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Most of metallic elements (except noble metals) present in the most stable state
having low energy, normally oxides (as metallic ores)
The responsible factors for the corrosion of a metal are the metal itself, the
environmental chemicals, temperature and the design.
Oxidation: It is type of corrosion involving the reaction between a metal and air or
oxygen at high temperature in the absence of water or an aqueous phase. It is also
called dry-corrosion. At normal temperatures, the oxides of metals (except gold) are
more stable than the metals.
Cu2+ + Fe → Cu + Fe2+
In terms of half-cell reactions: Cu ions will deposit
(electrodeposit) as metallic copper on the copper
electrode, while iron dissolves (corrodes) on the other
side of the cell and goes into solution as Fe2+ ions.
Standard half-cell
Fe → Fe2+ + 2e-
Cu2+ + 2e- → Cu
Cu2+ + Fe → Cu + Fe2+
Corrosion penetration rate (CPR), or the thickness loss of material per unit of time.
where W = weight loss after exposure time t; ρ = density, and A = exposed specimen
area, K is a constant.
where
i = current density (the current per unit surface area of material corroding)
n = number of electrons associated with the ionization of each metal atom
F = 96,500 C/mol.
For example,
cementite in steel is more noble (cathodic) with respect to ferrite.
Under corrosive conditions, ferrite will form the anode and corrode away.
If, in a region of the electrolyte, the metal ions are deficient, the
metal near that region will be anodic with respect to the metal
near a different region where the electrolyte has excess metal
ions.
In the zinc–copper cell, due to continued dissolution of zinc at the anode, the
zinc ion concentration near the anode builds up. The potential of the zinc
electrode will shift towards the noble end, that is, towards that of copper.
Similarly, at the cathode, the cupric ions are being used up in the cathode
reaction, resulting in a deficiency of these ions near the cathode.
This shifts the cathode potential towards the active side, that is, towards that
of zinc.
The electrodes are said to be polarized, as the current flows (as shown in
figure in next slide).
The variations in the cathode and the anode potentials with increasing current density.
E.g., general rusting of steel and iron and the tarnishing of silverware
The most common form of corrosion. It is also the least objectionable because it can be
predicted and designed for with relative ease.
Prevention:
1. Protective Coating
2. Inhibitors
3. Cathodic Protection
The less noble or more reactive metal in the particular environment will experience
corrosion; the more inert metal, the cathode, will be protected from corrosion.
For example,
1. If coupling of dissimilar metals is necessary, choose two that are close together in
the galvanic series.
4. Electrically connect a third, anodic metal to the other two; this is a form of
cathodic protection.
Difficult to detect: May be covered by corrosion products Depth and no of pits vary
Until Failure!!
Generally requires an initiation period. Once started the pits grow at an ever
increasing rate. Grow in the direction of gravity and on lower surfaces of the
equipment.
Pits are initiated at places where local increase in corrosion rates occurs. Local
structural and/or compositional heterogeneities.
These zones also called crevices and are very tiny and difficult to access for the
aqueous liquid that is covering the rest of the readily accessible surfaces.
This type of corrosion is also known as deposit attack.
Prevention
using welded instead of riveted or bolted joints,
using non-absorbing gaskets (like Teflon) when possible,
removing accumulated deposits frequently, and
designing containment vessels to avoid stagnant areas and ensure
complete drainage.
Disclaimer: This material is purely for teaching purpose only
Intergranular Corrosion
It occurs preferentially along grain boundaries for some alloys and in specific
environments. The net result is that a macroscopic specimen disintegrates along its
grain boundaries.
This type of corrosion is especially prevalent in some stainless steels. When heated
to temperatures between 500oC and 800oC for sufficiently long time periods, these
alloys become sensitized to intergranular attack. Temperature range is called as
sensitizing temperature range.
• This heat treatment permits the formation of small precipitate particles of chromium carbide
(Cr23C6) by reaction between the chromium and carbon in the stainless steel. These particles
form along the grain boundaries
• Both the chromium and the carbon must diffuse to the grain boundaries to form the
precipitates, which leaves a chromium-depleted zone adjacent to the grain boundary.
Consequently, this grain boundary region is now highly susceptible to corrosion.
Disclaimer: This material is purely for teaching purpose only
Intergranular Corrosion
Intergranular corrosion is an especially severe problem in the welding of stainless steels, when it
is often termed weld decay.
Stainless steels may be protected from intergranular corrosion by the following measures:
subjecting the sensitized material to a high-temperature heat treatment (heating followed by
water quenching) in which all the chromium carbide particles are re-dissolved.
lowering the carbon content below 0.03 wt.% C so that carbide formation is minimal.
Alloying the stainless steel with another metal such as niobium or titanium, which has a
greater tendency to form carbides than does chromium so that the Cr remains in solid
solution.
For example, most stainless steels stress corrode in solutions containing chloride
ions, whereas brasses are especially vulnerable when exposed to ammonia.
The stress that produces stress corrosion cracking need not be externally applied;
it may be:
a residual one that results from rapid temperature changes and uneven
contraction,
for two-phase alloys in which each phase has a different coefficient of
expansion
gaseous and solid corrosion products that are entrapped internally can give rise
to internal stresses.
It is especially harmful to alloys that passivate by forming a protective surface film; the
abrasive action may erode away the film, leaving exposed a bare metal surface. If the
coating is not capable of continuously and rapidly reforming as a protective barrier,
corrosion may be severe.
Protection:
1. Lower zinc content.
2. Change the alloy
3. Change the environment
4. Cathodic protection
Hydrogen attack: High temperature mode of attack in which hydrogen enters metals such
as steels and reacts with carbon to produce methane gas resulting in formation of cracks
or decarburization.
Blistering: atomic hydrogen diffuses into internal defects and precipitates as molecular
hydrogen which produces high internal pressure resulting in local plastic deformation and
blistering.
Prevention
1. Change the material susceptible.
2. Reverse hydrogen contamination: Bake out.
Disclaimer: This material is purely for teaching purpose only
Prevention of Corrosion
Cathodic Protection