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Stainless Steel Corrosion

There are five main types of stainless steel: ferritic, martensitic, austenitic, precipitation
hardening and duplex. The ferritic and martensitic grades are so named because of their
crystal structures. Both are iron-chromium-based alloys and were the type of stainless
steel first developed in the early 1900s. The ferritic and martensitic stainless steels are
magnetic. The martensitic stainless steels can be hardened by a heat treatment similar to
that used to harden ordinary steel, namely, heating to a high temperature, quenching, then
reheating to an intermediate temperature (tempering) to achieve the desired balance of
hardness and ductility.
Stainless and heat resisting steels possess unusual resistance to attack by
corrosive media at atmospheric and elevated temperatures, and are produced
to cover a wide range of mechanical and physical properties for particular
applications.
Along with iron and chromium, all stainless steels contain some carbon. It is
difficult to get much less than about 0.03 % and sometimes carbon is
deliberately added up to 1.00% or more. The more carbon there is, the more
chromium must be used, because carbon can take from the alloy about
seventeen times its own weight of chromium to form carbides. Chromium
carbide is of little use for resisting corrosion. The carbon, of course, is added
for the same purpose as in ordinary steels to make the alloy stronger.
Stainless steels are mainly used in wet environments. With increasing chromium
and molybdenum contents, the steels become increasingly resistant to
aggressive solutions. The higher nickel content reduces the risk of SCC.
Austenitic steels are more or less resistant to general corrosion, crevice
corrosion and pitting, depending on the quantity of alloying elements.
Resistance to pitting and crevice corrosion is very important if the steel is to be
used in chloride containing environments. Resistance to pitting and crevice
corrosion typically increases with increasing contents of chromium,
molybdenum and nitrogen.
Corrosion resistance of stainless steels is a function not only of composition,
but also of heat treatment, surface condition, and fabrication procedures, all
of which may change the thermodynamic activity of the surface and thus
dramatically affect the corrosion resistance. It is not necessary to chemically
treat stainless steels to achieve passivity. The passive film forms spontaneously
in the presence of oxygen. Most frequently, when steels are treated to improve
passivity (passivation treatment), surface contaminants are removed by
pickling to allow the passive film to reform in air, which it does almost
immediately. Most of the ferritic and martensitic stainless steels have limited

corrosion resistance in marine environments, but some of the newly developed


ferritic grade s (often called superferritics) have excellent marine corrosion
resistance and are widely used in applications such as tubes for power plant
condensers.

Pickling and Passivation


Stainless steel can corrode in service if there is contamination of the surface.
Both pickling and passivation are chemical treatments applied to the surface of
stainless steel to remove contaminants and assist the formation of a continuous
chromium-oxide, passive film. Pickling and passivation are both acid
treatments and neither will remove grease or oil. If the fabrication is dirty, it
may be necessary to use a detergent or alkaline clean before pickling or
passivation. (reference)

Stainless Steel Weld Decay


This type of intergranular corrosion can occur in the heat-affected zone of
welded components and also in cast components of stainless steel due to
precipitation, during cooling, of chromium carbides at the grain boundaries
(and hence loss of chromium in the immediately-adjacent zone). The local loss
in corrosion resistance arises because the chromium is crucial in promoting the
formation of a Cr-rich passive film on the surface of stainless steels. The
susceptibility to weld decay can be counteracted by carrying out a suitable
post-weld heat treatment to restore a uniform composition at the grain
boundaries but this is clearly often not a practicable proposition. Consequently
the usual strategy in combating weld decay is by the choice of stainless steel
with either of the two following features:
a. specification of a stainless steel containing a small amount of either
titanium or niobium; which have a higher affinity than does chromium
for carbon: hence carbides of these elements tend to form instead of
chromium carbides, thus avoiding the Cr-depletion problem: such steels
are usually termed stabilised stainless steels
b. specification of a stainless steel with low carbon content (< 0.03%); this
will clearly decrease the likelihood of carbide formation in the steel.
Such low-carbon grades of stainless steel are often designated by a L
in their code; for instance the 316 grade of steel (18%Cr/10Ni/2.5Mo)
is designated as 316L when its carbon content has been limited in this
way.

Stress corrosion cracking (SCC)


Austenitic stainless steels suffer from stress corrosion cracking in hot solutions
containing chloride. A high chloride concentration is required, although
relatively small amounts of chloride are sufficient at heated surfaces, where
chloride concentration can occur, or where chloride is concentrated by pitting
or crevice corrosion, and problems can be experienced in tap water.
The temperature usually needs to be above 70C, although SCC can occur at
lower temperatures in some situations, notably more acid solutions. The
cracking continues at low stresses and commonly occurs as a result of residual
stresses from welding or fabrication. The cracking is normally transgranular,
although it may switch to an intergranular path as a result of sensitization of
the steel.

Stainless Steel Rouging


Rouging is a thin film, usually reddish-brown or golden in color, of iron oxide or
hydroxide, typically on stainless steels. The contrast between this film and
shiny metal accentuates this aesthetics problem. The rouge film typically wipes
off easily with a light cloth (Figure 1), but it reforms while the process fluid is
in contact with the stainless steel. This problem is most chronic in the
pharmaceutical industry on the interior surfaces of high purity water (i.e.,
water for injection, WFI) distillation units, storage tanks, distribution systems
(piping, valves, pump housings, fittings, etc.) and process vessels. (reference)

Corrosion Theory
Humans have most likely been trying to understand and control corrosion for as
long as they have been using metal objects. The most important periods of
prerecorded history are named for the metals that were used for tools and
weapons (Iron Age, Bronze Age). With a few exceptions, metals are unstable in
ordinary aqueous environments. Metals are usually extracted from ores through
the application of a considerable amount of energy. Certain environments offer
opportunities for these metals to combine chemically with elements to form
compounds and return to their lower energy levels.
Corrosion is the primary means by which metals deteriorate. Most metals
corrode on contact with water (and moisture in the air), acids, bases, salts,
oils, aggressive metal polishes, and other solid and liquid chemicals. Metals will
also corrode when exposed to gaseous materials like acid vapors, formaldehyde
gas, ammonia gas, and sulfur containing gases.
Corrosion specifically refers to any process involving the deterioration or
degradation of metal components. The best known case is that of the rusting of
steel. Corrosion processes are usually electrochemical in nature, having the
essential features of a battery. When metal atoms are exposed to an
environment containing water molecules they can give up electrons, becoming
themselves positively charged ions, provided an electrical circuit can be
completed. This effect can be concentrated locally to form a pit or, sometimes,
a crack, or it can extend across a wide area to produce general wastage.
Localized corrosion that leads to pitting may provide sites for fatigue initiation
and, additionally, corrosive agents like seawater may lead to greatly enhanced
growth of the fatigue crack. Pitting corrosion also occurs much faster in areas
where microstructural changes have occurred due to welding operations.
Corrosion is the disintegration of metal through an unintentional chemical or
electrochemical action, starting at its surface. All metals exhibit a tendency to
be oxidized, some more easily than others. A tabulation of the relative strength
of this tendency is called the galvanic series. Knowledge of a metal's location in
the series is an important piece of information to have in making decisions
about its potential usefulness for structural and other applications.

The corrosion process (anodic reaction) of the


metal dissolving as ions generates some electrons,
as shown here, that are consumed by a secondary
process (cathodic reaction). These two processes
have to balance their charges. The sites hosting
these two processes can be located close to each
other on the metal's surface, or far apart
depending on the circumstances. This simple
observation has a major impact in many aspects of
corrosion prevention and control, for designing new
corrosion monitoring techniques to avoiding the
most insidious or localized forms of corrosion.
(more advanced reading)

The electrons (e- in this figure) produced by the corrosion reaction will need to
be consumed by a cathodic reaction in close proximity to the corrosion reaction
itself. The electrons and the hydrogen ions react to first form atomic hydrogen,
and then molecular hydrogen gas. If the acidity level is high (low pH), this
molecular hydrogen will readily become a gas as it is demonstrated by
exposing a strip of zinc to a sulfuric acid solution.
As hydrogen forms, it could inhibit further corrosion by forming a very thin
gaseous film at the surface of the metal. This "polarizing" film can be effective
in reducing water to metal contact and thus in reducing corrosion. Yet it is
clear that anything which breaks down this barrier film tends to increase the
rate of corrosion. Dissolved oxygen in the water will react with the hydrogen,
converting it to water, and destroying the film.
High water velocities tend to sweep the film away, exposing fresh metal to the
water. Similarly, solid particles in the water can brush the hydrogen film from
the metal. Other corrosion accelerating forces include high concentrations of
free hydrogen ions (low pH) which speed the release of the electrons, and high
water temperatures, which increase virtually all chemical reaction, rates. Thus
a variety of natural and environmental factors can have significant effects on
the corrosion rate of metals, even when no other special conditions are
involved.

Corrosion Rate Conversion


The following charts provide a simple way to convert data between the most
common corrosion units in usage, i.e. corrosion current (mA cm-2) , mass loss (g
m-2 day-1) and penetration rates (mm y-1 or mpy) for all metals or for steel
-2

mA cm
mm year-1
mpy
g m-2 day-1
where:

mA cm-2
1
0.306 nd/M
0.00777 nd/M
0.112 n/M

mm year-1
3.28 M/nd
1
0.0254
0.365 /d

g m-2 day-1
8.95 M/n
2.74 d
0.0694 d
1

mpy
129 M/nd
39.4
1
14.4 /d

mpy = milli-inch per year


n = number of electrons freed by the corrosion reaction
M = atomic mass
d = density

Note: you should read the Table from left to right, i.e.:
1 mA cm-2 = (3.28 M/nd) mm y-1 = (129 M/nd) mpy = (8.95 M/n) g m-2 day-1
For example, if the metal is steel or iron (Fe), n =2, M = 55.85 g and d = 7.88 g cm-3 and
the Table of conversion becomes:
mA cm-2
mm year-1
mpy
g m-2 day-1

mA cm-2
1
0.0863
0.00219
0.00401

mm year-1
11.6
1
0.0254
0.0463

mpy
456
39.4
1
1.83

g m-2 day-1
249
21.6
0.547
1

Note: you should read the Table from left to right, i.e.:
1 mA cm-2 = 11.6 mm y-1 = 456 mpy = 249 g m-2 day-1

Controlling Stress Corrosion Cracking (SCC)


In order for SCC to occur, we require a susceptible material, an environment
that will cause cracking of that material and a high enough stress or stress
intensity factor. There are, consequently, a number of approaches that we can
use to prevent SCC, or at least to give an acceptable lifetime. In an ideal world
a stress corrosion cracking control strategy will start operating at the design
stage, and will focus on the selection of material, the limitation of stress and
the control of the environment. The skill of the engineer then lies in selecting
the strategy that delivers the required performance at minimum cost. In this
context we should appreciate that a part of the performance requirement
relates to the acceptability of failure. For the primary containment pressure
vessel in a nuclear reactor we obviously require a very low risk of failure. For
the pressed brass decorative trim on a light switch, the occasional stress
corrosion crack is not going to be a serious problem, although frequent failures
would have an undesirable impact on product returns and the corporate image.
(reference)

Selection and control of material


The first line of defence in controlling stress corrosion cracking is to be aware
of the possibility at the design and construction stages. By choosing a material
that is not susceptible to SCC in the service environment, and by processing
and fabricating it correctly, subsequent SCC problems can be avoided.
Unfortunately, it is not always quite that simple. Some environments, such as
high temperature water, are very aggressive, and will cause SCC of most
materials. Mechanical requirements, such as a high yield strength, can be very
difficult to reconcile with SCC resistance (especially where hydrogen
embrittlement is involved). Finally, of course, Murphys Law dictates that the
materials that are resistant to SCC will almost inevitably be the most expensive
(and that they will be found to be susceptible to SCC in your environment as
soon as you have used them!).

Control of stress
As one of the requirements for stress corrosion cracking is the presence of
stress in the components, one method of control is to eliminate that stress, or
at least reduce it below the threshold stress for SCC. This is not usually feasible
for working stresses (the stress that the component is intended to support), but
it may be possible where the stress causing cracking is a residual stress
introduced during welding or forming.
Residual stresses can be relieved by stress-relief annealing, and this is widely
used for carbon steels. These have the advantage of a relatively high threshold
stress for most environments, consequently it is relatively easy to reduce the
residual stresses to a low enough level. In contrast austenitic stainless steels

have a very low threshold stress for chloride SCC. This, combined with the high
annealing temperatures that are necessary to avoid other problems, such as
sensitization and sigma phase embrittlement, means that stress relief is rarely
successful as a method of controlling SCC for this system.
For large structures, for which full stress-relief annealing is difficult or
impossible, partial stress relief around welds and other critical areas may be of
value. However, this must be done in a controlled way to avoid creating new
regions of high residual stress, and expert advice is advisable if this approach is
adopted.
Stresses can also be relieved mechanically. For example, hydrostatic testing
beyond yield will tend to even-out the stresses and thereby reduce the peak
residual stress. Similarly shot-peening or grit-blasting tend to introduce a
surface compressive stress, and are beneficial for the control of SCC. The
uniformity with which these processes are applied is important. If, for
example, only the weld region is shot-peened, damaging tensile stresses may
be created at the border of the peened area.

Control of environment
The most direct way of controlling SCC through control of the environment is to
remove or replace the component of the environment that is responsible for
the problem. Unfortunately, it is relatively rare for this approach to be
applicable. If the active species is present in an environment over which we
have some control, then it may be feasible to remove the active species,
although even then it may be difficult. For example, chloride stress corrosion
cracking of austenitic stainless steels has been experienced in hot-water
jackets around chocolate pipes (that is to say, pipes carrying molten chocolate)
in the food industry. In this situation we cant easily change the material or the
temperature, and it is virtually impossible to eliminate the residual stresses
associated with welding and forming of the stainless steel. However, we can
remove the chloride from the water by an ion exchange process, and, with
proper control and monitoring, this approach could be successful. Of course if
we were dealing with hot tomato ketchup, which has a low pH and may contain
enough chloride to cause SCC, we have a far more difficult problem!
In the latter situation, where the species responsible for cracking are a
required component of the environment, the environmental control options
consist of adding inhibitors, modifying the electrode potential of the metal, or
isolating the metal from the environment with coatings.
To take another example of chloride SCC of austenitic stainless steels, tube and
shell heat exchangers are frequently constructed using stainless steel tubes
(since these must be thin-walled and corrosion cannot be tolerated) with
carbon steel tube plates and shell (since these can be made much thicker to

provide a corrosion allowance). Chloride SCC is rarely experienced with this


construction. However, it is quite common for an enthusiastic engineer to
decide that the replacement heat exchanger should use an all-stainless
construction to avoid the unsightly corrosion of the carbon steel. The result is
frequently a rapid failure of the heat exchanger by SCC or pitting corrosion.
This is because the carbon steel adopts a relatively low electrode potential
that is well below that required to cause SCC or pitting of austenitic stainless
steel, which is thereby protected. When the all-stainless construction is
adopted, this unintentional electrochemical protection is lost and failure
occurs.
Corrosion inhibitors are chemicals that reduce the rate of a corrosive process.
They are generally rather specific to a particular alloy system, and they
typically also have specific requirements in terms of the composition of the
environment. Inhibitors may be effective at controlling SCC, although the
requirements are rather different from those for the inhibition of general
corrosion. Indeed chemicals that inhibit general corrosion may create the
necessary conditions for stress corrosion cracking (e.g. hydroxides, carbonates
and nitrates for carbon steel). Even when inhibitors are effective against SCC,
higher concentrations may be required than for the inhibition of general
corrosion.
Metallic coatings isolate the metal from the environment, and can, thereby,
prevent SCC. However, the possibility of the coating being penetrated by
imperfect application or by mechanical damage in service must be taken into
account. For this reason zinc is a popular coating for carbon steel. The normal
corrosion potential for zinc is relatively low, and if any of the underlying steel
is exposed, this will be cathodically protected. However, the low electrode
potential will also encourage hydrogen evolution, and this may lead to
hydrogen embrittlement. Hydrogen embrittlement may also occur as a result of
the hydrogen evolution during the initial electroplating operation, as noted
above. Consequently, zinc plating must be used with care on strong steels.
Cadmium adopts a rather more positive potential, and produces a much lower
risk of hydrogen embrittlement, while still protecting the underlying steel.
Unfortunately the toxicity of cadmium compounds means that it is essentially
banned as a coating material.
Paints and other polymeric coatings protect the underlying metal largely by
virtue of their high electrical resistance, which restricts the passage of current
from the anode to the cathode (both oxygen and water diffuse relatively easily
through most polymers, so paints dont, as is often thought, work by isolating
the metal from the environment). Paints may be effective at restricting SCC,
particularly where they incorporate inhibitors that can inhibit any solution that
does find its way to the metal. However, as with metallic coatings, it is
important to think about what will happen if the coating is removed by
mechanical damage.

Welding Stainless Steel


The stainless properties of stainless steels are primarily due to the
presence of chromium in quantities greater than roughly 12 weight
percent. This level of chromium is the minimum level of chromium to
ensure a continuous stable layer of protective chromium-rich oxide
forms on the surface. The ability to form chromium oxide in the weld
region must be maintained to ensure stainless properties of the weld
region after welding. In commercial practice, however, some stainless
steels are sold containing as little as 9 weight percent chromium and
will rust at ambient temperatures.
Stainless steels are generally classified by their microstructure and are
identified as ferritic, martensitic, austenitic, or duplex (austenitic and
ferritic). The microstructure significantly affects the weld properties
and the choice of welding procedure used for these stainless steel
alloys. In addition, a number of precipitation-hardenable (PH) stainless
steels exist. Precipitation-hardenable stainless steels have martensitic
or austenitic microstructures.
Iron, carbon, chromium and nickel are the primary elements found in
stainless steels and significantly affect microstructure and welding.
Other alloying elements are added to control microstructure or
enhance material properties. These other alloys affect welding
properties by changing the chromium or nickel equivalents and thereby
changing the microstructure of the weld metal. Generally, 200 and
300 series alloys are mostly austenitic and 400 series alloys are ferritic
or martensitic, but exceptions exist.
Stainless steels are subject to several forms of localized corrosive
attack. The prevention of localized corrosive attack is one of the
concerns when selecting base metal, filler metal and welding
procedures when fabricating components from stainless steels.
Stainless steels are subject to weld metal and heat affected zone
cracking, the formation of embrittling second phases and concerns
about ductile to brittle fracture transition. The prevention of cracking
or the formation of embrittling microstructures is another main concern
when welding or fabricating stainless steels.

Welding Austenitic Stainless Steels


Ideally, austenitic stainless steels exhibit a single-phase, the facecentered cubic (fcc) structure, that is maintained over a wide range of
temperatures. This structure results from a balance of alloying
additions, primarily nickel, that stabilize the austenite phase from
elevated to cryogenic temperatures. Because these alloys are
predominantly single phase, they can only be strengthened by solidsolution alloying or by work hardening. Precipitation-strengthened
austenitic stainless steels will be discussed separately below.
The austenitic stainless steels were developed for use in both mild and
severe corrosive conditions. Austenitic stainless steels are used at
temperatures that range from cryogenic temperatures, where they
exhibit high toughness, to elevated temperatures, where they exhibit
good oxidation resistance. Because the austenitic materials are
nonmagnetic, they are sometimes used in applications where magnetic
materials are not acceptable.
The most common types of austenitic stainless steels are the 200 and
300 series. Within these two grades, the alloying additions vary
significantly. Furthermore, alloying additions and specific alloy
composition can have a major effect on weldability and the as-welded
microstructure. The 300 series of alloys typically contain from 8 to 20
weight percent Ni and from 16 to 25 weight percent Cr.
A concern, when welding the austenitic stainless steels, is the
susceptibility to solidification and liquation cracking. Cracks can occur
in various regions of the weld with different orientations, such as
centerline cracks, transverse cracks, and microcracks in the underlying
weld metal or adjacent heat-affected zone (HAZ). These cracks are
primarily due, to low-melting liquid phases, which allow boundaries to
separate under the thermal and shrinkage stresses during weld
solidification and cooling.
Even with these cracking concerns, the austenitic stainless steels are
generally considered the most weldable of the stainless steels.
Because of their physical properties, the welding behavior of
austenitic stainless steels is different than the ferritic, martensitic, and
duplex stainless steels. For example, the thermal conductivity of
austenitic alloys is roughly half that of ferritic alloys. Therefore, the
weld heat input that is required to achieve the same penetration is

reduced. In contrast, the coefficient of thermal expansion of austenite


is 30 to 40 percent greater than that of ferrite, which can result in
increases in both distortion and residual stresses, due to welding. The
molten weld pool of the austenitic stainless steels is commonly more
viscous, or sluggish, than ferritic and martensitic alloys. This slows
down the metal flow and wettability of welds in austenitic alloys, which
may promote lack-of-fusion defects when poor welding procedures are
employed.

Welding Ferritic Stainless Steels


Ferritic stainless steels comprise approximately half of the 400 series
stainless steels. These steels contain from 10.5 to 30 weight percent
chromium along with other alloying elements, particularly
molybdenum. Ferritic stainless steels are noted for their stresscorrosion cracking (SCC) resistance and good resistance to pitting and
crevice corrosion in chloride environments, but have poor toughness,
especially in the welded condition.
Ideally, ferritic stainless steels have the body-centered cubic (bcc)
crystal structure known as ferrite at all temperatures below their
melting temperatures. Many of these alloys are subject to the
precipitation of undesirable intermetallic phases when exposed to
certain temperature ranges. The higher-chromium alloys can be
embrittled by precipitation of the tetragonal sigma phase, which is
based on the compound FeCr.
Molybdenum promotes formation of the complex cubic chi phase,
which has a nominal composition of Fe36Cr12Mo10. Embrittlement
increases with increasing chromium plus molybdenum contents. It is
generally agreed that the severe embrittlement which occurs upon
long-term exposure is due to the decomposition of the iron-chromium
ferrite phase into a mixture of iron-rich alpha and chromium-rich alphaprime phases. This embrittlement is often called "alpha-prime
embrittlement." Additional reactions such as chromium carbide and
nitride precipitation may play a significant role in the more rapid, early
stage 885 F embrittlement.
The ferritic stainless steels have higher yield strengths and lower
ductilities than austenitic stainless steels. Like carbon steels, and
unlike austenitic stainless steels, the ferritic stainless alloys exhibit a
transition from ductile-to-brittle behavior as the temperature is
reduced, especially in notched impact tests. The ductile-to-brittle
transition temperature (DBTT) for the ultrahigh-purity ferritic stainless
steels is lower than that for standard ferritic stainless steels. It is
typically below room temperature for the ultrahigh-purity ferritic

stainless steels. Nickel additions lower the DBTT and there by slightly
increase the thicknesses associated with high toughness.
Nevertheless, with or without nickel, the ferritic stainless steels would
need engineering review for anything other than thin walled
applications as they are prone to brittle failure.

Welding Martensitic Stainless Steels


Martensitic stainless steels are considered to be the most difficult of
the stainless steel alloys to weld. Higher carbon contents will produce
greater hardness and, therefore, an increased susceptibility to
cracking.
In addition to the problems that result from localized stresses
associated with the volume change upon martensitic transformation,
the risk of cracking will increase when hydrogen from various sources
is present in the weld metal. A complete and appropriate welding
process is needed to prevent cracking and produce a sound weld.
Martensitic stainless steels are essentially alloys of chromium and
carbon that possess a body-centered cubic (bcc) or body-centered
tetragonal (bct) crystal structure (martensitic) in the hardened
condition. They are ferromagnetic and hardenable by heat treatments.
Their general resistance to corrosion is adequate for some corrosive
environments, but not as good as other stainless steels.
The chromium content of these materials generally ranges from 11.5
to 18 weight percent, and their carbon content can be as high as 1.2
weight percent. The chromium and carbon contents are balanced to
ensure a martensitic structure after hardening. Martensitic stainless
steels are chosen for their good tensile strength, creep, and fatigue
strength properties, in combination with moderate corrosion resistance
and heat resistance.
The most commonly used alloy within this stainless steel family is type
410, which contains about 12 weight percent chromium and 0.1 weight
percent carbon to provide strength. Molybdenum can be added to
improve mechanical properties or corrosion resistance. Nickel can be

added for the same reasons. When higher chromium levels are used to
improve corrosion resistance, nickel also serves to maintain the desired
microstructure and to prevent excessive free ferrite. The limitations on
the alloy content required to maintain the desired fully martensitic
structure restrict the obtainable corrosion resistance to moderate
levels.

Welding Duplex Stainless Steels


Duplex stainless steels are two phase alloys based on the ironchromium-nickel system. Duplex stainless steels usually comprise
approximately equal proportions of the body-centered cubic (bcc)
ferrite and face-centered cubic (fcc) austenite phases in their
microstructure and generally have a low carbon content as well as,
additions of molybdenum, nitrogen, tungsten, and copper. Typical
chromium contents are 20 to 30 weight percent and nickel contents
are 5 to 10 weight percent. The specific advantages offered by duplex
stainless steels over conventional 300 series stainless steels are
strength, chloride stress-corrosion cracking resistance, and pitting
corrosion resistance.
Duplex stainless steels are used in the intermediate temperature
ranges from ambient to several hundred degrees Fahrenheit
(depending on environment), where resistance to acids and aqueous
chlorides is required. The weldability and welding characteristics of
duplex stainless steels are better than those of ferritic stainless steels,
but generally not as good as austenitic materials.
A suitable welding process is needed to obtain sound welds. Duplex
stainless steel weldability is generally good, although it is not as
forgiving as austenitic stainless steels. Control of heat input is
important. Solidification cracking and hydrogen cracking are concerns
when welding duplex stainless steels, but not as significant for some
other stainless steel alloys.

Current commercial grades of duplex stainless steels contain between


22 and 26 weight percent chromium, 4 to 7 weight percent nickel, up
to 4.5 weight percent molybdenum, as well as some copper, tungsten,
and nitrogen. Modifications to the alloy compositions have been made
to improve corrosion resistance, workability, and weldability. In
particular, nitrogen additions have been effective in improving pitting
corrosion resistance and weldability.
The properties of duplex stainless steels can be appreciably affected
by welding. Due to the importance of maintaining a balanced
microstructure and avoiding the formation of undesirable metallurgical
phases, the welding procedures must be properly specified and
controlled. If the welding procedure is improper and disrupts the
appropriate microstructure, loss of material properties can occur.
Because these steels derive properties from both austenitic and ferritic
portions of the structure, many of the single-phase base material
characteristics are also evident in duplex materials. Austenitic
stainless steels have good weldability and low-temperature toughness,
whereas their chloride SCC resistance and strength are comparatively
poor. Ferritic stainless steels have good resistance to chloride SCC but
have poor toughness, especially in the welded condition. A duplex
microstructure with high ferrite content can therefore have poor lowtemperature notch toughness, whereas a structure with high austenite
content can possess low strength and reduced resistance to chloride
SCC.
The high alloy content of duplex stainless steels also makes them
susceptible to the formation of intermetallic phases from extended
exposure to high temperatures. Significant intermetallic precipitation
may lead to a loss of corrosion resistance and sometimes to a loss of
toughness.
Duplex stainless steels have roughly equal proportions of austenite and
ferrite, with ferrite being the matrix. The duplex stainless steels
alloying additions are either austenite or ferrite formers. This is occurs
by extending the temperature range over which the phase is stable.
Among the major alloying elements in duplex stainless steels
chromium and molybdenum are ferrite formers, whereas nickel,
carbon, nitrogen, and copper are austenite formers.
Composition also plays a major role in the corrosion resistance of
duplex stainless steels. Pitting corrosion resistance can be adversely
affected. To determine the extent of pitting corrosion resistance
offered by the material, a pitting resistance equivalent is commonly
used.

Welding Precipitation-Hardenable Stainless Steels


Precipitation-hardening (PH) stainless steels are iron-chromium-nickel
alloys. They generally have better corrosion resistance than
martensitic stainless steels. The high tensile strengths of the PH
stainless steels is due to precipitation hardening of a martensitic or
austenitic matrix. Copper, aluminum, titanium, niobium (columbium),
and molybdenum are the primary elements added to these stainless
steels to promote precipitation hardening.
Precipitation-hardening stainless steels are commonly categorized into
three types martensitic, semiaustenitic, and austenitic based on their
martensite start and finish (Ms and Mf) temperatures and the resulting
microstructures. The issues involved in welding PH steels are different
for each group.
It is important to understand the microstructure of the particular type
of alloy being welded. Some of the PH stainless steels solidify as
primary ferrite and have relatively good resistance to hot cracking. In
other PH stainless steels, ferrite is not formed, and it is more difficult
to weld these alloys without hot cracking.
If your company is experiencing these or other welding problems you
can retain AMC to improve your weld processing. Hire AMC to act as
your welding specialist.