The corrosion phenomenon consists in a chemical or electrochemical

degradation that happens on the surface of the material, which is in contact with the
environment. As a result of those reactions, the integrity of many elements that are
present in the metal alloys is compromised, like iron, carbon, nickel, etc. The iron of a
component made of steel, for example, has a tendence to return to its original state (iron
oxide) due to the interactions with atmosphere, forming scale, in such a progressive way
that can eventually lead the part to failure. This problem is even more recurring in
aggressive media, like inside heat exchangers from power industries or components in
contact with compounds in chemical processing. In order to counteract this problem, the
development of the stainless steels had a huge importance, since the presence of
chromium in them significantly improves the corrosion and oxidation resistance of
steels, due to the formation of a thin, adherent, spontaneously created and self-healing
outer layer of Cr2O3, that protects the structure by providing a metal-atmosphere
isolation.

Firstly, the phenomenon of corrosion must be clearly understood. There are two
basic forms of corrosion: electrochemical corrosion, also known as wet corrosion; and
chemical corrosion, also known as high temperature oxidation or dry corrosion. The
electrochemical one is caused by a flow of electrons between metals (galvanic
corrosion); between different parts of the same material (pitting and crevice corrosion),
in such a way that the anode (receiver of electrons) is attacked, and the cathode
(provider of electrons) is not; or in a uniform and generalized way when the component
is exposed to a highly aggressive medium. The chemical one is characterized by the
oxidation of the metal alloy upon contact with atmosphere at high temperatures,
producing oxides and salts.

In the case of galvanic corrosion, whose scheme is illustrated in the diagram 1,

the higher the potential difference between the metals, the higher will be the rate of
degradation, even in a not so aggressive medium. It can be avoided by not putting
different surfaces into direct contact, or by inserting an electrical insulation between
them once the electric contact is a requirement for electrochemical corrosion to happen.
The pitting corrosion occurs when discrete areas are quickly attacked and their
surroundings are not, due to small breaks in the metal coating, or physic-chemical
irregularities and they can be significantly deep. The crevice corrosion occurs in the
presence of crevices, incrustations and geometrical discontinuities where the electrolyte
is locally in stagnation.

There are five main types of stainless steels: austenitic, ferritic, duplex,
martensitic and precipitation strengthening. The largest family of stainless steels are the
austenitic stainless steels, which are also among the most resistant, so they are going to
be the focus of the discussion about stainless steels for counteracting the corrosion
problem.

Austenitic stainless steels have a high content of chromium (ferritizing affect)

and also of nickel (austenitizing effect), which modifies the Fe-C diagram in such a way
that ferritizing action of chromium is overcome by the austenitizing effect of nickel, so
that the steel is completely austenitic at ambient temperature, which is characterized by
a face-centered cubic lattice and by an excellent resistance to atmospheric and water
corrosion. The increase of nickel content can increase the corrosion resistance.

However, austenitic stainless steels are subject to a sensitization, that consists in

the precipitation of chromium carbides in the grain boundaries at a certain temperature
range after a certain time of exposure (sensitization time), decreasing the chromium
content in the vicinity, making those areas more susceptible to corrosion. It can be
counteracted by keeping their carbon content as low as possible (0,02-0,03 %), which
significantly increases the sensitization time. Also, titanium or niobium can be added to
prevent this phenomenon, by forming stable carbides, so there is less carbon left to form
chromium carbides.
 Since there is no phase-transformation, austenitic stainless steels cannot be
hardened by heat treatment, so their mechanical properties are limited, due to the high
deformability of the austenitic matrix, showing low tensile strength and hardness, but
high ductility. Fortunately, their strength can still be increased by work hardening, in
such a way that this improved strength can be maintained up to high temperatures. They
are also good at low temperatures (good for cryogenic applications), due to the absence
of the ductile to brittle temperature transition. Their high corrosion resistance makes
them an interesting choice for boilers, heat exchangers, pipes, and chemical and food
industries.