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Corrosion And Degradation Of

Materials

Submitted By:
Madhav Aggarwal
2K13/ME/087
LMN Group

Corrosion Of Metals
Corrosion is the deterioration or destruction of metals and alloys in
the presence of an environment by chemical or electrochemical
means. In simple terminology, corrosion processes involve reaction
of metals with environmental species.
As per IUPAC, Corrosion is an irreversible interfacial reaction of a
material (metal, ceramic, polymer) with its environment which
results in its consumption or dissolution into the material of a
component of the environment. Often, but not necessarily, corrosion
results in effects detrimental to the usage of the material considered.
Exclusively physical or mechanical processes such as melting and
evaporation, abrasion or mechanical fracture are not included in the
term corrosion With the knowledge of the role of various
microorganisms present in soil and water bodies, the definition for
corrosion need be further widened to include microbially-influenced
factors. Corrosion can be classified in different ways, such as
Chemical and electrochemical
High temperature and low temperature
Wet corrosion and dry corrosion.
Dry corrosion occurs in the absence of aqueous environment, usually
in the presence of gases and vapours, mainly at high temperatures.
Electrochemical nature of corrosion can be understood by examining
zinc dissolution in dilute hydrochloric acid. Zn + 2HCl = ZnCl 2 + H2
Anodic reaction is Zn = Zn++ + 2e with the reduction of 2H+ + 2e = H2
at cathodic areas on the surface of zinc metal. There are two half
reactions constituting the net cell reaction. Environmental effects
such as those of presence of oxygen and other oxidizers, changes in
flow rates (velocity), temperature, reactant concentrations and pH
would influence rates of anodic and cathodic reactions.

For metallic materials, the corrosion process is normally


electrochemical, that is, a chemical reaction in which there is transfer
of electrons from one chemical species to another. As corrosion is
electrochemical in nature, temperature and concentration of
chemical does have an important role to play. In general, with
increase of either or both temperature and concentration, corrosion
rate increases. The electrode potential depends on the concentration
of the electrolyte. At 25C, the following equation, known as Nernst
equation, gives the electrode potential:

Where E is the electrode potential in a solution containing a


concentration Cion (in moles) of metals, n is the valence of the
metallic ion, E0 is the standard electrode potential in a 1M solution.
Faradays equation gives the amount (w, weight in gms.) of metal
plated on the cathode, or removed from the metal by corrosion:

Where I is the current (A), M is the atomic mass of the metal, n is the
valence of the metal ion, t is the time (secs), and F is the Faradays
constant (96,500C).
Metal atoms characteristically lose or give up electrons in what is
called an oxidation reaction. For example, the hypothetical metal M
that has a valence of n (or n valence electrons) may experience
oxidation according to the reaction:

The site at which oxidation takes place is called the anode. Oxidation
is sometimes called an anodic reaction.
The electrons generated from each metal atom that is oxidized must
be transferred to and become a part of another chemical species in
what is termed a reduction reaction. For example, some metals
undergo corrosion in acid solutions, which have a high concentration
of hydrogen (H+) ions; the H+ ions are reduced as follows:

The location at which reduction occurs is called the cathode.


Furthermore, it is possible for two or more of the reduction reactions
above to occur simultaneously.

Passivity
Even though the fundamental mechanism of corrosion involves
creation or existence of corrosion cells, there are several types or
forms of corrosion that can occur. It should however be borne in
mind that for corrosion to occur, there is no need for discrete
(physically independent) anodes and cathodes. Innumerable micro
level anodic and cathodic areas can be generated at the same
(single) surface on which anodic (corrosion) and cathodic (reduction)
reactions occur. Each form of corrosion has a specific arrangement of
anodes and cathodes and specific patterns and locations depending
on the type can exist. The most important types are

Uniform corrosion.
Galvanic corrosion, concentration cells, water line attack
Pitting.
Dezincification, Dealloying (selective leaching)
Atmospheric corrosion.

Erosion corrosion
Fretting
Crevice corrosion; cavitation
Stress corrosion, intergranular and transgranular corrosion,
hydrogen cracking and embrittlement
Corrosion fatigue.
Crevice corrosion is a localized attack on a metal adjacent to the
crevice between two joining surfaces (two metals or metal-nonmetal
crevices). The corrosion is generally confined to one localized area to
one metal. This type of corrosion can be initiated by concentration
gradients (due to ions or oxygen). Accumulation of chlorides inside
crevice will aggravate damage. Various factors influence crevice
corrosion, such as.
Materials: alloy composition, metallographic structure.
Environmental conditions such as pH, oxygen concentration,
halide concentrations, temperature.
Geometrical features of crevices, surface roughness.
Metal to metal or metal to nonmetal type.
Filiform corrosion is a special type of crevice corrosion. Pitting
corrosion is a localized phenomenon confined to smaller areas.
Formation of micro-pits can be very damaging. Pitting factor (ratio of
deepest pit to average penetration) can be used to evaluate severity
of pitting corrosion which is usually observed in passive metals and
alloys. Concentration cells involving oxygen gradients or ion
gradients can initiate pitting through generation of anodic and
cathodic areas. Chloride ions are damaging to the passive films and
can make pit formation auto-catalytic. Pitting tendency can be

predicted through measurement of pitting potentials. Similarly


critical pitting temperature is also a useful parameter.
Uniform corrosion is a very common form found in ferrous metals
and alloys that are not protected by surface coating or inhibitors. A
uniform layer of rust on the surface is formed when exposed to
corrosive environments Atmospheric corrosion is a typical example
of this type.

Corrosion Rate
The corrosion rate, or the rate of material removal as a consequence
of the chemical action, is an important corrosion parameter. This
may be expressed as the Corrosion Penetration Rate (CPR), or the
thickness loss of material per unit of time. The formula for this
calculation is

where W is the weight loss after exposure time t, and A represent


the density and exposed specimen area, respectively, and K is a
constant, its magnitude depending on the system of units used. The
CPR is conveniently expressed in terms of either mils (where 1mil =
0.001 in.) per year (mpy) or millimeters per year (mm/yr).
Inasmuch as there is an electric current associated with
electrochemical corrosion reactions, we can also express corrosion
rate in terms of this current, or, more specifically, current density
that is, the current per unit surface area of material corroding
which is designated i. The rate r, in units of mol/m2-s, is determined
using the expression

Where, again, n is the number of electrons associated with the


ionization of each metal atom, and is 96,500 C/mol.

Corrosion Of Ceramics
Ceramics, being compounds between metallic and nonmetallic
elements, may be thought of as having already been corroded. It is
often said that one of the biggest advantages which ceramics have
over other engineering materials is their corrosion resistance, that is,
their chemical inertness in corrosive environments.
Corrosion is generally understood as property degradation due to
environmental attack. Ceramics corrode by simple chemical
dissolution, in contrast to the electrochemical processes involved
with corrosion of metals. There are a number of environments in
which ceramics can degrade at a rapid rate. There exists a
tremendous need for reliable and corrosion resistant structural
ceramic or partly ceramic materials which can be used in aggressive
environments such as:
- High energy battery systems (such as sodium-sulphur): betaalumina is being investigated
- Gas turbines: silicon nitride and/or carbide are being investigated
- Heat exchangers: SiC, composites are being investigated
Ceramics are indeed much more environmentally stable, as
compared to any other group of engineering materials, e.g. metals or
plastics. Still, the potential for ceramics as corrosion resistant
engineering structural materials are far from being fully realized,
because of:

- Mechanical non-reliability of structural ceramic components


- Difficult design with brittle materials
- A shortage of information and standardization of ceramics
- Human reluctance to use non-ductile material

Prevention Strategies Design and Coatings


There are a number of methods to control corrosion. The choice of
any one control technique depends on economics, safety aspects and
other technical considerations.

Design
Materials selection
Protective coatings
Inhibitors and environmental alterations
Corrosion allowances

Engineering design with a view to corrosion abatement is important.


For example, a simple aspect such as providing drainage, as for an
automobile side panel. Choice of appropriate materials keeping in
mind the probability of corrosion in the existing environmental
conditions is very critical. Among the materials available for
selection; titanium, copper alloys, stainless steels, carbon steels
and aluminium and its alloys are often chosen.

Some general approaches for corrosion prevention are detailed in


Table

Since general corrosion is predictable, design considerations can


include preventive measures whenever and wherever possible. Some
examples:
Wall thickness control
Control of process stream composition
(Elimination of chlorides)
Prevention of acid contacts - neutralization.
Minimization of vapor condensations and collection.
Prevention of leakage of corrosives.
For carbon steels: Cathodic protection combined with coatings.
Channel and angle sections positioned to collect and drain water,
liquids and debris.

Coatings
Barrier between corrosive environment and metal. Coatings may
serve as sacrificial anodes (zinc on steels ) or release substances that
resist corrosion. Metal coatings - Noble coat - Silver, copper, nickel,

chromium, tin, lead on steels (ensure pore - free, uniform, adherent


coating; favorable anode / cathode ratio to minimise galvanic
attacks).
Sacrificial coatings Zinc, aluminium, cadmium on steels. (steel is
cathodic to plated metal). Coatings can be applied through hot
dipping, hot spraying, electroplating, electro-less plating, vapour
deposition and metal cladding. Aluminium, stainless steel, titanium,
platinum etc can be cladded on various metallic substrate for
enhanced corrosion protection (physical or chemical).

Other types of surface treatments


Modification of substrates through ion implantation and laser
processing. Inorganic coatings: glass, cement, ceramic and chemical
conversion coatings. Chemical conversion: Anodizing, oxide,
chromate, phosphatizing. Organic coatings: Paints, lacquers,
varnishes (Resin, solvent + pigment in the coating liquid). High
performance organic coatings used in petroleum industries.
Development of corrosion resistant synthetic resins.

Types of paint coatings


Good adhesion, flexibility, impact resistance and protection from
chemicals, moisture, and atmospheric conditions.
Lacquer synthetic resins (vinyl chloride, acrylic, rubber).
Latex (Acrylics and Vinyls)
Oil-based and Epoxy coatings (good bending, hard and flexible)
Coal tar epoxy.
Poly urethanes, polyester and vinyl ester (hard, brittle or
elastomeric).
Organic zinc rich coatings (organic barrier + galvanic Zn
protection)
Co-polymeric protective coatings.(thermoplastic copolymer aromatic coatings).
Anti - corrosion paints various types additives to improve corrosion
resistance, durability and impermeability.