MODULE 4

CORROSION and CORROSION

CONTROL
The secret of effective engineering lies in controlling
rather than preventing corrosion, because its is
impossible to eliminate corrosion.
-Michael Henthorne
 Module 4
Corrosion control methods: Cathodic protection – sacrificial anodic
`
and impressed current protection methods: Principle and
Applications.
Electroplating-processes ( Principle, Examples : Cu, Ni, Au, Ag
plating and its applications, Factors affecting plating of metals) and
typical applications; Electroless plating: Cu, Ni
Advanced coating processes (Superiority over Electroplating, hot
dipping and other conventional coating techniques) – Basic
concepts of PVD and CVD. (Principle of evaporation techniques,
PVD - Process description- Thermal evaporation and sputtering
only, Examples; CVD - Precursors (any two) -Differences between
PVD and CVD- Process description of CVD, Any four
Alloying for corrosion protection – Basic concepts of Eutectic
composition and Eutectic mixtures - Selected examples –non-
ferrous alloys.- Lead Silver system
Corrosion Inhibitors
Anodic Inhibitors
Cathodic inhibitors
`
Electroplating
Characteristics of electrodeposit
Characteristics of Electrodeposit
Electrolessplating

61
Electroless plating – plating metal by chemical means rather
than electrical, in which the piece to be plated is immersed in
a reducing agent that, when catalyzed by certain materials,
changes metal ions to metal that forms a deposit on the piece.
A major expansion of electroless plating has come in the area
of plastics, as in the plating of printed electronic circuits.
The most common electroless plating technique is electroless
nickel plating, although silver, gold and copper layers can also
be applied in this manner.
Electroless plating is also known as chemical plating or auto-
catalytic plating.

62
A non-galvanic plating method that involves several simultaneous
reactions in an aqueous solution, which occur without the use of external
electrical power. The reaction is accomplished when hydrogen is
released by a reducing agent, normally sodium hypophosphite (the
hydrogen leaves as a hydride ion), and oxidized, thus producing a
negative charge on the surface of the part.
Because electroless plating allows a consistent metal ion concentration
to bathe all parts of the object, it deposits metal evenly along edges,
inside holes and over irregularly shaped objects which are difficult to
plate evenly with electroplating. Electroless plating is also applied to
deposit a conductive surface on a nonconductive object to allow it to be
electroplated. Advantages of electroless plating include:
– Does not use electrical power
– Even coating
– No sophisticated jigs or racks required
– Flexibility in plating volume and thickness
– Chemical replenishment monitored automatically
– Complex filtration method is not required
– Matte, semi-bright or bright finishes available
63
Electroless plating techniques emerged as an alternative to
electroplating in certain cases. In fact, there are many
advantages to electroless plating, and many industries are
exploring electroless plating more and more as a cost-effective,
simple alternative to traditional electroplating techniques for
coating the parts with metal.

64
65
 Corrosion control

Protective coating
Metal coatings
Inorganic and organic coatings

Cathodic protection

66
Thin-Film Coatings
Deposition by Physical Vapour Deposition (PVD)
 Chemical Vapor Deposition (CVD)

CVD involves the formation of a solid film on a

surface of heated substrate by means of a chemical
reaction in a gas or in vapor phase.

The complex molecules in their vapor state impinges

on the hot substrate, decomposes and forms a thin
film. These reactions are promoted by resistance, RF
or infra red radiation heating.
Chemical Vapor Deposition (CVD) - Steps
1. The vapor source of the film forming material may
be a solid, liquid or a gas. Solid materials have
sufficient vapor pressures need to be vaporized to
transport them at moderate temperatures to the
deposition zone where the substrate is placed, and
this is normally achieved by heating.
2. The uniformity in the arrival of the vapor sources by
transport to the hot substrate is achieved with the
help of a transport medium (high vacuum or a fluid).
3. Deposition achieved by the process of developing
thin films, in which the actual growth of film over
the surface occurs.
4. Analyses of the coated thin films are done by various
techniques.
CVD Mechanism
Process of making thin film and further…..
High Energy Processes
Ion Implantation
 Alloying of Metals and Eutectic
A phase - any homogeneous, physically distinct and
mechanically separable portion of a system, which is
separated from other parts of system by definite
boundary surface.

Examples:
a. A completely miscible homogenous mixture of gases
(O2 & N2) or liquids (water & alcohol) gives a single
phase (P = 1)
b. Any pair of immiscible liquids (water & kerosene)
gives rise to two phases i.e. P = 2
c. At a specific condition, all the three phases of water
co-exists, ice water & vapour (P = 3)
Degrees of Freedom or Variance

The “state of a system” is defined by thermodynamic

variables like, pressure (p), temperature (T) and
composition (C) etc.

Therefore, “the degree of a system (F)” is defined as

number of independent variable, such as pressure,
temperature and composition which must be specified
in order to define a state of a system.
 Component
• Component is defined as the smallest number of
independently variable constituents taking part in a
state of equilibrium by means of which composition
of each phase can be expressed in form of
chemical equations. Examples :
• Water system: all three phases has only H2O, it’s
a one component system.
• Lead and tin are miscible in all proportions in the
molten state and gives a homogeneous solution of
two constituents. To define the composition of
homogeneous molten single phase, we need both
constituents. It’s a two component system.
 Alloying of Metals and Eutectic

One component water can be in the phase of liquid,

solid and gaseous. Whether water will be in one of
the states can be known or defined by temperature
(T) and pressure (p). Hence any one of the phase has
the degrees of freedom 2. therefore F = 2.
A generalized formula of phase rule is F = C – P + 2
Now consider the
equilibrium point where
the two phases of
water coexist. Then
either it will be
melting point or boiling
point or a point where
water just sublimes. If
you know pressure of
the system, you will be
knowing the
temperature of boiling
1 atm = 101.325 kPa
or melting and
sublimation.
Hence to define the system you need only variable, hence
 Alloying of Metals and Eutectic
A simple Eutectic System
Consider a case of binary solids A & B that are
completely miscible in all proportions in the molten
state and also the do not form any compound.
Lead – Silver system
degrees of
freedom
327 °C F = C – P +1
is reduced phase
rule as effect of
pressure is
negligible as alloy
has practically no
vapour phase

Area of molten phase (ACB): within this area both solids Pb & Ag are
completely miscible. Being two component system degrees of freedom F =
C – P +1. i.e. F = 2 – 1 + 1 = 2
 Alloying of Metals and Eutectic
Melting point curves AC and BC: In the phase diagram A & B
denotes melting point of pure Lead (327 °C) & silver (961 °C),
respectively. AC denotes the variation of melting temperature
of Ag in Pb and BC decrease in melting temperature of Ag with
the addition of Pb.
327 °C

 The states of equilibrium, curves AC and BC, represent two-phase equilibrium

1. Solid Lead molten liquid
2. Solid Silver molten liquid
 Alloying of Metals and Eutectic
Applying phase we can find out degrees of freedom for AC and BC melting
point curves and it s F = C-P+1 where C = 2, P = 2 hence F = 1. This means if
you know composition you will be knowing the temperature of the system
and vice versa. State is univariant.

327 °C

Eutectic of Pb – Ag is a unique composition and for that C is a eutectic point where

solid Pb & solid Ag coexist with the molten state with same composition of Pb & Ag
in solid. 3 phase 2 component system provides F = 0
 Alloying of Metals and Eutectic
Important feature of Pb-Ag eutectic is it has constant composition
of Pb:Ag = 97.4:2.6. It has melting point of 303 °C. The composition
in the solid maintain the homogeneity even after cooling down from
their molten state.

327 °C

Rest of the composition after cooling down below eutectic

temperature will be the mixture of eutectic composition and either
excess solid lead or solid silver
 Alloying of Metals and Eutectic
Iron – Carbon system – (ferrous alloy)
Classification of ferrous alloys:
Iron: less than 0.008% C in a-ferrite at room T.
Steels: 0.008 – 2.14 % wt C, a-ferrite + Fe3C at room T

Cast Iron: 2.14 – 6.7% wt C (usually < 4.5 %)

Cementite: 6.67 % C
• Iron exists in 3 forms : i) BCC upto 910 0c ii) fcc
from 910 0c to 1403 0c iii) bcc from 1403 0c to 1535
0c

• Different Phases of Fe-C system: Phase diagram

has 4 solid phases and one homogeneous liquid
phase
A solid solution is a solid mixture containing a minor
component uniformly distributed within the crystal
lattice of the major component.
Single Phases:
1) Solid solution of C in BCC Fe is alpha Ferrite : area
AGA1 : refer to diagram: C=2, P=1, F= C – P+1 = 2
Bivariant (dependent on temp and Composition
(T&C) to define the system)
2) Area A1DBCK : solid solution of C in  - iron is
called Austentite : P=1, C=2,F=2-1+1=2 (T&C)
3) area IKJ: -ferrite : solid solution of carbon in
iron and has bcc structure
 -ferrite : P=1, C=2,F=2-1+1 = 2 (T &C are
required)
• These areas are bivariant & are dependent on T &C.
• Two phases
1) Area EFL : Fe3C + liquid : C=2, P=2, F=2-2+1=1
Univariant, dependent on T or C.
2) Area IKCBE :  - Austentite + liquid : C=2,P=2,F=1
E : Eutectic point 4.3% C,
Liquid,  - Austentite + Fe3C, P=3, C=2, F= 0
• At the eutectic point E, all 3 phases coexist.
Lowest fusing temperature of Fe-C mixture.
Eutectic liquid will solidfy to cementite Fe3C and  -
Austentite.
• Point D : Eutectoid : Steel of composition D will
become mixture of -ferrite and cementite having
0.83% Carbon.
 - Austentite Fe3C + -ferrite
This part of the diagram looks like an eutectic
except that the upper material is solid austentite,
not a liquid. Its called Eutectoid, “like an eutectic“
though no melting is involved.
`
Electroplating
Characteristics of electrodeposit
Characteristics of Electrodeposit
Electrolessplating

143
Electroless plating – plating metal by chemical means rather
than electrical, in which the piece to be plated is immersed in
a reducing agent that, when catalyzed by certain materials,
changes metal ions to metal that forms a deposit on the piece.
A major expansion of electroless plating has come in the area
of plastics, as in the plating of printed electronic circuits.
The most common electroless plating technique is electroless
nickel plating, although silver, gold and copper layers can also
be applied in this manner.
Electroless plating is also known as chemical plating or auto-
catalytic plating.

144
A non-galvanic plating method that involves several simultaneous
reactions in an aqueous solution, which occur without the use of external
electrical power. The reaction is accomplished when hydrogen is
released by a reducing agent, normally sodium hypophosphite (the
hydrogen leaves as a hydride ion), and oxidized, thus producing a
negative charge on the surface of the part.
Because electroless plating allows a consistent metal ion concentration
to bathe all parts of the object, it deposits metal evenly along edges,
inside holes and over irregularly shaped objects which are difficult to
plate evenly with electroplating. Electroless plating is also applied to
deposit a conductive surface on a nonconductive object to allow it to be
electroplated. Advantages of electroless plating include:
– Does not use electrical power
– Even coating
– No sophisticated jigs or racks required
– Flexibility in plating volume and thickness
– Chemical replenishment monitored automatically
– Complex filtration method is not required
– Matte, semi-bright or bright finishes available
145
Electroless plating techniques emerged as an alternative to
electroplating in certain cases. In fact, there are many
advantages to electroless plating, and many industries are
exploring electroless plating more and more as a cost-effective,
simple alternative to traditional electroplating techniques for
coating the parts with metal.

146
147