Corrosion

CORROSION AND ITS CONTROL.

 What are intergranular and erosion corrosion,
explain?
Intergranular corrosion occurs along grain
boundaries and only where the material, especially
sensitive to corrosive attack exists, and corrosive
liquid possesses a selective character of attacking
only at the grain boundaries, but leaving the grain
interiors untouched or only slightly attacked.

This type of corrosion is due to the fact that the

grain boundaries contain material, which shows
electrode potential more anodic than that of the
grain centre in the particular corroding medium.
 This may be due to precipitation of
certain compounds at the grain
boundaries, thereby leaving the solid
metal solution impoverished in one
constituent.

 The impoverished solid solution is anodic

with respect to the grain centres as well
as to the precipitated compound, so that it
will be attacked preferentially by the corrosive
environment. The grain boundary type of
corrosion is, generally, encountered in
alloys.
For ex., during the welding of stainless steel(an
alloy of Fe, C & Cr) chromium carbide is
precipitated at the grain boundaries, thereby,
region just adjacent to grain boundaries
becomes depleted in chromium composition
and is more anodic with respect to the
particles of the chromium carbide so-
precipitated.

Intergranular corrosion follows the path of

grain boundaries and occurs on microscopic
scale, without any apparent external signs of
any intensive attack. The remedy is proper
heat-treatment, followed by rapid quenching
to avoid the heterogeneous precipitation that,
usually, occurs due to slow-cooling.
Eg: welding of stainless steel
 Erosion corrosion is a degradation of material surface due to
mechanical action, often by impinging liquid, abrasion by slurry,
particles suspended in fast flowing liquid or gas, bubbles or
droplets, cavitations, etc. The mechanism can be described as follows:
 mechanical erosion of the material, or protective (or passive) oxide
layer on its surface,
 Enhanced corrosion of the material, if the corrosion rate of the
material depends on the thickness of the oxide layer.
The mechanism of erosion corrosion, the materials affected by it, and
the conditions when it occurs is generally different than that of flow-
accelerated corrosion, although the last one is sometimes classified as a
sub-type of erosion corrosion.
Surface chemistry can play a role in erosion corrosion due
to mechanochemical effects.
Erosion corrosion is the second most common cause of copper tube
failure.
Erosion Corrosion Mechanism:

Streams of Gases or Vapors or Liquids

Strike on the surface

Combined effect will work on it

1) Abrading action of turbulent flow And

2) Mechanical rubbing action of particles over a metal surface
Leads to the break down of protective layer at the spot of
Impingement.

Formation of differential cell set up

Corrosion
 What are the factors involved in corrosion, explain?

1. Nature of the metal:

a) Position in galvanic series: When two metals or alloys are in electrical
contact, in presence of an electrolyte, the more active metal suffers
corrosion. Greater is the difference, the faster is the corrosion of
the anodic metal/ alloy.
b) Overvoltage: when a metal, which occupies a high position in galvanic
series, is placed in 1N H2SO4, it undergoes corrosion forming a film and
evolving hydrogen gas, the initial rate of reaction is quite slow, because of
high overvoltage (=0.70 V) of zinc metal, which reduces the effective
electrode potential to a small value. Add CuSO4 then (Over voltage is
0.33V) which forms Cathode layer.
ie. High Over Voltage , Less corrosion
a) Relative areas of the anodic and cathodic parts: when two
dissimilar metals or alloys are in contact, the corrosion of the anodic part
directly proportional to the ratio of areas of the cathodic part and the
anodic part. Ie less Cathode area, less corrosion
d) Purity of metal: Impurities in a metal, generally, cause
“heterogeneity”, and form minute/tiny electrochemical cells,
and the anodic parts get corroded. Purity increases,
Corrosion decreases
e) Physical state of metal: Small the grain size greater
the solubility and hence greater will be its corrosion.
f) Nature of surface film: In aerated atmosphere, practically
all metals get covered with a thin surface film of metal
oxide.The ratio of the volume of the metal
g) Passive character of metal: Metal like Tl, Al, Cr, Mg, Ni
and Co are passive and they exhibits much higher corrosion-
resistance than expected from their positions in galvanic
series, due to the formation of highly protective, but very thin
film on the metal or alloy surface.
 Solubility of corrosion products: In electrochemical
corrosion, if the corrosion products is soluble in the
corroding medium, then corrosion proceeds at a faster rate.
On the contrary, if the corrosion product is insoluble in the
medium or it interacts with the medium to form another
insoluble product.
i) Volatility of corrosion products: If the corrosion products is
volatile, it volatilizes as soon as it is formed, thereby leaving the
underlying metal surface exposed for further attack.

2. Nature of the corroding environment:

a) Temperature: With increase of temperature of environment, the
reaction as well as diffusion rate increase, thereby corrosion rate is
generally enhanced.
b) Humidity of air is the deciding factor in atmospheric corrosion.
“critical humidity” is defined as the relative humidity above
which the atmospheric corrosion rate of metal increases sharply.
c) Presence of impurities in atmosphere: Atmosphere, in the
vicinity of industrial areas, contains corrosive gases like CO2, H2S,
SO2 and fumes oh HCl, H2SO4, etc. In presence of these gases, the
acidity of the liquid, adjacent to the metal surface, increase and its
electrical conductivity also increases.
d) Presence of suspended particles in atmosphere: In case
of atmospheric corrosion:
 if the suspended particles are chemically active in nature, they
absorb moisture and act as strong electrolytes, thereby causing
enhanced corrosion
 if the suspended particles are chemically inactive in nature, they
absorb both sulphur gases, and moisture and slowly enhance
corrosion rate
e) influence of pH: Generally, acidic media more corrosive than
alkaline and neutral media.
f) Nature of ions present: Presence of anions like silicate in the
medium leads to the formation of insoluble reaction
products, which inhibit further corrosion.
g) Conductance of the corroding medium: In corrosion of
underground or submerge structures, the conductance of the
medium is of prime importance to increase the corrosion rate.
h) Formation of oxygen concentration cell: With the
increases in supply of oxygen/air to the moist-metal surface,
the corrosion is promoted.
i) Flow velocity of process stream: Flow velocity plays an
important role in a corrosion, which is diffusion controlled,
when a metal that does not passivate, is under diffusion
control, an increase in flow velocity of the medium enhances
diffusion rate, thereby increasing the corrosion rate.
j) Polarization of electrodes: The potential difference
between the anode and the cathode is the driving force of an
electrochemical corrosion process, but the corrosion rate is
controlled by the current flowing in the circuit.
 HIGH POLYMERS.
 What are polymers?
Polymers are ‘macromolecules’ built-up by the linking
together of a large number of small molecules (called
monomers). For example, polythene is a polymer formed by
linking together of a large number of ethane (C2H4)
molecules. Thus:
the number of repeating units (n) in chain formed in a polymers is
known as the “degree of polymerization” (DP). There may be
hundreds or thousands or tens of thousands or more monomer
molecules linked together in a polymers molecules.
Functionality.
For a substance to act as a monomer, it must have at least two
reactive sites or bonding sites. The number of bonding sites in a
monomer, is referred to as its functionality.
E.g.: Ethylene is considered to be bifunctional.

 depending upto the functionality of monomeric units, it is

possible to obtain different types of structures. In case of a
bifunctional monomer, two reactive groups attach side by
side to each other forming a linear or straight-chain
molecule.
 During the chain growth, side chains may also form, resulting in
branching-chain molecules.
 TYPES OF POLYMERIZATION.
1. Addition or chain polymerization is a reaction that
yields a product, which is an exact multiple of the original
monomeric molecule. The addition polymerization reaction
must be instigated by the application of heat, light, pressure or
a catalyst for breaking down the double covalent bonds of
monomers.
2. Condensation or step-polymerization may be defined as
a “ a reaction occurring between simple polar-group-
containing monomers with the formation of polymer and
elimination of small molecules like water, HCl, etc.”
3. Copolymerization is the joint polymerization of two or
more monomer species. High molecular-weight compounds
obtained by copolymerization, are called copolymers.
 CLASSIFICATION OF POLYMERS

Polymers can be classified in a number of ways:

1) Classification on the basis of source:

 National polymers (which are found in nature in animals and
plants).
 Synthetic polymers (man-made polymers) like polyethylene (PE)

2) Classification on the basis of structure:

 Linear polymers in which monomeric units are joined in the form of
long straight chain.
 branched chain polymers are mainly linear in nature, but also
possess some branches along the main chain.
 Three-dimensional network polymers conatins monomers
connected to each other by only covalent bonds.
3) Classification on the basis of their methods of synthesis:
 Addition polymers are obtained by addition polymerization method,
which involves the repeated addition of monomers (unsaturated
derivatives of ethane) to yield long chains.
 Condensation polymers are obtained by a series of condensation
reaction, generally involved two monomers.

4) Classification on the basis of growth polymer chain:

 Step growth polymers are formed by the successive addition of
monomer unit to the growing chain carrying a reactive intermediate.
 Step-growth polymers are formed though a series of independent
reactions involving bond formation (condensation) between two
different monomers with loss of small molecules like H20, HCl,
NH3,etc.

5) Classification based on molecular forces:

 Thermoplastic polymers are linear, long chain polymers, which can
be softened on heating and hardened on cooling reversibly.
 Thermosetting polymers (or thermosets) are those
polymers , which during moulding (by heating, etc.) get
hardened and once they have solidified, they cannot be
softened.
 Elastomer (or synthetic rubber) is any rubber-like
elastic polymer, which can be stretched to al least thrice its
length, but it returns to its original shape and dimensions as
soon as stretching force is released.
 Fibres are those polymers whose chains are held by strong
intermolecular forces like hydrogen bonding.