Corrosion by Motin Sir

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Corrosion

Dr. Md. Abdul Motin (AAA)


Professor, Department of Chemistry
KUET
Introduction

Except noble metals (e.g., gold, platinum etc.) almost all


metals are found in nature as compounds such as, oxides,
hydroxides, carbonates, bicarbonates, chlorides, sulfides,
silicates etc. From this, it can be said that most of the
metals have the natural tendency to form compounds.
These compounds obviously do not have metallic
properties. Thus metals have the natural tendency to lose
their characteristic metallic properties by the formation of
their compounds. The process by which a metal reacts with
its environment and thereby loses its characteristic metallic
properties is known as corrosion.
• Corrosion is an electro chemical process that
removes electrons from one material and
passes them to another.

• Corrosion is caused by having two dis-similar


metals in contact through an electrolyte and
results in an electric current passing between
them.
• Corrosion is defined as unintentional destruction of a solid
body by chemical or electrochemical reactions starting from
the surface.
• Non-Metals corrode by chemical reactions & metals mostly by
electrochemical reactions.
• Metals are at high energy levels & hence there is natural
tendency to go to the low energy state i.e. they try to form
oxides, hydroxides, carbonates, sulphides etc. depending on
the type of environment to which they are exposed.
Corrosion is the deterioration of materials by chemical interaction with their
environment. The term corrosion is sometimes also applied to the
degradation of plastics, concrete and wood, but generally refers to metals.
The most widely used metal is iron (usually as steel) and the following
discussion is mainly related to its corrosion.
Industrial atmospheres
▪ An industrial atmosphere is typically identified as one with heavy
industrial manufacturing facilities.
▪ These atmospheres can contain concentrations of sulfur dioxide,
chlorides, phosphates, nitrates, or other specific industrial emissions.
▪ These emissions combine with precipitation or dew to form the liquid
corrosive.
Industrial atmospheres
Marine Atmospheres
▪ A marine atmosphere is laden with fine particles of sea salt carried by
the winds and deposited on materials.
▪ The marine atmosphere is usually one of the more corrosive
atmospheric environments.
▪ It has been shown that the amount of salt (chlorides) in the marine
environment decreases with increasing distance from the ocean and
is greatly influenced by wind direction and velocity.
Marine Atmospheres
Rural atmospheres
▪ A rural atmosphere is normally one that does not contain chemical
pollutants but does contain organic and inorganic dust.
▪ Its principal corrodent is moisture and, of course, oxygen and carbon
dioxide.
▪ Arid or tropical atmospheres are special cases of the rural
environment because of their extreme relative humidities and
condensation.
▪ The rural atmosphere is generally the least corrosive.
Rural atmospheres
Engineer finds corrosion in collapsed bridge at North
Carolina speedway (2000)
Corrosion under insulation
Corrosion and
Degradation of
Materials
Electrochemistry of corrosion
For corrosion to take place, the formation of a corrosion cell is essentially
comprised of the following four components.
a) Anode
b) Cathode
c) Electrolyte
d) Metallic path.
Anode:
An anode is an electrode through which electric current flows in to a
polarized electrical device. The misconception is that anode polarity is
always positive (+). This is often incorrectly inferred from the correct fact
that in all electrochemical device negatively charged anions moves towards
the anode (or oppositely charged cations move away from it). Anode
polarity depends on the device type and sometimes even in which mode it
operates.
Cathode:
One of the two electrodes in an electrolytic cell represented as a positive
terminal of a cell. Reduction takes place at the cathode and electrons are
consumed.
Electrolyte:
It is the electrically conducting solution (e.g. salt solution) that must be present for corrosion
to occur. Note that pure water is a bad conductor of electricity. Positive electricity passes
from anode to cathode through the electrolyte as cations, e.g. Zn++ ions dissolve from a zinc
anode and thus carry positive current away from it, through the aqueous electrolyte.

Metallic Path:
The two electrodes are connected externally by a metallic conductor. In the metallic
conductor, 'conventional' current flows from (+) to (—) which is really electrons flowing
from (—) to (+). Metals provide a path for the flow of conventional current which is actually
passage of electrons in the opposite direction.
Current Flow:
Conventional current flows from anode (—) to cathode (+) as Zn++ ions
through the solution. The current is carried by these positive charged ions.
The circuit is completed by passage of electrons from the anode (—) to the
cathode (+) through the external metallic wire circuit (outer current).
Electrochemical mechanism of corrosion
Structure of electrode of Galvanic
cell
CLASSIFICATION OF CORROSION

• Dry corrosion

• Wet corrosion
DRY CORROSION

• Dry corrosion occurs when the metals are exposed to


gaseous environment
• The extent of corrosion & protective values depends
on the following factors
1. Chemical affinity between the environment & the metal.
2. Protective value of film.
3. Nature of film formed.
4. Adhesion between the film & the metal surface.
5. For non ferrous film, the extent of corrosion depends on the
electronic & ionic conductivities of the film.
WET CORROSION
• Wet corrosion occur when a metal or an alloy comes in contact
with an aqueous solution of salt, acid or alkali by an
electrochemical type of reaction.
• When a metal is immersed in an aqueous electrolyte,it dissolve /
dissociate into metal ion + electron.
• This tendency of metal is called as electrolytic pressure or
solution pressure (p)
• The dissolved ion from the solution tend to deposit on the
immersed metal surface& oppose the solution pressure of
metal. This tendency is called as osmotic pressure of metal ion
(p)
• When these forces become equal, equilibrium is reached and
under this condition, a definite number of electrons accumulate
on the metal surface & a definite potential will be developed on
What is the voltage difference
between Zinc (Zn) and Copper
(Cu)?
An. 0.67v
What is more noble than
Stainless Steel (Passive)?
An. Graphite
MECHANISM OF WET CORROSION
• The reaction at anode is always oxidation reaction & is
associated with the dissolution of metal i.e.
Metal Metal ions + electron
• The reaction at cathode is always a reduction reaction
with no corrosion of cathode & varies depending on the
nature of electrolyte in contact
1. Hydrogen evolution :
2. Oxygen absorption :
1.Hydrogen evolution :
• The hydrogen evolution occurs at the cathode in concentrated
acidic environment (pH < 4) usually iron surface is covered
with oxide at least at few points or it may difference in
hydrogen over potential from point to point
• Due to this some areas act as cathode with respect to other
areas which behaves as anode of the cell & galvanic corrosion
occurs.
• At the anode : Fe Fe++ + 2e
• At the cathode : 2H+ + 2e H2
• it is clear from the reaction that hydrogen evolution type of
corrosion occurs by simple displacement of hydrogen ion from
acidic solution by metal ion.
• All metals above hydrogen in the electrochemical series
will have tendency to corrode by this type of corrosion
• It is clear that both the electrodes will get polarized as the
corrosion proceed.
2. OXYGEN ABSORPTION
• Oxygen absorption mechanism of corrosion occurs in mild acidic
or alkaline environment (pH > 4)
• The above process for the rusting of iron taking an electrolyte of
aqueous solution of sodium chloride.
• The area which are not covered with the oxide become anodic
with respect to the areas covered with the oxide which become
cathodic & corrosion occurs by the following reactions :
• Reaction at anode :Fe Fe++ + 2e & Fe++ + 2Cl- FeCl2
• Reaction at cathode : 4e + O2 + 2H2O 4OH-
• OH- + Na+ NaOH
• Both the anodic product FeCl2 & cathodic product NaOH are
soluble in water & diffuse towards each other.
continue….
• When both meet ferrous hydroxide is formed. In the
presence sufficient dissolved oxygen, ferrous hydroxide is
further oxidized to ferric hydroxide which has very little
solubility in water & precipitate out as yellow rust.
• It is clear that there is no concentration polarization at
both the electrode.
Classification of Wet Corrosion

1. Atmospeheric corrosion
2. Underwater corrosion
3. Underground corrosion
Atmospeheric corrosion
Effect of different factors on the rate
of
under water corrosion
• Dissolved oxygen
• Temperature
• pH of water
• Dissolved electrolytes or salts
• Velocity of water
CORROSION
⚫Other corrosion mechanisms
⚫See section 4 of Block 5 Part 1
• Pitting corrosion (doesn’t require 2
dissimilar metals – usually a scratch
in a protective surface)
Protective Coating
Surface preparation for Coating:
1. Cleaning:
- To prepare for suitable condition
- Removing contaminants to prevent detrimental reaction product
- E.g. de-greasing, sand blasting, vapour degreasing, pickling and
alkaline cleaning.
2. Solvent Cleaning:
- Must be non-inflammable and nontoxic
- Trichloro trifluoroethane which has low toxicity are costlier
- Vapour de-greasing is economical and advantageous because of
continuous cleaning with small quantities of solvent.
3. Electrolyte Pickling:
- Provides better and rapid cleaning by increasing hydrogen evolution
resulting in agitation and blasting action
- Sand blasting is mechanical cleaning.
4. Alkaline Cleaning:
- Cheaper and less hazardous
- Used in conjunction with surface active (wetting) agent
- Ability depends on pH, rapidly decreases below 8.5
- Other abilities are rinsability, detergent properties, sequestering,
wetting etc.

5. Acid Cleaning
- Acid such as HCl, H2SO4, H3PO4 is very effective.
- 5-10% H2SO4 and HCl used to remove inorganic contaminants.
- Pickling are performed at high temp. (60 ̊C)
- Is effective for removal of grease, oil , dirt and rust.
Methods of Application of Metallic Coating

1. Hot Dipping:
- Metal is kept in molten state and base metal is dipped into it.
- Used for producing a coating of low M.P
- E.G. Tinning (Tin coating on Iron)
- Process is followed by cooling the coating through a palm oil to
prevent oxidation of tin plate to its oxide.
- Palm oil layer is removed by alkaline cleansing agent.

2. Metal Cladding:
- The surface to be protected is sandwiched between two layers of
the coating metals and pressed between rollers.
- E.g. Alclad Sheeting– Plate of duralumin is sandwiched between
99.5%pure aluminum
3. Electro Plating:
- Pure metal is made as cathode and base metal as anode.
- Electrochemically coat metal is deposited on base metal.
- This metal gives smooth, fine and uniform coating
- It depends on
(i) Temperature (ii) Current density (iii) Electrolyte Concentration
(iv) Nature of base metal (v) Time

4. Electroless Plating:
- Nobel metal is deposited catalytically on less noble metal by using
reducing agent without using electrical energy.
- Advantage over Electro plating
(i) More economical since no electricity required
(ii) Irregular shape can be plated uniformly
(iii) Plating on plastics can also be done
5. Metal Spraying:
- Coating is applied by means of spraying device
- E.g. Aluminum is plated in this way on Aircrafts.

Chemical Conversion Coating


• These are formed on metal surface by chemical reaction b/w metal
surface and inorganic salt solution
• Coating base metal is converted into one of the resultant protective
film.
• These films are insoluble, adherent, crystalline or amorphous in
nature.
• Can be done in 3 ways
1. Phosphate coating
2. Chromate coating
3. Anodized coating
1. Phosphate Coating

- Produced by chemical reaction b/w base metal and aq. H3PO4, Zn or


Fe or Mn Phosphate
- Phosphate coating are applied Iron, Steel, and Zinc
- Film formed on base metal after coating consist of Zn-Fe, Mn-Fe
Phosphates.

2. Chromate Coating

- Produced by dipping the base metal in Potassium chromate (acidic)


followed by immersion in neutral chromate bath.
- Resulting film consist of trivalent and hexavalent chromium.
- Used as base for paints, lacquers and enamels.
3.Anodized Coating
- Formed by anodic oxidation process
- This is produced on non-ferrous metals like Al, Zn, Mg
- In this method base metal is made as anode
- Process is carried out by passing moderate direct current through a
bath in which the metal is suspended as anode.
- Coating are formed as a result of Progressive oxidation starting at
surface of base metal.

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