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Metallurgy of Mo in stainless steel

Molybdenum adds corrosion resistance and high temperature strength


Molybdenum primarily increases the corrosion resistance of stainless steels (see Grades and Properties).
Molybdenum containing grades of stainless steels are generally more corrosion resistant than
molybdenum-free grades. They are used in applications that are more corrosive, such as chemical
processing plants or in marine applications. There are many grades of stainless steels with different
molybdenum (and chromium, nickel, nitrogen, etc.) contents. The best grade for a given application is
selected based on the corrosivity of the service environment.
As a large atom, molybdenum increases the elevated temperature strength of stainless steels through solid
solution hardening. This effect is used in heat exchangers and other elevated temperature equipment such
as in automotive exhaust systems.

Molybdenum is a ferrite former

To discuss the influence of molybdenum on the metallurgy of stainless steels it is useful to look at the
metallurgy of stainless steels in general. Based on their microstructure, stainless steels are divided into the
following families:
austenitic
ferritic
martensitic
duplex
precipitation hardenable
The division based on microstructure is useful because the members within one family tend to have similar
physical and mechanical properties. However, the properties for one family can be very different from the
properties for another family. For example, austenitic stainless steels are non-magnetic, while ferritic and
duplex stainless steels are magnetic.

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The difference between the families is fundamental on an atomic level. The arrangement of atoms in the
ferrite crystal is different from the one in the austenite crystal:
In the ferritic stainless steel, the iron and chromium atoms are arranged on the corners of a cube and in the
center of that cube. In the austenitic stainless steels the atoms, here iron, chromium and nickel, are
arranged on the corners of the cube and in the center of each of the faces of the cube.
This seemingly small difference profoundly affects the properties of these steels.

Fig 1: The ferritic stainless steel on the left has a body centered cubic (bcc) crystal structure. By adding nickel to this stainless
steel the structure changes from bcc to face centered cubic (fcc), which is called austenitic.

Select properties of austenitic and ferritic stainless steels


Properties

Austenitic

Ferritic

Toughness

Very high

Moderate

Ductility

Very high

Moderate

Weldability

Good

Limited

Thermal expansion

High

Moderate

Stress corrosion cracking resistance

Low

Very high

Non-magnetic

Ferro magnetic

Magnetic properties

Because of their good mechanical properties and the ease of fabrication, austenitic stainless steels are
much more widely used than ferritic stainless steels. About 75% of all stainless steel used worldwide is
austenitic and about 25% is ferritic. The other families, martensitic, duplex and precipitation hardenable
stainless steels each represent less than 1% of the total market.
Besides nickel there are other elements that tend to make the structure austenitic. These elements are
called austenite formers. Alloying elements that tend to make the structure ferritic are called ferrite formers.

Ferrite and austenite formers


Ferrite formers

Austenite formers

Iron

Nickel

Chromium

Nitrogen

Molybdenum

Carbon

Silicon

Manganese
Copper

Molybdenum is a ferrite former. That means that when molybdenum is added to improve the corrosion
resistance of an austenitic stainless steel, there has to be an austenite former such as nickel or nitrogen
added in order to keep the structure austenitic.
Duplex stainless steels have a mixture of austenitic and ferritic grains in their microstructure; hence they
have a duplex structure. This effect is achieved by adding less nickel than would be necessary for making
a fully austenitic stainless steel.

Molybdenum is mainly used for added corrosion resistance in austenitic and duplex stainless steels. In
austenitic stainless steels between two and seven percent are added, in duplex stainless steels, between
three and five percent. The addition of one or two percent molybdenum to ferritic stainless steels also
significantly increases the corrosion resistance and the elevated temperature strength of these stainless
steels.

Fig 2: Adding 8% nickel to a ferritic chromium stainless steel makes an austenitic chromium-nickel stainless steel, for example
Type 304 stainless steel. If less nickel is added to a chromium steel, about four or five percent, a duplex structure, a mixture of
austenite and ferrite, is created as in 2205 duplex stainless steel.

Molybdenum grade Alloy Steels & Irons

Molybdenum is used efficiently and economically in alloy steel & iron to


improve hardenability
reduce temper embrittlement
resist hydrogen attack & sulphide stress cracking
increase elevated temperature strength
improve weldability, especially in high strength low alloy steels (HSLA)
In the present section the focus is on grades and properties of Mo containing alloy steel and iron. End uses
cover the whole world of engineered products for:
Automotive, shipbuilding, aircraft and aerospace
Drilling, mining, processing
Energy generation, including boilers, steam turbines and electricity generators
Vessels, tanks, heat exchangers
Chemical & Petrochemical processing
Offshore; Oil Country Tubular Goods (OCTG)
In most cases molybdenum is needed to meet the high end of the application properties, which is
accomplished with comparatively small molybdenum additions. In fact, with the exception of High Speed
Steel and Maraging Steel the Mo content often ranges between 0.2 and 0.5% and rarely exceeds 1%.

Properties of Molybdenum
Typical % Mo content
Heat Treatable Engineering Steel

0.25 - 0.5

Case Hardened Steel

0.15 - 0.5

High Temperature Steel

0.3 - 1.2

Oil Country Tubular Goods (OCTG)

0.3 - 1.0

HSLA Steel

0.15 - 0.25

Maraging Steels

4.0 - 5.0

Tool & High Speed Steel

0.5 - 9.0

Cast Iron

1.0 -3.0

Duplex stainless steel


Duplex stainless steels are called duplex because they have a two-phase microstructure consisting of
grains of ferritic and austenitic stainless steel. The picture shows the yellow austenitic phase as islands
surrounded by the blue ferritic phase. When duplex stainless steel is melted it solidifies from the liquid
phase to a completely ferritic structure. As the material cools to room temperature, about half of the ferritic
grains transform to austenitic grains (islands). The result is a microstructure of roughly 50% austenite and
50% ferrite.

Duplex stainless steels have a two-phase microstructure of austenite and ferrite grains.

The duplex structure gives this family of stainless steels a combination of attractive properties:
Strength: Duplex stainless steels are about twice as strong as regular austenitic or ferritic stainless steels.
Toughness and ductility: Duplex stainless steels have significantly better toughness and ductility than
ferritic grades; however, they do not reach the excellent values of austenitic grades.
Corrosion resistance: As with all stainless steels, corrosion resistance depends mostly on the
composition of the stainless steel. For chloride pitting and crevice corrosion resistance, their chromium,
molybdenum and nitrogen content are most important. Duplex stainless steel grades have a range of
corrosion resistance, similar to the range for austenitic stainless steels, i.e from Type 304 or 316 (e.g. LDX
2101) to 6% molybdenum (e.g. SAF 2507) stainless steels.
Stress corrosion cracking resistance: Duplex stainless steels show very good stress corrosion cracking
(SCC) resistance, a property they have inherited from the ferritic side. SCC can be a problem under
certain circumstances (chlorides, humidity, elevated temperature) for standard austenitics such as Types
304 and 316.
Cost: Duplex stainless steels have lower nickel and molybdenum contents than their austenitic
counterparts of similar corrosion resistance. Due to the lower alloying content, duplex stainless steels can
be lower in cost, especially in times of high alloy surcharges. Additionally, it may often be possible to
reduce the section thickness of duplex stainless steel, due to its increased yield strength compared to
austenitic stainless steel. The combination can lead to significant cost and weight savings compared to a
solution in austenitic stainless steels.

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