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ELECTROPLATING AND SURFACE MODIFICATION

By: Monika Singh

A dissertation submitted in partial fulfillment of the degree of

MASTERS OF SCIENCE

IN

CHEMISTRY

Submitted to:

Dr. Surender Kumar

CSIR-ADVANCED MATERIAL AND PROCESSES RESEARCH INSTITUTE

Bhopal,(M.P.)

FEBRUARY 2019

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Acknowledgement

I would like to express my sincere gratitude to my guide Dr. Surendra Sharma for providing his
invaluable guidance, comments and suggestions throughout the course of the training. His
moral support and continuous guidance enabled me to complete this project. I would specially
thanks Dr. Deepti Mishra and Dr. Archana Singh for sharing her research knowledge with us
and Dr. Prem Kumar for getting us the samples as well as accompanied us to visit different
laboratories and explaining us the phenomenon of raman spectrophotometer as well as chemical
vapour deposition(CVD).
I have highly benifited by this training and have gained a lot of knowledge about various
process and techniques related to my topic “ELECTROPLATING AND SURFACE
MODIFICATIONS”.
Finally, I would like to thank all the employees of CSIR-AMPRI, who have helped me and co-
operated with me during my training and project work.

Monika Singh

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CONTENT
1. Introduction……………………………………………………4
 Electrochemistry
 Electroplating
 Corrosion
 Surface modification
 geopolymers
2. Electrochemistry……………………………………………..6
 Electrochemical cell
 Electrode potential
 Redox reaction
 Applications
3. Electroplating…………………………………………………15
 Experiment
 Redox reaction
 Faraday law
 Electroplating of different metals with copper
 Electroplating of different metals with zinc
 Electroplating of different metals with nickel
 Applications of electroplating
4. Corrosion……………………………………………………….21
 Definitions
 Forms of corrosion
 Corrosion rate measurement
 Galvanic series
5. Surface Modification…………………………………………38
 Definition with example.
 Surface Preparation For Film AndCoating Deposition Processes.
 Surface Modification Of Colloidal Silica Nanoparticles.
 Corrosion protective coating.
 Sol-gel method
 Dip coating
 Spin coating
6. Geopolymers………………………………………...…………42
 Definition
 Geopolymer cement
 OPC versus geopolymer cement.

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INTRODUCTION
Electrochemistry is the branch of chemistry which deals with the chemical changes caused in
the matter by passage of electric current and conversion of chemical energy into electrical
energy and vice versa. Electrochemistry deals with the study of electrical energies. It is the
study of production of electricity from energy released spontaneous chemical reactions.
Chemical changes involving electric current are called electrochemical changes. A large
number of metals, sodium hydroxide, chlorine, fluorine and many other chemicals are produced
by electrochemical methods.

Batteries and fuel cells convert chemical energy into electrical energy. The reactions carried out
electrochemically can be energy efficient and less polluting. The transmission of sensory
signals through cells to brain and vice versa and communication between the cells are known to
have electrochemical origin.

The reactions involve electron transfer, and so they are oxidation-reduction (or redox)
reactions.Many metals may be purified or electroplated using electrochemical methods.
Devices such as automobiles, smartphones, electronic tablets, watches and many other use
batteries for power.
Electroplatingis the process of coating a metal object with another metal, using electrical
current passed through a chemical solution. This process produces a thin, metallic coating on
the surface of the metal object. The main purposes of electroplating are to improve the
appearance of the material and provide protection against corrosion. Electroplating uses
electric current and electrochemical reaction for making metal coatings. Coating may be formed
by copper, nickel, chromium, zinc, tin, cadmium, silver, gold and others. During electroplating
a thin layer of desirable metal is deposited on another object. Coating of zinc on copper metal is
one of the most common process of electroplating performed in wide range of industrial sector.

Corrosionis the deterioration of materials by chemical interaction with their environment. The
very common meaning of corrosion to the great majority of the people is rust. The word “Rust”
is more specifically reserved for iron, whereas corrosion is commonly defined as the destruction
of material by chemical or electrochemical reaction with environment. Corrosion is a natural
occurring phenomenon and just like all natural processes, corrosion of materials is spontaneous
and it drives the materials to its lowest possible energy states. Most of the metals and alloys
have a tendency to combine with water and oxygen present in its environment and return to its
most stable state. Iron and steel quite often interact with its environment and return to their
native and stable oxide states.

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Surfacemodification is the deliberate attachment of (macro) molecules to the surface of an
inorganic colloid to change its physical properties or chemical functionality. It have been
applied to metallic biomaterials in order to improve mechanical, chemical, and physical
properties- such as wear resistance, corrosion resistance, biocompatibility and surface
wettability.
For enhancing the mechanical retention between two surfaces, one or both surfaces are
normally modified to increase effective surface area by a sandblasting, shot-peening, or laser-
peening method. Surface modification can include surface treatments such as roughening or
smoothing the surface, making a harder surface by plasma treatment, or by activating a polymer
surface by plasma treatment. Surface preparation includes surface treatments to change the
properties of the surface in a desirable way as well as cleaning, which is the reduction of the
surface contamination to an acceptable level.
Geopolymers are a type of inorganic polymer that can be formed at room temperature by using
industrial waste or by-products as source materials to form a solid binder that looks like and
performs similar function to OPC. Geopolymer binder can be used in applications to fully or
partially replace OPC with environmental and technical benefits, including and 80-90%
reduction in CO2 emissions and improved resistance to fire and aggressive chemicals.

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ELECTROCHEMICAL CELLS

As described previously in the introduction electrochemistry deals with chemical reactions that
produce electricity and the changes associated with the passage of electrical current through
matter. A spontaneous chemical process is the one which can take place on its own and in such
a process the Gibb’s energy of the system decreases. It is this energy that gets converted to
electrical energy. The reverse process is also possible in which we can make non-spontaneous
processes occur by supplying external energy in the form of electrical energy. The inter
conversions are carried out in equipments called Electrochemical Cells.

Electrochemical cells consists of:-

1. Electrode(anode and cathode)


2. Electrolyte
3. Salt Bridge

Electrochemical cells are of two types:-

1. Galvanic Cells: Electrochemical cells that converts chemical energy into electrical energy.
2. Electrolytic Cells: Electrochemical cells that converts electrical energy into chemical
energy.

Galvanic Cell
The device used to convert the chemical energy produced on a redox reaction into electrical
energy is called an electrochemical cell or simply a chemical cell. These are also called
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galvaniccells or voltaic cell after the names of Luigi Galvanic and Alessandro Volta who were
first to perform experiments on the conversion of chemical energy into electrical energy.

In electrochemical cell, a spontaneous redox reaction is carried out in an indirect manner and
the decrease in free energy during chemical reaction appears as electrical energy. An indirect
redox reaction is such that reduction and oxidation processes are carried out in two separate
vessels called half-cells.

Cell energy is extracted from a spontaneous chemical process or reaction and is converted to
electric current.

For example, Daniell Cell is a Galvanic Cell in which Zinc and Copper are used for the redox
reaction to take place.

Zn (s) + Cu 2+ (aq) ¬˃ Zn 2+ (aq) + Cu(s)

Reduction Half:Cu 2+ (aq) + 2e –˃ Cu(s)

Oxidation Half:Zn (s) ¬˃ Zn 2+ (aq) + 2e –

Zn is the reducing agent and Cu 2+ is the oxidising agent.The half cells are also known as
Electrodes. The oxidation half is known as Anode and the reduction half is called Cathode.
Electrons flow from anode to cathode in the external circuit. Anode is assigned negative
polarity and cathode is assigned positive polarity. In Daniell Cell, Zn acts as the anode and Cu
acts as the cathode.

Electrolytic Cell
It is a device in which electrolysis (chemical reaction involving oxidation and reduction) is
carried out by using electricity or in which conversion of electrical energy into chemical energy
is done.These electrodes are dipped in and electrolytic solution containing cations and anions.
On supplying current the ions move towards electrodes of opposite polarity and simultaneous
reduction and oxidation takes place.

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ELECTRODE POTENTIAL
When a metal is placed in a solution of its ions the metal acquires either a positive or negative
change with respect to the solution due to this.A potential differencedevelops between the
electrode and electrolyte is called anelectrode potential. The electrode potential will be named
as oxidation or reduction potential depending upon whether oxidation or reduction has taken
place.When the concentration of all the species involved in the half-cell is unity then the
electrode potential is known as standard electrode potential.

For example when a plate of zinc placed in a solution having Zn2+ ions, it becomes negatively
charged with respect to the solution and thus a potential difference is set up between zinc plate
and solution. This potential difference is termed electrode potential of zinc. Similarly when
copper is placed in a solution having Cu2+ ions it becomes positively charged with respect to
the solution. A potential is setup between the copper plate and the solution. The potential
difference is established due to the formation of electrical double layer at the interface of metal
and the solution.

Characteristics
(a) Both oxidation and reduction potentials are equal in magnitude but opposite in sign.
(b) It is not a thermodynamic property, so values of E are not additive.

Measurement of Electrode Potential


The absolute value of the electrode potential of a single electrode (called single
electrode potential) cannot be determined because oxidation half reaction or reduction
half reaction cannot takes place. It can only be measured by using some electrode as the
reference electrode. The reference electrode used is the standard or normal hydrogen
electrode (SHE or NHE). So the electrode potential of a given electrode is measured by
connecting a standard hydrogen electrode through a salt bridge. The e.m.f of the cell is
measured either by a calibrated potentiometer or by a high resistance voltmeter.
In the standard hydrogen gas electrode, hydrogen gas at atmospheric pressure is passed
into 1M HCl at 298K in which a foil of platinum coated with platinum black (finely
divided platinum) remains immersed.
The electrode is usually represented as:
Pt, H2(g) | H+(1m)

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Example: Determination of standard electrode potential of Zn/ Zn2+ electrode.
A cell comprising of a Zn electrode immersed in 1m ZnSO4 solutions and standard
hydrogen is setup and connected to it through a salt bridge. Both the electrodes are
connected with a voltmeter

Electrochemical Series
By measuring the potential of various electrodes again at standard hydrogen electrode (SHE), a
series of standard electrode potential has been established. When the electrodes (metals and non
metals) in contact with their ions are arranged on the basis of the values of their standard
reduction potential or standard oxidation potential, the resulting series is called the
electrochemical or electromotive or activity series of the elements.
By international convention, the standard potential of electrodes are tabulated for reduction half
reactions, indicating the tendencies of the electrodes to behave as cathode towards SHE. Those
with positive Eo values for reduction half reactions do in fact act as cathode vs SHE while those
with negative Eo values of reduction half reactions behave instead as anodes vs SHE.

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Fig. no. Electrochemical Series.

Redox Reaction
Redox reactions are comprised of two parts, a reduced half and an oxidized half, that always
occurs together. The reduced half gains electrons and the oxidation number decreases, while the
oxidized half loses electrons and the oxidation number increases. There no net change in the
number of electrons in a redox reaction. Those given off in the oxidation half are taken up by
another species in the reduction half reactions.

The ion or molecule that accepts electrons is called the oxidizing agent; by accepting electrons
it causes the oxidation of another species. Conversely, the species that donates electrons is
called the reducing agent; when the reaction occurs, it reduces the other species.
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For example, the thermite reaction, in which iron atoms in ferric oxide lose O atoms to Al
atoms, producing Al2O3

Fe2O3(s) + 2Al(s) ¬¬˃ Al2O3(s) + 2Fe (l)

Redox reaction are of two types:

 Direct Redox Reaction: When a strip of zinc metal is placed into a blue solution of CuSO 4.
A reaction immediately begins to darken. If left in the solution for a longer period of time
the zinc will gradually decay dueto oxidation to zinc ions. At the same time, the copper
metal which causes the copper sulphate solutions to become colorless.

Redox reaction: Zn (s) + Cu 2+ (aq) ¬˃ Zn 2+ (aq) + Cu(s)


Reduction reaction:Cu 2+ (aq) + 2e –˃ Cu(s)
Oxidation reaction:Zn (s) ¬˃ Zn 2+ (aq) + 2e –

 Indirect Redox Reaction:The redox reaction in which oxidation and reduction takes place
in two separate cells(half cells) is called indirect redox reaction.
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There are two kinds of indirect redox reactions:
 Spontaneous indirect redox reaction
 Forces indirect redox reaction

Applications of electrochemistry:

 In medicine: Electrochemistry is the design and development of medical technologies and


devices. Electrochemical energy is produced in every cell of every plant and animal. An
animal’s nervous system sends its signals by means of electrochemical reactions.
 Batteries: Electrochemistry has a number of different uses, particularly in industry, the
principles of cells are used to make electrical batteries. In science and technology, a battery
is a device that stores chemical energy and make it available in an electrical form. Batteries
are made of electrochemical devices such as one or more galvanic cells or fuel cells.

 In Electroplating:the process of coating an electrically conductive object with a thin layer


of metal using an electrical current.Electroplating is used to give a metal particular
properties:
o Corrosion protection
o Abrasion and wear resistance
o For the production of jewellery.

Electro-refining(also sometimes called as electrowinning) is electroplating on a large


scale. Copper plays a major role in the electrical industry as it is very conductive and is used
in electric cables.

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 In chloralkali industry: the chlorine-alkali(chloralkali) industry is an important part of
the chemical industry, which produces chlorine and sodium hydroxide through the
electrolysis of the raw material brine. Brine is a saturated solution of sodium chloride(NaCl)
that is obtained from natural salt deposits.
 In Electrometallurgy: aluminium is a commonly used metal in industry, where its
properties of being both light and strong can be utilized. It is used in the manufacture of
products such as aeroplanes and motor cars. The metal is present in deposits of bauxite.
Bauxite is a mixture of silicas, iron oxides and hydrated alumina(Al2O3.xH2O). Electrolysis
can be used to extract aluminium from bauxite.

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Electroplating
Objective: To perform electroplating of copper, zinc and nickel on different metal
surfaces.

Theory:
Electroplating
Electroplating is the process of coating a metal with another metal, using electrical current
passed through a chemical solution. This process produces a thin, metallic coating on the
surface of the metal object. The main purposes of electroplating are to improve the appearance
of the material and provide protection against corrosion. This process uses electric current to
reduce dissolved metal cations so that they form a thin coherent metal coating on an electrode.

The process used in electroplating is called electrodeposition. Since metal is being taken from
the solution it must be replenished. This is done by hanging pieces of the metal to replenished in
the solution called electrolyte containing one or more dissolved metal salts as well as ions that
permit the flow of electricity. The chunks of metal are called anodes and the positive electrical
lead is attached to these chunks of metal. They dissolve in the solution as metal being removed
from the anode and deposited on the cathode. Cathodes are the part being plated.

The anode and cathode in the electroplating cell are both connected to an external supply of
direct current- a battery or more commonly a rectifier. The anode is connected to the positive
terminal of the supply and the cathode is connected to the negative terminal.

When the external power supply is switched on, the metal at the anode is oxidized from the zero
valence state to form cations with a positive charge. These cations associate with the anions in
the solution. The cations are reduced at the cathode to deposit in the metallic, zero state.The rate
at which the anode is dissolved is equal to the rate at which the cathode is plated and thus the
ions in the electrolyte bath are continuously replenished by the anode.

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Redox Reactions:
Redox reactions, or oxidation-reduction reactions, describe the transfer of electrons between
two chemical species. These reactions are made up of two half-reactions which always occur
simultaneously. The reduction half reaction represents the gain of electrons to the oxidizing
agent. The oxidation half reaction represents the loss of electrons to the reducing agent. A
simple way to remember the difference between oxidation and reduction is to use the mnemonic
‘OIL RIG,’ which stands for ‘oxidation is loss; reduction is gain,’ and represents the movement
of the electrons. When put together, these two ½ reactions will simplify to the overall balanced
net ionic equation.

Faraday’s Law:
Using Faraday’s Law, the amount of anode material deposited on the cathode can be calculated:

𝐼×𝑡×𝑀
Mass deposited=
𝐹×𝑛

Where I = the amount of current (in Amperes)

t = the deposition time (in seconds)

M = the molar mass of the anode material

(
F = Faraday’s constant 96,500
𝐴.𝑠
𝑚𝑜𝑙
)
n = the number of moles of electrons per mole of anode material

(i.e., the oxidation number)


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Materials:
 metal to be plated(Cu, Zn, Al, and stainless steel on cathode)
 copper acetate(electrolyte)
 nickel sulphate(electrolyte)
 nickel(anode)
 zinc acetate(electrolyte)
 zinc oxide(anode)
 copper oxide(anode)
 electrochemical cell
 electrodes
 battery or DC

Part1: Electroplating of different metals with copper:


Procedure:
1. Clean the metal (Al, Zn, Fe or stainless steel) to be plated and copper oxide with cleaning
solution or sand paper.
2. Weigh the metal and copper oxide, record the mass.
3. Connect the metal to the cathode (negative electrode) and copper oxide to the anode
(positive electrode).
4. Now, submerge these electrode in the copper acetate(electrolyte) solution of the
electrochemical cell.
5. Turn on the power source and make sure the electrodes doesn’t touch each other.
6. Remove metal and rinse with DI bottle, acetone, and carefully pat dry with paper towel.
7. Record mass of cathode and anode.
8. Dispose of waste in the proper container.

Observation:
S.no. Metal plated Metal Plated Voltage
1. Aluminium (Al) Plated 7V
2. Zinc (Zn) Plated 4.8V
3. Iron (Fe) Plated 7V
4. Stainless steel Not plated -

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Part2: Electroplating of different metals with zinc:
Procedure:
1. Clean the metal (Al, Zn, Fe or stainless steel) to be plated and zinc oxide with cleaning
solution or sand paper.
2. Weigh the metal and zinc oxide, record the mass.
3. Connect the metal to the cathode (negative electrode) and zinc oxide to the anode (positive
electrode).
4. Now, submerge these electrode in the zinc acetate(electrolyte) solutionof the
electrochemical cell.
5. Turn on the power source and make sure the electrodes doesn’t touch each other.
6. Remove metal and rinse with DI bottle, acetone, and carefully pat dry with paper towel.
7. Record mass of cathode and anode.
8. Dispose of waste in the proper container.

Observation:
S.no. Metal plated Reaction Potential
1. Aluminium (Al) Not plated -
2. Copper (Cu) Plated 6V
3. Iron (Fe) Not plated -
4. Stainless steel Not plated -

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fig.no. Zinc plating on copper sheet.

Part3: Electroplating of different metals with nickel:


Procedure:
1. Clean the metal (Al, Zn, Fe or stainless steel) to be plated and nickelwith cleaning solution
or sand paper.
2. Weigh the metal and nickel, record the mass.
3. Connect the metal to the cathode (negative electrode) and nickel to the anode (positive
electrode).
4. Now, submerge these electrode in the electrolyte solution (i.e., nickel sulphate) of the
electrochemical cell.
5. Turn on the power source and make sure the electrodes doesn’t touch each other.
6. Remove metal and rinse with DI bottle, acetone, and carefully pat dry with paper towel.
7. Record mass of cathode and anode.
8. Dispose of waste in the proper container.

Observation:
S.no. Metal plated Reaction Potential
1. Aluminium (Al) Not plated -
2. Zinc (Zn) Plated 7.5V
3. Iron (Fe) Plated 8.5V
4. Stainless steel Not plated -
5. Copper (Cu) Not plated -

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Results: Thus, electroplating of different metals is performed successfully.

Applications of electroplating:
Electroplating is widely used in numerous sectors for coating metal objects with a thin layer of
a different metal. The added metal has a desired property the original object lacks and is
primarily used to improve corrosion resistance. Chromium plating is a great example. So
much so that you’ll see it on many objects such as car parts, bath taps, gas burners, wheel rims
and many others.
Other uses include:

 Increase wear resistance


 Protect against surface abrasions
 Reduce friction
 Improve electrical conductivity (copper layer onto an electrical component)
 Prepare surfaces for better adhesion before painting or re-coating

Common metals used in electroplating include zinc, copper and tin but also precious metals like
gold, silver and palladium. Plating is possible using single metals or with various combinations
(alloys) that can provide additional value to the electroplating process.

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Corrosion
Corrosion is the destructive attack of a metal by chemical reaction with its environment.
Deterioration by physical causes is not called corrosion but is descried as erosion, galling or
wear. In some instances, chemical attack accompanies physical deterioration as described by the
term. Corrosion is an electrochemical process. It is an irreversible interfacial reaction of a
material (metal, ceramic, polymer) with its environment which results in consumption of the
material or in dissolution into the material of a component of the environment).

Corrosion is generally taken to be the wastage of a metal by the action of corrosive agents.
Corrosion can include non-metallic materials such as concrete and plastics and mechanisms
such as cracking in addition to wastage.In essence, the corrosion of metals is an electron
transfer reaction. An uncharged metal atom loses one or more electrons and becomes a charged
metal ions:

M ¬˃ M++ electron

Rusting applies to the corrosion of iron or iron-base alloys with formation of corrosion
products largely of hydrogen ferric oxides. Non-ferrous metals, therefore, corrode but do not
rust.

A natural process- corrosion:

Iron oxide + Refining + Iron =


Energy consuming processes

Iron + corrosion = Iron oxide


Loss of mass/money

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Definition:
Practical definition: The tendency of a metal to revert to its native state.

Scientific definition: Electrochemical degradation of metal as a result of an electrochemical


reaction.

ORE

CORROSION METAL

EQUIPMENT ALLOY

Corrosion return the metal to its oxidised state or combined state in chemical compounds that
are similar or even identical to the materials from which the metal are extracted.

Aqueous corrosion:
Zn + 2HCl ¬˃ ZnCl2 + H2
2Al + 3H2O ¬˃ Al2O3 + 6H2O
Al2O3 increases the corrosion resistance after depositing on the surface of Al.
Oxidation: 2Fe + 3O2 ¬˃ Fe2O3
Rusting: 2Fe(OH)2+ H2O ¬˃ 2Fe(OH)2
2Fe(OH)2+ H2O + O2 ¬˃ 2Fe(OH)3

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An Electrochemical cell consist of the following:-

 Electrode:The interface betweeb a metal and a solution across which a charge transfer
results from an electrochemical reaction.
 Anode:The electrode on which an anodic oxidation reaction occurs.
 Cathode:The electrode on which an cathodic reduction reaction occurs.
 Electrolyte: An ionic conductor.
 Metal path: An external circuit that connects the anode & the cathode.

Forms of corrosion:
Some of the eight forms of corrosion are unique, but all of them are more or less interrelated.

1. Uniform or general attack.


2. Galvanic or two-metal corrosion.
3. Crevice corrosion
4. Pitting
5. Intergranular corrosion
6. Selective leaching or parting
7. Erosion corrosion
8. Stress corrosion
9. Hydrogen damage

1. Uniform Attack:-It is the most common form of corrosion. It is normally characterized


by a chemical or electrochemical reaction which proceeds uniformly over the entire
exposure surface or over a large area.The metal becomes thinner and eventally fails.
For example, a piece of steel or zinc immersed in dil. H2SO4 will normally dissolve at a
uniform rate over its entire surface.

Prevention:
Uniform attack can be prevented or reduced by
 Proper materials including coatings.
 Inhibitors
 Cathodic protection

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Uniform attack corrosion

2. Galvanic or two-metal corrosion:-A potential difference usually exists between


two dissimilar metals when they are immersed in a corrosive or conductive solution.
If these metals are placed in contact( or otherwise electrically connected) this potential
difference produces electron flow between them corrosion of the less corrosion resistant
metal is usually increased and attach of the more resistant material is decreased as
compared with the behaviour of these metals when they are not in contact.
The less resistant metal becomes anodic and the more resistant metal cathodic.
Usually the cathode metal corrodes very little or not at all in this type of couple because of
the electric currents and dissimilar metals involved.This form of corrosion is called
Galvanic or two-metal corrosion.

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3. Crevice corrosion:-Intense localized corrosion frequently occurs within crevices and
other shielded areas or metal surfaces exposed to corrosives.This type of attack is usually
associated with the small volumes of straight solutions caused by holes, gasket surfaces, lap
joints and crevices under bolt & river heads.
As a result this form of corrosion is called crevice corrosion or sometimes deposit or gasket
corrosion.

4. Pitting corrosion:-A form of extremely localised attack that results in holes in the
metal. These holes may be small or large in diameter, but in most cases they are relatively
small. Pits are sometimes isolated or so close together they look like a rough surface.
Generally a pit may be described as a cavity or hole with the surface diameter about the
same as or less than the depth.
Pitting is the most destructive and insidious form of corrosion. It causes equipments to fail
because of perforation with only a small percent weight loss of the entire structure.It is
often difficult to detect pits because of their small size and because the pits are often
covered with corrosion product. Sometimes the pits require a long time-several months or
years to show up in actual service.

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5. Intergranular corrosion:-This is a corrosion type that attacks the boundaries of the
metal crystallites, as opposed to attacking the surface of the metal. Intergranular corrosion
can also be referred to as intergranular attack under a condition known as grain boundary
depletion. Metals and alloys, like other elements, have micro-structures that can be
described as grains. Metals can contain multiple grains, and these are separated by a grain
boundary.
Intergranular corrosion can be defined as an attack along the boundaries of several grains
in the metal or near the grain boundary with the largest portion of the grain remaining
unaffected. Stainless steels and weld decay sensitization are the best examples of
intergranular corrosion.
It can be caused by impurities at the grain boundaries enrichment of one of the alloying
elements in the grain boundary areas.

6. Selective leaching:- It is the removal of one element from a solid alloy bycorrosion
processes. The most common example is the selective removal of zinc in brass
alloys(dezincification).
Similar processes occur in other alloy systems in which Al, Fe, Co, Cr and other elements
are removed.
Selective leaching is the general term to describe these processes and its use precludes the
creation of terms such as dealuminification, decobaltification etc. Parting is metallurgical
term that is sometimes applied, but selective leaching is preferred.

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7. Erosion leaching:-It is the acceleration or increase in rate of deterioration or attack on
a metal because of relative movement between a corrosive fluid and the metal surface.
Generally, this movement is quite rapid and mechanism wear effects or abrasion are
involved.
Metal is removed from the surface as dissolved ions or it forms solid corrosion products
which are mechanically swept from the metal surface. Sometimes movement of
environment decreases the corrosion. Particularly when localized attack occur under
stagnant conditions but this is not erosion corrosion because deteriorations is not increases.
Most metals and alloy are suspectible to erosion corrosion damage.
Example, Al, Pb, and stainless steels.

8. Stress corrosion:- Stress Corrosion cracking refers to cracking caused by the


simultaneous presence of tensile stress and specific corrosion medium. Many investigators
have classified all cracking failures occurring in corrosive mediums as stress corrosion
cracking, including failures due to hydrogen embrittlement.
However, these two types of cracking failure responds differently to environment failures.
During stress corrosion cracking the metal or alloy is virtually unattached over most of its
surface, while fine cracks progress through it.
CAUSES:-
1. Season cracking of brass
2. Caustic embrittlement of steel

Both of these obsolete terms describe the environmental conditions present which led to
stress corrosion cracking.

“Season cracking” refers to the stress corrosion cracking failures of brass cartridge cases.
During periods of heavy rainfall, especially in the tropics, cracks were observed in the brass
cartridge cases at the point where the case was crimped to the bullet.

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“Caustic embrittlement” was first used to describe the cracking of riveted mild steel boiler
plates due to local deposition of concentrated hydroxide at temperature of 200-250˚C (400
to 480˚F). It was later known as “stress corrosion cracking” which is in turn replaced by
“caustic cracking”.

9. Hydrogen damage corrosion:-Hydrogen damage refers to the mechanical damage


of metal that occurs due to the interaction with or presence of hydrogen. It creates structural
damage in various materials. The use of high-strength structural materials is a necessity;
thus, material problems caused by hydrogen damage are key considerations in storage, large
scale production and transportation.

Types of hydrogen damage include:

 Solid solution hardening


 Internal defect creation
 Hydride embrittlement
 Hydrogen embrittlement

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Corrosion Rate Measurement:
Mixed potential theory forms the basis for two electrochemical methods used to determine
corrosion rate:

1. Weight Loss Measurement


2. The Tafel Extrapolation
3. Linear Polarization Technique

1. Weight loss measurement:-


The rate of uniform corrosion can be measured using corrosion coupon testing by
weight loss measurement. Coupon corrosion testing is predominantly designed
to investigate uniform corrosion

2. The TafelExtraplation:-
The Tafel extrapolation method for determining corrosion rate was used by Wager &Traud
to verify the mixed potential theory. This technique was data obtained from cathodic and
anodic polarization measurements. Cathodic polarization data are preferred, since these are
easier to measure experimentally.
A schematic diagram for conducting a cathodic polarization measurement is given below:-

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fig.no., Electric circuit for cathodic polarization measurements

Fig.no., applied current cathodic polarization curve of a


corrodingmetal showing Tafel Extrapolation.

3. Linear Polarization:-The disadvantages of the Tafel Extrapolation method can be


largely overcome by using a linear-polarization analysis. Within 10mv more noble or more
active than the corrosion potential, it is observed that the applied current density is a linear
function of the electrode potential. The corrosion potential is used as an overvoltage
reference point and a plot of overvoltage versus applied anodic and cathodic current. This
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plot represents the first 20mv polarization of the curve. The slope of this linear-polarization
curve is related to the kinetic parameters of the system as follows:

Fig.no. Applied-current linear-polarization curve

Where ßa and ßc are the Tafel slopesof the anodic and cathodic reactions respectively.

The advantages of electrochemical corrosion-rate measurements, particularly linear-polarization


techniques, are:-

1. The permit rapid corrosion rate measurements and can be used to monitor corrosion rate
in various process streams.
2. These techniques may be used to accurately measure very low corrosion rates(less than
0.1 mpy) which are both difficult and tedious to perform with conventional weight loss or
chemical analytical techniques. The measurement of low corrosion rates is especially

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important in nuclear, pharmaceutical, and food processing industries, where trace impurities
and contamination are problems.

3. Electrochemical corrosion-rate measurements may be used to measure the corrosion rate


of structures which cannot be visually inspected or subjected to weight-loss tests.
Underground pipes and tanks and large chemical plant components are examples.

Galvanic series:-

MODIFYING THE ENVIRONMENT-CORROSION CONTROL


Environment plays a major role in the corrosion of metals. Hence, we can prevent corrosion to
a great extent by modifying the environment. Some of the methods are

i)Deaeration: Fresh water contains dissolved oxygen. The presence of increased amount
of oxygen is harmful and increases the corrosion rate. Deaeration involves the removal of
dissolved oxygen by increase of temperature together with mechanical agitation. It also
removes dissolved carbon dioxide in water.

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ii)Corrosion Inhibitors:A corrosion inhibitor is a chemical additive, which, when added
to a corrosive aqueous environment, reduces the rate of metal wastage. It can function in one of
the following ways:

Inhibitors are organic or inorganic substances which decrease the rate of corrosion. Usually the
inhibitors are added in small quantities to the corrosive medium. Inhibitors are classified into:-

1) Anodic inhibitors (chemical passivators)

2) Cathodic inhibitors (adsorption inhibitors)

3) Vapour phase inhibitors (volatile corrosion inhibitors)

1) Anodic Inhibitors:

Inhibitors which retard the corrosion of metals by forming a sparingly soluble compound with
a newly produced metal cations. This compound will then adsorb on the corroding metal
surface forming a passive film or barrier. Anodic inhibitors are used to repair a) the crack of
the oxide film over the metal surface

b) the pitting corrosion

c) the porous oxide film formed on the metal surface. Examples: Chromate, phosphate,
tungstate, nitrate, molybdate etc.

2)Cathodic Inhibitors:

Depending on the nature of the cathodic reaction in an electrochemical corrosion, cathodic


inhibitors are classified into

a) In an acidic solution: the main cathodic reaction is the liberation of hydrogen gas, the
corrosion can be controlled by slowing down the diffusion of H+ ions through the cathode.
Eg., Amines, Mercaptans, Thiourea etc.

2 H+ + 2 e- ¬˃ H2

b) In a neutral solution: in a neutral solution, the cathodic reaction is the adsorption of oxygen
or formation of hydroxyl ions. The corrosion is therefore controlled either by eliminating
oxygen from the corroding medium or by retarding its diffusion to the cathodic area. The
dissolved oxygen can be eliminated by adding reducing agents like Na2SO3. The diffusion

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of oxygen can be controlled by adding inhibitors like Mg, Zn or Ni salts. Eg., Na2SO3,
N2H4, Salts of Mg, Zn or Ni.

½ O2 + H2O + 2e- ¬˃ 2OH-

3)Vapour phase inhibitors:

These are organic inhibitors which are readily vapourised and form a protective layer on the
metal surface. These are conveniently used to prevent corrosion in closed spaces, storage
containers, packing materials, sophisticated equipments etc. Examples are
Dicyclohexylammonium nitrate, dicyclohexyl ammonium chromate, benzotriazole,
phenylthiourea etc.

CATHODIC PROTECTION:
The reduction or prevention of corrosion by making metallic structure as cathode in the
electrolytic cell is called cathodic protection. Since there will not be any anodic area on the
metal, corrosion does not occur. There are two methods of applying cathodic protection to
metallic structures.

a) Sacrificial anodic protection (galvanic protection)

b) Impressed current cathodic protection

SACRIFICIAL ANODIC PROTECTION METHOD:

In this method, the metallic structure to be protected is made cathode by connection it with
more active metal (anodic metal). Hence, all the corrosion will concentrate only on the active
metal. The parent structure is thus protected. The more active metal so employed is called
sacrificial anode. The corroded sacrificial anode block is replaced by a fresh one. Metals
commonly employed as sacrificial anodes are magnesium, zinc, aluminium and their alloys.
Magnesium has the most negative potential and can provide highest current output and hence is
widely used in high resistivity electrolytes like soil.

Applications:

1. Protection as buried pipelines, underground cables from soil corrosion.


2. Protection from marine corrosion of cables, ship hulls, piers etc.
3. Insertion of magnesium sheets into the domestic water boilers to prevent the formation of
rust.
4. Calcium metal is employed to minimize engine corrosion.
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IMPRESSED CURRENT CATHODIC PROTECTION METHOD

In this method, an impressed current is applied in opposite direction to nullify the corrosion
current and convert the corroding metal from anode to cathode. Usually the impressed current
is derived from a direct current sources (like battery or rectifier on AC line) with an insoluble,
inert anode (like graphite, scrap iron, stainless steel, platinum or high silica iron). A sufficient
DC current is applied to an inert anode, buried in the soil (or immersed in the corroding
medium) and connected to the metallic structure to be protected.

The anode is, usually, a back fill, composed of coke breeze or gypsum, so as to increase the
electrical contact with the surrounding soil. Impressed current cathodic protection has been
applied to open water box coolers, water tanks, buried oil or water pipes, condensers,
transmission line towers, marine piers, laid up ships etc. This kind of protection technique is
particularly useful for large structures for long term operations.

ANODIC PROTECTION
This is an electrochemical method of corrosion control in which an external potential control
system, called potentiostat, is used to produce and maintain a thin non corroding, passive film
on a metal or an alloy. The use of potentiostat is to shift corrosion potential into passive
potential so that the corrosion of the metal is stopped. The potential of the object (say acid
storage tank) to be protected is controlled by potential controller (potentiostat) so that under
certain potential range, the object becomes passive and prevents further corrosion. This
potential range depends upon the relationship between the metal and the environment.

Applications:
1. Used in acid coolers in dilute sulphuric acid plants

2. used in storage tanks for sulphuric acid

3. used in chromium in contact with hydrofluoric acid


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Limitations:

1. This method cannot be applied in the case of corrosive medium containing aggressive
chloride.

2. This cannot be applied if protection breaks down at any point, it is difficult to reestablish.

PROTECTIVE COATINGS
Introduction: In order to protect metals from corrosion, it is necessary to cover the surface by
means of protective coatings. These coatings act as a physical barrier between the coated metal
surface and the environment. They afford decorative appeal and impart special properties like
hardness, oxidation resistance and thermal insulation.

Classification:
Protective coatings can be broadly classified into two types.They are:

1) Inorganic coatings

2) Organic coatings

Inorganic coatings are further classified into two types.They are

i)Metallic coating:

1. Hot dipping- Galvanising, Tinning

2. Metal cladding

3. Cementation-Sherardising, Chromising, Calorising

4. Electroplating.

ii)Non-metallic coating:

1. Surface coating or chemical conversion coating – Chromate coating, Phosphate coating and
Oxide coating.

2. Anodising

3. Enamel coating or Vitreous or Porcelain coating.

Organic coatings consists of Paints, Varnishes, Lacquers and Enamels.


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Surface modification
Surface modification is the deliberate attachment of (macro) molecules to the surface of an
inorganic colloid to change its physical properties or chemical functionality.This process
changes the properties of the surface, but the substrate material is still present on the surface.

Surface modifications have been applied to metallic biomaterials in order to improve


mechanical, chemical, and physical properties—such as wear resistance, corrosion resistance,
biocompatibility, and surface wettability. For enhancing the mechanical retention between two
surfaces, one or both surfaces are normally modified to increase effective surface area by a
sandblasting, shot-peening, or laser-peening method.

It is an effective means to alter biological interactions to a particular material and offers a


number of advantages in biomedical fabrication. By changing only the composition at the
outermost surface of a biomaterial, the mechanical properties and fabrication method of an
implant can remain unaffected while modulating the surface chemistry and properties that direct
bilogical reactions.

In addition, since surface modification techniques require only minute amounts of material to
completely alter the surface properties of a device or implant, expensive materials can be
economically used in commercially competitive biomedical products. Furthermore, the
mechanical properties of the surface layer are not of extreme concern because the mechanical
performance is largely dictated by the underlying layer; thus, materials with low tensile strength
(e.g.hydrogels) can be used for surface modification. Finally, surface modification can provide
accessible, chemically reactive sites that can be used to immobilize drugs, enzymes, antibodies
or other biologically active species.

Typical reasons for modifying the surface of an existing biomaterial include the following:
(a)Improve blood compatibility.
(b)Reduce (or increase) tissue adhesion.
(c)Improve lubricity.
(d)Increase (or decrease) the wettability of a surface.
(e)Add biologically active substances to the surface layer.
(f)Alter the protein adsorption characteristics.
(g)Modify the appearance.
(h)Protect the device from the body.
(i)Protect the body from the device.
(j)Act as a rate-limiting membrane.

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Example of surface modification:-
LOTUS EFFECT:- The surface of a lotus leaf is an example of superhydrophobicity. On a
superhydrophobic surface, the contact angle is greater than 150o, meaning almost no wetting of
the surface by the liquid takes place. This leads to the second property associated with lotus
plants — the ability to stay spotlessly clean. As rain falls on a superhydrophobic surface like the
lotus leaf, the water droplets roll easily off the leaf surfaces (see Figure 3). As the droplets
travel along the leaves, they pick up any dirt or other matter they encounter along the way. This
process keeps the lotus leaves dry, clean and free of pathogens such as bacteria and fungi.
The self-cleaning and water-repellent qualities of superhydrophobic surfaces have the potential
for many practical applications. House paints, roof tiles and various surface coatings are already
on the market (see Figure 3). These products are examples of "biomimicry."

SURFACE PREPARATION FOR FILM AND COATING DEPOSITION


PROCESSES
Surface modification can include surface treatments such as roughening or smoothing the
surface, making a harder surface by plasma treatment, or by activating a polymer surface by
plasma treatment. Surface preparation includes surface treatments (surface modification) to
change the properties of the surface in a desirable way as well as cleaning, which is the
reduction of surface contamination to an acceptable level. One objective of any surface
preparation procedure is to produce as homogeneous a surface as possible.

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SURFACE MODIFICATION OF COLLOIDAL SILICA NANOPARTICLES:

Surface modification of colloidal silica nanoparticles without disrupting the electric double
layer of nanoparticles is a major challenge. In the work, silane was employed to modify
colloidal silica nanoparticles without inducing bridge flocculation obviously. The effect of pH
value of the silica sol, the amount of silane in feed, and reaction temperature on the graft
amount and the final size of modified particles was investigated. The increased weight loss by
TG and the appearance of T2 and T3 except for Q2 and Q3 signals by CP/MAS 29Si NMR of
the modified samples verified the successful grafting of silane. The graft amount reached 0.57
mmol/ g, which was slightly lower than theory value, and the particle size remained nearly the
same as unmodified particles for acidic silica sol at the optimum condition. For alkaline silica
sol after modification, aggregates composed of several nanoparticles connected together with
silanemoleculars as the bridge appeared.

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CORROSION PROTECTIVE COATINGS FOR TI AND TI ALLOYS USED
FOR BIOMEDICAL IMPLANTS:
Sol-gel method:-The sol-gel process is a wet chemical technique also known as chemical
solution deposition, and involves several steps, in the following chronological order: hydrolysis
and polycondensation, gelatin, drying, densification, and crystallization.

Sol-gel process is a method for producing solid materials from small molecules that is suitable
for preparing different coatings (e.g., silicium and titanium oxides) on the surface of Ti-based
materials. It involves conversion of small molecules (precursors) into a colloidal solution (sol)
and then into an integrated network (gel) consisting of either discrete particles or network
polymers.

Benefits:

The main advantages of the sol-gel method are:-


(1) low processing temperature (avoiding volatilization of entrapped species),
(2) the possibility to cast coatings in complex shapes, and
(3) the use of compounds that do not introduce impurities into the end product.
The sol-gel process involves four stages:-
(1) hydrolysis,
(2) condensation/polymerization of monomers,
(3) growth of particles, and
(4) gel formation.

D IP - COATING :
By this technique, the material from which the film is produced is put into solution, and then the
substrate is progressively dipped into and is extracted from the solution at a controlled rate.
After the solvent evaporates, a thin and homogeneous film is produced. The thickness of
deposited liquid film coatings depends on the coating solution properties such as density,
viscosity, and surface tension, as well as surface withdrawal speed from the coating solution.
The thickness of the film is generally bigger than that prepared by spin-coating with the same
solutions.

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Dip-coating was successfully used, for example, to prepare sol-gel-derived Al2O3 films on γ-
TiAl-based alloys.

S PIN - COATING
In the case of spin-coating, an amount of solution is placed on the substrate that is rotated at
high speed in order to spread the fluid by centrifugal force. After the evaporation of the solvent,
a thin, homogeneous film is formed. As in the case of dip-coating, final film thickness and other
properties will depend on the nature of the sol-gel coating (viscosity, drying rate, surface
tension, etc.) and on the parameters chosen for the spin process. Higher spin speeds and longer
spin times give birth to thinner films.
Generally, a moderate spinning speed is recommended. The drying rate should also be slow in
order to ensure film uniformity. A supplementary drying step is sometimes necessary after the
high-speed spin step to further dry the film without substantially thinning it.

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Geopolymers
Geopolymers are a type of inorganic polymer that can be formed at room temperature by using
industrial waste or by-products as source materials to form a solid binder that looks like and
performs a similar function to OPC. Geopolymer binder can be used in applications to fully or
partially replace OPC with environmental and technical benefits, including an 80 - 90%
reduction in CO2 emissions and improved resistance to fire and aggressive chemicals.

They have following basic characteristics:-

a) Nature of the hardened material:

 X-ray amorphous at ambient and medium temperatures.


 X-ray crystalline at temperatures > 500°C.

b) Synthesis Routes:

 alkaline medium (Na, K, Ca) hydroxides and alkali-silicates yielding poly(silicates) –


poly(siloxo) type or poly(silico-aluminates) – poly(sialate) type
 acidic medium (Phosphoric acid) yielding poly(phospho-siloxo) and poly(alumino-
phospho) types

As an example, one of the geopolymeric precursors, MK-750 (metakaolin) with its


alumoxyl group –Si-O-Al=O, reacts in both systems, alkaline and acidic. Same for siloxo-
based and organo-siloxo-based geopolymeric species that also react in both alkaline and
acidic medium.

Geopolymers are presently developed and applied in 10 main classes of


materials:-

1. Waterglass-based geopolymer, poly(siloxonate), soluble silicate, Si:Al=1:0


2. Kaolinite / Hydrosodalite-based geopolymer, poly(sialate) Si:Al=1:1
3. Metakaolin MK-750-based geopolymer, poly(sialate-siloxo) Si:Al=2:1
4. Calcium-based geopolymer, (Ca, K, Na)-sialate, Si:Al=1, 2, 3
5. Rock-based geopolymer, poly(sialate-multisiloxo) 1<Si:Al<5
6. Silica-based geopolymer, sialate link and siloxo link in poly(siloxonate) Si:Al>5
7. Fly ash-based geopolymer
8. Ferro-sialate-based geopolymer
9. Phosphate-based geopolymer,
10. AlPO4-based geopolymer
11. Organic-mineral geopolymer

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FLY ASH-BASED GEOPOLYMER:
Fly ash is the fine solid particulate residue driven out of the boiler with the flue gases in coal-
fired power plants. Now it can be used for making geopolymerwhich acts as a cement-like
product. The geopolymer technology provides an alternative good solution to the utilization of
fly ash with little negative impact on environment. The production of fly ash-based geopolymer
is mainly based on alkali activated geopolymerization which can occur under mild
conditions and is considered as a cleaner process due to much lower CO2 emission than that
from the production of cement. The geopolymerization can trap and fix the trace toxic
metal elements from fly ash or external sources.

Factors of geopolymerization process:


1. Si/Al ratios,
2. Type and the amount of the alkali solution,
3. Temperature,
4. Curing conditions
5. additives

The mechanical performances of the fly ash-based geopolymer, including compressive


strength, flexural and splitting tensile strength, and durability such as the resistance to
chloride, sulfate, acid, thermal, freeze-thaw and efflorescence, are the primary concerns. These
properties of fly ash-based geopolymer are inherently dependent upon the chemical
composition and chemical bonding and the porosity.

The mechanical properties and durability can be improved by fine tuning Si/Al ratios, alkali
solutions, curing conditions, and adding slag, fiber, rice husk-bark ash and red mud. Fly ash-
based geopolymer is expected to be used as a kind of novel green cement. Fly ash-based
geopolymer can be used as a class of materials to adsorb and immobilize toxic or radioactive
metals.

Geopolymer cement and its properties:-


Geopolymer cement is made from aluminium and silicon, instead of calcium and silicon. The
sources of aluminium in nature are not present as carbonates and therefore, when made active
for use as cement, do not release vast quantities of CO2. The most readily available raw
materials containing aluminium and silicon are fly ash and slag – these are the materials that
Zeobond uses to create its low carbon emission binder.
The main process difference between OPC(ordinary Portland cement) and geopolymer
cement is that OPC relies on a high-energy manufacturing process that imparts high potential
energy to the material via calcination. This means the activated material will react readily with a
low energy material such as water.
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On the other hand, geopolymer cement uses very low energy materials, like fly ashes, slags and
other industrial wastes and a small amount of high chemical energy materials (alkali
hydroxides) to bring about reaction only at the surfaces of particles to act as a glue.

This approach results in a very large energy saving in the production of geopolymer cement.
The properties of geopolymer cement, when used to make concrete, have been repeatedly and
independently shown to be equivalent to other cements in terms of the structural qualities of the
resulting concrete.
Indeed, the fire resistance of E-Crete™ has been tested to be well in excess of double that of
traditional concrete. This is a highly significant technical benefit of E-Crete™ and will drive
wide scale adoption in high-rise construction in the near term, including in some government
department buildings.

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To produce geopolymer from kaolin or other clay materials three main steps
are necessary:-

(i) Thermal activation: the aim of which is to obtain a clay material with a high
chemical activity. In this process dehydroxylation of clay mineral leads to an unstable
amorphous solid
(ii) Alkali activation: an activated alumino-silicate material is dissolved in a highly
alkaline solution to produce silicate and aluminate monomers (Xu and van Deventer,
2000)
(iii) Reactive setting or polycondensation: in which the silicate and aluminate
monomers condense to a stable polymer network (Davidovits, 1991). The
polymerisation process involves a substantially fast chemical reaction under alkaline
condition on Si-Al minerals that results in a three dimensional polymeric chain and ring
structure consisting of Si-O-Al- O bonds.

Portland cement chemistry vs Geopolymer cement chemistry:-

Left: hardening of Portland cement (P.C.) through simple hydration of Calcium Silicate into
Calcium Di-Silicate hydrate (CSH) and lime Ca(OH)2.

Right: hardening (setting) of Geopolymer cement (GP) through poly- condensation of


Potassium Oligo- (sialate-siloxo) into Potassium Poly(sialate-siloxo) cross linked network.

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Reference:-
1. 12th n.c.e.r.t chemistry book.
2. Www.sciencedirect.com
3. Modern electroplating by mordechay schlesinger & milan parnovic.
4. Corrosion engineering by mars g fontana/ norbert d greene

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