FUNDAMENTAL OF POLYMER NOTES

1. Chemistry of Polymerization Reaction

Functionality

 Number of reactive sites on a monomer.

 Determines the structure of the polymer (linear, branched, cross-linked).

Polymerization Reactions

 Addition Polymerization: Monomers add without by-products. Involves:

o Initiation (free radicals),
o Propagation (chain growth),
o Termination (combination or disproportionation).
 Condensation (Polycondensation): Monomers react with elimination of small molecules (e.g.,
H₂O, HCl).
 Free Radical Polymerization: Uses radicals to start chain growth.
 Chain Polymerization: Growth via reactive centers (radical, cation, or anion).
 Copolymerization: Two or more different monomers polymerized together (e.g., random,
alternating, block, graft).
 Block Polymerization: Blocks of different monomers joined together.
 Graft Polymerization: Chains of one monomer grafted onto backbone of another.
 Stereo Specific Polymerization: Control over stereochemistry (isotactic, syndiotactic, atactic).

2. Kinetics of Polymerization

Free Radical Polymerization Kinetics

 Rate = kₚ[M][R•], depends on monomer and radical concentration.

 Involves steps: initiation, propagation, termination.

Chain Polymerization

 Growth in steps; rate determined by initiation and propagation steps.

Ionic Polymerization

 Anionic and Cationic mechanisms.

 Very fast, sensitive to impurities and moisture.

Copolymerization Kinetics

 Reactivity ratios (r₁, r₂) determine monomer incorporation.

 Mayo-Lewis equation describes copolymer composition.
3. Molecular Weight Estimation

Types of Average Molecular Weight

 Number Average (Mn): Total weight / number of molecules.

 Weight Average (Mw): Accounts for size distribution.
 Polydispersity Index (PDI) = Mw / Mn (measure of distribution).

4. Polymerization Processes

Bulk Polymerization

 Only monomer + initiator.

 High purity, but heat management difficult.

Solution Polymerization

 Monomer in solvent.
 Good heat control, but difficult solvent removal.

Suspension Polymerization

 Monomer droplets in water with stabilizer.

 Spherical beads form; easy separation.

Emulsion Polymerization

 Monomer + water + surfactant + initiator.

 High rate, latex product formed.

5. Polymer Composites

Thermoplastic Composites

 Can be remelted.
 Reinforced with fibers or fillers.

Fibre Reinforcement & Fillers

 Improve strength, stiffness.

 Examples: glass, carbon, aramid fibers.

Surface Treatment

 Improve adhesion between fiber and matrix.

Reinforced Thermoset Composites

 Thermosets: can't remelt; form cross-linked network.

 Used for high-performance applications.

Resins, Fibers, Additives

 Resins: Matrix (e.g., epoxy, polyester).

 Additives: Plasticizers, stabilizers, pigments.

Fabrication Methods

 Hand lay-up, Spray-up, Pultrusion, RTM (Resin Transfer Molding), Compression molding,
Filament winding.

Types of Polymers

1. Natural Polymers: Found in nature (e.g., cellulose, proteins, rubber).

2. Synthetic Polymers: Man-made (e.g., nylon, polyethylene).
3. Addition Polymers: Formed by addition reaction (e.g., polyethylene).
4. Condensation Polymers: Formed by condensation reaction with by-product (e.g., nylon,
polyester).
5. Linear, Branched, and Cross-linked Polymers:
o Linear: Long straight chains (e.g., HDPE).
o Branched: Side chains attached (e.g., LDPE).
o Cross-linked: Chains linked together (e.g., Bakelite).

Polymer Blends

 Definition: Physical mixtures of two or more polymers to achieve improved properties.

 Types:
o Miscible Blends: Single-phase (e.g., PC/ABS).
o Immiscible Blends: Multi-phase with interfacial bonding.
 Applications: Automotive, packaging, electronics.

Polymer Composites

 Definition: Polymers reinforced with fibers or fillers to improve strength and durability.
 Types:
o Fiber-reinforced (e.g., glass, carbon fiber).
o Particulate-reinforced (e.g., silica).
 Applications: Aerospace, construction, sports equipment.
Materials and Applications of Polymers

 Polyethylene: Packaging, bottles.

 Polypropylene: Automotive parts, textiles.
 PVC: Pipes, cables.
 Polystyrene: Insulation, packaging.
 PTFE (Teflon): Non-stick cookware, electrical insulation.
 Nylon (Polyamide): Gears, clothing.
 Polycarbonate: Lenses, safety helmets.

Engineering Polymers

Polymers with superior mechanical, thermal, and chemical properties used in engineering applications.

Types of Engineering Polymers

1. Thermoplastics
o Soften on heating, harden on cooling.
o Examples: Polyethylene, Polypropylene, Polycarbonate.
2. Thermosets
o Irreversibly hardened by curing.
o Examples: Epoxy, Bakelite.
3. Elastomers
o Elastic and flexible.
o Examples: Natural rubber, Silicone rubber.
4. Polyolefins
o Derived from olefins (e.g., ethylene, propylene).
o Examples: PE, PP.
5. Polyethylene (PE)
o Types: HDPE (rigid), LDPE (flexible).
o Applications: Containers, pipes, films.
6. Polypropylene (PP)
o Good fatigue resistance.
o Applications: Hinges, automotive parts.
7. Polyesters
o E.g., PET (Polyethylene terephthalate).
o Applications: Bottles, textiles.
8. Polycarbonate (PC)
o High impact resistance.
o Applications: Eyewear lenses, bulletproof glass.
9. Polyamides (PA)
o Known as Nylon.
o Applications: Mechanical parts, clothing.
10. Polyetherimide (PEI)
 o High strength, flame resistance.
o Applications: Medical devices, aerospace.
11. Polyamide-imide (PAI)
o Excellent heat and chemical resistance.
o Applications: Automotive, electronics.
12. High Performance Polymers
o Withstand extreme conditions.
o Examples: PEEK, PSU, PTFE.
o Applications: Medical implants, aerospace.
13. High Temperature Resistant Polymers
o Withstand >200°C.
o Examples: PBI, PI, PEEK.
o Applications: Jet engines, electronics.
Characterization of Polymers

Techniques and Instruments Used

1. Molecular Weight Determination

o Gel Permeation Chromatography (GPC): Determines molecular weight distribution.
o Osmometry: Measures number average molecular weight.
o Light Scattering: Measures weight average molecular weight.
2. Thermal Analysis
o Differential Scanning Calorimetry (DSC): Determines Tg, Tm, crystallinity.
o Thermogravimetric Analysis (TGA): Measures thermal stability and decomposition.
3. Spectroscopy
o FTIR (Fourier Transform Infrared): Identifies functional groups.
o NMR (Nuclear Magnetic Resonance): Determines structure and monomer sequence.
4. Mechanical Testing
o Tensile, Flexural, and Impact Testing: Assesses strength, elongation, and toughness.
5. Morphology
o Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM):
Studies surface and internal morphology.
o X-ray Diffraction (XRD): Evaluates crystallinity.

BIS Standards for Polymers

 Bureau of Indian Standards (BIS): Formulates quality standards for polymers used in
packaging, construction, automotive, etc.
 Ensures safety, performance, and environmental compliance.
 Examples:
o IS 10146 for polyethylene used in food packaging.
o IS 7328 for polypropylene for molding and extrusion.

Polymerization Engineering

 Concerned with scaling up polymerization processes for industrial production.

 Focuses on:
o Reactor design (batch, continuous, emulsion).
o Control of reaction kinetics and heat transfer.
o Product quality and consistency.
Polymer Processing

 Conversion of raw polymer into usable products.

 Involves steps like melting, shaping, and solidifying.

Techniques

1. Extrusion – Used to make pipes, films.

2. Injection Molding – Used for precision parts like bottle caps.
3. Blow Molding – For hollow objects like bottles.
4. Compression Molding – Thermosets and large parts.
5. Calendering – Produces thin films and sheets.

Additives in Polymers

 Enhance processing or end-use properties.

 Types:
o Plasticizers – Increase flexibility.
o Stabilizers – Improve thermal/UV resistance.
o Fillers – Reduce cost, improve strength.
o Colorants – Add color.
o Flame Retardants, Lubricants, Antioxidants.

Polymer Products

 Common items:
o Consumer goods: bottles, bags.
o Construction: pipes, panels.
o Automotive: dashboards, bumpers.
o Medical: syringes, catheters.

Introduction to Rheology

 Rheology: Study of flow and deformation of polymer melts.

 Important for understanding processability.
 Viscosity, elasticity, and shear behavior are key parameters.

Polymer Processing Equipment

 Extruder – Continuous processing, used for films and tubes.
 Injection Molding Machine – High-precision parts.
 Blow Molding Machine – Containers and bottles.
 Calendars – For making sheets.
 Mixers (Banbury, Twin-screw) – For compounding polymers and additives.
Manufacturing of Polymers

1. Polyethylene (PE)

 Types: LDPE, HDPE

 Monomer: Ethylene (CH₂=CH₂)
 Process: Free-radical polymerization (LDPE); Ziegler–Natta or metallocene catalysts (HDPE)
 Applications: Packaging, bottles, pipes

2. Polypropylene (PP)

 Monomer: Propylene (CH₂=CH–CH₃)

 Process: Ziegler–Natta catalysis
 Applications: Containers, automotive parts, textiles

3. Polyvinyl Chloride (PVC)

 Monomer: Vinyl chloride (CH₂=CHCl)

 Process: Free radical suspension/emulsion polymerization
 Applications: Pipes, cables, flooring

4. Copolymers

 Definition: Polymers made from two or more different monomers

 Types: Random, alternating, block, graft
 Examples: ABS (Acrylonitrile Butadiene Styrene), SBR (Styrene Butadiene Rubber)

5. Polystyrene (PS)

 Monomer: Styrene (CH₂=CH–C₆H₅)

 Process: Free-radical polymerization
 Applications: Packaging, insulation, disposables

6. Polyamides (e.g., Nylon)

 Monomer: Diamine + dicarboxylic acid (e.g., Hexamethylenediamine + Adipic acid)

 Process: Condensation polymerization
 Applications: Textiles, gears, automotive parts

7. Polyesters (e.g., PET)

 Monomer: Diol + dicarboxylic acid (e.g., Ethylene glycol + Terephthalic acid)

 Process: Condensation polymerization
 Applications: Fibers, bottles, films

8. Acrylics (e.g., PMMA)

 Monomer: Methyl methacrylate (MMA)

 Process: Free-radical polymerization
  Applications: Lenses, displays, signage

9. Phenol-Formaldehyde (PF)

 Monomer: Phenol + Formaldehyde

 Process: Condensation (step-growth)
 Applications: Electrical insulators, adhesives

10. Melamine-Formaldehyde (MF)

 Monomer: Melamine + Formaldehyde

 Process: Condensation polymerization
 Applications: Dinnerware, laminates

11. Polyurethane (PU)

 Monomer: Diisocyanate + polyol

 Process: Addition polymerization
 Applications: Foams, coatings, elastomers

12. Epoxides (Epoxy Resins)

 Monomer: Epichlorohydrin + Bisphenol-A

 Process: Step-growth polymerization
 Applications: Adhesives, coatings, composites

13. Rubbers and Elastomers

 Types: Natural Rubber, Synthetic (e.g., SBR, NBR)

 Process: Addition or condensation polymerization
 Applications: Tires, seals, gaskets

Polymer Mixtures

1. Polymer Compatibilization

 Purpose: Improve miscibility and performance of polymer blends

 Methods: Use of compatibilizers (copolymers, reactive agents)

2. Thermodynamic Theories for Polymer Solutions

 Flory-Huggins Theory: Describes polymer-solvent interactions

 Key Factor: Gibbs free energy change (ΔG = ΔH – TΔS)

3. Solubility Parameter

 Definition: Quantifies polymer-solvent compatibility

  Rule: "Like dissolves like" (closer values = better solubility)

4. Solvents and Plasticizers

 Solvents: Dissolve or swell polymers

 Plasticizers: Lower Tg, increase flexibility (e.g., phthalates in PVC)

5. Polymer Blending

 Definition: Physical mixture of two or more polymers

 Types: Miscible, immiscible
 Uses: Enhance mechanical/thermal properties

6. Reinforced Plastics and Elastomers

 Reinforcements: Fibers (glass, carbon), fillers

 Purpose: Improve strength, stiffness, durability

7. Additives for Polymers

 Types: Stabilizers, antioxidants, UV absorbers, pigments, flame retardants

 Function: Enhance processability, appearance, and performance

8. Polymer Composites

 Definition: Polymer matrix + reinforcing material (fiber/filler)

 Types: Thermoplastic composites, thermoset composites
 Applications: Aerospace, automotive, sports equipment

Plastics

Plastics are synthetic polymers that can be molded into various shapes and forms. They are widely used
due to their light weight, corrosion resistance, and ease of processing.

Molding Processes

1. Extrusion
  Process: Plastic granules are melted and forced through a die to form continuous shapes (pipes,
sheets).
 Used for: Pipes, straws, films, insulation of wires.

2. Injection Molding

 Process: Molten plastic is injected into a closed mold under pressure, then cooled and ejected.
 Used for: Toys, bottle caps, containers, automotive parts.

3. Blow Molding

 Process: Air is blown into a heated plastic tube (parison) inside a mold to expand and form
hollow shapes.
 Types: Extrusion blow molding, injection blow molding.
 Used for: Bottles, containers, tanks.

4. Compression Molding

 Process: A pre-measured amount of plastic is placed in a heated mold, compressed into shape,
and cured.
 Used for: Electrical components, automotive parts, appliance housings.

5. Transfer Molding

 Process: Plastic is heated in a chamber and forced into a mold through a sprue or runner.
 Used for: Electrical and electronic parts, encapsulation of components.

Recycling of Polymers

 Importance: Reduces plastic waste, conserves resources, and lowers pollution.

 Types of Recycling:
o Primary: Reusing waste plastics with minimal processing.
o Secondary: Mechanical recycling into new products.
o Tertiary: Chemical breakdown into monomers.
o Quaternary: Energy recovery through incineration.
 Challenges: Sorting, contamination, degradation of quality.

Applications of Polymers in Commodity Products

 Household Items: Buckets, containers, chairs (HDPE, PP).

 Packaging: Bags, bottles, wraps (LDPE, PET).
 Textiles: Synthetic fibers like nylon, polyester.
 Toys and Utensils: ABS, polystyrene-based items.
 Construction: PVC pipes, sheets, insulation.