been galvanized or coated with zinc containing coatings. For
detecting cracks, use MT for ferritic steel and PT for 300 Series SS and nickel
base alloys. Radiography can be used to locate mercury deposits inside heat
exchanger tubes. 
Polythionic Acid Stress Corrosion Cracking

Foundational Concepts

Stress Corrosion Cracking

Polythionic Acid Stress Corrosion Cracking (PASCC) is an affliction of many

refineries processing sulfur containing feedstocks. PASCC occurs when
sensitized stainless steels that have been in service develop intergranular cracks
after exposure to air and moisture, often during shutdowns. It typically does not
occur during normal processing, but after equipment is shut down and opened up
for inspection, i.e. when moist air contacts the surface of equipment that has
been exposed to sour hydrocarbons in service.

Certain types of 300 series stainless steels that are exposed to elevated
temperatures between 800 F (427 C) and 1700 F (927 C) during manufacture,
fabrication (especially welding), or even in process environments (like furnace
tubes), can become sensitized, which means their crystalline structure changes
such that they become susceptible to intergranular corrosion. PASCC is just one
type of intergranular corrosion that affects sensitized stainless steels. The
commonly used types of stainless steels, 304/304H and 316/316H are
particularly susceptible, whereas the stabilized grades like 321/347 and low
carbon grades 304L/316L are much less susceptible.

A common form of prevention is to do a soda ashwash of the equipment before

or right after it is exposed to air and moisture, e.g. opened for inspection during a
shutdown (refer to NACE RP0170 for neutralization guidelines).

Adequate checks and QA/QC are required to make sure that one does not
inadvertently install sensitized equipment.
PASCC can be found with penetrant testing. Welds are typically most susceptible
because welding heating and cooling rates can cause significant alloy
sensitization. 

Sulfate Stress Corrosion Cracking

Foundational Concepts

Stress Corrosion Cracking

Sulfate SCC can occur with copper alloys that are in sulfate solutions. This type
of cracking is associated with tubes in heat exchanger bundles in overhead
distillation systems where sulfates can form. Some copper alloys are highly
susceptible; however, the 90/10 and 70/30 copper nickel alloys are more
resistant.

Eddy Current or visual inspection techniques can be used to inspect heat

exchanger tubes for this type of cracking. Also, physical bending of sample tubes
can detect early-stage Sulfate SCC cracks.

Wet H2S Damage (Blistering/HIC/SOHIC/SSC)

Wet H2S Damage is a common problem that can occur when carbon steel
equipment becomes exposed to wet H2S service environment. There are a
variety of forms of Wet H2S Cracking, including Hydrogen Induced Cracking
(HIC) and Stress-Oriented Hydrogen Induced Cracking (SOHIC).

This damage mechanism can be a particularly dangerous form of corrosion

because (1) damage caused by it takes place on the interior of vessels, (2) it can
occur without warning, and (3) it can only be detected using complicated
inspection methods.
Wet H2S Damage occurs due to the effects of aqueous hydrogen charging of
steel in wet H2S process environments. This process can happen at relatively
low temperatures, largely as a result of atomic hydrogen from wet H2S corrosion
reactions which enter the steel and collect at inclusions or impurities within the
steel. This happens because the H2S prevents the hydrogen recombination
reaction that would normally occur, forcing the hydrogen atoms into the metal
structure, leading to corrosion and weakness.

Wet H2S damage primarily occurs under acidic conditions, which are present in
most oil refining environments. Any equipment that runs in conditions that are
both above 50 ppm of H2S content and below 180F temperature in aqueous sour
waters is likely susceptible to wet H2S cracking.

Hydrogen Induced Cracking (HIC) is a form of tiny blistering damage caused

by a high concentration of hydrogen in steel. The blistering damage tends to form
parallel to the surface and to the direction of hoop stress. Because of this, it
usually doesn’t become damaging until it either becomes extensive and affects
material properties, or gives rise to cracking that propagates into a weld or
begins to go stepwise through the wall. On the surface, HIC is often horseshoe
shaped and no bigger than the cuticle of one’s small finger.

Stress-Oriented Hydrogen Induced Cracking (SOHIC) is much more insidious.

SOHIC is made up of a series of HIC cracks that are stacked perpendicularly in
the direction of through wall cracks and driven by high residual or applied
stresses. Because this damage can easily lead to integrity failures, facility
owners should take measures to prevent or mitigate it when possible.

Sulfide Stress Cracking (SSC) occurs at locations where atomic hydrogen is

able to diffuse at sites of high internal stress, such as grain boundaries,
inclusions and regions of triaxial stress at notches. When placed in proximity to
tensile stresses, embrittlement and the beginnings of brittle fracture may occur.
The most common NDE method for detecting wet H2S cracking is Wet
Fluorescent Magnetic Particle Inspection (WFMP). This method is able to detect
subsurface cracks in the steel that are caused by HIC, SOHIC, and SSC. For
cracked piping and other components which cannot be inspected using WFMP,
an alternative technique is Phased Array Ultrasonic Testing (PAUT).

Although detection is important, new stainless alloys can be implemented to

replace traditional steels in applications where corrosion can be particularly
severe. When coupled with chemical inhibitors, these alloys are effective at
mitigating corrosion, although they may in some cases still be susceptible to
SSC.

Equipment that is specifically susceptible to SOHIC can be made more resilient

by incorporating post weld heat treatment (PWHT) and/or by being alloyed up.
HIC-resistant steels and polymeric coatings have also been successfully used to
prevent damage. In more aggressive environments, another solution might be
using stainless steel clad materials, as they are more resistant to this sort of
damage.
 Other Mechanisms

High Temperature Hydrogen Attack

Some processes, such as hydrotreaters, utilize hydrogen gas at relatively high
temperatures and pressures. The hydrotreating process temperatures promote
hydrogen dissociation. Diffusing hydrogen atoms can affect ferritic steel welds
and parent metal (carbon steel and low-alloy Cr-Mo steels), especially when they
combine with unstable carbides that are typically created during the fabrication
process.

The rate of dissociation is very slow, and its effects can be ignored, at
temperatures less than about 400°F (205°C). At elevated temperatures,
dissolved hydrogen atoms react with local iron carbides to form methane gas
(CH4); as the methane concentration and pressure increases, cracks are
generated (usually in the grain boundaries). While the cracking reaction is very
slow, it will eventually result in significant degradation of structural integrity.

HTHA mitigation measures include:

 In some processes, austenitic steels (e.g., 300-series stainless) are used.

The chromium carbides in these alloys do not significantly react with
diffusing hydrogen.
 If the pressure containing envelope is carbon or a low-alloy Cr-Mo steel, a
300-series stainless steel internal overlay or cladding may help prevent
HTHA from occurring in the envelope. Note that hydrogen embrittlement
may still be of concern.
 For carbon and low-alloy Cr-Mo steel envelopes, post-weld heat treatment
is required (regardless of Code requirements).
IMAGE GALLERY

Titanium Hydriding
Titanium (Ti) hydriding is a somewhat unusual metallurgical degradation
phenomena that can result in brittle fracture. Unlike many other steel
embrittlement phenomena, this one most often occurs in thin wall Ti tubes that
have been selected for their superior corrosion resistance of overhead
condensers.
In certain pH ranges and under some galvanic corrosion conditions above 165 F
(75 C), hydrogen penetrates the Ti tube and reacts to form an embrittling hydride
phase. It can also occur when iron has contaminated the surface of the titanium
tube, promoting a galvanic couple that drives hydrogen into the Ti tube.

Fabrication and repair cleanliness are vital to the avoidance of titanium hydriding.
The hydriding reaction may continue until there is a complete loss of ductility, and
any form of transient stress can fracture the tubes. Those stresses may occur
from upset process conditions or during bundle removal or repairs.