STAINLESS STEEL OVERVIEW:
ALLOYING ELEMENTS IN STAINLESS STEEL
Most metals are not used in their pure form but have alloying elements added
to change their properties. The addition of a second element such as chromium
to iron can significantly alter the corrosion properties. “Stainless
Steel” is the general name for a large family of alloys that contain
at least 10.5% chromium. At and above this level, an extremely thin surface
layer is instantaneously formed (as long as oxygen is present) that prevents
the diffusion of oxygen atoms through this layer and protects the iron in
the matrix from rusting. This is called “passivation” and the
material in the passive condition is highly corrosion resistant. Several other
alloying elements can be added to this chrome-iron matrix to form well over
150 different compositions, each with unique characteristics. This family
of stainless steels can be divided into five (5) categories:
1) AUSTENITIC STAINLESS STEELS Fe-Cr-Ni (Mo) alloys
The carbon content is generally held to a maximum of 0.08% (302, 309 &
310 have slightly higher levels). Chromium is in the range of 16.0 to 28.0%
and nickel between 3.5 & 32.0%. These alloys cannot be hardened by heat
treatment and are non-magnetic. They all exhibit excellent corrosion resistance
(Molybdenum is added for resistance to chlorides), have great ductility and
2) FERRITIC STAINLESS STEELS Fe-Cr (Mo) alloys
The carbon levels here are also low, generally below 0.12% (442, 446 are
at 0.20). The chromium content can vary from 10.5 to 30.0%. These grades cannot
be hardened by heat treatment but they are magnetic. They have good corrosion
resistance (particularly to chloride stress corrosion cracking) but are generally
not chosen for toughness.
3) MARTENSITIC STAINLESS STEELS Fr-Cr-C (Ni Mo) alloys
These grades do have a relatively high carbon level compared to the other
categories. Carbon can range from 0.15 to 1.20%. Chromium levels between 11.5
& 18.0%. They can be heat-treated to very high hardness levels. They are
4) DUPLEX STAINLESS STEELS Fe-Cr-Ni_(Mo)-N alloys
These are a combination of both austenitic and ferritic structures. The carbon
levels are very low (below 0.03%). Chromium between 21.0 & 26.0% with
nickel from 3.5 to 8.0% and may contain molybdenum up to 4.5% and nitrogen
0.05 to 0.30% These alloys are magnetic, and offer increased tensile and yield
strength over the other categories.
5) PRECIPITATION HARDENING STEELS Fe-Cr-Ni (Mo-Cu-Al-Nb)- N alloys
Also low carbon (0.09 max.), they have good corrosion resistance and are
characterized by ease of fabrication. High strength can be developed at relatively
low temperature (500-800C) so distortions are minimized. Chromium between
12.25 & 18.0%, with nickel 3.0 to 8.5%. Molybdenum, in some grade between
2.0 and 2.5%, with additions of Aluminum, copper, rare earths and nitrogen.
ROLE OF ALLOYING ELEMENTS IN STAINLESS STEEL
Carbon is always present in stainless steel. The amount of carbon is the
key. In all categories except martensitic, the level is kept quite low. In
martensitic grade the level is deliberately increased to obtain high strength
and hardness. Heat treating by heating to a high temperature, quenching and
then tempering develops the martensitic phase.
Carbon can have an effect on the corrosion resistance. If the carbon is allowed
to combine with the chromium (to form chrome carbides), it may have a detrimental
effect on the ability of the “passive” layer to form. If, in localized
areas, the chrome is reduced to below 10.5%, the layer will not form
Chromium is a highly reactive element and accounts for the “passive”
nature of all stainless steels. The resistance to the chemical effects of
corrosion and the typical “rusting” (oxidation) that occurs with
unprotected carbon steel, is the direct result of the presence of chromium.
Once the composition contains at least 10.5% chromium, an adherent and insoluble
surface film is instantaneously formed that prevents the further diffusion
of oxygen into the surface and prevents the oxidation of the iron in the matrix.
The higher the chromium level the greater the protection.
Nickel is the essential allying element in the 300 series stainless steel
grades. The presence of nickel results in the formation of an “austenitic”
structure that gives these grades their strength, ductility and toughness,
even at cryogenic temperatures. It also makes the material non-magnetic. While
the role of nickel has no direct influence on the development of the “passive”
surface layer, it results in significant improvement in resistance to acid
attack, particularly with sulfuric acid.
The addition of molybdenum to the Cr-Fe-Ni matrix adds resistance to localized
pitting attack and better resistance to crevice corrosion (particularly in
Cr-Fe ferritic grades). It helps resist the detrimental effects of chlorides
(316 with 2% moly is preferred over 304 in coastal and de-icing salt situations).
The higher the molybdenum content (there are stainless steels at 6% moly),
the better the resistance to higher chloride levels.
Generally manganese is added to stainless steels to assist in de-oxidation,
during melting, and to prevent the formation of iron sulfide inclusions which
can cause hot cracking problems. It is also a “austenite” stabilizer
and when added in higher levels (from 4 to 15%) replaces some of the nickel
in the 200 series stainless steel grades.
SILICON & COPPER
Small amounts of silicon and copper are usually added to the austenitic stainless
steels containing molybdenum to improve corrosion resistance to sulfuric acid.
Silicon also improves oxidation resistance and is a “ferrite”
stabilizer. In “austenitic stainless steels, high silicon contents improves
resistance to oxidation and also prevents carburizing at elevated temperatures
(309 and 310 are examples)
In “austenitic” and “duplex” stainless steels, nitrogen
increases the resistance to localized pitting attack and inter-granular corrosion.
Low carbon “austenitic” grades (designated with an “L”
since they contain less than 0.03% carbon), are suggested for welding operations,
since the lower carbon minimizes the risk of sensitization. The low carbon
levels, however, tend to reduce the yield strength. The addition of nitrogen
helps to raise the yield strength levels back to the same level as standard
Niobium additions prevents inter-granular corrosion, particularly in the
heat effected zone after welding. Niobium helps prevent the formation of chrome
carbides, that can rob the microstructure of the required amount of chromium
for passivation. In “ferritic” stainless steels the addition of
niobium is an effect way to improve thermal fatigue resistance.
Titanium is the main element used to stabilize stainless steel before the
use of AOD (Argon-Oxygen Decarburization) vessels. When stainless steel is
melted in air, it is difficult to reducing the carbon levels. 302, the most
common grade before AOD’s, was allowed to have a maximum carbon level
of 0.15%). At this high level, something was needed to stabilize the carbon
and titanium was the most common way. Titanium will react with the carbon
to form titanium carbides and prevent the formation of chrome carbides, that
could affect the formation of the “passive” layer. Today all stainless
steel are finished in an AOD vessel and the carbons levels are generally low
due to the absence of oxygen. The most common grade today is 304 (with 0.08
max carbon, although in reality the levels are lower).
Sulfur is generally kept to low levels as it can form sulfide inclusions.
It is used to improve machinability (where these inclusion act as “chip
breakers). The addition of sulfur, however, does reduce the resistance to