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Exhaust System Materials

Hannu Jääskeläinen
Abstract: The most common types of steel used in exhaust systems include ferritic and austenitic
stainless steels, as well as various grades of aluminized steels. Exhaust system materials are exposed
to a variety of harsh conditions, and must be resistant to such degradation mechanisms as high
temperature oxidation, condensate and salt corrosion, elevated temperature mechanical failure, stress
corrosion cracking, and intergranular corrosion.
Overview
Material Failure
Aluminized Steel And Aluminized Stainless Steel
Exhaust System Components
Overview
Materials used for exhaust piping, mufflers, and other exhaust system components—which are
discussed in this paper—consist mainly of ferrous alloys. Aluminum alloys are sometimes used as a
coating on ferrous alloys to impart additional corrosion resistance. In some cases, nonferrous nickel
and titanium alloys are used in exhaust system components in especially demanding and/or high
performance applications. Ceramics have also seen limited use in exhaust systems to take advantage
of their insulating properties.
Ceramics and specialized metal alloys, albeit with different compositions and properties than those
used in piping systems, are also commonly used in substrates for aftertreatment devices—ceramic
and metallic catalyst substrates and particulate filter substrates. These materials are discussed in more
detail in the papers dealing with aftertreatment.
Ferrous alloys are based on iron-carbon alloys and include carbon steel, alloy steels, stainless steel
and cast iron. Alloying elements are added to:
 provide solid solution strengthening of ferrite,

 cause the precipitation of alloy carbides rather than cementite Fe3C,
 improve corrosion resistance and other special characteristics.
The choice of exhaust system materials is driven by a number of factors including cost, warranty
requirements and legislated and customer demands for long service life. As a result, materials used in
OEM exhaust systems have changed dramatically and continue to evolve.
Mild carbon steel was the material of choice for exhaust systems for many decades. An iron oxide
coating on the exhaust system protected it from atmospheric corrosion to varying degrees. However,
it suffered from poor corrosion resistance when exposed to road salt and exhaust condensate. As a
http://www.dieselnet.com/tech/diesel_exh_mat.html 25/5/2011
result, exhaust systems made from this material had a very short life if exposed to the environment
experienced by many on-road vehicles. Applications for carbon steel are currently limited to selected
nonroad applications that operate in relatively non-corrosive environments. The corrosion resistance
of carbon steel can be greatly improved through the use of a hot dipped aluminum coating. This is
often referred to as aluminized steel.
One particularly important ferrous alloy alloying element is chromium. By adding sufficient
chromium, stainless steel is formed. When stainless steel is heated, chromium forms a protective
chromium oxide coating that delays further oxidation. A minimum of about 10.5% chromium is
usually required to passivate the surface and to classify a material as stainless steel. So long as this
oxide layer is stable and continuous, the metal substrate is well protected from corrosion. It should be
noted that nickel, while used in many grades of stainless steel, is not contained in all grades of
stainless steel.
Since about the mid-1990s, plain carbon and low alloy steels have been replaced by stainless steel as
the primary material for exhaust systems downstream of the exhaust manifold or turbocharger. This
transition has taken place because of market demands for extended warranties, and because of
demands mandated by emission standards. Technologies to meet increasingly stringent emission
standards can raise exhaust temperatures which makes the task of meeting strength and durability
requirements especially challenging. Emission standards also require that exhaust systems are
designed in a manner that facilitates leak-free assembly, installation and operation for the full useful
life of the vehicle.
From the early part of the 21st century, commodities including many of the alloying elements used in
stainless steel, have experienced wide and rapid price fluctuations (see Figure 4 for example). In
some cases, costs for these materials have increased by up to ~1000%. In response, stainless steel
producers have added an alloy surcharge that can be adjusted as needed to account for these price
variations. Many producers have focused considerable research efforts on reducing the sensitivity of
the finished product’s price to these alloy surcharges.
Emission control systems such as actively regenerated diesel particulate filters (DPFs) and urea
selective catalytic reduction (SCR) have also created new demands on material properties. Active
DPF regeneration can produce exhaust temperatures as high as 800°C in parts of the exhaust system
that would otherwise operate at much lower temperatures. Also, some commonly used stainless
steels, such as type 304, have been found to corrode after exposure to urea decomposition products in
high temperature environments.
Common alloying elements found in stainless steel and their effects are summarized in Table 1 [ASM
2001][Arlt 2007].
Table 1
Common Alloying Elements Found in Stainless Steel
Element Effect
 Essential in forming the passive film. Oxidation resistance increases at Cr
levels above 10.5%
Chromium
 High Cr content can adversely affect mechanical properties, fabricability and
weldability
 Stabilize the austenitic structure to enhance mechanical properties and
fabrication characteristics
Nickel  Resistance to stress-corrosion cracking is poorest at approximately 8 to 10%
Ni but is restored at levels of about 30% Ni
 Can minimize spalling of surface oxide during temperature cycling
 In moderate quantities and when nickel is present, performs many of the
functions attributed to nickel

 Interacts with sulfur to form manganese sulfides which can effect corrosion
Manganese
resistance
 Can improve the adhesion of oxide film and improve oxidation resistance
 In combination with chromium is very effective for passive film stabilization in
the presence of chlorides
Molybdenum
 Especially effective in increasing resistance to the initiation of pitting and
crevice corrosion
 Provides strength in the high-temperature applications
 Detrimental to corrosion resistance through reaction with chromium to form
Carbon
chromium carbides
 Detrimental to toughness in ferritic grades
 Enhances pitting resistance in austenitic grades
Nitrogen
 Detrimental to the mechanical properties of the ferritic grades
Aluminum  Enhance high-temperature oxidation resistance
 Stabilizers used to preferentially combine with carbon and nitrogen to reduce
Niobium and the formation of chromium carbides and nitrides. This reduces the possibility
Titanium of intergranular corrosion.
 Titanium oxide may adversely affect brazability
 Provide corrosion resistance to sulfuric acid
Copper
 Improve formability
 Provides high-temperature oxidation resistance
Silicon  Provides resistance to stress corrosion cracking and to corrosion by
oxidizing acids
Of the varieties of stainless steel available, two that are important exhaust system materials are:
 Ferritic stainless steel, and

 Austenitic stainless steel.
Ferrous alloys can contain three important grain structures: ferrite, austenite and martensite. In ferrite,
the iron atoms form a body centered cubic (BCC or α-iron) structure with iron atoms at each corner
of a cube and one in the center of the cube, Figure 1. Austenite is a face centered cubic (FCC or γ-
iron) structure with iron atoms at each corner and on the center of each face of a cube. Interstitial
holes in the FCC structure allow austenite to accommodate a greater number of carbon atoms, up to
2.11% by weight, than the BCC structure of ferrite which can accommodate up to 0.0218% carbon.
Austenite can be transformed into martensite, a very hard and brittle grain structure that is not
normally used in exhaust piping systems.
Figure 1. Structure of Ferrite and Austenite
In the North American AISI classification, ferritic and martensitic grades are designated as 400
series, while austenitic grades are designated as 300 series. There are a number of differences
between ferritic and austenitic grades:
 Ferritic alloys have good ductility, formability and resistance to oxidation and corrosion. High
temperature strength as well as welding and forming characteristics are relatively poor in
comparison to austenitic grades.
 Ferritic grades have a lower coefficient of thermal expansion than austenitic grades. This
offers better high temperature oxidation resistance because the coefficient of thermal
expansion is closer to that of the protective chromium oxide film. This makes the oxide film
less prone to cracking at high temperature.
 Ferritic and martensitic grades of stainless steel are ferromagnetic while austentitic grades are
antiferromagnetic. This means that a magnet will be attracted to grades of stainless containing
sufficient ferrite or martensite (400 series) but not to those composed mainly of austenite (300
series).
The amount of ferrite and austenite phases in a steel can be controlled through the concentrations of
nickel and chromium and their equivalents, as shown in the Schaeffler diagram in Figure 2 [Arlt
2007]. Ferritic stainless steel contains up to about 30% chromium, less than 0.12% carbon and little or
no nickel. While the low carbon content limits high temperature strength (Figure 3), this may not be a
concern for many exhaust system components. Its moderate ductility, excellent corrosion resistance
and relatively low cost have made it a very popular exhaust system material. A commonly used grade
developed in the 1960’s for mufflers, type 409, is a chromium ferritic stainless steel having nominally
11% chromium and stabilized with titanium. Higher chromium steels are also used and provide
greater oxidation and corrosion resistance.
Figure 2. Schaeffler Diagram—Effect of Equivalent Chromium and Nickel Contents on Grain Structure
of Stainless Steel
Chromium equivalent = %Cr + 1.5 %Si + 0.5 %Nb + 2.0 %Ti + 1.4 %Mo
Nickel equivalent = %Ni + 0.5 %Mn + 30 (%C + %N)
In addition to chromium and carbon, austenitic stainless steels contain nickel. Nickel contents are
generally between 6 and 35%. Nickel is an austenite stabilizer and greatly enhances mechanical
properties and fabrication characteristics. Significantly more carbon can be added to austenitic grades
than ferritic grades to increase strength at high temperatures, Figure 3. While used in exhaust
systems, its cost is considerably higher due to the relatively high nickel content thus limiting it to
applications where a suitable ferritic stainless steel is not available. Austenitic stainless steels provide
a much more refined surface finish and are more often used in higher priced luxury cars.
Figure 3. Yield Strength of Austenitic (304 and 316) and Ferritic (409 and 439) Stainless Steels
Table 2 lists some stainless steel alloys that may be used in exhaust system components and their
composition. Also included is a non-ferrous nickel based alloy (AISI 625) whose importance will be
discussed later. This list is by no means exhaustive, as many other alloys are available and new ones
continue to be developed.
Table 2
Composition of Common Stainless Steel Alloys, %
(Maximum content of alloying element shown unless otherwise indicated)
Austenitic Ferritic Ni Alloy

304 304L 316 316L 332 409 439 441 625
C 0.08 0.03 0.08 0.03 0.10 0.03 0.07 0.03 0.03
1.00 -
Mn 2.00 2.00 1.00 1.00 1.00 0.50
1.50
P 0.045 0.045 0.040 0.040 0.040 0.015
S 0.030 0.030 0.02 0.030 0.030 0.015
Si 0.75 0.75 0.75 1.00 1.00 1.00 0.15
20.0 - 10.50 - 17.00 - 17.5 - 20.0 -
Cr 18.00-20.00 16.00-18.00
23.0 11.70 19.00 19.5 23.0
bal.
31.0 -
Ni 8.00-12.00 10.00 - 14.00 0.50 0.50 1.00 (58.0
35.0
min)
N 0.10 0.10 0.10 0.03 0.04 0.03 0.02
0.20+4
0.10 -
Ti 8(C+N) (C+N) 0.40
0.50
to 1.10
0.25 - 0.3+9C Nb+Ta:
0.60 to 0.9 3.15 -

Nb
4.15
8.0 -
Mo
10.0
Co 1.0
Fe bal. bal. bal. bal. bal. bal. 5.0
Al 0.15 0.40
Ferritic grades have a significant cost advantage over austenitic grades because they contain little or
no nickel. Unlike nickel, the price of chromium has historically been relatively stable, Figure 4.
Figure 4. Nickel, Chromium and Molybdenum Prices from 2002-2009

[USGS data]
Material Failure
Failure Mechanisms
Exhaust system materials are exposed to a variety of very harsh conditions. Materials can be exposed
to temperatures ranging from ambient to as high as 800°C or even higher under some extreme
conditions. A variety of chemical conditions are also encountered including exposure to alkaline and
acidic exhaust condensate inside the system and to road salt on the exterior. As a result, exhaust
system materials must provide not only sufficient strength and fatigue resistance but also excellent
corrosion resistance under a variety of very demanding conditions.
While metals will form a protective oxide layer on the surface, a number of mechanisms can disrupt
this oxide layer and expose the metal substrate to rapid degradation. Important exhaust system
material failure mechanisms include:
 High temperature corrosion (dry hot corrosion)

 Condensate and salt corrosion (wet corrosion)
 Elevated temperature mechanical failure
 Stress corrosion cracking
 Intergranular corrosion
High Temperature Material Degradation

Oxidation. Metals exposed to oxygen in air will form oxides at the air metal interface. At high
temperatures, this reaction is enhanced. The stability of this oxide layer determines whether it
passivates and protects the metal substrate or causes the material to degrade.
One important factor determining the stability of this layer is the Pilling-Bedworth ratio, the ratio of
the volume of oxide produced and the volume of substrate metal consumed by the oxidation process:
R = (volume of metal oxide produced) / (volume of metal oxidized) (1)

If R is less than 1, the oxide layer will be porous and non-protective. If the ratio is equal to or
moderately greater than 1, the oxide layer will be continuous and protective. If it is significantly
greater than 1, the oxide layer will eventually buckle and flake off (spall) as it grows and expose the
metal substrate to further oxidation.
Other important factors include the adherence of the oxide layer to the substrate and the relative
difference in thermal expansion coefficients between the metal oxide and metal substrate. For the
chromium oxide layer found on stainless steel, the Pilling-Bedworth ratio is about 2.0 so that the
oxide layer is continuous and protects the metal substrate. However, the coefficient of thermal
expansion for the oxide layer is less than that of the metal substrate (Table 3). As stainless steel is
heated in air and the metal and oxide layer expands, a temperature is eventually reached where the
oxide layer cracks. Once this happens, the underlying metal is exposed to oxygen and oxides of iron
(and nickel if it is present) rapidly form. If the component is held at this temperature for a long period
of time, the oxide layer will continue to grow leading to progressive scaling followed eventually by
spalling. Thermal cycling can facilitate spalling and lower the maximum temperature at which
spalling occurs in some metals.
Table 3
Coefficients of Thermal Expansion (CTE)
Material CTE, K-1
Cr2O3 9.6 × 10-6
Ferritic stainless steel ~10.5-12.5 × 10-6
Austenitic stainless steel ~17-20 × 10-6
A number of alloying elements including chromium, nickel, manganese, silicon and aluminum can
affect high temperature oxidation resistance. Aluminum is commonly used to improve high
temperature oxidation resistance of metallic catalyst substrates.
With the exception of some stressed components such as exhaust manifolds and turbine housings,
maximum use temperatures for exhaust system materials are generally determined by their resistance
to oxidation at high temperature. The high temperature strength of most exhaust system materials is
usually more than sufficient for their application. Figure 5 shows some maximum use temperatures in
air for a few materials of interest [AK Steel 2007][ATI 2005].
Figure 5. Maximum Use Temperatures for Different Grades of Steel

AL MS - aluminized mild steel; 304, 409, 439, 441 - grades of stainless steel
In the exhaust environment, the value associated with cyclic service is of more interest. Many
common austenitic grades have values comparable to 304. Based on the maximum use temperature in
cyclic service only, ferritic stainless steel offers as good (409) or better (439 and 441) performance
compared to austenitic grades at a lower cost (little or no nickel). This is mainly due to the fact that
ferritic grades have a lower coefficient of thermal expansion that is more closely matched to the
chromium oxide layer than austenitic grades (Table 3) and are therefore much less prone to spalling
at high temperatures. Austenitic stainless steel does offer increased oxidation resistance over many
ferritic grades in continuous high temperature service.
While maximum use temperature is an important consideration, especially near the hot end of the
exhaust system, in actual service other factors can have significant impacts on exhaust system life at
far lower temperatures.
Nitridation. Another form of high temperature degradation that stainless steels can be susceptible to
is nitridation. Nitrogen from the external environment permeates the surface oxide layer through
cracks and pores and diffuses into the metal underneath to react with elements that are strong nitride
formers. One nitride former found in all stainless steels is chromium. The nitrogen and chromium
react to form chromium nitrides.
When the external environment contains ammonia, nitridation can be especially rapid. While
nitridation attack is most common in industrial equipment used for such processes as case hardening
of metals with ammonia and the production of ammonia, nitric acid, melamine and nylon 6-6, recent
descriptions in the literature of material degradation in automotive exhaust systems equipped with
urea SCR systems also appear to involve nitridation [Saedlou 2010][Floyd 2009].
At least two factors are important in determining how susceptible a material is to nitridation [Lai
2007]:
 The integrity of the surface oxide layer. An integral oxide layer is an important barrier that can
prevent nitrogen from reaching the base metal. Thermal cycling that causes oxide layer
spalling can accelerate nitridation.
 The solubility of nitrogen in the base metal solubility. Alloys with higher nitrogen solubility
are more susceptible to nitridation. Nickel is one alloying element that can reduce the
solubility of nitrogen in an alloy. Ferritic alloys also have low nitrogen solubility. Nitrogen
solubility increases with temperature.
While nitridation generally leads to material embrittlement, in stainless steel, the formation of
chromium nitride has important consequences. In regions where chromium nitride is formed, less
chromium is available to ensure the metal remains passivated and the metal becomes susceptible to
corrosive attack. This is discussed below in the section on Intergranular Corrosion.
Condensate And Salt Corrosion

Corrosion of metals can occur as a result of an electrochemical reaction between the metal and a
condensed film of moisture containing water soluble ions or as a result of chemical reactions of the
metal in the presence of an acidic or alkaline liquid. Factors that contribute to initiation, maintenance,
and acceleration of corrosion include temperature, shape of the structure, the presence of crevices,
joints, improperly made welds, vibrations, stresses and processing and fabricating operations.
Condensate Corrosion. At engine start-up from cold conditions, the exhaust system is still at
ambient temperature. Moisture contained in the exhaust gas condenses and accumulates in the
muffler and aftertreatment system and adheres to the walls of the tubes. This condensate can contain
compounds such as CO32-, NH4+, SO42-, NO3-, Cl- and organic compounds.
 Ammonia, often present in spark ignition engines, is usually created over three-way catalysts
under reducing conditions [Chattha 1990]. Ammonia may also be present in diesel engines
utilizing SCR systems or NOx adsorbers. As the exhaust system warms up, any ammonia
contained in the condensate evaporates and changes the condensate from alkaline (pH ~ 8) to
acidic (pH ~ 3). This condensate can have a significant corrosive effect on the exhaust
system—especially components such as mufflers and pipes at the cold end of the system that
are exposed to this condensate the longest.
 While urea condensate found in the exhaust systems of engines with SCR systems is non-
corrosive, its decomposition products can lead to nirtidation attack followed by corrosion (see
discussion later).
 Chlorides may be present on startup of new vehicles due to carryover from catalyst
manufacture. They are especially aggressive towards stainless steel and make the initial
condensate much more aggressive than would otherwise be expected [Inoue 2003].
 Sulfur most commonly originates from sulfur compounds in the fuel and its concentration
depends on fuel regulatory requirements. Exhaust system materials, such as type 409, that may
be a suitable material in markets such as North America and Europe that have relatively strict
limits on sulfur in fuels can corrode relatively easily in other regions of the world that allow
higher sulfur fuels to be used [Yang 2010].
Salt Corrosion. Alloys used in automotive exhaust systems often experience conditions in which
elevated temperature exposure occurs after the alloy has been exposed to contaminants such as road
de-icing salts. These salts contain halides such as chlorides and can be especially aggressive towards
stainless steel by acting as fluxing agents and removing the protective oxide scale. Material
degradation can be quite rapid under such conditions.
Both condensate corrosion and salt corrosion can be manifested as crevice and/or pitting corrosion in
stainless steel. Exposure to salt can also significantly lower the temperature at which scale spalling
occurs to 500-600°C.
Crevice corrosion is a form of electrochemical attack. Instead of having two electrodes made of
different materials, variation in the character of the medium is responsible for the creation of a cell
that leads to localized attack of the metal. One of the most common is the differential oxygen or
aeration cell. If the access to oxygen on the surface of a metal is not uniform, a differential aeration
cell is created. This can occur for example at an overlapping joint. The contact area under the joint
can form a capillary and draw in a certain amount of liquid from which the oxygen is quickly
eliminated. The liquid film outside the capillary, on the other hand, is constantly saturated with
oxygen. Aluminum and stainless steels are notoriously susceptible to attack in oxygen-deficient
situations.
Pitting corrosion is a very damaging form of corrosion and few metals are immune to this form of
attack. As the name suggests, it results in the formation of small pits in the material surface. Even the
most highly alloyed metals are vulnerable under certain conditions. In the case of stainless steel, the
presence of chloride ions in a slightly acidic solution can disrupt the protective film and result in
widely scattered pit formation. Stimuli for pitting include residual stresses along a line of bending in
fabrication and certain types of inclusions inherent in the steel making process.
Resistance to pitting corrosion is most easily affected by alloy composition; namely the concentration
of important alloying elements. Pitting resistance is often expressed by the pitting resistance
equivalent (PRE). It is obtained by summing the weight percentage of the elements that impact pitting
resistance (chromium, molybdenum and nitrogen) and then normalizing by the effect of 1% Cr. One
formula commonly used to quantify the susceptibility of a stainless steel alloy to pitting corrosion is:
PRE = %Cr + 3.3 (%Mo) + x (%N) (2)

where x = 16 is commonly used but it can range between 0 and 30.
While molybdenum and nitrogen are more effective than chromium against pitting corrosion (about
3.3 and 30 times as effective, respectively), chromium is always essential for providing the basic
corrosion resistance. Molybdenum and nitrogen cannot replace the “base” amount of chromium in
stainless steels but can be used to enhance corrosion resistance. Ferritic stainless steels hold very little
nitrogen in solution so their pitting resistance must be derived entirely from chromium and
molybdenum.
It should be noted that the PRE number calculated from Equation 2 may not reflect the influence of
all important alloy elements that can impact the progress of pitting corrosion. For example, in some
materials nickel can retard the growth of corrosion sites [Gumpel 2008].
Figure 6 shows the PRE for several alloys. No clear distinction between austenitic and ferritic grades
is apparent.
 Ferritic grades have a PRE that ranges from about 11 for 409 stainless steel to about 18-20 for
most other grades. While ferritic stainless steel is available with Cr contents as high as 30%,
for exhaust applications the Cr content is limited to less than about 20% to avoid embitterment.
For ferritic stainless steel suitable for exhaust applications to have PRE higher than about 20,
high priced Mo would need to be added. One ferritic alloy that can have a PRE as high as
about 28 that is promoted for exhaust applications is 444 (Cr: 17.5-19.5% and Mo: 1.75-
2.50%).
 The chromium in many common austenitic grades is normally maintained around 17 to 18%
because this level of chromium requires the least amount of nickel to stabilize the austenitic
phase (Figure 2). Thus the PRE in many austenitic grades is similar to that of many ferritic
grades. While austenitic alloys are available that have PRE values higher than about 20, they
require the use of high cost alloys such as nickel (to stabilize the austenitic structure when
adding chromium) or molybdenum. While nitrogen addition can enhance corrosion resistance,
its maximum level is normally less than 0.1%.
 Very high PRE value materials are available if the application demands it. For example, the
austenitic nickel based alloy 625 has a PRE of about 51 derived mainly from a high level of
molybdenum.
Corrosion resistance to exhaust condensate and road salt vary approximately in proportion to PRE.
This is illustrated in Figure 7 which shows the weight loss for materials with different PRE values
measured during an accelerated cyclic oxidation/corrosion test where samples were heated in 649°C
air for one hour followed by natural cooling in air to ambient temperature [ATI 1999]. These oxidized
samples are then exposed to a 5 percent salt spray at 35°C for 24 hours. This cycle was repeated 100
times.
Figure 6. Pitting Resistance Equivalent (PRE) for Several Alloys
Figure 7. Cyclic Exposure to Salt And Heating to 649°C
It should be noted that the results presented in Figure 7 through Figure 13 are from accelerated tests
that are intended to rapidly simulate field problems over the course of several days. Similar levels of
degradation in field service may take several years to develop.
Because of the strong dependence of the resistance to exhaust condensate and salt corrosion on PRE,
the performance of exhaust materials under these conditions is governed mainly by the concentration
of important alloying elements (Cr, Mo and N) in the alloy. Austenitic grades therefore do not
necessarily offer an advantage over ferritic grades and vice versa. Ferritic grades would provide good
performance at a lower cost. If increased protection is required, a grade with higher Cr or added Mo
and N can be used.
The effect of salt exposure is strongly dependent on the maximum temperature that a component
experiences. Figure 8 shows the effect of salt exposure on samples tested at different temperatures
[AK Steel 2007]. At temperatures below about 550°C that would be experienced in the cold end of the
exhaust system downstream from the aftertreatment system, pitting is the main form of corrosion.
The pitting rate increases with temperature. A material that may perform well in the cold end of the
exhaust may not do as well at the hot end because of higher temperatures and the increased likelihood
of scale spalling.
Figure 8. Pitting Rate After Exposure to Salt
While the pitting rate shown in Figure 8 seems to start to level off at higher temperatures, material
loss still increases due to scale spalling. The 409 grade started to show evidence of scale spalling at
550°C. Figure 9 shows the effect of temperature on scale spalling after salt exposure [AK Steel 2007].
Figure 9. Scale Spalling Weight Loss After Exposure to Salt
In comparison to high temperature exposure to oxygen, scale spalling can occur at a much lower
temperature when stainless steel is exposed to salt. This can significantly lower the maximum use
temperature shown in Figure 5. In Figure 8, 409 grade starts to show scale spalling at temperatures
below 600°C. This is significantly lower than the 800°C maximum use temperature during
temperature cycling shown in Figure 5. Grade 439 shows scale spalling during the salt expose tests at
temperatures below 700°C.
Elevated Temperature Mechanical Failure

The life of a metal component subjected to either sustained or oscillatory loads at elevated
temperatures is limited. Failure at elevated-temperatures can occur by excessive creep deformation
and creep fracture, fatigue and creep-fatigue interaction, thermal fatigue, tension overload or
combinations of these.
Stress applied at elevated temperatures produces a continuous strain in the component, resulting in a
time-dependent deformation that can eventually lead to failure. This time-dependent deformation is
referred to as creep. The temperature at which the mechanical strength of an alloy becomes limited by
creep rather than by yield strength is approximately 370°C for low-alloy steels, 540°C for austenitic
stainless steels and 650°C for nickel-based high-temperature alloys [ASM 2001].
Mechanical loading is not the only potential damaging force for components at elevated temperatures.
Transient thermal gradients can induce plastic strains. Cyclic strain resulting from repeatedly applied
temperature gradients can result in thermal fatigue. Thermal-fatigue cracks can form and lead to
component failure. These cracks initiate along the surface and progress inward and can be the starting
point for corrosion or oxidation.
Mechanical failure is mainly a concern for stressed exhaust system components such as exhaust
manifolds and turbine housings. It is also a concern for bellows type flexible exhaust connectors.
Stress Corrosion Cracking

Stress-corrosion cracking (SCC) occurs when sustained tensile stresses and chemical exposure
combine to initiate and propagate cracks in materials. Generally only a few chemical species are
effective in causing SCC. For stainless steels, chlorides are the principle culprit.
Failure due to this mechanism involves crack initiation, subcritical-crack growth, and final failure.
Stress-corrosion cracking is the subcritical crack-growth phase of this process.
Stress-corrosion cracking can be initiated by a number of mechanisms. The loss of a protective

surface film can lead to the formation of a corrosion pit or trench that can lead to the initiation of a
crack. Severe stress concentration, a pre-existing flaw, or a crack that formed previously by a
different mechanism can also initiate the process. The amount of pitting or crevice attack needed to
start the process can be so small as to be undetectable.
Propagation occurs as a result of continued corrosion of the crack tip combined with the action of the
tensile stress. Crack corrosion can occur via galvanic corrosion or by the absorption of impurities. For
stainless steel, chlorides are the principal chemical species of concern and the level required to
produce stress corrosion is very low. Tensile stresses do not have to be from applied loads. Residual
stresses are common reasons for SCC.
Stress-corrosion cracking occurs primarily in alloys and susceptibility is a function of the content of a
major alloying element, such as nickel in austenitic stainless steel. The austenitic stainless steels most
susceptible to chloride stress corrosion cracking are those with 5-10% nickel such as Types 302, 304,
304L and 305. Resistance to SCC initially decreases as nickel content increases to about 5-10%, but
can be regained at approximately 30% Ni. Most ferritic grades show good resistance to SCC because
they either have little or no nickel. Ferritic grades with nickel addition may however be susceptible to
SCC in some cases.
Flexible bellows type connectors are usually made of austenitic grades because of the need for high
temperature strength (Figure 3). These connectors can be under significant residual stresses due to
fabrication, welding or thermal cycling. As a result, SCC is a particular concern for these
components.
Intergranular Corrosion
Stainless steel becomes susceptible to intergranular corrosion when chromium in the grain boundary
regions combines with carbon or nitrogen to form chromium carbide or chromium nitride. If enough
chromium is tied up this way, not enough chromium remains available to passivate the metal in these
regions and corrosion can result. This effect is called “sensitization” and its extent depends mainly on
the carbon and/or nitrogen content of the metal. Sensitization is especially common in areas around
welds and when components are exposed to temperatures in the sensitization temperature range
during use.
Austenitic Grades. The sensitization temperature range for chromium carbides in austenitic grades is
425 - 815°C. At sufficiently high temperature, above about 1035°C, chromium carbides and nitrides
are completely dissolved in austenitic grades. As the material cools slowly from these temperatures
and passes through the sensitization temperature range or if it is reheated into the sensitization
temperature range, chromium carbides and/or chromium nitrides form in the grain boundary regions.
In austenitic stainless steel, the solubility of nitrogen is relatively high and chromium carbides are
primarily responsible for loss of passivity in the grain boundary region. The diffusion rate of
chromium in austenite is slow so that if the material passes quickly through the sensitization
temperature range, chromium carbide formation can be avoided. Another way to eliminate carbides
formed during welding is to anneal the part after welding at 1035°C or higher and cool rapidly.
However, this may not always be practical and further, does not guard against carbide formation
during use. Temperatures in the austenite sensitization temperature range may be difficult to avoid in
exhaust system applications.
Another approach to reduce the formation of chromium carbides in austenitic grades is to ensure the
carbon content of the material is low. Low carbon steel (less than about 0.03% carbon) can extend the
time necessary to precipitate a harmful level of chromium carbides and reduce their formation during
welding and is often used for parts put into service in the as-welded condition. The letter “L” after a
stainless steel type (e.g. 304L) indicates that its carbon content is kept at 0.03% or less. However, this
approach sacrifices some material strength and may not be effective if long term exposure to
temperatures in the sensitization temperature range occurs during use.
Still another approach to provide intergranular corrosion resistance and further extend the time
needed to form chromium carbides is stabilization using titanium (Ti) and niobium (Nb).
(Columbium (Cb) was the name originally given to niobium and occasionally still used today.) These
stabilizing elements form carbides that—being much more stable than chromium carbide—tie up the
carbon in the steel during heat treatment and prevent it from combining with chromium. This makes
these grades more resistant to intergranular corrosion when exposed to temperatures in the
sensitization temperature range. If Ti is used to limit chromium carbide formation in austenitic
grades, nitrogen must still be controlled to avoid tying up titanium as titanium nitride which is very
stable.
Stabilized austenitic grades can still be susceptible to intergranular corrosion after welding because
the base metal immediately adjacent to the weld line is heated to a temperature high enough to
dissolve the stabilizing carbides but cooled rapidly enough to prevent their reformation. Subsequent
welding passes can reheat this region into the sensitization temperature range and both chromium and
stabilizing carbides can form. Chromium carbides formed in this region leave it susceptible to
intergranular corrosion. This so called knife-line attack or knife-line corrosion can be avoided by
suitable welding variables and by the use of stabilizing heat treatments.
Ferritic Grades. While the process of sensitization in ferritic stainless steel is largely the same as
that for austenitic stainless steel, there are some notable differences. One difference is that the
solubility of nitrogen in ferritic grades is relatively low and chromium carbides and chromium
nitrides can be responsible for loss of passivity in the grain boundary region. Another difference is
that the sensitization temperature range for most ferritic grades is 925°C and higher because of the
much lower solubility of carbon and nitrogen. Annealing at temperatures below 925°C after welding
is a common way to diffuse chromium than may have formed carbides or nitrides back into the
depleted zones.
When annealing is not possible or if in-use temperatures of 925°C or higher are expected, similar
alternative approaches to those used with austenitic grades can be used to minimize the risk of
intergranular corrosion. One of these is to keep the level of carbon and nitrogen very low. The
concentrations of carbon and nitrogen needed to avoid intergranular corrosion are very restrictive, in
some cases well below 100 ppm. This makes the use of the stabilizing elements Ti and Nb attractive.
The minimum amount of Ti and Nb required is tied to the level of carbon and nitrogen in that
material. For some alloys it is given by:
Ti + Nb > 0.2 + 4(C + N) (3)

Table 4 summarizes suggested measures to minimize the effects of intergranular corrosion for
selected applications of austenitic and ferritic grades [Arlt 2007][Davis 1994].
Table 4
Methods to Minimize Intergranular Corrosion
Austenitic grades Ferritic grades
 Maximum carbon ~ 0.07%  Maximum
Consistent intergranular  Solution annealing (>1035°C) and rapid carbon ~ 0.08%
corrosion resistance cooling  Annealing below
 Stabilization with Ti, Nb if in-use ~925°C
Resistance after welding temperatures in the sensitization
thin sections (<~7 mm) temperature range are expected
 Stabilization with Ti, Nb if in-use
 Stabilization with
temperatures in the sensitization
Resistance after welding Ti, Nb
temperature range are expected
thick sections (>~7 mm)
 Reduction of the maximum carbon content
to ~0.03%
Intergranular Corrosion After Nitridation. While the above discussion focused on intergranular
corrosion due the presence of nitrogen or carbon in material before it is put into service, nitrogen and
carbon can also be introduced into the material during service. In automotive exhaust systems
utilizing urea SCR, the introduction of nitrogen into the material substrate from urea degradation
products and the formation of chromium nitrides, nitridation has been observed to lead to the
presence of chromium nitrides in the grain boundary regions. Intergranular corrosion can result
[Saedlou 2010][Floyd 2009]. Some grades of ferritic stainless steel may experience intragranular
corrosion as well. Table 5 shows some corrosion data for a number of stainless steel grades from one
of these studies [Floyd 2009]. Note that some common exhaust system materials, such as types 409
(whether coated or not) and 304, performed relatively poorly. Types 316Ti, 436, 439, 444 and 18 Cr-
Cb seemed to perform well over all temperatures. Especially interesting is the fact that 439 and 18
Cr-Cb performed well. These ferritic alloys contain neither nickel nor molybdenum meaning that they
would be relatively low cost materials. They also contain Ti and Nb which are strong nitride formers
and about 18% Cr to provide a good high temperature oxidation resistance. A number of other alloys
with similar composition (e.g., type 441 and 1.4607) are also available—they are currently being
promoted for use in exhaust system applications as alternates to type 304.
Table 5
Corrosion Pit Depth [µm] in Stainless Steels Exposed to Urea†
Temperature, °C
Material
170 300 500 650
304L 0 0 3 27
316Ti 0 0 4 5
316L 0 0 19 0
409 0 55 38 45
409Al 0 138 554 35
409, ceramic coated No. 1 0 13 17 15
409, ceramic coated No. 2 0 88 27 25
436 0 0 8 4
436 BA 0 0 2 12
439 0 2 1 9
444 0 1 1 1
18 Cr-Cb 0 2 1 9
† After exposure to 48 one hour cycles involving (1) ramp up to the temperature indicated, (2) a 45
minute hold at that temperature while urea in injected onto the sample and (3) a cool down to ambient
temperature.
Aluminized Steel And Aluminized Stainless Steel
Mild steel with a hot dipped aluminum coating protects the steel substrate from the action of alkaline
condensate, hot salt and high temperature corrosion. For high temperature applications, alloying
elements such as silicon are added to the aluminum alloy to improve adherence. This type of coating
is referred to as Type 1. Type 2 coatings are pure aluminum and are not used in high temperature
applications.
As shown in Figure 5, aluminized steel has considerably lower high temperature oxidation resistance
compared to even the most basic stainless steel (409).
If the coating is defect free, it can also protect the steel substrate from acidic corrosion; providing
superior corrosion resistance to zinc. However, defect free coatings are difficult to achieve and
defects in the aluminum coating such as pin holes and cracks formed upon shaping and local coating
loss as a result of welding, expose the steel substrate. The exposed steel substrate is then subjected to
acidic corrosion when exposed to condensate. The resulting corrosion products can cause the
aluminum coating to peel. Additionally, when the defects are exposed to moisture, an electrochemical
cell is created causing additional corrosion of the steel substrate.
The effect of the hot dipped aluminum coating on weight loss for low temperature alkaline and high
temperature acidic corrosion is shown in Figure 10 and 9 [Shinoda 1988]. It is apparent that an
aluminized coating can significantly increase the resistance to corrosion and extend the life of the
exhaust system. However, while a hot dipped aluminum coating does provide improved durability, it
is generally not sufficient to allow mild steel to meet the durability requirements for emission control
systems. For US light-duty vehicles, this can be 120,000 miles or higher while for heavy-duty trucks,
the requirement is 435,000 miles. As a result, aluminized mild steel plays a diminishing role in
vehicle exhaust systems for new on-road vehicles.
Figure 10. Effect of Aluminum Coating on Corrosion Resistance of Mild Steel
Figure 11. Effect of Low Temperature Alkaline Corrosion on Thickness Loss of Mild Steel
Stainless steel can also be aluminized. This significantly enhances its resistance to corrosion. This is
illustrated in Figure 12 and 11 [AK Steel 2007] which shows the hot salt and exhaust condensate
corrosion rates of hot dipped aluminum coated ferritic stainless steel. Data for the uncoated materials
from Figure 8 is included in Figure 12.
Figure 12. Effect of Hot Dipped Aluminum Coating on Hot Salt Corrosion of Ferritic Stainless Steel
Figure 13. Effect of Hot Dipped Aluminum Coating on Condensate Corrosion of Ferritic Stainless
Steel
It is interesting to note in Figure 12 that the pitting rate for the aluminized stainless steels is highest at
about 430°C. In the particular coating used in these tests, an alloy layer was applied between the
stainless steel substrate and the aluminum coating. A temperature higher than 430°C was required to
diffuse the aluminum and alloy layers together and provide the full protection of the coating.
Exhaust System Components
Exhaust system material requirements depend on numerous factors including temperature, strength
requirements and chemical exposure—factors that differ depending on the exhaust system
component.
Front Pipe. The front pipe should minimize heat loss for the catalyst. It also needs to have adequate
high temperature oxidation resistance and resist high temperature chloride corrosion. These
components are also exposed to vibration from the engine. Ferritic stainless steels are commonly
used. While 409 has served well in for this component in many applications, more demanding
applications often require ferritic grades such as 439 to provide adequate oxidation and corrosion
resistance at higher temperatures. Thin double wall pipes are becoming common for this application,
with austenitic stainless steel used for the inner pipe in some designs.
In applications with an SCR catalyst, urea may be injected in the front pipe. For these applications, a
material resistant to nitridation and subsequent intergranular corrosion may be required. Grades with
about 18% chromium and stabilized with Ti and Nb (441, 436, 18 Cr-Cb and 1.4607) are commonly
promoted for such an application.
Flexible Connectors. Automotive bellows type flexible connectors operate under difficult
conditions. The walls are very thin in order to provide flexibility and therefore they can tolerate little
material loss if they are to remain leak proof for the useful life of the vehicle. Stress levels can also be
quite significant. Important material properties for these components include resistance to high
temperature oxidation, good high-temperature fatigue properties, formability, resistance to high-
temperature corrosion from road salt, and resistance to stress corrosion cracking. Poor material
selection for stainless steel bellows often leads to failure as a result of hot salt corrosion and chloride
stress corrosion cracking [Crum 1998].
Austenitic stainless steel is commonly used for this demanding application. One lower cost austenitic
stainless steel sometimes considered for this application is type 304. In the presence of road salt and
residual stresses in the material, this grade is very susceptible to stress corrosion cracking (SCC)
because of its relatively low nickel content. It can also be susceptible to intergranular corrosion if
welded.
Austenitic stainless steels with higher nickel contents such as Type 316 alloys offer improved
resistance to corrosion and stress corrosion cracking over 304 and are also sometimes considered.
Type 316L offers improved resistance to intergranular corrosion compared to 316 but at the expense
of some loss of strength. Type 316Ti offers similar strength to 316 but also resistance to intergranular
corrosion. Type 316 alloys can however corrode rapidly when exposed to elevated temperatures and
are not generally used if temperatures exceed approximately 650°C.
For connectors subjected to elevated temperature corrosive environments, an austenitic nickel-based

superalloy such as AL625 is one option. This alloy possesses excellent resistance to oxidation and
corrosion over a broad range of corrosive conditions and has excellent formability and strength.
However, it contains approximately 58% Ni by weight and is quite expensive compared to Type
316Ti alloys and other iron-based alloys.
Lower cost alternatives to nickel superalloys are iron based austenitic stainless steels with 30-38% Ni
such as Al 332Mo and Incoloy 864. They use molybdenum to increase resistance to corrosion by salt
at a broad temperature range up to about 760-800°C.
Aftertreatment Shell. The shell material for catalytic aftertreatment devices can see a variety of
temperatures extremes. Ferritic stainless steel is preferred to austenitic for reasons not only of cost
and high temperature oxidation resistance but also because of the lower coefficient of thermal
expansion and resulting dimensional stability that makes it easier to hold catalyst substrates in the
catalytic converter. For catalyst systems that are close coupled to the engine or that generate
significant heat such as oxidation catalysts and DPFs, shell temperatures may reach considerable
levels and materials with higher heat resistance may be necessary.
Center Pipe. This pipe connects the aftertreatment system to the muffler. For systems without an
actively regenerated diesel particulate filter, the temperature of the exhaust gas is lower and
consequently, the high-temperature properties are less demanding. Common ferritic stainless steels
serve well in this component for many applications. For vehicles equipped with a DPF, the
temperature in this pipe may be as high as or even higher than in the front pipe during DPF
regeneration, especially if an active regeneration strategy is used, and more heat resistant alloys may
need to be considered. Resistance to corrosion from exhaust condensate is required at the inner
surface and to corrosion from road salt at the outer surface.
In some applications with an SCR catalyst, urea may be injected into the system at this point and as
with applications where the urea is injected into the front pipe, a nitridation resistant material may be
required.
Muffler. Mufflers are mainly exposed to exhaust condensate corrosion on their inner surfaces and
salt corrosion on their outer surfaces. Vehicle driving cycles that consist of numerous short trips can
create a very corrosive environment inside the muffler. During such driving, exhaust condensate can
collect inside the muffler and if the temperature of the muffler does not rise high enough to
completely evaporate it, it will remain in the muffler. Driving over longer distances is less severe as
the muffler generally operates at a high enough temperature that condensation does not occur except
during cold starting. After vehicle shut-down, moist exhaust gas can remain in exhaust system and
some condensation can also occur as the vehicle cools down.
Tailored materials—including tailored strips, blanks and pipes—are a development that can provide
weight savings and reduce the influence of alloy surcharges in the muffler. Tailored strips are formed
by welding two or three long strips of metal of different thickness and/or grade together along their
edges (Figure 14). In tailored blanks, sections made of different materials can have different shapes,
such as trapezoidal or triangular.
Figure 14. Process of Manufacturing Tailored Strips

(Courtesy of ThyssenKrupp)
Figure 15 shows an example of a muffler made from type 304 tailored strips. Instead of building the
entire muffler shell out of one thickness of material, material characteristics can be matched with
their location. The thickest material can be confined to the portions of the muffler shell where it is
required—in this case the ends—while thinner material can be used for the central section. The
overall effect was a muffler that was 0.8 kg or 27% lighter [Zimmermann 2011].
Figure 15. Muffler Manufactured from Type 304 Tailored Strips

Strip 1: 1.2 mm thick, 112 mm wide; Strip 2: 0.7 mm thick, 366 mm wide; Strip 3: 1.2 mm thick, 97
mm wide
References
AK Steel, 2007. “15 Cr-Cb Stainless Steel Ultra Form”, AK Steel Corporation, West Chester, OH, USA, Product Data
Bulletin
AK Steel, 2007. “Aluminized Steel Type 1 Stainless 409 and 439”, AK Steel Corporation, West Chester, OH, USA, Product
Data Bulletin
AK Steel, 2007. “Aluminized Type 1 Steels”, AK Steel Corporation, West Chester, OH, USA, Product Data Bulletin
Arlt, N., 2007. “Korrosions- und hitzebeständige Stähle in Abgassystemen”, CTI Exhaust Materials Forum 21- 22.11.2007,
Frankfurt, Germany
ASM, 2001. “Metals Handbook”, ASM International, Materials Park, OH, USA
ATI, 1999. “Stainless Steels Type 439/AL 439 HP”, ATI Allegheny Ludlum Corporation Blue Sheet Technical Data
ATI, 2005. “Stainless Steels AL441HP Alloy”, ATI Allegheny Ludlum Corporation Blue Sheet Technical Data
Chattha, M.S., et al., 1990. “Corrosion of aluminized low carbon steel exhaust system in vehicles equipped with three-way
catalytic converters and development of a protective polymeric coating”, Ind. Eng. Chem. Res., 29, 1438-1442
Crum, J.R., et al., 1998. “Flexible alloy and components made therefrom”, US Patent 5,827,377,
http://www.google.com/patents?vid=USPAT5827377
Davis, J.R., 1994. “Stainless Steels”, ASM International
Floyd, R., et al., 2009. “Material Corrosion Investigations for Urea SCR Diesel Exhaust Systems”, SAE Tecnhical Paper
2009-01-2883, doi:10.4271/2009-01-2883
Gumpel, P., C. Hoffmann, 2008. “Corrosion resistance of stainless steels to wet condensates in automotive exhaust
systems”, Proceedings of the 6th European Stainless Steel Conference, Helsinki
Inoue, Y., Kikuchi, M., 2003. “Present and future trends of stainless steel for automotive exhaust system”, Nippon Steel
Technical Report No. 88, July 2003
Lai, G.Y., 2007. “High-Temperature Corrosion And Materials Applications”, ASM International, Materials Park, OH, USA
Saedlou, S., et al., 2010. “Influence of Selective Catalytic Reduction (SCR) System on Stainless Steel Durability”, INOX
2010 10th Brazilian Stainless Steel Conference, Sept 20-22, 2010, http://www.nucleoinox.org.br/inox-
2010/downloads/trabalhos/W6-HTOofSSforDieselVehicles%28AMittal%29.pdf
Shinoda, K., Fujita, S., 1988. “Highly corrosion resistant aluminized steel sheet for the manufacture of parts of exhaust gas
system”, US Patent 4,729,929, http://www.google.com/patents?vid=USPAT4729929
Yang, Z., et al., 2010. “The benefit of molybdenum in stainless steel”, International Seminar on Applications of Mo in
Steels, June 27-28, 2010, Beijing Friendship Hotel
Zimmermann, K., 2011. “Lightweight design in exhaust systems using tailored products”, 9th International CTI Forum
Exhaust Systems, January 26, 2011, Stuttgart, Germany
###

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DieselNet Technology Guide » Diesel Exhaust Systems

www.DieselNet.com. Copyright © Ecopoint Inc. Revision 2011.03

Exhaust System Materials

Aluminized Steel And Aluminized Stainless Steel

Exhaust System Components

 provide solid solution strengthening of ferrite,

functions attributed to nickel

 Ferritic stainless steel, and

Figure 1. Structure of Ferrite and Austenite

Austenitic Ferritic Ni Alloy

0.25 - 0.3+9C Nb+Ta:

0.60 to 0.9 3.15 -

Figure 4. Nickel, Chromium and Molybdenum Prices from 2002-2009

 High temperature corrosion (dry hot corrosion)

High Temperature Material Degradation

R = (volume of metal oxide produced) / (volume of metal oxidized) (1)

Figure 5. Maximum Use Temperatures for Different Grades of Steel

Condensate And Salt Corrosion

PRE = %Cr + 3.3 (%Mo) + x (%N) (2)

Figure 6. Pitting Resistance Equivalent (PRE) for Several Alloys

Figure 7. Cyclic Exposure to Salt And Heating to 649°C

Figure 8. Pitting Rate After Exposure to Salt

Figure 9. Scale Spalling Weight Loss After Exposure to Salt

Elevated Temperature Mechanical Failure

Stress Corrosion Cracking

Stress-corrosion cracking can be initiated by a number of mechanisms. The loss of a protective

Ti + Nb > 0.2 + 4(C + N) (3)

Aluminized Steel And Aluminized Stainless Steel

Figure 10. Effect of Aluminum Coating on Corrosion Resistance of Mild Steel

Exhaust System Components

For connectors subjected to elevated temperature corrosive environments, an austenitic nickel-based

Figure 14. Process of Manufacturing Tailored Strips

Figure 15. Muffler Manufactured from Type 304 Tailored Strips

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