Facts At Your Fingertips

Steel Corrosion
Department Editor: Scott Jenkins

orrosion of steel is a key

concern in many industrial
settings, both from an assetmanagement perspective and from
a safety perspective. The following
briefly describes corrosion mechanisms for various classes of steel,
and provides information on the corrosion resistance of these ubiquitous
iron-based alloys.
Carbon steels contain only iron
and carbon, with carbon making up
between 0.002 and 2.1 wt.%. Lowalloy steels contain a variety of other
elements added to achieve desired
properties of corrosion resistance,
strength, formability and other characteristics. Steel is classified as stainless steel if its chromium content is at
least 10.5 wt.%, and its carbon content is less than 1.20 wt.%, as defined in ASTM Standard A240 (ASTM
International; West Conshohocken,
Pa.; www.astm.org).

Iron oxidation
Steel corrosion is an electrochemical
process requiring the simultaneous
presence of water and oxygen. The
anode reaction involves the formation of Fe2+ ions and the release of
electrons, while the cathode reaction
involves a reduction of dissolved oxygen, with water as an electrolyte.
Fe0 > Fe2+ + 2e
O2 + 2H2O + 4e > 4OH
Iron ions react with the hydroxide to form iron hyroxides [such as
Fe(OH)2], which react further with
oxygen to give Fe2O3H2O (rust). The
presence of acids and chlorides accelerates the corrosion process.

Stainless steel
The chromium in stainless steels allows the generation of a complex
chromium-oxide surface layer that
resists further oxidation (passive layer). The chromium-oxide layer is thin
(microns) but tough. It will reform if
removed by scratching or machining.
The addition of nickel to the structure
(8 wt.% Ni minimum in the commonly
used 304 type stainless steel and 10
46

TABLE 1. ALLOYING ELEMENTS AFFECT STAINLESS-STEEL CORROSION PROPERTIES

ELEMENT
Chromium

Molybdenum
Copper
Manganese
Titianium/Niobium

EFFECT ON STAINLESS STEEL

Forms a passive film with oxygen that prevents further diffusion of oxygen into the
surface of the steel
Increases ductility and toughness; increases corrosion resistance to acids;
Ni addition creates non-magnetic structure
Increases pitting and crevice corrosin resistance; increases resistance to chlorides
Increases corrosion resistance to sulfuric acid
Acts as a substitute for nickel in 200-series stainless steel
Ties up carbon and prevents inter-granular corrosion in welded zone of ferritic grades

Nitrogen

Increases strength and corrosion resistance in austenitic and duplex grades

Silicon

Improves resistance to high-temperature scaling

Nickel

Sulfur

Usually kept low except for free-machining grades

Carbon

Usually kept low; used in martensitic grades to increase strength and hardness

Source: Alloying Elements in Stainless Steel by Pierre-Jean Cunat,

Published by the Internation Chromium Development Association

wt.% Ni minimum in the more corrosion-resistant 316) broadens the

range of passivity established by the
chromium. Further, addition of molybdenum (2 wt.% minimum in 316)
further expands the passivity range
and improves corrosion resistance
(see table).

Corrosion mechanisms
Stainless steel resists general corrosion well, but several mechanisms
can result in localized corrosion of
stainless steel. For example, pitting
occurs in areas where the stainless
steels protective passive layer breaks
down on an exposed surface. Once
initiated, the growth rate of the pit can
be relatively rapid and can result in localized, deep cavities.
Crevice corrosion occurs in locations where oxygen cannot freely circulate, such as tight joints, under fastener heads and in other areas where
pieces of metal are in close contact.
Pitting and crevice corrosion of
stainless steels generally occurs in
the presence of halide ions (chloride
is most common). Moisture from the
environment, along with chloride salts
and pollutants, accumulates in the
crevices, creating an acidic environment inside the crevice where oxygen
is depleted and chloride concentration is elevated. This environment
promotes the breakdown of the passive film and anodic dissolution.
The main environmental factors
that favor localized attack include
higher chloride concentration, elevated temperature, lower pH and
more cathodic corrosion potentials.
CHEMICAL ENGINEERING

Specific corrosive environments,

such as the presence of chlorides,
combined with tensile stress, can
crack stainless steels in a mode of
attack known as stress corrosion
cracking (SCC).
Another corrosion mechanism involves the metals microscopic grain
structure. Rapid corrosive attack of
immediately adjacent grain boundaries with little or no attack of the grains
is called intergranular corrosion.

Corrosion resistance
Corrosion of carbon steel can be
minimized with protective paints and
coatings, or by cathodic protection,
such as galvanizing (applying a zinc
coating to interfere with the natural
electrochemical reactions in corrosion). Modifying the operating environment with corrosion inhibitors can
also be effective in some cases. The
resistance of a stainless steel to localized attack is strongly related to
its alloy content.
Chemical passivation refers to the
chemical treatment of stainless steel
with a mild oxidant, such as nitric
acid or citric acid solution, for the
purpose of enhancing the spontaneous formation of the protective passive chromium oxide film.
n
For more on corrosion, see Chem. Eng., March 2014, pp.
4043 and July 2012, pp. 2629.

Relevant links
1. Specialty Steel Industry of North America. www.ssina.
com/overview/alloyelements_intro.html
2. ASTM International. Standard A380. www.astm.org/
Standards/A380/
3. Steelconstruction.info
4. Corrosionist. www.corrosionist.com/Pitting_Crevice_Corrosion.htm

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MARCH 2015