Module-3 ➢ A small quantum dot has a longer bandgap, and hence it requires more energy to excite

its electron.

Quantum Materials and Polymers ➢ As the frequency of emitted light is proportional to the energy, smaller quantum dots
emit radiation of higher energy or frequency, that is, shorter wavelengths.
Quantum Dots: Introduction, size-dependent properties-quantum confinement effect, surface-
to volume ratio & band gap. Synthesis of Cd-Se Quantum dots by wet chemical method and its ➢ A larger quantum dots have closely spaced energy levels and emit photons of lower
applications. Construction, working principle and applications of quantum dot sensitized solar energy or frequency, that is, longer wavelengths.
cells (QDSSCs).
➢ It means that as the size of quantum dots increases, the quantum dot will emit photons
Polymer: Introduction, number average and weight average molecular weight of the polymers with lower energy or frequency and higher wavelength and vice versa.
and numerical problems. Structure-properties relationship of polymers (Crystallinity, Strength,
Elasticity and chemical resistivity]. Synthesis and properties of nylon-6,6 and its advantages in
3D printing applications. Synthesis and properties of chlorinated polyvinyl chloride (CPVC),
and polymethyl methacrylate (PMMA) and their uses in device applications. Conducting
polymers- Introduction, synthesis of polyaniline, conduction mechanism and its engineering
applications.

Introduction

Quantum dots (QDs): Quantum dots (QDs) are nanoscale semiconductor particles typically
TYPES OF QD’S BY MATERIAL
ranging from 2 to 10 nanometres in size. Due to their quantum confinement effects, QDs exhibit
unique optical and electronic properties, such as size-dependent light emission. These 1. Inorganic quantum dots (IQDS): These are traditional semiconductor quantum dots,
properties make them highly valuable in various applications including display technology, with common examples being Cadmium Selenide (CdSe) and Cadmium Sulfide (CdS).
solar cells, biomedical imaging, and quantum computing. Their ability to emit specific They offer excellent optical properties but can be toxic.
wavelengths of light by simply changing their size makes them a versatile tool in 2. Carbon-based quantum dots (CQDs): Made from carbon derivatives, they are water-
nanotechnology and materials science. soluble and are considered less toxic than some inorganic dots. A subtype of carbon-
based dots made from graphene.
Graphene quantum dots (GQDs):
Carbon nanodots (CNDs): Another subtype of carbon-based dots, often spherical in
shape.
3. Perovskite quantum dots: These have a perovskite crystal structure and are known for
their strong light-emitting properties.

Electrical Properties of quantum dots Quantum Confinement Effect: quantum confinement effect when they are very small-around
the size of a few nanometres. At this tiny scale, the movement of electrons and holes inside the
• Surface-to-Volume Ratio: As quantum dots decrease in size, their surface-to-volume
QD is limited in all directions. This causes the energy levels to become separate, like steps,
ratio increases significantly. A greater proportion of atoms are located on the surface,
instead of being continuous. As the size of the QD gets smaller, the gap between energy levels
which can influence chemical reactivity, electronic states, and optical behaviour.
(called the band gap) becomes larger. Because of this, small QDs give off blue light, while
➢ For a spherical quantum dot with diameter D, the surface-to-volume bigger ones give off red light. So, the colour of light from a QD depends on its size.
ratio is (6/D). As the diameter decreases (e.g., from a bulk material size
to the nanoscale range of 2–10 nm), this ratio increases dramatically.
➢ As ratio increases, quantum dot size decreases.

Size-Dependent Properties of Quantum Dots (QDs)

Quantum dots (QDs) are semiconductor nanoparticles typically 2–10 nm in diameter. Their
properties depend strongly on particle size due to the quantum confinement effect.
Band Gap Variation: The band gap in quantum dots is not fixed, unlike in bulk 1. Bandgap Energy Increases as Size Decreases Smaller QDs have larger bandgap energy.
semiconductors. Due to quantum confinement, reducing the size of the QD increases its band Larger QDs have smaller energy. “Electrons and holes are confined in a very small volume →
gap energy. This size-dependent tunability of the band gap allows precise control over the energy levels become quantized → increasing or decreasing the bandgap depending on size.”
colour of light absorbed or emitted by the QD, making them highly useful in applications such
Effect:
as LEDs, lasers, and biomedical imaging.
Small QDs → absorb & emit blue / high-energy light.
Large QDs → absorb & emit red / low-energy light.
2. Tuneable Optical Properties (Color Change)
• Changing QD size changes the color of light emitted.
• Small QDs → blue, green
• Medium QDs → yellow
This tunability is widely used in QD-LEDs, QD-LCD displays, and optical sensors.
3. Size Affects Exciton Bohr Radius
• When particle size < exciton Bohr radius → strong quantum confinement.
• Leads to discrete electronic states, similar to atoms. 3. Addition of Stabilizer / Capping Agent: Agents like mercaptoethanol,
4. Electrical Conductivity Changes with Size thioglycolic acid (TGA), or trioctylphosphine oxide (TOPO) are added. These
prevent aggregation and control nanoparticle growth.
• Smaller QDs → lower conductivity due to wide bandgap.
CdSe + R-SH → CdSe-(SR)surface
• Larger QDs → higher conductivity.
4. Nucleation and Growth: Controlled heating (50-100 °C) with constant
Used in solar cells (QDSSCs), photodetectors, and field-effect transistors (FETs).
stirring. Selenium precursor is slowly introduced into the cadmium solution.
5. Enhanced Photoluminescence in Smaller QDs Reaction is often carried out under inert atmosphere (nitrogen/argon) to prevent
• Smaller QDs show brighter photoluminescence. • Emission wavelength depends on size. oxidation. Particle size (2–8 nm) is tuned by varying temperature, precursor
Useful in bioimaging, displays, and quantum dot
ratio, and reaction time.
lasers. Cd²⁺ + Se²⁻ → CdSe (Quantum Dots)
6. Thermal Properties Are Size Dependent 5. Separation and Purification: The quantum dots are precipitated, centrifuged,
• Smaller QDs have lower melting point. and washed with solvents. Excess unreacted species and surfactants are
removed.
• Surface atoms dominate → influence heat capacity and stability.
6. Final Product: Stable colloidal Cd-Se quantum dots with size-dependent
7. Size Controls Magnetic Properties
photoluminescence (emission colours ranging from blue to red).
• Quantum dots made from magnetic materials show super paramagnetism at small sizes.
Applications:
• Important for spintronic devices.
8. Chemical Reactivity Increases as Size Decreases 1. Optoelectronics: Used in light-emitting diodes (QLED displays), lasers, and

• Smaller QDs have higher surface area-to-volume ratio. photovoltaic cells.

2. Biological Imaging: Serve as fluorescent probes due to tuneable emission and
• More reactive; useful in catalysis and sensing.
high photostability.
3. Solar Cells: Improve efficiency of quantum dot-sensitized solar cells
Synthesis of Cd-Se Quantum Dots by Wet Chemical Method (QDSSCs).
➢ Principle: Cd-Se quantum dots (QDs) are semiconductor nanocrystals whose optical 4. Sensors: Employed in chemical and biosensors for detecting heavy metals,
properties depend on particle size. They are synthesized by controlled wet chemical biomolecules, and pH changes.
routes using cadmium and selenium precursors in the presence of stabilizers/capping 5. Photocatalysis: Useful in degradation of pollutants and water splitting for
agents. hydrogen production.
1. Selection of Precursors 6. Medical Applications: Potential use in targeted drug delivery and cancer
Cadmium source: CdCl₂, Cd(CH₃COO)₂, or Cd(NO₃)₂. therapy (though toxicity issues exist due to Cd).
CdCl₂ → Cd²⁺ + 2Cl⁻ 7. Quantum Computing: Investigated for qubit development due to discrete
Selenium source: Na₂Se, or Na₂SeO₃ energy levels.
Na₂SeO₃ + 4NaBH₄ + 7H₂O → Na₂Se + 4B(OH)₃ + 14H₂↑
2. Preparation of Reaction Medium: Dissolve cadmium precursor in aqueous or
Quantum Dot Sensitized Solar Cells (QDSSC):
organic solvent. Adjust pH to mildly alkaline if needed.

Introduction:

• Quantum dots (QDs) are often referred to as artificial atoms.

• They are semiconductor nanocrystals, only a few nanometres in size, with unique
optical and electronic properties distinct from bulk materials.
• A Quantum Dot Solar Cell (QDSC) is a photovoltaic device that uses QDs as the
primary light-absorbing material.
• QDs can replace conventional bulky materials such as silicon or copper indium gallium
selenide. Advantages:
• Their band gap can be tuned by simply altering the size of the dots, making them highly
➢ High power-to-weight ratio with excellent efficiency.
adaptable across a wide range of energy levels.
➢ Low power consumption during operation.
Construction ➢ Cost-effective with improved electrical performance.
➢ Flexible in use, enabling applications not limited to rooftops but also windows and other
1. Photoanode: A conducting glass substrate is coated with a semiconductor
transparent surfaces.
layer (commonly TiO₂). The outer surface is then sensitized with QDs.
2. Electrolyte: A redox electrolyte, usually polysulfide, acts as a hole Disadvantages:
conductor and facilitates charge transfer.
➢ Cadmium selenide (CdSe)-based QDs are highly toxic and require a stable polymer
3. Cathode electrode: It helps regenerate the electrolyte and completes the
shell for safe use.
circuit.
➢ Cadmium and selenium ions are cytotoxic, raising environmental and health concerns.
Working Principle
Applications:
1. QDs absorb sunlight and electrons are excited from the valence band to the conduction band.
➢ Biological labelling and imaging.
2. The excited electrons are transferred to the semiconductor layer, leaving holes behind on the ➢ Detection systems and fluorescence resonance energy transfer donors.
QD surface. ➢ Used in LEDs, photodetectors, photoconductors, and photovoltaic devices.
➢ Biomedical and environmental applications.
3. The electrolyte captures these holes and undergoes reduction reactions:
➢ Catalysis and chemical reactions.
2− 2ℎ
S +S + → 𝑆

𝑆+𝑆𝑥2− → 𝑆𝑥+1 2− (𝑥 =2) POLYMERS

4. Electrons move from the photoanode to the cathode through the external circuit, producing Polymers are macromolecules that have high molecular mass built up by linkage together of a
current. large number of small molecules called monomers. In Greek Poly means many, mers means

5. At the cathode, the electrolyte is regenerated by gaining electrons: units or parts. The molecular mass of polymers is high and ranges from 10,000 to 1,00,000.
Example: Polythene is a polymer formed by linkage of large numbers of ethylene.
S𝑥2− → 𝑆 +𝑆𝑥−1 2− ; 𝑆+2𝑒− →𝑆2−
Important commercial polymers are:

❖ Resins: These are the base materials used in the manufacturing of plastics by mixing
with fillers, plasticizers, lubricants, coloring agents and stabilizers.

❖ Plastics: The materials which soften at certain temperature and harden at characteristic
temperature are known as plastics.

❖ Elastomers: These consist of zigzag or helical chain of molecules, undergo elastic

changes when subjected to external source, but regain their original shape when the
force is withdrawn.

❖ Fibers: Fibers are long thin thread like polymer chain, which do not stretch or undergo
deformation like elastomers. The molecular chains are arranged in parallel, spiral,
helical pattern.
Polymerization: The chemical process in which the monomers are converted into polymers is
❖ Basic definitions: Polymer: A polymer is a large molecule formed by the repeated
called Polymerization.
covalent linkage of small units called monomers". Ex: Starch, Polyvinyl chloride,
Polyethylene, Nylon 6, 6 and etc. Degree of Polymerization: The number of times the unit is repeated in a homopolymer chain
is referred to as the degree of polymerization. High polymers have high degree of
❖ Monomer: Monomer is defined as a simple molecule or single unit representing in a
polymer with two or more binding sites either unsaturation or having two or more polymerization.
than two functional groups through which it forms covalent linkages with other
monomeric units to form the macromolecule". Addition polymerization: It is a process in which unsaturated monomers, typically containing
double or triple carbon-carbon bonds, repeatedly join together to form long polymer chains
❖ Polymerization: “Polymerization is the process of formation of a polymer by the
repeated covalent linkage of monomeric units” or The chemical process in which the without the elimination of any byproducts.
monomers are converted into polymers is called Polymerization.
o Polyethylene (from ethene)
❖ Homo polymers: If all the monomeric units are same in a polymer called homo
polymer Ex: Polyethylene. o Polypropylene (from propene)

❖ Hetero polymer: If the monomeric units are different in a polymer chain called o PVC (polyvinyl chloride, from vinyl chloride)
hetero polymer. Ex: Nylon 6, 6

Condensation polymerization: The polymerization process involves the reaction of

bifunctional or multifunctional monomers, each containing two or more reactive groups such
Weight average molecular weight: It is various molecular species in proportion to their
as –OH, –COOH, or –NH₂. During the formation of the polymer, small molecules like water,
weights in the given material.
hydrochloric acid, or methanol are eliminated as byproducts.

• Nylon (e.g., Nylon-6,6 from hexamethylenediamine and adipic acid)

• Terylene / PET (from ethylene glycol and terephthalic acid)

• Bakelite (from phenol and formaldehyde)

Molecular weight of polymers: The two main types of molecular mass are Polydispersity index:

a) Number average molecular Weight ➢ In order to have an idea about the homogeneity of a polymer, the term polydispersity
b) Weight average molecular weight index is used.

➢ It is the ratio of mass average molecular mass to the number average molecular mass.
Number average molecular Weight: It is defined as the total mass (Mn) of all the molecules ̅̅̅̅̅̅
𝑀
PDI = 𝑊
̅̅̅̅̅
𝑀
in a polymer sample divided by total number of molecules present. 𝑛

➢ For natural polymers, PDI is usually equal to one, which means that they are
monodisperse. Such polymers are more homogeneous.

➢ Synthetic polymers on the contrary generally have PDI > l which means that they are
less.
Where n and M represent the number and molecular mass of each species respectively present
Numerical: 1. A polymer sample contains 1, 2, 3 and 4 molecules having molecular weight
in the polymer.
1×105, 2×105, 3×105 and 4×105 respectively calculate the number average and weight average
The number average molecular weight M is calculated as
n molecular weight of the polymer.
∑𝑖 𝑁𝑖 𝑀𝑖
𝑀𝑛 = Solution: Number of molecules n1=1 n2=2 n3=3 n4=4 Molecular weight of the polymer:
∑𝑖 𝑁𝑖
m1 =1×105 m2 =2 ×105 m3 =3×105 m4=4×105
where M is the molecular weight of a chain, N is the number of chains of that
i i
molecular weight, and i is the number of polymer molecules
Molecular weight of the polymer:
a) m1 = (3×12+6 ×1) ×400=16800
b) m2 =(3×12+6 ×1) ×500=21000
c) m3 =(3×12+6 ×1) ×600=25200

Assignment numerical:

1. A polymer has following composition 100 molecules of molecular mass 1000 g/mol, 2000
molecules of molecular mass 2000g/mol and 500 molecules of molecular mass 5000 g/mol.

Calculate the number average and weight average molecular weight of the polymer. (June resistance. In recent years, Nylon-12 has become a key material for 3D printing and additive
manufacturing applications.
2016)
2. In a polymer sample, 20% molecules have molecular mass 15000 g/mol, 45% molecules
Synthesis of Nylon-12

have molecular mass 25000 g/mol remaining molecules have molecular mass 27000 g/mol. Nylon-12 can be synthesized by ring-opening polymerization of laurolactam (ω-laurolactam),
which is derived from 12-aminododecanoic acid.
Calculate the number average and weight average molecular weight of the polymer. (Dec
[Link] Preparation: Laurolactam (C₁₂H₂₃NO) is obtained from ω-amino dodecanoic
2015) acid by cyclization.
3. In a polymer sample, 20% of molecules have molecular mass 15000g/mol, 35% molecules
have molecular mass 25000 g/mol and remaining molecules have molecular mass 20000
g/mol. Calculate the number and weight average molecular weights of the polymer.
4. A polymer sample contains 100,200,300 and 400 molecules having molecular mass 1000,
2000, 3000 and 4000 respectively. Calculate the number and weight average molecular
weights of the polymer.
5. A polymer sample containing 50, 100 and 150 molecules having molar mass 1000, 2000
[Link] (Ring-Opening Polymerization): The laurolactam undergoes ring-opening
and 3000 respectively. Calculate the number and weight average molecular weights of polymerization under heat (~250°C) and pressure in the presence of a catalyst (e.g., water or
acid). This forms Nylon-12 polymer chains through amide bond formation (-CO–NH-).
polymer. [Dec.2015/ Jan 2016]
6. In a polymer sample, 20% of molecules have molecular mass 15000g/mol, 45% molecules
have molecular mass 25000 g/mol and remaining molecules have molecular mass 27000
g/mol. Calculate the number and weight average molecular weights of the polymer.
[Dec.2015/ Jan 2016]
7. A polymer sample contains 200 molecules of molecular mass 2000, and 200 molecules of
molecular mass 40,000 g/mol. Calculate the number and weight average molecular weights
of polymer. Advantages of Nylon-12 in 3D Printing Applications
8. A polymer sample contains 100 molecules of molecular mass 20,000 g/mol , 300 molecules Excellent Dimensional Stability

of molecular mass 3000 and 500 molecules of molecular mass 5000. Calculate the number 1. Absorbs less moisture compared to other nylons, ensuring accurate printing and

and weight average molecular weights of polymer. [June/July- 2016]. minimal warping.

Nylon-12 High Strength and Flexibility

Nylon-12 (Polyamide-12 or PA-12) is a synthetic polyamide composed of repeating units 1. Combines toughness and impact resistance, ideal for functional prototypes and
derived from 12-amino dodecanoic acid (H₂N–(CH₂)₁₁–COOH). It is a high-performance mechanical [Link] and Durable.
engineering thermoplastic known for its excellent flexibility, toughness, and chemical
2. Provides metal-like performance at much lower density, useful for automotive and
aerospace parts.
Chemical and Abrasion Resistance Vinyl chloride monomers (VCM) undergo free-radical addition polymerization in the presence
1. Can withstand fuel, oil, and chemical exposure, suitable for industrial of a peroxide initiator under controlled heat and pressure to form polyvinyl chloride (PVC).

components.
Low Shrinkage and Smooth Finish.
1. Ensures precise layer bonding and a clean surface finish in Selective Laser Sintering
(SLS) 3D printing.
Temperature Resistance
1. Retains mechanical integrity even at elevated temperatures, enabling engineering grade
applications.
Chlorination of PVC
Recyclable and Reusable Powder
The obtained PVC is exposed to chlorine gas under UV irradiation, during hydrogen atoms
1. In SLS printing, unused Nylon-12 powder can be reused, minimizing waste.
in the PVC chain are replaced by chlorine atoms, leading to the formation of chlorinated
Applications of Nylon-12 in 3D Printing
polyvinyl chloride (CPVC).
• Automotive: Air ducts, fuel lines, clips, and lightweight brackets.
• Aerospace: Structural parts, housings, and functional prototypes.
• Medical: Customized prosthetics, surgical tools (biocompatible grades available).
• Consumer Products: Wearable devices, phone cases, and durable housings.
• Industrial: Gears, fittings, and chemical-resistant components.

Polyvinyl Chloride (PVC)

Polyvinyl chloride (PVC) is a synthetic thermoplastic polymer produced from vinyl chloride
monomer (CH₂=CHCl). It is one of the most widely used plastics in the world due to its
chemical resistance, electrical insulation, and mechanical stability.

PVC is used in electronic, medical, and smart device applications because of its
excellent dielectric and structural properties.

Monomer Preparation

Vinyl chloride monomer (VCM) is produced by chlorination of ethylene:

Properties of PVC

1. PVC is a rigid and strong thermoplastic polymer.

Preparation of PVC
2. It has good chemical resistance to acids, alkalis, and salts.
3. PVC is a good electrical insulator and has high dielectric strength.

4. It is self-extinguishing and flame-retardant due to chlorine content. 2. UV Resistance: Resists yellowing and degradation from sunlight, ensuring longevity.
5. PVC shows good weathering and corrosion resistance.
3. Refractive Index: Around 1.49, useful for lenses.
6. It can be made flexible or rigid by adding suitable plasticizers.
3. Lightweight: Lighter than glass, easier to handle.
Properties of CPVC
4. Strength: Good tensile (30-50 MPa) and compressive strength (85-110 MPa).
1. CPVC is stronger and tougher than normal PVC.
5. Impact Resistance: Better than glass, though can be scratched.
2. It has higher chlorine content, which makes it more rigid.
3. CPVC can withstand higher temperatures (up to about 90–110 °C). 6. Dimensional Stability: Low moisture absorption, reliable in varying conditions.
4. It has good resistance to corrosion and many chemicals.
[Link] Sealing: Can be bonded with heat for sealed microfluidic devices.
5. CPVC is fire-retardant due to its high chlorine content.
8. Electrical Insulator: Low dielectric constant, suitable for electronic components.
Properties of PVC for Device Applications:
9. Biocompatible: Safe for implants, intraocular lenses, dental prosthetics.
1. PVC is a good electrical insulator, making it ideal for wire coatings, cables, and
10. Chemical Resistance: Resistant to water, alcohols, and many solvents, but susceptible to
electronic devices.
strong acids/bases.
2. It has high chemical and corrosion resistance, suitable for sensor housings and
biomedical devices. PMMA in Device Applications
3. PVC is mechanically strong and durable, providing structural stability for device
• Optical devices: Used in lenses, optical fibers, and light guides due to high
components.
transparency.
4. It is self-extinguishing and flame-retardant because of its chlorine content, enhancing
• Display panels: Utilized in LCD and LED screens for light transmission.
device safety.
• Medical devices: Applied in intraocular lenses, bone cement, and dentures.
5. PVC offers good dimensional stability and weather resistance, ensuring long service
• Solar cells: As a transparent protective layer and encapsulant.
life in various environments.
6. It can be easily molded, extruded, and fabricated, enabling cost-effective • Microfluidic devices: Due to easy machining and chemical resistance.

manufacturing of device parts. • Automobile parts: Headlight covers and indicator lamps because of clarity and
weather resistance.
Polymethyl methacrylate (PMMA) or Plexiglass
• Protective shields: Used as a glass substitute in safety windows and aquariums.
PMMA is synthesized by the free-radical bulk polymerization under an inert atmosphere using
Structure property relationship of polymer
methyl methacrylate (MMA) monomers using initiators such as benzoyl peroxide or potassium
persulfate and heat by addition polymerization. Crystallinity:

• Linear polymers have straight chains without side branches or large groups sticking out. This
lets the chains pack closely and neatly, making them crystalline.
Properties of PMMA:
For example, polyethylene has a repeating unit:
1. High Transparency: Up to 92-93% light transmission, better than glass for some uses.
 −𝐶𝐻2 − 𝐶𝐻2 − 𝐶𝐻2 − 𝐶𝐻2 − Elasticity:
so the chain is straight, allowing the sections to line up easily. Elasticity is the ability of a polymer to stretch when a force is applied and to return to its original
shape when the force is removed. This behavior occurs because the molecular chains uncoil
• Polymers like polyvinyl acetate have branches:
during stretching and recoil when the force is released. Polymers exhibit elasticity as long as
These branches keep the chains from fitting closely, making them less crystalline.
the chains do not separate from each other, preventing breakage during extended stretching.
• Factors increasing crystallinity: Elasticity can be enhanced by:

1. Linear and regular chains, especially with polar groups, boost crystallinity. • Introducing cross-links at appropriate molecular positions to connect the chains,
2. Isotactic polymers, where all side groups are on the same side, are more crystalline • Avoiding bulky groups such as aromatic and cyclic structures in the repeating units,
than atactic polymers (random side groups). which hinder chain movement,
• Incorporating more non-polar groups in the chain to increase cohesion between chains,
How Crystallinity Affects Properties
thereby reducing chain separation during stretching.
• High crystallinity makes polymers stronger, stiffer, opaquer, and less soluble in solvents.
• As crystalline increases, solubility decreases.

Tensile strength

Tensile strength is the maximum stress that the material can withstand. Tensile strength of a
polymer depends on the molecular weight. Tensile strength increases with molecular weight up
to 2,000 and thereafter increase is negligible.

Low molecular weight polymers are soft and gummy, but high molecular mass
polymers are tough and heat resistant. Cross-linked polymers are stronger than linear polymers
and less than branched polymer.
Chemical Resistivity:

• Chemical resistivity of a polymer refers to its ability to resist swelling, softening, dissolving,
and loss of strength when exposed to solvents or chemicals.

• Polymers containing polar groups such as –OH or –COOH are typically dissolved by polar
solvents like water or alcohols.

• Polymers with non-polar groups such as –CH₃ and C₆H₅ are not easily dissolved by polar
solvents but dissolve readily in non-polar solvents like petrol, benzene, and carbon
tetrachloride.

• Polymers with a higher degree of crystallinity exhibit greater chemical resistance than their
amorphous counterparts.

• Chemical resistivity increases as the degree of cross-linking in the polymer structure Ex: synthesis of polyaniline.
increases. synthesis of polyaniline, conductions mechanism and its engineering applications.
Synthesis of polyaniline
Plastic deformation (Rheology)
When n number of aniline molecules undergo oxidative polymerization in presence of dil HCl
Some polymers on the application of heat and pressure become soft, flexible, rubbery matter and ammonium persulfate to form polyaniline.
and undergo deformation. On further heating beyond Tm they melt and flow. Such property of
the polymer is called plasticity. On cooling they turn to original state.

CONDUCTING POLYMERS

"An organic polymer with highly delocalized 𝝅-electron system, having electrical conductance
of the order of a conductor is called a conducting polymer". The conducting polymers are
synthesized by doping, in which charged species are introduced in organic polymers having
𝜋-back bone. The important doping reactions, are;

1. Oxidative doping (p-doping), Conductions Mechanism of Polyaniline

2. Reductive doping (n-doping) and
The synthesis of conducting polyaniline is an example of doping technique. In this technique
3. Protonic acid doping (P-doping)
current carrying species ( -ve / +ve ) are created by the protonation of imine nitrogen.
Oxidative doping (p-doping):
NH NH NH NH
In this process, 𝜋 -back bone of a polymer is partially oxidized using a suitable oxidizing agent.
n
This creates positively charged sites on polymer back bone, which are current carriers for
(NH 4)2S2O 8/1MHCl
conduction. The oxidizing agents used for this process are iodine vapour, I2 in CCl4, perchloric
partial oxidation
acid and benzoquinone.
Ex: Synthesis of conducting polyacetylene.
N N NH NH
Reductive doping (n-doping): n
base form of Polyaniline
In n-doping, 𝜋 -back bone of a polymer is partially reduced by a suitable reducing agent. This
protonation
creates negatively charged sites on polymer back bone. These sites are responsible for Aq 1M HCl

conduction. The most common reducing agent used for n-doping is a solution of sodium
H H
naphthalidein tetrahydrofuran. + +
N N NH NH
Ex: Synthesis of conducting polyacetylene. Cl
-
Cl
-

n
Protonic acid doping (p-doping):
Polyaniline exists in several different oxidation states of which only emaraldine salt (Reduced
In this technique, current carrying charged species (-ve/+ve) are created by the protonation of
form aniline) conducting. Polyaniline is partially oxidized using a suitable oxidizing agent, into
imine nitrogen.
a base form of aniline which contains alternating reduced and oxidized forms of aniline
 polymer back [Link] form of aniline treated with aqueous HCl (1M), undergoes protonation MODULE-4
of imine nitrogen atom, creating current carrying species (+ve) in the polymer backbone. These Sensors and Corrosion Science
charges are compensated by the anions (Cl-) of the doping agent giving the corresponding salt. Sensors: Introduction, terminologies-Transducer, Actuators and Sensors. Conductometric sensor-
principle, construction and its application in the estimation of acid mixture. Colorimetric sensor-
Applications principle, instrumentation and its application in the estimation of copper in PCB. Electrochemical
gas sensors- principle, construction and its application in the detection of NOx and SOx in air
• Conductive coatings for electronics and textiles (antistatic applications). sample. Biosensor-principle, construction and working for the detection of glucose in biofluids.
• Corrosion protection on metals through protective coatings.
Corrosion: Introduction, electrochemical theory of corrosion, types of corrosion-differential metal
• Chemical and biosensors for detecting gases, humidity, and biomolecules. and differential aeration corrosion-waterline and pitting corrosion. Corrosion control-galvanization
• Electrode material in batteries, super capacitors, and rechargeable devices. and anodization. Vapour corrosion inhibitors for protecting computer circuit boards, corrosion
penetration rate (CPR)-definition and numerical problems.
• Flexible electronics such as OLEDs, wearable sensors, and smart textiles.
• Electromagnetic interference (EMI) shielding in electronic devices. Introduction:
A sensor is a device that measures or detects a physical or chemical quantity such as temperature,
• Environmental and biomedical applications, including water purification and drug
pressure, humidity, ion concentration, light, sound, or motion. The sensor converts this quantity into
delivery. an electrical signal that can be processed by computers or electronic systems.

Sensor: Sensors are electronic or electrochemical devices that detect and measure physical or
chemical phenomena and convert them into electrical signals.

Examples:

o pH Sensor (glass electrode): Detects H⁺ ion concentration in solutions.

o Conductivity Sensor: Measures the ionic conductivity of an electrolyte.

o Gas Sensor: Detects CO₂, H₂S, or O₂ levels in chemical or environmental systems.

Transducer: A transducer is a device that converts a non-electrical physical or chemical quantity

into an electrical signal.

Examples in Chemistry:

o Electrochemical Oxygen Sensor: Converts dissolved oxygen concentration into an

electrical current.

Actuator: An actuator is a device that receives an electrical signal and produces a physical or
chemical action. It is often used for control in experiments.

• Examples in Chemistry/Electrochemistry:

o Electrolysis Cell: Converts electrical current into chemical products (H₂ and O₂
gases).

Receptor: it is a chemical element which is capable of interacting with analyte specifically and
selectively. It produces signal corresponding to interaction in the form of change in potential,
conductivity heat, pH etc.

Subject code: 1BCHES102/202 Page 1

Construction

The electrode system is a conductivity cell, made up of two platinum foils of unit cross-sectional
area separated by unit distance. The volume between electrodes = 1 cm³. Conductance of unit
volume is called specific conductance (κ) and is given by:

Electrochemical sensor:
An electrochemical sensor is a device that detects chemical substances by converting their
concentration into an electrical signal through redox reactions. It typically consists of a working, κ = (1/R) × (l/a)
reference, and counter electrode immersed in an electrolyte. The measured signal (current, voltage, where R = resistance, and l/a = cell constant.
or conductivity) corresponds to the analyte concentration. Based on the detection principle, they are An alternating current (AC) source is used to prevent polarization, and the output is measured by a
classified as potentiometric, amperometric, or conductometric sensors. They offer high sensitivity, conductometer.
selectivity, and fast response. Working:
Examples: pH electrodes, glucose sensors, and oxygen sensors. When a potential difference is applied, an electric field is generated in the electrolyte. Cations
Applications: environmental monitoring, biomedical diagnostics, food quality control, and industrial migrate toward the cathode, and anions toward the anode. At electrodes, ions are neutralized or
process monitoring. deposited, producing a chemical change, which is sensed and converted to an electrical signal by the
transducer.
Conductometric Sensors: Principle, Construction, and Application in Acid
Estimation of Acid Mixture
Mixture Estimation
Example: Mixture of HCl and CH₃COOH titrated with NaOH

• Initially, high conductance due to free H⁺ ions from HCl.

Definition
• As NaOH is added, H⁺ ions are neutralized, conductance decreases sharply due to Highly
Conductometric detection is based on measurement of specific conductance of an analyte and is
preferable because it can be applied for detection of both electroactive and electro inactive species. The mobile H⁺ ions are replaced by less mobile Na⁺ ions,
conductivity electrodes can either be in contact with the solution or insulated using a thin layer.
Conductivity detection is mostly associated with capillary electrophoresis (CE). HCl+NaOH→NaCl+H2O

Principle • After HCl is neutralized, acetic acid starts neutralizing; conductance decreases more slowly
The principle is based on the dissociation of analyte into ionic species under applied electric felid. due to partial dissociation.
This leads to migration of towards oppositely, charged electrodes, results in change in electrical CH3COOH+NaOH→CH3COONa+H2O
conductivity of the solution. The change in the conductivity is measured by the conductivity sensor.
During titration, conductivity changes as ions are consumed or replaced. In acid mixture estimation, • After all acids are neutralized, excess OH⁻ ions increase conductance sharply.
the neutralization of a strong acid (HCl) and a weak acid (CH₃COOH) with a strong base (NaOH)
produces characteristic conductivity changes, allowing their individual quantification.

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 Application of conductometric sensor

• It is used for to estimate the acid bases and their mixtures.

• To check the amount of ionic impurities in water samples.

• In measuring acidity or alkalinity of sea water or fresh water.

• Used in enzyme catalyzed reaction to determine the analyte concentration and enzyme activity

• Advanced Nanoparticle-Based Biosensors for Diagnosing Foodborne Pathogens

• Microfluidic electrochemical devices for pollution analysis. Working:

• It is used for DNA Detection as a biomedicine/biosamples. Monochromatic light passes through the analyte solution. Part of the light is absorbed by the
deep blue colored complex. Absorbance depends on concentration and path length.
Colorimetric sensor-principle, instrumentation and its application in the Detector converts light intensity into electrical signal → displayed as concentration.
estimation of copper in PCB.
Estimation of Copper in PCB Using Ammonia Complex:

Draw out 5,10,15 & 20 Cm3 of given copper sulphate solution into four separate 50 cm3
Definition
standard flasks. Add 5 cm3 of NH3 to each one of them and also into the test and blank
These are the electronic components designed to convert incident light rays to interacted with analyte solution, dilute up to the mark with distilled water and mix well. Measure the absorbance of
into measurable electrical signals for detecting and measuring physical or chemical properties of each of these against blank solution (only ammonia and water) at 620 nm. Plot a graph of
analyte. absorbance (OD) (ordinate) against concentration of copper (abscissa) and determine the
Principle of Colorimetric Sensor: concentration of copper in the e-waste solution.

• Optical sensors work on the interaction of electromagnetic radiation (UV, visible, or IR) with • Copper ions (Cu²⁺) react with ammonia (NH₃) to form a deep blue complex:
a chemical species. Interaction can result in absorption, emission, scattering, or reflection of
Cu2+ + 4NH3 → [Cu(NH3 )4]2+
light. The intensity of light after interaction provides information about the analyte
concentration. The intensity of the blue color is proportional to the copper concentration.
Measurement is performed at ~620 nm using absorbance, following Beer-Lambert Law: Application of Optical Sensors
o Used in the hospitals and laboratories, for the estimation of biochemical samaples like
𝑨 = 𝜺𝒍𝒄 plasma, serum, urine ect,.
Where: o Used for quantitative estimation of glucose, proteins, and other biochemical
A = absorbance, ε = molar absorptivity, l = path length, c = analyte concentration compounds.
o Used to detect the hazardous or heavy metals such as cadmium present in the
For copper estimation in PCB using ammonia: environmental samples.
o Used in on-site detection of pesticides in agricultural products, food products and soil
Instrumentation : contamination.
1. Light Source: Provides monochromatic or filtered light at the wavelength absorbed by
the copper-ammonia complex (~620 nm). Examples: LED, tungsten lamp.
Electrochemical Gas Sensors:
2. Filters / Monochromator: Selects the desired wavelength.
Electrochemical gas sensors are devices that detect specific gases by chemically reacting with the
3. Sample Holder / Cuvette: Holds the solution of the copper-ammonia complex. target gas and converting this reaction into an electrical signal. They are widely used in
environmental monitoring, industrial safety, and automotive emission testing.
4. Photocell / Detector: Converts transmitted or absorbed light into an electrical signal.

5. Signal Processor / Display: Records and displays the signal as absorbance or concentration.
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Electrochemical gas sensors- principle, construction and its application in the Advantages:
detection of NOx and in air sample • Real-time NOx detection
Principle of Operation • High sensitivity and selectivity

The sensor works on the oxidation or reduction of the target gas at an electrode, which produces a • Compact, low-power operation suitable for continuous monitoring
current proportional to the gas concentration.
• High sensitivity (ppb level)
• The target gas diffuses through a gas-permeable membrane into the sensor. • Selective detection of NO and NO₂
• Fast response and recovery
• It reacts at the working electrode in the presence of an electrolyte, producing electrons.
• Portable and compact
• The measured current is directly proportional to the gas concentration in air.
• Low power requirement.
For NOx (NO and NO₂) detection, the reactions are:
Principle
1. Oxidation of NO at the working electrode: Electrochemical gas sensors work on the principle of redox reactions occurring at the electrode–
2𝑁𝑂 + 𝑂2 → 2𝑁𝑂2 + 2𝑒− electrolyte interface. When a target gas (e.g., SO₂) diffuses into the sensor, it undergoes oxidation or
2. Reduction of NO₂ (in some sensor types): reduction at the working electrode. This reaction generates a current proportional to the gas
𝑁𝑂2 + 2𝑒− → 𝑁𝑂 + 𝑂2− concentration, which can be measured and correlated with its amount in the air sample.

These electron transfers generate a current that can be calibrated to determine the NOx
SOx Electrochemical gas sensors- principle, construction and its application in
concentration in the air sample.
the detection of NOx and in air sample
Construction of the Sensor Construction
An electrochemical gas sensor typically consists of:
• Working Electrode (WE): Metal oxide-coated electrode where NOx reduction occurs.
• Reference Electrode (RE): Usually gold; maintains stable potential.
• Counter Electrode (CE): Completes the circuit.
• Electrolyte: Liquid or solid medium that facilitates ion transport between electrodes.
• Gas-permeable Membrane: Controls diffusion of NOx gas and prevents electrolyte leakage.
• Housing: Encases the sensor and provides electrical connections.
Working

NOx gas diffuses through the membrane to the working electrode. At the metal oxide-coated
working electrode, NOx is reduced to NO, producing a flow of electrons. The current
generated flows through the circuit and is measured to determine the NOx concentration.

Applications
• Working electrode (WE): coated with a catalyst where the analyte gas undergoes
• Environmental monitoring: Air quality measurement in urban and industrial areas. oxidation/reduction.
• Counter electrode (CE): balances the current by completing the circuit.
• Automotive emission control: Detecting NOx in exhaust gases. The primary use is in modern
diesel vehicles (light and heavy-duty) with Selective Catalytic Reduction (SCR) systems • Reference electrode (RE): maintains a stable potential for accurate measurement.
• Electrolyte: ionic medium that facilitates charge transfer (commonly acidic or alkaline
• Industrial safety: Monitoring NOx levels in workplaces to prevent health hazards. solution).
• Gas diffusion membrane allows controlled diffusion of the gas into the sensor, preventing
interference.
• Housing: protects the components and ensures selective entry of the gas.

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Application in SOx Detection (e.g., SO₂ in Air Samples)
• Detection principle:
o At the working electrode, SO₂ undergoes oxidation:
SO₂ + 2H₂O → SO₄²⁻ + 4H⁺ + 2e⁻
o At the counter electrode, oxygen reduction occurs to complete the electrochemical circuit:
O2 + 4H+ + 4e− → 2H2O

oThe generated electrons produce a measurable current proportional to SO₂

concentration.
Applications
▪ Monitoring SOx emissions in power plants, refineries, and cement industries
Working:
▪ Air quality monitoring to control pollution and acid rain
• The operation of a first-generation glucose biosensor involves the following steps:
▪ Worker safety in chemical industries and mines
• A small volume of biofluid (such as blood or urine) is introduced onto the biosensor surface.
▪ Automotive and marine exhaust emission control
• Glucose molecules in the sample are specifically oxidized by the enzyme glucose oxidase
▪ Corrosion prevention in industrial equipment and pipelines
(GOx). During this step, the coenzyme flavin adenine dinucleotide (FAD) present in GOx is
reduced:
• Practical use:
Glucose + GOx(FAD) → Gluconic acid + GOx(FADH𝟐)
o Widely employed in air quality monitoring stations to measure SO₂ levels in urban
and industrial environments. • The reduced enzyme GOx(FADH₂) is then re-oxidized by molecular oxygen, producing
o Used in occupational safety to detect SO₂ in confined spaces (factories, smelters,
hydrogen peroxide:
refineries). GOx(FADH𝟐) + 𝑶𝟐 → GOx(FAD) + H𝟐𝑶𝟐
o Incorporated in portable detectors for environmental and health monitorin • At the working electrode, the hydrogen peroxide undergoes electrochemical oxidation,
releasing protons and electrons:
Glucose Biosensor: Principle, Construction and Working 𝑯𝟐𝑶𝟐 → 𝑶𝟐 + 𝟐𝑯+ + 𝟐𝒆−
• The released electrons generate a measurable current, which is directly proportional to the
Principle: glucose concentration in the original sample.

Glucose biosensors are analytical devices that measure glucose concentration in biofluids such as Applications
blood, urine, and saliva. They function by combining a biological recognition element with a • Medical diagnosis and continuous monitoring of blood glucose in diabetic patients.
transducer to generate an electrical signal proportional to glucose concentration.
• Point-of-care testing in hospitals and home-based glucose meters.
Construction: • Food and beverage industry for sugar content analysis and fermentation control.
• Biotechnology and bioprocess monitoring (cell culture and fermentation systems).
• Biorecognition layer: Contains immobilized glucose oxidase enzyme, fixed using cross- • Clinical research and drug testing.
linking agents (e.g., glutaraldehyde) or entrapped in polymeric matrices such as Nafion. • Wearable and implantable biosensor devices.

• Transducer element: A modified electrode made from materials like graphite rod, glassy
carbon, or gold nanostructures, which converts the biochemical reaction into an electrical
signal.

• Nanomaterial modifications: Incorporation of carbon nanotubes, gold nanoparticles, or

Prussian blue to enhance electron transfer and provide larger surface area for enzyme
attachment.

• Protective membrane: Covers the sensor to prevent enzyme leaching while permitting
glucose diffusion toward the enzyme layer.

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anodic region through the metal. Depending on the surrounding medium, four possible reduction
Corrosion: reactions occur at the cathodic region:

Introduction: Corrosion is a process of destruction or deterioration of metal by the environment 1) Hydrogen Liberation (Absence of Oxygen):
through chemical or electrochemical reactions. (a) In acidic medium without oxygen:
2H⁺ + 2e⁻ → H₂↑
Most of the metals and alloys undergo corrosion except the noble metals. Corrosion is like
(b) In neutral or alkaline medium without oxygen, hydroxide ions form with simultaneous
“Cancer” for the metals.
hydrogen liberation:
Eg: Rusting of Iron- it is due to formation of hydrated ferric oxide. 2H₂O + 2e⁻ → 2OH⁻ + H₂↑

2) Oxygen Absorption (Presence of Oxygen):

Types of corrosion: (a) In acidic medium with oxygen:
1. Dry Corrosion: Corrosion taking place in the absence of moisture that is direct 2H⁺ + ½O₂ + 2e⁻ → H₂O
chemical reaction taking place between metal and dry gases.
2. Wet Corrosion: Corrosion taking place in the presence of moisture or aqueous wet (b) In neutral or alkaline medium with oxygen, hydroxide ions form:
environment.
H₂O + ½O₂ + 2e⁻ → 2OH⁻

Electrochemical Theory of Corrosion: Formation of Rust:

Corrosion of iron produces Fe²⁺ ions at the anode and OH⁻ ions at the cathode. These ions diffuse
• Corrosion occurs due to the formation of anodic and cathodic regions on the same or toward each other to produce insoluble ferrous hydroxide:
different metals in a conducting medium. Fe²⁺ + 2OH⁻ → Fe(OH)₂
• At the anode, oxidation takes place, and the metal corrodes into ions by releasing
electrons.
In an oxidizing environment, ferrous hydroxide oxidizes to ferric oxide, forming yellow rust
• At the cathode, reduction occurs by consuming the liberated electrons, keeping the (hydrated ferric oxide):
cathodic region protected. 4Fe(OH)₂ + O₂ + 2H₂O → 2[Fe₂O₃·3H₂O] (Brown rust)

• Corrosion continues as long as anodic and cathodic reactions proceed simultaneously,

influenced by impurities and oxygen concentration differences.
Types of corrosion

Differential Metal Corrosion (galvanic corrosion):

Differential metal corrosion occurs when two dissimilar metals are in contact with each other and are
exposed to corrosive environment. The two metals differ in their electrode potential. The metal with
lower electrode potential acts as anode, the metal with higher electrode potential acts as cathode. The
potential difference between two metals is a driving force for corrosion. Here anode undergoes
corrosion.
Eg: When iron is in contact with copper.

At the Anodic Region:

Iron liberates Fe²⁺ ions and electrons at the anodic region:
Fe → Fe²⁺ + 2e⁻

At the Cathodic Region:

Chemical species in the cathode's surroundings undergo reduction by accepting electrons from the
Subject code: 1BCHES102/202 Page 10 Subject code: 1BCHES102/202 Page 11
 Fe has lower electrode potential when compared to copper. Hence iron undergoes oxidation and get
corroded.
at anode: Fe → Fe2+ + 2e− Water line corrosion:
at cathode: H2O+ 12 O2 + 2𝑒− → 2𝑂𝐻−
When a steel/Iron tank is partially filled with water for a long time, the inner portion of the tank
overall reaction: Fe2+ + 2OH− → Fe(OH)2 ↓ (insoluble & unstable)
below the water line is exposed only to dissolved oxygen whereas the portion above waterline
2Fe(OH) +H2O+ 2 O2 → Fe2O3.3H2O (Rust)
1
2 is exposed to more oxygen. Thus, the portion below the water acts as anode and undergoes
corrosion. The upper portion acts as cathode and it is unaffected.
Other examples:
1. Steel screws in copper sheet at anode: Fe → Fe2+ + 2e−
2. Steel screws with copper washer at cathode: H2O+ 1 O2 + 2𝑒− → 2𝑂𝐻−
2
3. Nut and bolts are made of different metals.
overall reaction: Fe2+ + 2OH− → Fe(OH)2 ↓ (insoluble & unstable)
Mechanism (Step-by-Step)
2Fe(OH) +H2O+ O2 → Fe2O3.3H2O (Rust)
1
Two different metals (e.g., Al or Fe and copper) are connected.
• Electrolyte (rainwater, seawater, moisture) forms a conductive path.
• The metal that is more reactive becomes the anode:
M → M2+ + 2𝑒 −
• Electrons travel to the cathodic metal, where reduction occurs:
O2 + 2𝐻2 𝑂 + 4𝑒 − → 4𝑂𝐻 −
The anodic metal dissolves and undergoes corrosion

Differential aeration corrosion:

Differential aeration corrosion occurs when a metal surface is exposed to different
oxygen concentration. Part of metal exposed to higher oxygen concentration acts as
cathode and metal exposed to lower oxygen concentration acts as anode. The anodic Mechanism
region undergoes oxidation and gets corroded.
• The region just below the waterline becomes anodic (less oxygen → more corrosion).
Eg: When iron rod partially dipped in • The region above the waterline becomes cathodic (more oxygen → less corrosion).
• At the anode, the metal dissolves:
water.
M → M2+ + 2𝑒 −
at anode: Fe → Fe2+ + 2e− • At the cathode, oxygen is reduced:
at cathode: H2O+ 12 O2 + 2𝑒− → 2𝑂𝐻− O2 + 2𝐻2 𝑂 + 4𝑒 − → 4𝑂𝐻 −
overall reaction: Fe2+ + 2OH− → Fe(OH)2 ↓ (insoluble & unstable) • Because the anodic area is concentrated at the waterline, corrosion rate is maximum at this interface,
forming a narrow, aggressive corrosion band.
2Fe(OH) +H2O+ 2 O2 → Fe2O3.3H2O (Rust)
1
2
Other examples:

a) Part of nail inside the wall undergoes corrosion.

b) Partially buried pipeline in soil undergoes corrosion.
c) Partially filled iron tank undergoes corrosion inside water.

This differential aeration corrosion is divided into two types

i) Waterline
j) Pitting corrosion

Subject code: 1BCHES102/202 Page 12 Page 13

Pitting Corrosion: Preventing the formation of galvanic cells.

Protective Coatings: Application of protective coating is one of the important methods of

corrosion control. The protective coating protects the metal from corrosion by acting as a
barrier between the metal and the corrosion environment. The principle types of coatings
applied on the metal surface are

a) Metal coating b) Inorganic coating c) Organic coating

a) Metal coating: The process of covering base metal with a layer of protective metal
isknown as metal coating. They are divided into two types,

Definition i) Anodic coatings: It is produced by coating a metal surface with more active metalswhich acts
Pitting corrosion is a highly localized form of corrosion in which small holes or pits are formed on the as anodic to base metal.
metal surface due to the breakdown of a protective passive film.
Corrosion Control: Corrosion can be controlled by protecting the surface of the metal or by
When a dust particle settles on an iron surface, the area beneath experiences reduced aeration, acting as the preventing the formation of galvanic cells.
anode, while the exposed surface acts as the cathode. Corrosion initiates under the dust particle, leading to
the formation of deep cavities or pits. Inside the pit, oxygen is depleted, and metal cations accumulate, Protective Coatings: Application of protective coating is one of the important methods of
creating a highly aggressive local environment that accelerates metal dissolution. corrosion control. The protective coating protects the metal from corrosion by acting as a
The anodic barrier between the metal and the corrosion environment. The principle types of coatings
reaction occurs within the pit. applied on the metal surface are
at anode: Fe → Fe2+ + 2e− a) Metal coating b) Inorganic coating c) Organic coating
at cathode: H2O+ 1 O 2 + 2𝑒− → 2𝑂𝐻−
2
b) Metal coating: The process of covering base metal with a layer of protective metal
overall reaction: Fe2+ + 2OH− → Fe(OH)2 ↓ (insoluble & unstable) isknown as metal coating. They are divided into two types,

2Fe(OH) +H2O+ O2 → Fe2O3.3H2O (Rust)2

1
i) Anodic coatings: It is produced by coating a metal surface with more active
Causes of Pitting Corrosion metalswhich acts as anodic to base metal.

• Presence of chloride ions (Cl⁻) (sea water, salts)

• Damage or breakdown of passive oxide layer Eg: Galvanization of Iron
• Stagnant conditions
• Low oxygen concentration Galvanization is a process of coating base metal like iron or its alloy surface with anodic and
• Surface defects or impurities active Zn metal. One of the important characteristics of anodic coating is even if coating is
ruptured, base metal does not undergo corrosion because base metal exposed to environment
Mechanism will be cathodic in nature with respect to coating metal.
• Breakdown of passive layer occurs at a small spot.
• That spot becomes the anode, and the nearby metal becomes the cathode.
• At the anodic point:
M → M𝑛+ + 𝑛𝑒 −
• Metal ions accumulate in the pit, attracting Cl⁻ ions, forming metal chlorides.
• These metal chlorides hydrolyze to produce H⁺ ions, making the pit highly acidic.
• The acidic environment accelerates further dissolution → pit grows deeper.

Page 14 Page 15
 Galvanization process involves following steps:
Uses: It is used as soap boxes, tiffin boxes, window frames etc. Anodic films are also used for
▪ Metal surface is washed with organic solvents to remove organic matter. number of cosmetic effects.
▪ Rust and other deposits removed by washing with hot dil. H2SO4 is called Vapour Corrosion Inhibitors (VCIs) for Protecting Computer Circuit Boards
picklingprocess.
▪ Then it is well washed with water. • Concept of VCIs:
Vapour Corrosion Inhibitors are chemical compounds such as Carboxylates (e.g., benzoates,
▪ It is air dried by-passing hot air. sebacates) – effective for steel and copper. that slowly vaporize and release protective molecules into the
▪ Then it is dipped in molten zinc, maintained at 430-4500C and covered with flux of surrounding atmosphere.
ammonium chloride and zinc chloride to increase adhesion property. • Adsorption on Metal Surfaces:
▪ Excess of zinc on surface is removed by passing a pair of hot rollers, which removes excess of The vaporized inhibitor molecules travel through the air and adsorb onto the exposed metal
zinc and produces thin coating. surfaces of the circuit board, such as copper tracks, connectors, and solder joints.
Application: Galvanized materials are used in fencing wire, buckets, bolts, nuts, nails, screw etc.
• Formation of Protective Film:
Once adsorbed, the molecules form a thin, invisible, and stable protective film. This layer
Inorganic coating: It is chemical conversion coating where metal surface is converted to a
compound by chemical or electrochemical process which forms barrier. There are two prevents corrosive agents like moisture, oxygen, and acidic contaminants from reacting with the
types metal.

• Neutralization of Aggressive Species:

Anodizing (Anodizing of aluminium VCIs can neutralize or block the action of corrosive ions (e.g., chlorides or sulfates) present in
the environment, reducing the electrochemical reactions that cause corrosion.

• Self-Replenishing Mechanism:
If the protective film is disturbed or partially removed, nearby vapor molecules continuously
replenish the coating, ensuring long-term protection.

• Advantages for Circuit Boards:

Non-conductive and safe for electronic components.

Protects even in enclosed spaces without direct application.

Extends the service life of circuit boards stored or operated in humid or polluted environments

It is a electrochemical process which forms protective passive (non-reactive) oxide film on metal
surface. Here aluminium metal is made as anode in a suitable oxidizing electrolyte like sulphuric acid,
chromic acid, oxalic acid bath at a temperature of 30 - 400 C and moderate current density. A thin film
of Al2O3is deposited on surface, this acts as protective layer preventing the corrosion. This film tends to
be porous and provides good adherence for paint and dyes.

At anode: 2Al + 3H2O → Al2O3 + 6H+ + 6e− (Oxidation)

At cathode: 6H+ + 6e− → 3H2𝗍

Overall reaction: 2𝐴𝑙 + 3𝐻2𝑂 → 𝐴𝑙2𝑂3 + 3𝐻2O

Page 16 Page 17

Corrosion penetration rate (CPR)/ corrosion rate: 1 Square Centimeter = 0.155 square inch 1 square inch = 6.4516 sq cm

Corrosion penetration rate is defined in three ways Problems:

i) A thickness of brass sheet of area 400 inch2 is exposed to air near the ocean. After two years period
The speed at which any metal in a specific environment deteriorates due to chemical it was found to experience a weight loss of 375g due to corrosion. If the density of Brass is 8.73
reaction in the metal when it is exposed to a corrosive environment. g/cm3. Calculate the CPR in mm/year mpy.
The amount of corrosion loss per year in thickness.
Solution:
The speed at which corrosion spreads to the inner portions of a material.
The speed or rate of deterioration depends on the environment conditions and the type of • Given Area 𝑨 = 𝟒𝟎𝟎 in𝟐
metalunder study. The equation for CPR (Corrosion Penetration Rate) is:
• Weight loss 𝑾 = 𝟑𝟕𝟓 g = 𝟑𝟕𝟓, 𝟎𝟎𝟎 mg
Formula:
• Density of Brass 𝝆 = 𝟖. 𝟕𝟑 g/cm𝟑
𝑲𝑾
𝑪𝑷𝑹 = Time 𝒕 = 𝟐 years = 𝟐 × 𝟑𝟔𝟓 × 𝟐𝟒 = 𝟏𝟕, 𝟓𝟐𝟎 hours
𝝆𝑨𝒕
CPR in Mpy
Where: 𝐾 = 534 534 × 375000
CPRmpy =
𝑊 = 375,000 mg 8.73 × 400 × 17520
• CPR = Corrosion Penetration Rate (measured in miles per year, mpy) 1 mpy = 0.001 inch per year
𝜌 = 8.73 g/cm 3
• K = A constant 𝐴 = 400 in2
• 200250000
W = Total weight loss due to exposure to a corrosive environment 𝑡 = 17,520 hrs CPRmpy = ≈ 3.27 mpy
• ρ = Density of the material 61186560
• A = Surface area of the exposed metal CPR in Mmpy_-𝐾 = 87.6 87.6 × 375000
Convert area from in² to cm²: CPR mmpy =
• t = Time taken for the loss of metal (exposure time) 8.73 × 2580.64 × 17520
𝐴 = 400 in2 = 400 × 6.4516 = 2580.64 cm2
𝑊 = 375,000 mg, 32850000
𝜌 = 8.73 g/cm3, = ≈ 0.0833 mm/year
394248859.4
CPR mpy mmpy 𝑡 = 17,520 hrs

K 534 87.6
1. A metal iron plate was found in a vessel containing acidic media, it was estimated that the
W mg mg original area was 20 inch2 that approximately 1.2 kg had corroded. Assuming a corrosion
penetration rate of 400mpy for this iron in acidic, calculate time in years, density of iron 7.87g/
𝜌 g/cm3 g/cm3 cm3.
Given:
A In2 cm2
𝐾⋅𝑊
Area (A) = 20 in² CPR =
T hrs hrs Weight loss (W) = 1.2 kg = 1,200,000 mg 𝜌⋅𝐴⋅𝑡
CPR = 400 mpy Solve for time 𝑡:
Conversions: 𝐾⋅𝑊
Density of iron (ρ) = 7.87 g/cm³ 𝑡=
𝜌 ⋅ 𝐴 ⋅ CPR
1 Gram = 1000 Milligram or 103 K (for mpy) = 534
We are solving for time (t in hours), then 534⋅1,200,000 640,800,000
1 Kg = 1000000 Milligram or 106 𝑡= = ≈ 10,175.2 hours
convert to years 7.87⋅20⋅400 62,960

1 Day = 24 Hours Convert hours to years:

1 Month = 30 days = 30 * 24 Hours 10,175.2 10,175.2
Years = = ≈ 1.16 years
1 Year = 1 * 365 * 24 Hours 24 ⋅ 365 8760

Page 18 Page 19
 2. A thick steel sheet of area 400 inch² is exposed to moist air. After 2 years of exposure, it was For mmpy:
found to experience a weight loss of 375 g due to corrosion. If the density of steel is 7.9 g/cm³, 87.6 × 385,000 33,726,000
calculate CPR in mpy and mmpy. CPRmmpy = = = 1.085 mmpy
7.9 × 450 × 8,760 31,099,800

where:
4. A steel sheet with an area of 400 cm² (or 62 in²) is exposed to moist air. After one year, it is
𝐾 is a constant (534 for mpy, 87.6 for mmpy) found to have lost 375 grams in weight due to corrosion. Given that the density of steel is 7.9
Weight loss: 375 g = 375,000 mg g/cm³, calculate the corrosion penetration rate (CPR) in both mils per year (mpy) and millimeters
Area: 400 in2 = 400 × 6.4516 = 2,580.64 cm2 per year (mmpy). Use the constants K = 534 for mpy and K = 87.6 for mmpy in your
Time: 2 years = 2 × 365 × 24 = 17,520 hours calculations.
Density: 7.9 g/cm3
Given Data
• Area (𝐴): 400 cm2 (also given as 62 in2)
Calculate CPR in mpy
• Weight loss (𝑊): 375 g = 375,000 mg
534 × 375,000 200,250,000 • Density (𝜌): 7.9 g/cm3
CPRmpy = = = 3.62 mpy
7.9 × 400 × 17,520 55,286,400 • Time (𝑡): 1 year = 365 × 24 = 8,760 hours
• Constants: 𝐾 = 534 for mpy, 𝐾 = 87.6 for mmpy
Apply the CPR Formula
Calculate CPR in mmpy
𝐾×𝑊
87.6 × 375,000 32,850,000 CPR =
𝜌×𝐴×𝑡
CPRmmpy = = = 0.092 mmpy
7.9 × 2,580.64 × 17,520 357,646,755.2
For mpy:
534 × 375,000 200,250,000
3. A steel plate with a surface area of 450 cm² is exposed to air in a coastal environment. After one CPRmpy = = = 46.72 mpy
7.9 × 62 × 8,760 4,287,672
year, the plate shows a weight loss of 385 grams due to corrosion. Given that the density of
steel is 7.9 g/cm³, calculate the corrosion rate in both mils per year (mpy) and millimeters per
year (mmpy). Use k = 534 for mpy and k = 87.6 for mmpy in your calculations.
For mmpy:
87.6 × 375,000 32,850,000
Given Data CPRmmpy = = = 1.19 mmpy
7.9 × 400 × 8,760 27,676,800
Area (𝐴): 450 cm2 = 450 cm2 ÷ 6.4516 = 69.8 in2
Weight loss (𝑊): 385 g = 385 g = 385,000 mg
Density (𝜌): 7.9 g/cm3
Time (𝑡): 1 year
Constants: 𝐾 = 534 for mpy, 𝐾 = 87.6 for mmpy
Time in hours: 1 year = 365 × 24 = 8,760 hours
𝐾×𝑊
CPR =
𝜌×𝐴×𝑡

For mpy:
534 × 385,000 205,890,000
CPRmpy = = = 42.74 mpy
7.9 × 69.8 × 8,760 4,819,927.2

Subject code: 1BCHES102/202 Page 20 Subject code: 1BCHES102/202 Page 21

• Office Equipment: Printers, photocopiers, scanners, fax machines, and other office
machinery.
• Lighting Equipment: Fluorescent lamps, LED bulbs, and other lighting devices.
• Medical Devices: Monitoring instruments, diagnostic machines, pacemakers, defibrillators,
and other medical equipment.
DEPARTMENT OF CHEMISTRY • Industrial Equipment: Motors, pumps, transformers, and other machinery used in industry.
• Electrical and Electronic Tools: Power drills, saws, gardening tools, and similar electronic
MODULE-5
tools.
Green Materials and E-Waste Management • Toys and Recreational Devices: Electronic toys, video game consoles, and electronic musical
instruments.
Green Chemistry: Introduction, properties and applications of green solvents for server heat • Chargers and Batteries: Non-functional or obsolete chargers and batteries from various
management. Synthesis and properties of glycerol trioleate ester and its uses in IT infrastructure devices.
applications. Green synthesis of ZnO nanoparticles and its uses in magnetic Radio Frequency
Identification (RFID) and Internet of Nano Things (IONT) system applications.
Composition of e-waste:
Biomaterials: Introduction, synthesis and properties of polylactic Acid (PLA) and polyethylene
glycol (PEG) and its uses in touch screen applications. Synthesis and properties of Alginate • Metals: E-waste contains valuable metals such as copper, gold, silver, aluminum, ferrous
Hydrogel and its uses in Brain-Computer Interfaces (BCIs) applications. metals (iron and steel), and special metals like cobalt, indium, tin, and antimony.
• Plastics: Many electronic devices include plastic components such as casings, insulation, and
E-waste: Introduction, sources, composition of e-waste, effects of e-waste on environment and cables, constituting about 21% of e-waste.
human health, Artificial intelligence in e-waste management, extraction of gold from e-waste by • Glass: Found mainly in screens, lenses, and cathode ray tubes (CRTs).
bioleaching method. • Circuit boards: Printed circuit boards (PCBs) contain a complex mixture of metals and
hazardous substances.
• Batteries: Contain hazardous materials such as lead, mercury, cadmium, lithium, nickel, and
Define waste. cobalt.
Waste refers to any material that is not wanted or needed and is discarded or disposed of. • Hazardous materials: Include heavy metals (lead, mercury, cadmium, arsenic, beryllium,
hexavalent chromium), flame retardants (brominated flame retardants), polychlorinated
Classification of Waste: Waste can be classified into several categories including biphenyls, and other toxic chemicals.
household waste, industrial waste, hazardous waste, and e-waste (waste from electronic devices). • Other materials: Components of ceramics, rubber, wood, plywood, and concrete found in
some electronic devices.
Define waste management. Waste management refers to the collection, transportation,
treatment, and disposal of waste materials to reduce their negative impact on the environment Effects of E-Waste on Environment and Human Health
and human health.
Define E-waste management. E-waste management refers to the processes and systems used to • Soil contamination: Toxic metals (lead, cadmium, mercury) seep into soil, reducing fertility
collect, transport, treat, and dispose of electronic waste (e-waste) in an environmentally and entering the food chain.
responsible and safe manner. Water pollution: Leaching of heavy metals and acids contaminates groundwater and surface
water sources.
Sources of electronic waste (e-waste): The main sources of electronic waste (e-waste) include: • Air pollution: Open burning of plastics and circuit boards releases dioxins, furans, and other
harmful gases.
• Household Appliances: Refrigerators, washing machines, microwaves, vacuum cleaners,
• Loss of biodiversity: Toxic chemicals harm aquatic life, plants, and animals, disrupting
irons, air conditioners, and dishwashers.
ecosystems.
• IT and Telecommunication Devices: Computers, laptops, printers, smartphones, tablets, and
• Resource depletion: Failure to recycle valuable metals increases dependence on mining.
other communication devices.
• Consumer Electronics: Televisions, DVD players, cameras, video game consoles, stereos, and
On Human Health
other entertainment devices.
• Neurological damage: Lead and mercury exposure affects brain function, especially in
children.
• Respiratory issues: Inhalation of toxic fumes from burning e-waste causes lung diseases and
breathing problems.
• Kidney and liver damage: Cadmium and other metals accumulate in vital organs, impairing
their function.
• Cancer risk: Long-term exposure to carcinogenic substances like dioxins, arsenic, and
brominated flame retardants.
• Reproductive and developmental disorders: Toxic chemicals affect fertility, pregnancy, and
child development.
• Skin and eye irritation: Direct contact during informal recycling causes rashes, burns, and eye
problems.

Artificial intelligence in e-waste management

Artificial intelligence (AI) is increasingly being applied in e-waste management to improve

collection, sorting, recycling, and overall sustainability.
Artificial Intelligence (AI) in E-Waste Management (Chemistry Perspective)

• Identification of hazardous chemicals: AI tools detect and classify toxic chemicals such as
lead, mercury, cadmium, and brominated flame retardants in e-waste using advanced sensor data
and pattern recognition.
• Chemical composition analysis: Machine learning models process spectral data (XRD, XRF,
FTIR) to rapidly determine the composition of metals, plastics, and semiconductors, enabling
targeted recycling.
• Intelligent sorting and separation: AI-driven robotic systems utilize chemical property data
(conductivity, density, magnetic behavior) to efficiently separate recyclable metals from
hazardous or non-recyclable substances.
Prediction of toxic leaching: AI predicts the leaching behaviour of chemicals from e waste into
soil and water, supporting the design of eco-friendly chemical treatments and containment
strategies.
• Optimization of recycling processes: Algorithms recommend green chemical methods such as
bioleaching and solvent extraction for efficient recovery of valuable metals like gold, copper,
and palladium.
• Environmental impact monitoring: AI models continuously track chemical pollution levels
in air, water, and soil around e-waste sites, ensuring compliance with environmental safety
standards.
• Waste-to-resource conversion: AI supports chemical upcycling, transforming hazardous e-
waste materials into valuable products such as nanomaterials and catalysts.
• Data-driven policy and management: AI systems provide actionable insights for
policymakers to regulate toxic chemical disposal and promote sustainable, advanced recycling
technologies.

Extraction of Gold from E-Waste by Bioleaching:

Bioleaching is a sustainable and eco-friendly technique that uses microorganisms to recover gold
from electronic waste, replacing toxic chemical-intensive methods.

Pre-treatment of E-Waste: Printed circuit boards and gold-plated parts are shredded and
pulverized to increase surface area. Chemical leaching with nitric/sulfuric acid and hydrogen
peroxide removes base metals like copper, nickel, and zinc that interfere with gold dissolution.

Microbial Culture Preparation: Cyanogenic bacteria such as Chromobacterium violaceum or

Pseudomonas aeruginosa are cultured under optimized pH, temperature, and nutrient conditions.
These microbes enzymatically convert substrates (e.g., glycine) into hydrogen cyanide (HCN),
which dissociates into cyanide ions (CN⁻).

Microbial cyanide generation:

𝐶2𝐻5𝑁𝑂2 + 𝑂2 → 𝐻𝐶𝑁 + 𝐶𝑂2 +𝐻2𝑂
Bio-Cyanidation (Two-Step Leaching):
Step 1: Microbes are grown until exponential phase to maximize cyanide production.

Step 2: The spent culture medium (rich in CN⁻) is separated and added to pre treated e-waste. GREEN CHEMISTRY:
This indirect contact avoids microbial exposure to toxic heavy metals. Introduction to Green Chemistry
Green chemistry focuses on designing chemical products and processes that reduce or eliminate
Gold Leaching Reaction: Cyanide ions dissolve metallic gold in the presence of oxygen, hazardous substances, promoting sustainability, environmental safety, and energy efficiency.
forming a stable dicyanoaurate complex:
Introduction to Green Solvents: Green solvents are environmentally benign liquids used to
4𝐴𝑢 +8𝐶𝑁−+𝑂2+2𝐻2𝑂 →4[𝐴𝑢(𝐶𝑁)2]− +4𝑂𝐻− dissolve substances or facilitate chemical processes without harming humans or ecosystems.
They aim to replace hazardous organic solvents with safer alternatives
Recovery of Gold: Gold is recovered from the leachate by zinc cementation, activated carbon • Water – the ultimate green solvent.
adsorption, or electrowinning, followed by refining to pure metal. • Supercritical fluids – like supercritical CO₂ for efficient heat transfer.
• Ionic liquids (ILs) – tunable, non-volatile, and thermally stable.
Extraction of gold from e-waste by Bio-leaching Process • Bio-based solvents – derived from renewable feedstocks like glycerol or ethyl lactate.
It is a TWO Step Process
Properties of Green Solvents for Server Heat Management
Step 1-Dissolution of Cu and Gold For modern server cooling and data center thermal management, green solvents must have
specialized properties:
Electronics crap Materials
1. High Thermal Conductivity & Heat Capacity – Efficiently absorb and transfer heat from
Ground in the vibratory cup
CPUs, GPUs, and other components.
mill
Crushed po der particle si e m 2. Low Viscosity – Ensures smooth circulation in cooling systems with minimal energy
Acid digestion consumption.
3. Electrical Non-Conductivity – Prevents short circuits when in contact with electronics.
Cu and Au solution
4. Chemical & Thermal Stability – Resistant to degradation at high temperatures; protects
65% nitric acid, boil until brown gas
of NO2 was depleted hardware from corrosion.
Gold solution
5. Non-Toxic & Biodegradable – Safe for humans and the environment, reducing risk in case of
leaks.
6. Freeze & Boil Point Stability – Maintains performance under varying operating
temperatures.
7. Leak Detection Capability – Some solvents are dyed or fluorescent for easy monitoring.
Examples: Propylene glycol-based fluids, silicone-based immersion fluids, and specially
formulated ionic liquids. These are engineered to be compatible with metals like aluminum,
copper, and steel in server hardware.

Green Solvents Applications in Server Heat Management: Green solvents are revolutionizing
data centre cooling through advanced technologies:

Direct Liquid Cooling (DLC): Solvents circulate directly over CPUs, GPUs, and power
components, removing heat efficiently and reducing energy consumption.

Immersion Cooling: Entire servers are submerged in non-conductive green solvents, enabling Uses in IT Infrastructure Applications Green Dielectric Coolant: Used as a non-toxic
higher server density, uniform cooling, and reduced infrastructure footprint. insulating liquid in data centre transformers and server cooling systems. Prevents short circuits
and improves heat dissipation.
Hybrid Cooling Systems: Combines air and liquid cooling using green solvents to optimize
thermal efficiency and energy use. High-Temperature Lubricant for Hardware: Can act as a biodegradable lubricant for
mechanical components like hard disk drives or server fans.
Sustainable Operations: Green solvents with low global warming potential (GWP) and zero
ozone depletion potential (ODP) help achieve eco-friendly, carbon-neutral data center Phase Change Cooling Media: With high thermal stability, used in immersion cooling of CPUs
operations. and GPUs to maintain optimal temperatures. Reduces thermal hotspots in high performance
computing.
Synthesis and properties of glycerol trioleate ester and its uses in IT infrastructure
applications. Fire-Safe Alternative to Mineral Oils: Low flammability makes it a safer alternative for liquid
Synthesis of Glycerol Trioleate cooling in server racks.
on esterification reaction between glycerol (a triol) and oleic acid (a fatty acid) in presence of
acid catalyst (e.g., p-toluenesulfonic acid or H₂SO₄) under heat 140–220°C to form Glycerol Eco-Friendly Thermal Management: Being biodegradable and non-toxic, it minimizes
Trioleate. environmental hazards in IT facility maintenance.

Enhanced Reliability of Electronics: Reduces thermal stress on sensitive ICs, prolonging the
lifespan of critical infrastructure.

Green Solution Combustion Synthesis of ZnO Nanoparticles and its uses in magnetic Radio
Frequency Identification (RFID) and Internet of Nano Things (IONT) system applications.

Solution combustion synthesis (SCS) is a rapid and energy-efficient route for producing zinc
oxide (ZnO) nanoparticles. The process becomes greener when sugarcane juice is used as the
fuel.

Sugarcane juice contains sucrose, glucose, and fructose, which act as natural reducing and
complexing agents. During combustion, these sugars decompose to release gases (CO₂, H₂O), ZnO Nanoparticles in Magnetic RFID
creating porosity and leaving ZnO nanoparticles as the final product. • Magnetic Properties: Doping ZnO with Fe, Ni, or Co induces room-temperature
ferromagnetism.
• Dissolve 3.65g of zinc nitrate hexahydrate [Zn(NO₃)₂·6H₂O] in distilled water. • Enhanced Data Storage: Magnetic ZnO allows higher data density and non-volatile
• Zn(NO₃)₂ → Zn²⁺ + 2NO₃⁻ memory in RFID tags.
• Add 7.3 ml Sugarcane juice typically has ~12% w/v sugar in the stoichiometric fuel-to • Improved Security: Magnetic behavior makes RFID tags harder to clone or tamper with.
oxidizer ratio. For sucrose (C₁₂H₂₂O₁₁) as the main fuel: • Sensor Integration: ZnO NPs can detect gases, chemicals, or temperature changes for
• Stir and ultrasonicate the solution for 30 minutes to form a homogeneous mixture. smart RFID tags.
• Heat gently at ~80–90 °C until a viscous gel forms. • Chipless & Passive Tags: ZnO/metal oxide nanocomposites (e.g., ZnO/TiO₂) enable
• Place the gel in a preheated furnace (300–600 °C). passive sensing RFID systems.
• Combustion occurs spontaneously, producing flame and froth as gases (CO₂, H₂O, N₂) • Miniaturization & Flexibility: Nanoparticle form allows small, flexible, and wearable
evolve. RFID tags.
• 24 Zn(NO₃)₂·6H₂O + 5 C₁₂H₂₂O₁₁ → 24 ZnO + 60 CO₂ + 199 H₂O + 24 N₂
(i.e., 24 mol Zn(NO₃)₂ requires 5 mol sucrose). ZnO Nanoparticles in Internet of Nano Things (IoNT)
Cool to obtain porous ZnO ash.
Calcine the powder at 400–500 °C for 2–3 h to remove carbon residues and enhance • Nanoscale Sensing: High surface area and semiconducting properties enable sensitive
crystallinity. detection of environmental or biomedical signals.
• Energy Harvesting: Piezoelectric ZnO nanowires or NPs provide self-powered IoNT
devices.
• Flexible Electronics: ZnO NPs support durable, bendable nanosensors for health
monitoring or smart infrastructure.
• Targeted Biomedical Applications: Magnetic ZnO NPs can deliver drugs or monitor
health internally.
• Autonomous Networks: Magnetic interactions help self-assembly of nanosensor
networks.
• Cost-effective Large-scale IoNT: Enables distributed sensing systems for industrial,
environmental, and medical applications.

Biomaterials / Biodegradable polymers:

Biomaterials are materials—natural or synthetic—engineered to interact with biological systems

for medical, industrial, or technological applications. They are used in implants, drug delivery
systems, tissue engineering, and electronic devices.

Synthesis and properties of Alginate Hydrogel and its uses in Brain Computer Interfaces
(BCIs) applications.
Key Advantages of Green-Synthesized ZnO NPs:
[Link] size and morphology Synthesis of Alginate Hydrogel (Ionotropic Gelation)
[Link] functionalization with biomolecules
[Link]-toxic and sustainable • Starting Material: Sodium alginate, a linear polysaccharide from brown seaweed. Composed
of β-D-mannuronic acid (M) and α-L-guluronic acid (G) units.
• Dissolution: Sodium alginate is dissolved in water to form a viscous polymer solution.
• Cross-linking: A solution of divalent cations, typically CaCl₂, is added. Calcium ions Polylactic Acid (PLA)
(Ca²⁺) replace sodium ions (Na⁺) in G-blocks of alginate chains.
• PLA is one of the most promising biopolymers produced from non-toxic, renewable, and
• Gelation: Ionic bridges form between polymer chains, entrapping water. Results in a stable, 3D naturally occurring lactic acid.
hydrogel network. Described by the “egg-box model”, where Ca²⁺ fits into cavities of G-blocks. • It is a thermoplastic polymer with good mechanical strength, high biocompatibility, and
biodegradable properties.
• Lactic acid is obtained by fermentation of sugars from renewable sources like sugarcane,
maize, or tapioca.

Synthesis of PLA

1. Direct Polycondensation of Lactic Acid

Chemical Reaction

• 2Na(Alg) + CaCl2 → Ca(Alg)2 +2NaCl

Properties of Alginate Hydrogel

• Biocompatibility & Biodegradability: Supports cell adhesion and growth.

• High ater content & Porosity: Facilitates nutrient and ion transport.
• Ionic Conductivity: Hydrated ions allow electrical signal conduction.
• Tissue-like Mechanical Properties: Soft, flexible, tunable stiffness.
• Low Immunogenicity: Minimal inflammatory response; resistant to protein adsorption.
• Electrochemical Adaptability: Can form conductive composites with polymers/nanoparticles.
Properties of PLA
Applications in Brain-Computer Interfaces (BCIs)
• Linear, thermoplastic polymer with ~37% crystallinity.
▪ Soft Electrode Interface: Conforms closely to brain tissue, reducing inflammation and motion • Glass transition temperature: 50–80 °C
artifacts. • Melting point: 170–180 °C
▪ Signal Enhancement: Ionic conductivity and integration with conductive materials improve • Mechanical properties: Good tensile strength; can be processed into fibres.
signal-to-noise ratio (SNR) for electrophysiological recordings. • Solubility: Soluble in chlorinated solvents, dioxane, benzene, and THF. • Biodegradable and
▪ Chronic Implant Stability: Supports long-term recording by reducing tissue scarring and biocompatible, suitable for human contact applications.
immune response.
▪ Flexible, Implantable Electrodes: Used in electrocorticography (ECoG) and local field Uses of PLA in Touch Screen Applications
potential (LFP) recording.
▪ Hybrid Hydrogel Systems: Can incorporate conductive polymers/nanoparticles to enhance • Flexible Substrate: PLA films can be used as a lightweight, flexible substrate for touch
electrical properties while maintaining softness. screens.
▪ Can be engineered for transparency, enabling optical and electrical monitoring. Eco-friendly Material: Reduces environmental impact compared to petroleum-based plastics.

• Protective Coating: Transparent PLA coatings improve scratch resistance. • Electrolyte Component: Used in solid polymer electrolytes for capacitive touch sensors and
• Printable Surface: PLA allows for easy deposition of conductive layers (like ITO or silver flexible electronics.
nanowires) for capacitive touch sensors. Direct Recycling Method of Lithium-Ion Batteries (LIBs)
• Biocompatibility: Safe for devices with frequent human contact.
Direct recycling (also called cathode-to-cathode recycling) is an advanced approach that recovers
Polyethylene Glycol (PEG) and reuses battery materials without breaking them down into elemental metals. Unlike
pyrometallurgical or hydrometallurgical methods, this process preserves the crystal structure and
1. Introduction: PEG is a hydrophilic polymer made from ethylene oxide. Known for electrochemical functionality of active materials, especially the cathode.
solubility in water and organic solvents, biocompatibility, and flexibility. Used in
pharmaceuticals, cosmetics, medical devices, and electronics. Principle

2. Synthesis of PEG The method focuses on:

Selective separation
• A. Ring-Opening Polymerization of Ethylene Oxide: The initiator (water or alcohol) Structural healing (re-lithiation)
attacks the strained ethylene oxide ring in presence of NaOH or KOH as catalyst, opening Reconditioning of electrode materials
it and forming an active alkoxide site. This active site repeatedly attacks additional This enables recovered materials to be reused directly in new batteries.
ethylene oxide monomers, extending the polymer chain until termination, yielding
hydroxyl-terminated linear PEG. Step-by-Step Process

1. Discharging and Dismantling

• Spent LIBs are fully discharged for safety.
• Batteries are dismantled into components:
cathode, anode, separator, current collectors.
2. Physical Separation
• Mechanical processes such as:
• Crushing
• Sieving
3. Properties of PEG: • Magnetic separation
• Cathode and anode powders are separated from aluminum and copper foils.
• Hydrophilic polymer, soluble in water and many organic solvents. 3. Removal of Binders and Electrolyte
• Flexible chain; low glass transition temperature (~ -60°C). • Polyvinylidene fluoride (PVDF) binder is removed using:
• Melting point: Depends on molecular weight (solid for high MW, liquid for low MW). • Green solvents
• Non-toxic, biocompatible, and chemically stable. • Thermal treatment (low temperature)
• Low viscosity for low molecular weight PEG; high viscosity for high molecular weight PEG. • Residual electrolyte and contaminants are eliminated.
4. Cathode Material Recovery
4. Uses of PEG in Touch Screen Applications: • Cathode active materials such as:
• LiCoO₂ (LCO)
• Flexible Coatings: PEG can be used as a transparent, flexible layer to protect touch screens. • LiNiMnCoO₂ (NMC)
• Anti-fouling Coatings: Prevents fingerprint smudges and dust accumulation. • LiFePO₄ (LFP)
• Surface Modifier: Enhances adhesion of conductive layers (ITO, silver nanowires) on flexible • These are collected without destroying their crystal lattice.
substrates. 5. Re-Lithiation (Structural Regeneration)
• Hydrophilic Layer: Improves moisture management in flexible or foldable touch panels. • Lithium loss during battery cycling is restored by:
• Adding lithium salts (Li₂CO₃ or LiOH)
 • Heat treatment (solid-state sintering)
• This step restores electrochemical capacity.
6. Reuse in New Batteries
• Regenerated cathode material is re-fabricated into electrodes.
• Performance is often comparable to commercial virgin materials.

Advantages

• ♻ High material value retention

• 🔋 Superior electrochemical performance
• 🌱 Low energy consumption
• ฀ Minimal chemical waste
• 💰 Cost-effective in long term